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Chemically-Controlled Ultrafast Photothermal Response in Plasmonic Nanostructured Assemblies

  • Andrea Schirato
    Andrea Schirato
    Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    Istituto Italiano di Tecnologia, via Morego 30, I-16163 Genova, Italy
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  • , 
  • Luca Moretti
    Luca Moretti
    Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
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    Orcidhttps://orcid.org/0000-0001-8092-0752
  • , 
  • Zhijie Yang
    Zhijie Yang
    Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, 250100 Jinan, China
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    Orcidhttps://orcid.org/0000-0002-5012-9852
  • , 
  • Andrea Mazzanti
    Andrea Mazzanti
    Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
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  • , 
  • Giulio Cerullo*
    Giulio Cerullo
    Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    Istituto di Fotonica e Nanotecnologie - Consiglio Nazionale delle Ricerche, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    *E-mail: [email protected]
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    Orcidhttps://orcid.org/0000-0002-9534-2702
  • , 
  • Marie-Paule Pileni
    Marie-Paule Pileni
    Department of Chemistry, Sorbonne University, 75005 Paris, France
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    Orcidhttps://orcid.org/0000-0001-6750-0577
  • , 
  • Margherita Maiuri
    Margherita Maiuri
    Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    Istituto di Fotonica e Nanotecnologie - Consiglio Nazionale delle Ricerche, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
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    Orcidhttps://orcid.org/0000-0001-9351-8551
  • , and 
  • Giuseppe Della Valle*
    Giuseppe Della Valle
    Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    Istituto di Fotonica e Nanotecnologie - Consiglio Nazionale delle Ricerche, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    *E-mail: [email protected]
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    Orcidhttps://orcid.org/0000-0003-0117-2683
Cite this: J. Phys. Chem. C 2022, 126, 14, 6308–6317
Publication Date (Web):March 30, 2022
https://doi.org/10.1021/acs.jpcc.2c00364

Copyright © 2022 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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Plasmonic nanoparticles are renowned as efficient heaters due to their capability to resonantly absorb and concentrate electromagnetic radiation, trigger excitation of highly energetic (hot) carriers, and locally convert their excess energy into heat via ultrafast nonradiative relaxation processes. Furthermore, in assembly configurations (i.e., suprastructures), collective effects can even enhance the heating performance. Here, we report on the dynamics of photothermal conversion and the related nonlinear optical response from water-soluble nanoeggs consisting of a Au nanocrystal assembly trapped in a water-soluble shell of ferrite nanocrystals (also called colloidosome) of ∼250–300 nm in size. This nanoegg configuration of the plasmonic assembly enables control of the size of the gold suprastructure core by changing the Au concentration in the chemical synthesis. Different metal concentrations are analyzed by means of ultrafast pump–probe spectroscopy and semiclassical modeling of photothermal dynamics from the onset of hot-carrier photogeneration (few picosecond time scale) to the heating of the matrix ligands in the suprastructure core (hundreds of nanoseconds). Results show the possibility to design and tailor the photothermal properties of the nanoeggs by acting on the core size and indicate superior performances (both in terms of peak temperatures and thermalization speed) compared to conventional (unstructured) nanoheaters of comparable size and chemical composition.

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 Special Issue

Published as part of The Journal of Physical Chemistry virtual special issue “Marie-Paule Pileni Festschrift”.

Introduction

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The photothermal properties of plasmonic (i.e., metal-based) nanostructures and nanocomposite materials have been the subject of intensive research over the last years. (1,2) The control of light-to-heat conversion processes at the nanoscale, both in terms of efficiency and dynamics, is indeed pivotal in a variety of fields in science and technology. (3,4) For instance, applications of plasmon-based nanoheating range from hydrogen production (5,6) to photocuring, (7) from light harvesting (8,9) and photocatalysis (10−12) to steam generation (13−15) and water purification. (16,17) Similarly, in nanomedicine, molecule detection, (18,19) together with drug delivery (20,21) and cancer therapies, (22,23) are further examples of techniques exploiting the photothermal dynamical response of plasmonic nanocrystals (NCs). Such a great interest in plasmonic materials is motivated by the efficient and easily tunable light-to-heat conversion upon the excitation of localized surface plasmon resonances (LSPRs), (24,25) that is, coherent oscillations of the metal conduction electrons. The latter rapidly decay nonradiatively into a nonequilibrium distribution of hot carriers that equilibrate with the colder metal lattice, (26) entailing the heating of the surrounding microenvironment. (27−30) Importantly, such a mechanism occurs at an ultrafast rate and generates a strongly localized and finely controllable increase in temperature, which makes plasmonic nanostructures particularly suitable as nanosources for local heating.
In most photothermal studies and applications, ensembles of noninteracting plasmonic NCs are employed. However, in pioneering works on plasmonic heating, (31) the most favorable configuration to heat up the environment has been shown to be in the form of NC assemblies. Indeed, as NCs aggregate, collective thermal effects take place thanks to the interaction between neighboring nanostructures, effectively promoting a substantial heating. In this collective regime, hot spots at high temperatures featuring fast dynamics can be generated in the embedding environment, outperforming isolated NCs both in the speed and magnitude of the temperature change. (31−33) Assemblies giving rise to such a collective heating mechanism are mainly of two kinds: they can either be supported on a planar substrate or they can be in the form of free-standing aggregates. In the former case, assemblies are more often periodic arrays, that is, so-called quasi two-dimensional metamaterials. (34,35) However, the presence of the substrate prevents such structures from being employed as real-world photothermal agents for light-driven in vivo applications. On the contrary, free-standing assemblies, also referred to as suprastructures, can be synthesized in water-soluble configurations. (36) Interestingly, despite the theoretical predictions (31,33) of superior nanoheating performances from plasmonic assemblies, comprehensive studies on the advantages of collective effects in suprastructures as well as applications of nanoassemblies to localized heating have been limited until very recently. (37−40) This holds particularly true for assemblies in the free-standing configuration, the synthesis and design of which is of great interest, for example, for nanomedicine applications, such as photothermal therapies and targeted drug/cell delivery, requiring biocompatible solutions.
Toward this direction, recent advances in the chemical synthesis of suprastructures with finely controlled size, shape, and chemical composition have been reported. (41−43) Inorganic colloidal NCs have been demonstrated to self-assemble in 3D ordered aggregates embedded in an organic polymeric matrix, allowing novel approaches to the control over photothermal effects. (44−46) Such manufacturing techniques have thus enabled the synthesis of free-standing shells of ferrite (Fe3O4) NCs, referred to as colloidosomes, as well as supraballs (spherical assemblies of Fe3O4 NCs) and colloidosomes semifilled with NCs. (47)
In this work, we produce new supracrystalline colloidal eggs called nanoeggs. These suprastructures are colloidosomes (shells of ferrite NCs) having at their center assemblies of Au NCs. By acting on the Au NCs concentration, the size of the metallic core can be finely adjusted. The average sizes of these nanoeggs are 250–300 nm, whereas the Au NC assembly core size can increase to reach that of the whole colloidosome. A combination of femtosecond pump–probe spectroscopy and semiclassical modeling of the thermomodulational nonlinearities in Au is employed to investigate the ultrafast photothermal dynamical response of such water-soluble aggregates. Our results provide insight into the light-induced energy relaxation processes and the impact of the plasmonic assembly size on both the optical and the thermal response. By comparing the ultrafast differential transmittance of samples with different Au concentrations, we demonstrate the possibility to control the photothermal ultrafast response of such nanoeggs by tuning the size of the plasmonic suprastructure core. Moreover, by means of numerical simulations, we report a direct comparison between nanoeggs and unstructured nanoheaters under ultrashort laser pulse excitation. Both optical and thermal results demonstrate unambiguously the crucial role of the nanostructure for the engineering of the ultrafast photothermal properties of NC assemblies. Compared to standard nanoheaters with equivalent sizes and compositions, the nanoeggs achieve higher peak temperatures and faster thermalization dynamics. Our results extend current opportunities for the application of plasmonic nanoassemblies to light-driven drug release and photothermal therapy.

Materials and Methods

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Fabrication

We synthesized inverted spinel ferrite NCs with magnetite and wurtzite traces as previously described, (48) which we refer to as Fe3O4 NCs. They are coated with oleic acid (OA, [CH3-(CH2)7-CH═CH-(CH2)7-COOH]) and characterized by a 10-nm average diameter, with 8% size distribution. Au NCs coated with dodecanethiol (C12H25SH) are characterized by an average 5-nm diameter, with a 5% size distribution. (49,50)
To produce colloidosomes, shells of Fe3O4 NCs, 3 mg of Fe3O4 NCs were dispersed in a mixed solvent with 400 μL of chloroform and 8 μL of octadene (ODE, [CH3-(CH2)5-CH═CH2]). This colloidal solution was added to an aqueous solution containing 18 mg of dodecyltrimethylammonium bromide (DTAB, [C12H25N(CH3)3+Br–)]). The resulting solution was intensely agitated by a vortex for 30 s. Subsequently, 5 mL of ethylene glycol solution containing 0.4 g of polyvinylpyrrolidone (PVP, K30, Mw = 40000) was added swiftly into the emulsion and subjected to agitation with a vortex for another 30 s. The emulsion was then heated to 70 °C under a N2 protective atmosphere and kept at this temperature for 15 min to evaporate the inner chloroform phase. The suspension was finally allowed to cool to room temperature. The resulting NC assemblies were washed twice with water and redispersed in deionized water.

Experimental Pump–Probe Measurements

Ultrafast pump–probe experiments were performed using an amplified Ti:sapphire laser (Coherent Libra), producing ∼100 fs pulses at 1 kHz repetition rate, 800 nm central wavelength, and 4 mJ total output energy. The 400 nm pump pulses used to excite the samples were obtained by the second harmonic generation of the laser output using a 1 mm thick β-barium borate crystal. The broadband probe pulses were instead generated by means of a white-light continuum generation process, achieved by focusing the 800 nm beams into a 2-mm thick sapphire plate, thus providing a probe spectrum spanning the 450–780 nm wavelength range. The pump pulses were focused to a spot size radius w0 = 137.5 μm (corresponding to an effective area and the energy used per pulse was Ep = 100 nJ, thus achieving a fluence of ∼340 μJ/cm2. The temporally delayed probe pulses were focused on an 87.5 μm spot size and were collected after the sample by a high-speed spectrometer (Entwicklungsbuero EB Stresing) working at the full 1 kHz laser repetition rate. The measured quantity is the differential transmission of the probe pulses with and without the pump pulses as a function of the probe wavelength and pump–probe delays, ΔT/T(λ, t). All samples were measured at room temperature in solution in a 1-mm optical path quartz cuvette.

Numerical Modeling

To describe the optical behavior of the samples both in static conditions and upon ultrashort laser pulse illumination, a combination of finite element-method (FEM) models and a semiclassical description of the ultrafast light-to-heat conversion dynamics has been employed. With the former we simulated either in unperturbed or photoexcited conditions the electromagnetic response of the nanoeggs, while the latter was used to determine the photoinduced dynamical changes in the optical properties of the structures. With the aim of capturing the most significant spectral and temporal features of the complex sample response while keeping the numerical tool agile, a reduced two-dimensional (2D) FEM model has been developed. Albeit in 2D, the considered geometry reproduces the in-plane nanostructured configuration of the suprastructures without an effective-medium-like description of the nanocomposite material, namely considering an assembly of Au NCs embedded in a polymeric matrix (mimicking dodecanethiol), surrounded by the ferrite colloidosome (which forms the shell of our nanoeggs), and immersed in water. Note that the reduction of the structure into a 2D (in-plane) geometry, introducing translational invariance in the third dimension, implies that NCs are treated numerically as nanowires infinitely extended in the out-of-plane direction. Despite this approximation, our model allows us to reproduce the most relevant aspects of the system and, in particular, to capture the plasmonic resonance behavior of the Au NCs as well as the photonic effects induced by the assembly configuration. Regarding the former, it is worth noticing that, contrary to the case of nanospheres, the plasmonic resonance in nanowires can be excited only when the electric field of incident light is transverse to the nanowire axis. Therefore, in our simulations we consider p-polarized plane waves. Of course, the polarizability and extinction cross-section of nanowires scale differently to those of nanospheres (see, e.g., ref (51) and references therein). However, for p-polarized light, the 2D model is capable of capturing the qualitative behavior in terms of the linear and nonlinear response of the plasmonic resonance of Au NC assemblies, (39) yet keeping the numerical analysis relatively agile. Further comments on our modeling assumptions, together with the geometrical parameters used in the model, are provided in the Supporting Information, Section S1. This FEM model, simulating the electromagnetic interaction between the egg-like structure and light, enables us to estimate the wavelength dependent suprastructure transmittance, T(λ), in static conditions. Details on the implementation of the model are provided in the Supporting Information, Section S2.
To simulate the ultrafast pump–probe spectroscopy experiments, a dynamical rate-equation model has been employed. Its implementation is an extension of the well-established three-temperature model (3TM), (52) widely used to describe photoexcitation of metallic (53) as well as semiconducting (54) nanostructures upon ultrashort laser pulse illumination. In this framework, the photoexcitation of hot carriers in the plasmonic material and subsequent ultrafast energy exchanges are described in terms of three internal degrees of freedom: the excess energy stored in a nonthermalized portion of out-of-equilibrium carriers, N, the temperature of the thermalized hot electrons, ΘE, and the metal lattice temperature, ΘL. To include a dissipation channel related to the thermal energy transfer from the metallic system to the polymeric matrix, a fourth temperature, ΘO, referred to the organic compound, has been introduced in the coupled rate equations. The resulting four-temperature model (4TM) reads, in agreement with previous studies, (39) as follows:
(1)
(2)
(3)
(4)
In eq 1, pa(t) represents the electromagnetic power density absorbed by the plasmonic system following photoexcitation, while the coefficients in the four equations above govern the energy relaxation processes involved in photoexcitation. Details on definitions and values of the parameters set in the simulations are provided in the Supporting Information, Section S3. The following step in the simulation of the ultrafast response of the nanostructures starts from the temporal evolution of the energetic degrees of freedom in the hybrid plasmonic–organic system to determine the corresponding permittivity modulation photoinduced by the pump pulse absorption. To this purpose, based on the dynamical energetic variables referred to the metal (N, ΘE, ΘL), we followed a well-established description of Au thermomodulation nonlinearities, (53) detailed in the Supporting Information, Section S3. In addition to the modulation of the transient permittivity in the metal, an increase in the polymer temperature ΔΘO is also able to affect the system optical properties. Indeed, a thermo-optical effect is induced in the organic matrix, resulting in a transient permittivity modulation ΔεO. By considering the most general case of a complex-valued thermo-optical coefficient η + iζ, the resulting permittivity variation is complex as well, with a real part and an imaginary part , with nO representing the organic matrix refractive index.
As a final step, the FEM model detailed above is employed to determine the transient transmittance of the structure by simulating the interaction of the perturbed structure with a probe pulse impinging at a fixed delay time with respect to the pump. Numerical results are then compared to the ΔT/T signal from pump–probe spectroscopy measurements by following a perturbative approach (its implementation being detailed in the Supporting Information, Section S3).
For the system thermal response, time-dependent simulations have been performed on the same 2D geometrical domain used in electromagnetic simulations. The model implements the standard heat transfer problem in terms of the Fourier equation for heat diffusion, solved for the temperature field across the structure and considering a heat source mimicking the thermal effect of photoexcitation. Further information on expressions and parameters employed can be found in the Supporting Information, Section S4.
Lastly, regarding the comparison between suprastructures and unstructured plasmonic nanoheaters, both optical and thermal simulations have been performed for a fictive homogeneous hybrid structure, consisting of a Au nanocrystal coated with a polymeric layer, with Au and polymer content being equivalent to those considered in the corresponding assembly configuration. In the 2D model implemented, such a structure becomes a circle of radius Rc, set so to match the Au volume of the 2D suprastructure model, namely , with n2D the number of Au NCs in the 2D simulation and r being their radius. The obtained values roughly range between 15 and 35 nm. Except for the structure of the metallic domain, the FEM model and the dynamical optical simulations are performed following the same procedure detailed above.

Results and Discussion

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To produce colloidal “egg” structures called, for simplicity, nanoeggs, 5-nm Au NCs coated with dodecanethiol are added to the 10-nm Fe3O4 NCs dispersed in chloroform (see Materials and Methods). At the end of the procedure, “nanoeggs” are produced. Figure 1a shows that Au NCs self-assemble at the center of the colloidosomes. By keeping the same Fe3O4 concentration (3 mg) and increasing the Au concentration from 0.3 to 3 mg in 400 mL, the size of the Au NC assemblies at the center of colloidosomes progressively increases. Hence, the fixed ratio between the concentrations (C) of Au and Fe3O4 (i.e., metallic core versus colloidosome), determines the size of the plasmonic suprastructure core. Here, we investigate the impact of the size of the Au NC assembly on the photothermal response of nanoeggs, with three samples corresponding to cr = 0.1, 0.3, and 1 from left to right, respectively, in Figure 1a. The center-to-center distances between Au NCs and between Fe3O4 NCs are kept fixed (2 and 3 nm, respectively), while the Au NC assembly size undergoes substantial changes. This is clearly discernible by comparing images of the three samples, revealing that the chemically controlled size of the plasmonic core (darker spots in Figure 1a) is almost doubled between suprastructures with cr = 0.1 (Figure 1a, left) and cr = 1 (Figure 1a, right).

Figure 1

Figure 1. Static optical response of plasmonic suprastructures. (a) Transmission electron microscopy (TEM) images of the samples. Top labels refer to the Au concentration ratio cr, of 0.1, 0.3, and 1 from left to right, respectively. (b, c) Measured (b) and simulated (c) absorbance of the nanoeggs with cr = 0.1 (red curves), 0.3 (green curves), and 1 (blue curves), respectively. The inset shows a schematic of the geometry used in the simulation with the corresponding normalized spatial pattern of absorption at 400 nm.

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Importantly, a change in Au relative concentration has a direct impact on the static optical response of the samples, as shown in Figure 1b, which reports the measured absorbance from the three structures analyzed, namely the quantity A = – log10(T), with T being the sample transmission (see also Supporting Information, Section S1). Indeed, absolute values of absorbance increase with size over the entire visible range and the resonant feature, rather weak for the lowest concentration sample (cr = 0.1, red curve in Figure 1b), becomes gradually more pronounced and slightly red-shifts, while the Au NC assembly size increases, resulting in a well-defined peak at ∼580 nm when cr = 1 (blue curve, Figure 1b). The changes in the sample absorbance spectra induced by the difference in Au:Fe3O4 concentration ratio were interpreted with a newly developed model (details provided in Materials and Methods and in Supporting Information, Sections S1 and S2). Numerical results are shown in Figure 1c, where a schematic of the model is also reported (refer to panel inset). A reduced 2D geometry is defined to mimic the hybrid nanoegg configuration and excited with a monochromatic electromagnetic plane wave with in-plane polarization. The simulated absorbance spectra are in good agreement with measured data. This confirms that the spectral distortion observed when the size of the plasmonic suprastructure core is increased is ascribable to the onset of a photonic resonant mode of the Au assembly, in agreement with previous investigations. (39,41) In these terms, the resonant feature of the plasmonic supraparticle is dominated by a collective response of the metallic NCs, rather than being dictated by the quasi-static resonance of the single NCs. As such, colloidal nanoeggs with a large core size behave as Mie-like nanoscatterers.
The static behavior of nanoeggs with different values of cr suggests that the chemical control of the Au relative concentration, resulting in a tuning of the plasmonic core size, can act as a new and efficient degree of freedom to control the static optical response of these nanoassemblies. Interestingly, this degree of freedom can be exploited to control also the photothermal dynamics of the structures. To demonstrate such a capability, we performed ultrafast pump–probe spectroscopy experiments. The samples are excited with intense (pump) laser pulses of duration ∼100 fs at λp = 400 nm wavelength. The relative differential transmittance ΔT/T(λ, t) experienced by a broadband weak (probe) pulse, arriving on the sample at a time delay t with respect to the pump pulse, is then recorded as a function of t and probe wavelength λ (details of the experimental procedure provided in the Materials and Methods). We also performed simulations of the nonequilibrium optical response aimed at modeling quantitatively the pump–probe experiments (see Materials and Methods and Supporting Information, Section S3 for details on the theoretical model). The main results of this combined experimental and theoretical investigation on the transient optical response of the samples are reported in Figure 2, each row corresponding to a fixed value of relative concentration cr, namely 0.1 (Figure 2a–d), 0.3 (Figure 2e–h), and 1 (Figure 2i–l), from top to bottom. Both short (up to 20 ps) and long (up to 1 ns) time scales are analyzed for a probe pulse in the visible.

Figure 2

Figure 2. Transient optical response of plasmonic suprastructures for varying Au concentration. (a–d) Experimental (a, b) and simulated (c, d) 2D maps of the ultrafast transient differential transmittance from the suprastructure sample with 0.1 Au concentration, excited at λ = 400 nm pump wavelength and Fp ∼ 340 μJ/cm2 pulse fluence, shown at short (a, c) and long (b, d) pump–probe time delays. (e–h) Same as (a)–(d) for the sample with a concentration of 0.3. (i–l) Same as (a)–(d) for the 1 concentration sample.

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By focusing on the measurements of the sample with the lowest concentration, cr = 0.1 (Figure 2a,b), its transient response at short delays (Figure 2a) exhibits a short-lived positive lobe, centered at ∼550 nm and extinguished within ∼5 ps. Both at longer and shorter wavelengths, two negative bands arise on an ultrafast time scale as well. Such features can be attributed to the characteristic broadening and shift effects of the LSPR of the individual NCs, well reported in literature. (55,56) On the other hand, at longer time delays (Figure 2b), the ΔT/T signal displays a peculiar dynamic, which is not commonly observed in plasmonic systems on such ultrafast time scales and was almost unexplored until very recently. (39) Indeed, instead of decreasing monothonically toward the initial equilibrium state, the ΔT/T signal undergoes a delayed build-up. The onset of such further buildup of the signal occurs within less than 100 ps and gives rise to a long-lived broad (almost 200 nm) positive band in the ΔT/T spectrum. In agreement with previous studies, (39) this spectral feature can be related to the ultrafast thermo-optical response from the organic matrix embedding the Au assembly. Simulations of the sample with cr = 0.1 well match experiments, despite the reduced 2D model employed, which is still capable of accounting for the main features of the ultrafast optical response. At short delays (Figure 2c), the transient signal from the suprastructure is explained as a purely plasmonic fingerprint of the NC assembly. Indeed, its spectral and temporal features are reproduced by including in the model the photoinduced permittivity modulation of Au NCs, which is dictated by the ultrafast nonlinear dynamics of the internal degrees of freedom of the metal, namely the excess energy in a nonthermalizd portion of out-of-equilibrium carriers, an electronic temperature, and the Au lattice temperature (further details are in Materials and Methods and Supporting Information, Section S3). The mismatch in the red-shifted negative band of the differential transmittance, weaker in the simulations if compared to measurements, is expected to be due to the fact that the optical behavior of this sample (consisting of nanoeggs with the smallest core size) might be more sensitive to size dispersion and to the specific structural configuration within the Au assembly. The reduced 2D model, assuming identical and ordered (in a hexagonal lattice) NC aggregates, could therefore prevent the reproduction of the transient spectrum in all details. The simulated signal at longer delays (Figure 2d, to be compared with experiments on the same time scale in Figure 2b) is instead obtained by accounting for a modified permittivity of the organic matrix following a thermo-optical mechanism. The plasmonic assembly driven temperature increase in the polymer triggers a dynamical change in its optical properties, which results in a nonzero long-lived differential transmittance of the sample. The model implemented (details in Material and Methods and Supporting Information, Section S3) enables the retrieval of the main aspects of the signal, in particular its ultrafast onset and the two-sublobe structure.
Most importantly, pump–probe spectroscopy shows a significant impact of the relative Au content on the transient transmittance of the suprastructures, revealing the possibility to tailor the photothermal properties of nanoeggs by exploiting plasmonic assembly effects. The measured ΔT/T maps at short delays for the three samples with different Au content (Figure 2a,e,i) share the same plasmonic-related spectral features discussed above, which remain almost unchanged with concentration. The signal increases in absolute value when cr passes from 0.1 to 0.3 and 1, as a consequence of the larger size of the plasmonic NC assembly, without substantial distortions in the spectrum. Conversely, major differences are recorded at longer time delays (compare Figure 2b, f, and j). In particular, the positive band governed by the thermo-optical effect from the organic matrix in the nanoegg core is enhanced and its buildup becomes faster with increasing cr. Furthermore, the spectral width of the lobe broadens and the more pronounced peak at longer wavelengths undergoes a red-shift of several tens of nm (compare panels in the second column of Figure 2). The control over the photothermal properties of the sample by the modification of cr is also reproduced by numerical results (compare Figure 2d, h, and l). Simulated maps well correlate with measurements in both time regimes, namely when either plasmonic or thermo-optical effects govern the optical signal. The model, despite being a 2D simplified approach, is capable of accounting for all the main modifications in the differential transmittance introduced by the change in Au phase dimension within the nanoegg.
To further investigate the ultrafast dynamics of the optical signal and interpret it in terms of changes in the photothermal properties of the samples, time sections of the transient transmittance are analyzed, for the cr = 1 sample as an exemplary case. Figure 3a,b shows the measured ΔT/T for three selected probe wavelengths, corresponding to the spectral peaks of the ultrafast plasmonic lobes of Figure 2i. The signals at short (Figure 3a) and long (Figure 3b) time delays, corresponding to horizontal sections of 2D maps in Figure 2, are reported and compared to simulations (Figure 3c and d, respectively, the inset referring to the model structure). Numerical results are in good agreement with experiments, apart from a rigid shift in wavelengths. The optical signal exhibits the characteristic dynamics of photoexcited plasmonic nanostructures, with a sub-ps rise time, governed by the rate of photogeneration of thermally equilibrated hot carriers, (57) and a decay time of a few ps, dictated by the electron–phonon scattering time. On the long time scale, time traces clearly show the signal delayed buildup pointed out when commenting the 2D maps of Figure 2. Indeed, after an ultrafast decay, the ΔT/T increases again within a few hundreds of ps, then remains positive throughout the entire time scale explored, up to 1 ns.

Figure 3

Figure 3. Optical dynamics of suprastructure vs coated nanoparticle. (a, b) Experimental time traces selected at specific probe wavelengths λ of the transient signal of the differential transmittance at short (a) and long (b) pump–probe time delays for the sample with Au relative concentration cr = 1. (c, d) Simulated time sections of the optical signal at short (c) and long (d) pump–probe time delays for the same sample. (e, f) Simulated time sections of differential transmittance of a fictitious homogeneous (unstructured) system with equivalent Au volume.

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Most importantly, the assembly configuration of Au NCs has a pivotal role in the photothermal process of the matrix heating, which is responsible for the delayed buildup of the optical signal. Indeed, the observed behavior at longer times cannot be explained by the presence of the Au phase only, and the significant enhancement of thermo-optical effects is rather due to the nanostructuring within the suprastructure core. Hence, to ascertain the influence of collective effects from nanoassemblies on the photothermal dynamics of suprastructures, further optical simulations have been performed on a fictive unstructured system. In particular, an equivalent compact sphere (modeled as a cylinder in 2D) is considered, the volume of which is equal to the sum of the volumes of the single NCs present in the suprastructure core (details in the Materials and Methods). The obtained homogeneous nanoparticle is then embedded in the same organic matrix as the Au NC assembly, both in composition and in size. Such structure (sketched in the inset of Figure 3f) aims at mimicking more conventional colloidal nanoheaters, so to isolate the impact of nanostructuring on the photothermal properties of the water-dispersed nanoeggs. Results of the optical simulations of this fictitious structure are shown in Figure 3e and f at short and long time delays, respectively. While at short delays, no substantial differences are obtained in the predicted ΔT/T if compared to the suprastructure case (Figure 3c), a remarkable change in the signal dynamics is observed in the latter. Indeed, the differential transmittance drops and almost no optical signal is observed, despite the presence of the photoexcited metallic core, which releases heat toward the environment. In this regard, note that simulations have been performed by assuming the same scattering rate governing the heat transfer from phonons of the Au lattice to polymer phonons (the coefficient GO in equations detailed in Materials and Methods and Supporting Information, Section S3). This is the most conservative condition for a comparison between supra- and nanoparticle configurations, which are in fact expected to exhibit different energy relaxation characteristic times. In particular, as discussed more thoroughly later on, a single NC should be associated with a slower heating rate, due to its smaller surface-to-volume ratio if compared to an assembly of NCs with the same volume of gold. In other terms, the comparison between optical signals obtained for the two (clustered and unstructured) configurations, assuming they share the same thermal properties, shows a substantially different photothermal response, which is strongly enhanced in the presence of Au nanoassemblies. Collective effects can take place, and higher temperatures are reached, enabling a more efficient heating process governing the thermo-optics observed for suprastructures.
However, the impact of nanostructuring is not limited to the ultrafast optical behavior. Most interestingly, colloidal nanoeggs enable a refined control over the dynamics of heat flow and subsequent internal thermalization of the assembly. To investigate this aspect, we performed thermal simulations upon transient heating following absorption of ultrashort laser pulses for both colloidal nanoeggs and more conventional coated NCs with the same Au concentration (see Materials and Methods and Supporting Information, Section S4 for details). The main results are shown in Figure 4.

Figure 4

Figure 4. Thermal dynamics of suprastructure vs coated nanoparticles. (a, b) The average temperature increase ΔΘO in the organic coating of a conventional plasmonic nanoparticle (a) is compared with the average temperature achieved in the organic matrix of plasmonic suprastructures (b) under the same excitation conditions, for the Au:Fe3O4 relative concentration analyzed, that is, cr = 0.1 (red curves), 0.3 (green curves), and 1 (blue curves). Colored dots highlight the maximum value of the temperature change reached. (c) Absorption cross-section normalized to the Au volume for suprastructures (solid) and corresponding coated nanoparticles (dashed). All simulations are performed in a 2D configuration.

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The dynamical evolution of the average temperature increase in the organic matrix, ΔΘO, is reported up to 250 ns (a time range almost 2 orders of magnitude longer than the one investigated in the transient optical measurements). This quantity is of interest as it correlates with the performances of a nanoheater: its capability to feature higher peak temperatures and higher heating and cooling rates results in both higher temperatures and temperature gradients induced in its local environment. (2) Note that for conventional nanoparticles (Figure 4a) the cooling rate noticeably decreases with increasing amount of Au (i.e., with increasing size, for this nanoparticle configuration), thus, thermalization with the surrounding aqueous environment becomes slower. This general trend is retrieved also for nanoeggs (Figure 4b), since larger structures always exhibit larger thermal inertia, for a given configuration and chemical composition. However, the assembly configuration displays a decay time of ΔΘO, which is a factor of 2 shorter with respect to the corresponding unstructured configuration for cr = 1. Indeed, by fitting the blue dotted and solid curves in Figure 4a,b with an exponential decay function, a time constant of ∼45 ns is obtained for the former (nanoparticle), against ∼20 ns for the latter (suprastructure). An estimation of such decay times for the six structures is reported in Supporting Information, Section S5. Moreover, a key advantage from nanoeggs is provided in terms of peak temperatures, shown in the inset of Figure 4b. First of all, the rise time of ΔΘO is as fast as ∼200 ps and almost insensitive to Au concentration, its leading edge steepness being the same for the three structures (inset of Figure 4b). In fact, such feature in the dynamics of the simulated ΔΘO is confirmed experimentally by our pump–probe spectroscopy measurements, which provide a ΔT/T signal reaching a plateau with a time constant of the order of ∼200 ps for the three samples analyzed (Figure 2), giving an indirect information on the evolution of ΔΘO. Indeed, in this time scale, the differential transmittance is governed by the thermo-optical response from the organic matrix embedding the Au assembly, which is proportional to the matrix temperature (see Materials and Methods). Conversely, conventional nanoheaters reach their peak temperature at longer time delays for increasing amount of Au (note that the inset in Figure 4a is extended up to 30 ns). Indeed, for larger unstructured NCs, the heat diffusion time across the structure increases, thus resulting in a slower heating dynamics. Such a mechanism, since it is governed by the surface-to-volume ratio of the nanosource of heat, only marginally affects the rise times in the case of suprastructures. In addition, note that for cr = 1, the peak temperature is almost doubled in the assembly configuration (blue dot in the inset of Figure 4b) compared to the case of the unstructured configuration (blue dot in the inset of Figure 4a), under the same excitation conditions. Note also that in the former case the peak temperature increases (although slightly) with cr, whereas the latter case exhibits the opposite trend.
These effects can be interpreted as a direct consequence of the more efficient light-to-heat conversion process enabled by nanoassemblies. When a large number of small NCs is employed, the surface-to-volume ratio of the nanoheater becomes particularly favorable for heat exchange processes, explaining the much higher thermal performances of the assembly compared to an unstructured coated nanoparticle.
A further advantage of nanostructuring and finely controlling the metal concentration is related to the absorption of electromagnetic radiation, which in turns governs the photothermal heating process. Figure 4c shows the trend of the absorption cross-section, evaluated at the pump wavelength (λ = 400 nm) from electromagnetic simulations and normalized to the metallic volume, as a function of Au relative concentration cr, both for suprastructures (solid lines) and unstructured particles (dashed lines). Such a quantity directly affects the heat source driving the temperature increase across the structure [refer to Supporting Information, Section S4 and the expression for Q(t)]. Interestingly, the ratio σabs/VAu decreases with the Au concentration ratio in both suprastructures and nanoparticles, although to a lesser degree for the former. This can be understood by considering, for a fixed volume of Au, the higher penetration depth of radiation across the assembly if compared to a homogeneous configuration. In these terms, nanoassemblies enable the increase in the volume of metal with a more moderate impact on the nanoheater photothermal performances.

Conclusions

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In summary, water-dispersed colloidal nanoeggs consisting of a ferrite colloidosome surrounding a Au NC assembly embedded in a polymeric (dodecanethiol) matrix (i.e., a suprastructure) have been investigated. Different samples have been studied by modifying the Au:Fe3O4 relative concentration, cr, in the chemical synthesis, which acts as a degree of freedom to control the size of the metallic core within the nanoegg. By means of ultrafast pump–probe spectroscopy and modeling of the optical and thermal dynamical behavior of different suprastructures, we provided the evidence that their photothermal properties can be adjusted by varying the Au phase content. This holds true not only in terms of static absorbance, but also for the ultrafast transient optical response. While the plasmonic fingerprint in the differential transmittance spectra remains almost unchanged with cr, the contribution to the signal arising from the thermo-optical effect photoinduced in the organic matrix is substantially modified with Au concentration ratio. Such a mechanism is triggered by an increase of the matrix temperature (in turn, promoted by plasmonic light-to-heat conversion effects) and results in a broadband and pronounced delayed buildup of the differential transmittance optical signal within a few hundreds of ps. This in turns correlates with peculiar heat-flow dynamical features ascribable to collective effects taking place in the NCs assembly, having no counterpart in more conventional nanoheaters made of unstructured plasmonic nanoparticles. In particular, higher peak temperatures with associated faster rise times are achieved when assemblies are involved in the heating process. Also, a faster thermalization with the surrounding microenvironment is obtained, and the higher surface-to-volume ratio in suprastructures entails a more efficient heating process for a size increase if compared to unstructured systems. In a previous study, (46) we internalized selectively either colloidosomes or supraballs, that is, solid spherical fcc assemblies of Fe3O4 NCs in tumor cells. Surprisingly, for the assemblies the Fe3O4 NCs were found to be self-assembled to the lysosome membrane. Furthermore, a marked increase of cellular uptake by tumor cells compared to dispersion of the water-soluble NC building blocks was observed. Such assemblies target different compartments of the tumor microenvironment and trigger local photothermal damages that are inaccessible for isolated NCs. (44) Here with nanoegg suprastructures, we combine the flexibility of colloidosomes and the comparative rigidity of supraballs. (58) Furthermore, here we observed an increase in the global temperature, different from the results obtained with colloidosomes and supraballs. From these data we can reasonably assume a very high efficiency in the photothermal effect induced by water-soluble NC assemblies, which therefore exhibit high performances as nanoheaters and could be used in several research areas and as therapeutic agents.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.2c00364.

  • Notes S1: Reduced 2D geometry to model plasmonic nanoegg; S2: Model of the nanoegg optical response; S3: Dynamical model of nanoegg photoexcitation; S4: Model of the nanoegg thermal response; S5: Organic matrix temperature relaxation (PDF)

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Author Information

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  • Corresponding Authors
    • Giulio Cerullo - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Istituto di Fotonica e Nanotecnologie - Consiglio Nazionale delle Ricerche, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Orcidhttps://orcid.org/0000-0002-9534-2702;  Email: [email protected]
    • Giuseppe Della Valle - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Istituto di Fotonica e Nanotecnologie - Consiglio Nazionale delle Ricerche, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Orcidhttps://orcid.org/0000-0003-0117-2683;  Email: [email protected]
  • Authors
    • Andrea Schirato - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Istituto Italiano di Tecnologia, via Morego 30, I-16163 Genova, Italy
    • Luca Moretti - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Orcidhttps://orcid.org/0000-0001-8092-0752
    • Zhijie Yang - Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, 250100 Jinan, China;  Orcidhttps://orcid.org/0000-0002-5012-9852
    • Andrea Mazzanti - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy
    • Marie-Paule Pileni - Department of Chemistry, Sorbonne University, 75005 Paris, France;  Orcidhttps://orcid.org/0000-0001-6750-0577
    • Margherita Maiuri - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Istituto di Fotonica e Nanotecnologie - Consiglio Nazionale delle Ricerche, Piazza Leonardo da Vinci, 32, I-20133 Milano, Italy;  Orcidhttps://orcid.org/0000-0001-9351-8551
  • Author Contributions

    A.S., L.M., and Z.Y. contributed equally to this work.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This publication is part of the METAFAST project that received funding from the European Union Horizon 2020 Research and Innovation programme under Grant Agreement 899673. This work reflects only the author views, and the European Commission is not responsible for any use that may be made of the information it contains.

References

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    A review. The strong interaction of electromagnetic fields with plasmonic nanomaterials offers opportunities in various technologies that take advantage of photophys. processes amplified by this light-matter interaction. Recently, it has been shown that in addn. to photophys. processes, optically excited plasmonic nanoparticles can also activate chem. transformations directly on their surfaces. This potentially offers a no. of opportunities in the field of selective chem. synthesis. In this Review we summarize recent progress in the field of photochem. catalysis on plasmonic metallic nanostructures. We discuss the underlying phys. mechanisms responsible for the obsd. chem. activity, and the issues that must be better understood to see progress in the field of plasmon-mediated photocatalysis.
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  11. 11
    Swearer, D. F.; Robatjazi, H.; Martirez, J. M. P.; Zhang, M.; Zhou, L.; Carter, E. A.; Nordlander, P.; Halas, N. J. Plasmonic Photocatalysis of Nitrous Oxide into N2 and O2 Using Aluminum–Iridium Antenna–Reactor Nanoparticles. ACS Nano 2019, 13, 8076– 8086,  DOI: 10.1021/acsnano.9b02924
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    11
    Plasmonic Photocatalysis of Nitrous Oxide into N2 and O2 Using Aluminum-Iridium Antenna-Reactor Nanoparticles
    Swearer, Dayne F.; Robatjazi, Hossein; Martirez, John Mark P.; Zhang, Ming; Zhou, Linan; Carter, Emily A.; Nordlander, Peter; Halas, Naomi J.
    ACS Nano (2019), 13 (7), 8076-8086CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    Photocatalysis with optically active plasmonic nanoparticles is a growing field in heterogeneous catalysis, with the potential for substantially increasing efficiencies and selectivities of chem. reactions. Here, the decompn. of nitrous oxide (N2O), a potent anthropogenic greenhouse gas, on illuminated Al-Ir (Al-Ir) antenna-reactor plasmonic photocatalysts is reported. Under resonant illumination conditions, N2 and O2 are the only observable decompn. products, avoiding the problematic generation of NOx species obsd. using other approaches. Because no appreciable change to the apparent activation energy was obsd. under illumination, the primary reaction enhancement mechanism for Al-Ir is likely due to photothermal heating rather than plasmon-induced hot-carrier contributions. This light-based approach can induce autocatalysis for rapid N2O conversion, a process with highly promising potential for applications in N2O abatement technologies, satellite propulsion, or emergency life-support systems in space stations and submarines.
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  12. 12
    Cortés, E.; Besteiro, L. V.; Alabastri, A.; Baldi, A.; Tagliabue, G.; Demetriadou, A.; Narang, P. Challenges in Plasmonic Catalysis. ACS Nano 2020, 14, 16202– 16219,  DOI: 10.1021/acsnano.0c08773
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    12
    Challenges in Plasmonic Catalysis
    Cortes, Emiliano; Besteiro, Lucas V.; Alabastri, Alessandro; Baldi, Andrea; Tagliabue, Giulia; Demetriadou, Angela; Narang, Prineha
    ACS Nano (2020), 14 (12), 16202-16219CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    A review. The use of nanoplasmonics to control light and heat close to the thermodn. limit enables exciting opportunities in the field of plasmonic catalysis. The decay of plasmonic excitations creates highly nonequil. distributions of hot carriers that can initiate or catalyze reactions through both thermal and nonthermal pathways. In this Perspective, we present the current understanding in the field of plasmonic catalysis, capturing vibrant debates in the literature, and discuss future avenues of exploration to overcome crit. bottlenecks. Our Perspective spans first-principles theory and computation of correlated and far-from-equil. light-matter interactions, synthesis of new nanoplasmonic hybrids, and new steady-state and ultrafast spectroscopic probes of interactions in plasmonic catalysis, recognizing the key contributions of each discipline in realizing the promise of plasmonic catalysis. We conclude with our vision for fundamental and technol. advances in the field of plasmon-driven chem. reactions in the coming years.
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  13. 13
    Tao, P.; Ni, G.; Song, C.; Shang, W.; Wu, J.; Zhu, J.; Chen, G.; Deng, T. Solar-Driven Interfacial Evaporation. Nat. Ener. 2018, 3, 1031– 1041,  DOI: 10.1038/s41560-018-0260-7
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    Liu, H.; Huang, Z.; Liu, K.; Hu, X.; Zhou, J. Interfacial Solar-to-Heat Conversion for Desalination. Adv. Energy Mater. 2019, 9, 1900310,  DOI: 10.1002/aenm.201900310
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    There is no corresponding record for this reference.
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    Mascaretti, L.; Schirato, A.; Zboril, R.; Kment, S.; Schmuki, P.; Alabastri, A.; Naldoni, A. Solar Steam Generation on Scalable Ultrathin TiN Nanocavity arrays. Nano Energy 2021, 83, 105828,  DOI: 10.1016/j.nanoen.2021.105828
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    15
    Solar steam generation on scalable ultrathin thermoplasmonic TiN nanocavity arrays
    Mascaretti, Luca; Schirato, Andrea; Zboril, Radek; Kment, Stepan; Schmuki, Patrik; Alabastri, Alessandro; Naldoni, Alberto
    Nano Energy (2021), 83 (), 105828CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
    Plasmonic-based solar absorbers exhibit complete light absorption in a sub-Μm thickness, representing an alternative to mm-thick carbon-based materials most typically employed for solar-driven steam generation. In this work, we present the scalable fabrication of ultrathin plasmonic titanium nitride (TiN) nanocavity arrays that exhibit 90% broadband solar light absorption within ∼ 250 nm from the illuminated surface and show a fast non-linear increase of performance with light intensity. At 14 Suns TiN nanocavities reach ∼ 15 kg h-1 m-2 evapn. rate and ∼ 76% thermal efficiency, a steep increase from ∼ 0.4 kg h-1 m-2 and ∼ 20% under 1.4 Suns. Electromagnetic, thermal and diffusion modeling of our system reveals the contribution of each material and reactor component to heat dissipation and shows that a quasi-two-dimensional heat dissipation regime significantly accelerates water evapn. Our approach to ultrathin plasmonic absorbers can boost the performance of devices for evapn./desalination and holds promise for a broader range of phase sepn. processes.
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  16. 16
    Dongare, P. D.; Alabastri, A.; Pedersen, S.; Zodrow, K. R.; Hogan, N. J.; Neumann, O.; Wu, J.; Wang, T.; Deshmukh, A.; Elimelech, M.; Li, Q.; Nordlander, P.; Halas, N. J. Nanophotonics-Enabled Solar Membrane Distillation for Off-Grid Water Purification. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 6936– 6941,  DOI: 10.1073/pnas.1701835114
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    16
    Nanophotonics-enabled solar membrane distillation for off-grid water purification
    Dongare, Pratiksha D.; Alabastri, Alessandro; Pedersen, Seth; Zodrow, Katherine R.; Hogan, Nathaniel J.; Neumann, Oara; Wu, Jinjian; Wang, Tianxiao; Deshmukh, Akshay; Elimelech, Menachem; Li, Qilin; Nordlander, Peter; Halas, Naomi J.
    Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (27), 6936-6941CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    With more than a billion people lacking accessible drinking water, there is a crit. need to convert nonpotable sources such as seawater to water suitable for human use. However, energy requirements of desalination plants account for half their operating costs, so alternative, lower energy approaches are equally crit. Membrane distn. (MD) has shown potential due to its low operating temp. and pressure requirements, but the requirement of heating the input water makes it energy intensive. Here, we demonstrate nanophotonics-enabled solar membrane distn. (NESMD), where highly localized photothermal heating induced by solar illumination alone drives the distn. process, entirely eliminating the requirement of heating the input water. Unlike MD, NESMD can be scaled to larger systems and shows increased efficiencies with decreased input flow velocities. Along with its increased efficiency at higher ambient temps., these properties all point to NESMD as a promising soln. for household- or community-scale desalination.
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    Kaur, M.; Ishii, S.; Shinde, S. L.; Nagao, T. All-Ceramic Solar-Driven Water Purifier Based on Anodized Aluminum Oxide and Plasmonic Titanium Nitride. Adv. Sustain. Syst. 2019, 3, 1800112,  DOI: 10.1002/adsu.201800112
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    Jans, H.; Huo, Q. Gold Nanoparticle-Enabled Biological and Chemical Detection and Analysis. Chem. Soc. Rev. 2012, 41, 2849– 2866,  DOI: 10.1039/C1CS15280G
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    Gold nanoparticle-enabled biological and chemical detection and analysis
    Jans, Hilde; Huo, Qun
    Chemical Society Reviews (2012), 41 (7), 2849-2866CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Gold nanoparticles (AuNPs) are some of the most extensively studied nanomaterials. Because of their unique optical, chem., elec., and catalytic properties, AuNPs have attracted enormous amt. of interest for applications in biol. and chem. detection and anal. The purpose of this crit. review is to provide the readers with an update on the recent developments in the field of AuNPs for sensing applications based on their optical properties. An overview of the optical properties of AuNPs is presented first, followed by a more detailed literature survey. As the last part of this review, we compare the advantages and disadvantages of each technique, briefly discuss their commercialization status, and some tech. issues that remain to be solved in order to move the technique forward (151 refs.).
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    Wang, C.; Yu, C. Detection of Chemical Polluants in Water Using Gold Nanoparticles as Sensors: a Review. Rev. Anal. Chem. 2013, 32, 1– 14,  DOI: 10.1515/revac-2012-0023
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    Detection of chemical pollutants in water using gold nanoparticles as sensors: a review
    Wang, Chao; Yu, Chenxu
    Reviews in Analytical Chemistry (2013), 32 (1), 1-14CODEN: RACYAX; ISSN:0793-0135. (Walter de Gruyter GmbH)
    A review. Rapid and accurate evaluation of pollutant contamination in water is one of the key tasks of environmental monitoring. To make on-site assessment feasible, the anal. tools should be easy to operate, with minimal sample prepn. needs. Gold nanoparticle (AuNP)-based sensors have the potential to detect toxins, heavy metals, and inorg. and org. pollutants in water rapidly with high sensitivity, and they are expected to play an increasingly important role in environmental monitoring. In this article, the synthesis, fabrication and functionalization of AuNPs are discussed, and the recent advances in the development and application of AuNP-based sensors for the detn. of various pollutants contamination in water are reviewed.
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    Wang, Y.; Kohane, D. S. External Triggering and Triggered Targeting Strategies for Drug Delivery. Nat. Rev. Mater. 2017, 2, 17020,  DOI: 10.1038/natrevmats.2017.20
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    External triggering and triggered targeting strategies for drug delivery
    Wang, Yanfei; Kohane, Daniel S.
    Nature Reviews Materials (2017), 2 (2), 17020CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)
    A review. Drug delivery systems that are externally triggered to release drugs and/or target tissues hold considerable promise for improving the treatment of many diseases by minimizing nonspecific toxicity and enhancing the efficacy of therapy. These drug delivery systems are constructed from materials that are sensitive to a wide range of external stimuli, including light, ultrasound, elec. and magnetic fields, and specific mols. The responsiveness conferred by these materials allows the release of therapeutics to be triggered on demand and remotely by a physician or patient. In this Review, we describe the rationales for such systems and the types of stimuli that can be deployed, and provide an outlook for the field.
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    Goodman, A. M.; Neumann, O.; Nørregaard, K.; Henderson, L.; Choi, M. R.; Clare, S. E.; Halas, N. J. Near-Infrared Remotely Triggered Drug-Release Strategies for Cancer Treatment. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 12419– 12424,  DOI: 10.1073/pnas.1713137114
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    21
    Near-infrared remotely triggered drug-release strategies for cancer treatment
    Goodman, Amanda M.; Neumann, Oara; Noerregaard, Kamilla; Henderson, Luke; Choi, Mi-Ran; Clare, Susan E.; Halas, Naomi J.
    Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (47), 12419-12424CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    Remotely controlled, localized drug delivery is highly desirable for potentially minimizing the systemic toxicity induced by the administration of typically hydrophobic chemotherapy drugs by conventional means. Nanoparticle-based drug delivery systems provide a highly promising approach for localized drug delivery, and are an emerging field of interest in cancer treatment. Here, we demonstrate near-IR light-triggered release of two drug mols. from both DNA-based and protein-based hosts that have been conjugated to near-IR-absorbing Au nanoshells (SiO2 core, Au shell), each forming a light-responsive drug delivery complex. We show that, depending upon the drug mol., the type of host mol., and the laser illumination method (continuous wave or pulsed laser), in vitro light-triggered release can be achieved with both types of nanoparticle-based complexes. Two breast cancer drugs, docetaxel and HER2-targeted lapatinib, were delivered to MDA-MB-231 and SKBR3 (overexpressing HER2) breast cancer cells and compared with release in noncancerous RAW 264.7 macrophage cells. Continuous wave laser-induced release of docetaxel from a nanoshell-based DNA host complex showed increased cell death, which also coincided with nonspecific cell death from photothermal heating. Using a femtosecond pulsed laser, lapatinib release from a nanoshell-based human serum albumin protein host complex resulted in increased cancerous cell death while noncancerous control cells were unaffected. Both methods provide spatially and temporally localized drug-release strategies that can facilitate high local concns. of chemotherapy drugs deliverable at a specific treatment site over a specific time window, with the potential for greatly minimized side effects.
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    Jaque, D.; Martinez Maestro, L.; del Rosal, B.; Haro-Gonzalez, P.; Benayas, A.; Plaza, J. L.; Martin Rodriguez, E.; Garcia Sole, J. Nanoparticles for Photothermal Therapies. Nanoscale 2014, 6, 9494– 9530,  DOI: 10.1039/C4NR00708E
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    22
    Nanoparticles for photothermal therapies
    Jaque, D.; Martinez Maestro, L.; del Rosal, B.; Haro-Gonzalez, P.; Benayas, A.; Plaza, J. L.; Martin Rodriguez, E.; Garcia Sole, J.
    Nanoscale (2014), 6 (16), 9494-9530CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
    A review. The current status of the use of nanoparticles for photothermal treatments is reviewed in detail. The different families of heating nanoparticles are described paying special attention to the phys. mechanisms at the root of the light-to-heat conversion processes. The heating efficiencies and spectral working ranges are listed and compared. The most important results obtained in both in vivo and in vitro nanoparticle assisted photothermal treatments are summarized. The advantages and disadvantages of the different heating nanoparticles are discussed.
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    Abadeer, N. S.; Murphy, C. J. Recent Progress in Cancer Thermal Therapy Using Gold Nanoparticles. J. Phys. Chem. C 2016, 120, 4691– 4716,  DOI: 10.1021/acs.jpcc.5b11232
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    Recent Progress in Cancer Thermal Therapy Using Gold Nanoparticles
    Abadeer, Nardine S.; Murphy, Catherine J.
    Journal of Physical Chemistry C (2016), 120 (9), 4691-4716CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    In recent years, there has been a great deal of interest in the prepn. and application of nanoparticles for cancer therapy. Gold nanoparticles are esp. suited to thermal destruction of cancer due to their ease of surface functionalization and photothermal heating ability. Here, we review recent progress in gold nanoparticle-mediated thermal cancer therapies. We begin with an introduction to the properties of gold nanoparticles and heat-generating mechanisms which have been established. The pioneering work in photothermal therapy is discussed along with the effects of photothermal heating on cells in vitro. Addnl., radiofrequency-mediated thermal therapy is reviewed. We focus our discussion on the developments and progress in nanoparticle design for photothermal cancer therapy since 2010. This includes in vitro and in vivo studies and the recent progression of gold nanoparticle photothermal therapy toward clin. cancer treatment.
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    Richardson, H. H.; Carlson, M. T.; Tandler, P. J.; Hernandez, P.; Govorov, A. O. Experimental and Theoretical Studies of Light-to-Heat Conversion and Collective Heating Effects in Metal Nanoparticle Solutions. Nano Lett. 2009, 9, 1139– 1146,  DOI: 10.1021/nl8036905
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    24
    Experimental and Theoretical Studies of Light-to-Heat Conversion and Collective Heating Effects in Metal Nanoparticle Solutions
    Richardson, Hugh H.; Carlson, Michael T.; Tandler, Peter J.; Hernandez, Pedro; Govorov, Alexander O.
    Nano Letters (2009), 9 (3), 1139-1146CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
    The authors perform a set of expts. on photoheating in a H2O droplet contg. Au nanoparticles (NPs). Using photocalorimetric methods, the authors det. efficiency of light-to-heat conversion (η) which turns out to be remarkably close to 1, (0.97 < η < 1.03). Detailed studies reveal a complex character of heat transfer in an optically stimulated droplet. The main mechanism of equilibration is due to convectional flow. Theor. modeling is performed to describe thermal effects at both nano- and millimeter scales. Theory shows that the collective photoheating is the main mechanism. For a large concn. of NPs and small laser intensity, an averaged temp. increase (at the millimeter scale) is significant (∼7°), whereas on the nanometer scale the temp. increase at the surface of a single NP is small (∼0.02°). In the opposite regime, i.e., a small NP concn. and intense laser irradn., an opposite picture: a temp. increase at the millimeter scale is small (∼0.1°) but a local, nanoscale temp. has strong local spikes at the surfaces of NPs (∼3°) were found. These studies are crucial for the understanding of photothermal effects in NPs and for their potential and current applications in nano- and biotechnologies.
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    Schuller, J. A.; Barnard, E. S.; Cai, W.; Chul Jun, Y.; White, J. S.; Brongersma, M. L. Plasmonics for Extreme Light Concentration and Manipulation. Nat. Mater. 2010, 9, 193– 204,  DOI: 10.1038/nmat2630
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    Plasmonics for extreme light concentration and manipulation
    Schuller, Jon A.; Barnard, Edward S.; Cai, Wenshan; Jun, Young Chul; White, Justin S.; Brongersma, Mark L.
    Nature Materials (2010), 9 (3), 193-204CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    A review. The unprecedented ability of nanometallic (i.e., plasmonic) structures to conc. light into deep-subwavelength vols. has propelled their use in a vast array of nanophotonics technols. and research endeavours. Plasmonic light concentrators can elegantly interface diffraction-limited dielec. optical components with nanophotonic structures. Passive and active plasmonic devices provide new pathways to generate, guide, modulate and detect light with structures that are similar in size to state-of-the-art electronic devices. With the ability to produce highly confined optical fields, the conventional rules for light-matter interactions need to be reexamd., and researchers are venturing into new regimes of optical physics. The authors will discuss the basic concepts behind plasmonics-enabled light concn. and manipulation, make an attempt to capture the wide range of activities and excitement in this area, and speculate on possible future directions.
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    Brongersma, M. L.; Halas, N. J.; Nordlander, P. Plasmon-Induced Hot Carrier Science and Technology. Nat. Nanotechnol. 2015, 10, 25– 34,  DOI: 10.1038/nnano.2014.311
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    Plasmon-induced hot carrier science and technology
    Brongersma, Mark L.; Halas, Naomi J.; Nordlander, Peter
    Nature Nanotechnology (2015), 10 (1), 25-34CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)
    A review. The discovery of the photoelec. effect by Heinrich Hertz in 1887 set the foundation for over 125 years of hot carrier science and technol. In the early 1900s it played a crit. role in the development of quantum mechanics, but even today the unique properties of these energetic, hot carriers offer new and exciting opportunities for fundamental research and applications. Measurement of the kinetic energy and momentum of photoejected hot electrons can provide valuable information on the electronic structure of materials. The heat generated by hot carriers can be harvested to drive a wide range of phys. and chem. processes. Their kinetic energy can be used to harvest solar energy or create sensitive photodetectors and spectrometers. Photoejected charges can also be used to elec. dope two-dimensional materials. Plasmon excitations in metallic nanostructures can be engineered to enhance and provide valuable control over the emission of hot carriers. This Review discusses recent advances in the understanding and application of plasmon-induced hot carrier generation and highlights some of the exciting new directions for the field.
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    Rashidi-Huyeh, M.; Palpant, B. Thermal Response of Nanocomposite Materials under Pulsed Laser Excitation. J. Appl. Phys. 2004, 96, 4475,  DOI: 10.1063/1.1794894
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    Thermal response of nanocomposite materials under pulsed laser excitation
    Rashidi-Huyeh, Majid; Palpant, Bruno
    Journal of Applied Physics (2004), 96 (8), 4475-4482CODEN: JAPIAU; ISSN:0021-8979. (American Institute of Physics)
    The optical properties of nanocomposite materials made of matrix-embedded noble metal nanoparticles strongly depend on thermal effects from different origins. We propose a classical model describing the energy exchanges within the nanoparticles and between the latter and the surrounding dielec. host subsequent to a light pulse absorption. This model, which accounts for the thermal interactions between neighboring particles, allows us to calc. numerically the temp. dynamics of the electrons, metal lattice and matrix as functions of particle size, and metal concn. of the medium, whatever be the pulsed excitation temporal regime. It is illustrated in the case of Au:SiO2 materials under femtosecond and nanosecond pulse excitation. It is shown that, in the femtosecond regime, the heat transfer to the matrix cannot be neglected beyond a few picosecond delay from which particle size and metal concn. play a significant role in the electron relaxation. In the nanosecond regime, these morphol. parameters influence crucially the material thermal behavior with the possibility of generating a thermal lens effect. The implications in the anal. of exptl. results regarding both the electron relaxation dynamics and the nonlinear optical properties are also discussed. Finally, a method to adapt the model to the case of thin nanocomposite film is proposed.
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    Hartland, G. V. Optical Studies of Dynamics in Noble Metal Nanostructures. Chem. Rev. 2011, 111, 3858– 3887,  DOI: 10.1021/cr1002547
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    Optical studies of dynamics in noble metal nanostructures
    Hartland, Gregory V.
    Chemical Reviews (Washington, DC, United States) (2011), 111 (6), 3858-3887CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review.
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    Baffou, G.; Quidant, R.; García de Abajo, F. J. Nanoscale Control of Optical Heating in Complex Plasmonic Systems. ACS Nano 2010, 4, 709– 716,  DOI: 10.1021/nn901144d
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    Nanoscale Control of Optical Heating in Complex Plasmonic Systems
    Baffou, Guillaume; Quidant, Romain; Garcia de Abajo, F. Javier
    ACS Nano (2010), 4 (2), 709-716CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    The authors introduce a numerical technique to study the temp. distribution in arbitrarily complex plasmonic systems subject to external illumination. The authors perform both electromagnetic and thermodn. calcns. based upon a time-efficient boundary element method. Two kinds of plasmonic systems are studied to illustrate the potential of such a technique. First, the authors focus on individual particles with various morphologies. In analogy with electrostatics, the authors introduce the concept of thermal capacitance. This geometry-dependent quantity allows one to assess the temp. increase inside a plasmonic particle from the sole knowledge of its absorption cross section. The authors present universal thermal-capacitance curves for ellipsoids, rods, disks, and rings. Addnl., the authors study assemblies of nanoparticles in close proximity and show that, despite its diffusive nature, the temp. distribution can be made highly nonuniform even at the nanoscale using plasmonic systems. A significant degree of nanoscale control over the individual temps. of neighboring particles is demonstrated, depending on the external light wavelength and direction of incidence. The authors illustrate this concept with simulations of Au sphere dimers and chains in H2O. Work opens new possibilities for selectively controlling processes such as local melting for dynamic patterning of textured materials, chem. and metabolic thermal activation, and heat delivery for producing mech. motion with spatial precision in the nanoscale.
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  30. 30
    Berry, K. R.; Dunklin, J. R.; Blake, P. A.; Roper, D. K. Thermal Dynamics of Plasmonic Nanoparticle Composites. J. Phys. Chem. C 2015, 119, 10550– 10557,  DOI: 10.1021/jp512701v
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    30
    Thermal Dynamics of Plasmonic Nanoparticle Composites
    Berry, Keith R.; Dunklin, Jeremy R.; Blake, Phillip A.; Roper, D. Keith
    Journal of Physical Chemistry C (2015), 119 (19), 10550-10557CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Thermal response rates of plasmonic nanocomposite materials limit their capacity for adaptive control and scalable implementation. This work examines thermal dynamics in insulating and conductive dielecs. contg. two- and three-dimensional disordered distributions of plasmonic gold nanoparticles (AuNP). It is shown that a balance of micro- and macroscale internal and external dissipation rates can model overall thermal dynamics and dissipation rates measured for widely varying composite materials to within a few percent using independent geometric and thermodn. parameters. The independent ests. are within 2.6% of values measured for isolated colloid AuNP suspensions, between 0.15 to 13.4% for randomly sized AuNP embedded in polymer films, and within 5.4 to 30.0% for AuNP deposited on conductive ceramics. Estd. thermal dynamics for AuNP embedded in thin polymer film are higher than AuNP in fluid or on ceramic substrates. This modeling approach could guide design and deployment of thermally responsive plasmonic energy materials, sensors, and therapeutics for heat-sensitive applications.
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  31. 31
    Govorov, A. O.; Zhang, W.; Skeini, T.; Richardson, H.; Lee, J.; Kotov, N. A. Gold Nanoparticle Ensembles as Heaters and Actuators: Melting and Collective Plasmon Resonances. Nanoscale Res. Lett. 2006, 1, 84– 90,  DOI: 10.1007/s11671-006-9015-7
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    Palpant, B.; Guillet, Y.; Rashidi-Huyeh, M.; Prot, D. Gold Nanoparticle Assemblies: Thermal Behaviour under Optical Excitation. Gold Bull. 2008, 41, 105– 115,  DOI: 10.1007/BF03216588
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    Gold nanoparticle assemblies: Thermal behaviour under optical excitation
    Palpant, Bruno; Guillet, Yannick; Rashidi-Huyeh, Majid; Prot, Dominique
    Gold Bulletin (London, United Kingdom) (2008), 41 (2), 105-115CODEN: GOBUFW; ISSN:1027-8591. (World Gold Council)
    The optical response of materials based on gold nanoparticle assemblies depends on many parameters connected to both material morphol. and light excitation characteristics. The optical energy absorbed is then converted into heat through different nanoscale energy exchange mechanisms. This heating subsequently modifies itself the optical properties. We investigate the interplay between the optical and thermal responses of nanocomposite media under its theor. aspect. In this first paper, the thermal response of gold nanoparticle assemblies under pulsed optical excitation is considered. Both conventional and original modeling approaches are presented. We first underline the role of electromagnetic interactions between particles in a dense assembly in its linear optical response. We then show how the interaction of light with matrix-embedded gold nanoparticles can result in the generation of thermal excitations through different energy exchange mechanisms. Finally, we demonstrate the possible significant influence of the heat carrier ballistic regime and phonon rarefaction in the cooling dynamics of an embedded gold nanoparticle subsequent to ultrafast pulsed laser excitation.
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    Baffou, G.; Berto, P.; Bermúdez Ureña, E.; Quidant, R.; Monneret, S.; Polleux, J.; Rigneault, H. Photoinduced Heating of Nanoparticle Arrays. ACS Nano 2013, 7, 6478– 6488,  DOI: 10.1021/nn401924n
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    Photoinduced Heating of Nanoparticle Arrays
    Baffou, Guillaume; Berto, Pascal; Bermudez Urena, Esteban; Quidant, Romain; Monneret, Serge; Polleux, Julien; Rigneault, Herve
    ACS Nano (2013), 7 (8), 6478-6488CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    The temp. distribution throughout arrays of illuminated metal nanoparticles is studied numerically and exptl. The 2 cases of continuous and femtosecond-pulsed illumination are addressed. In the case of continuous illumination, 2 distinct regimes are evidenced: a temp. confinement regime, where the temp. increase remains confined at the vicinity of each nanosource of heat, and a temp. delocalization regime, where the temp. is uniform throughout the whole nanoparticle assembly despite the heat sources' nanometric size. The occurrence of 1 regime or another simply depends on the geometry of the nanoparticle distribution. In particular, the authors derived (i) simple expressions of dimensionless parameters aimed at predicting the degree of temp. confinement and (ii) anal. expressions aimed at estg. the actual temp. increase at the center of an assembly of nanoparticles under illumination, preventing heavy numerical simulations. All these theor. results are supported by exptl. measurements of the temp. distribution on regular arrays of Au nanoparticles under illumination. In the case of femtosecond-pulsed illumination, the authors explain the 2 conditions that must be fulfilled to observe a further enhanced temp. spatial confinement.
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    Kildishev, A. V.; Boltasseva, A.; Shalaev, V. M. Planar Photonics with Metasurfaces. Science 2013, 339, 1289,  DOI: 10.1126/science.1232009
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    Yu, N.; Capasso, F. Flat Optics with Designer Metasurfaces. Nat. Mater. 2014, 13, 139,  DOI: 10.1038/nmat3839
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    Flat optics with designer metasurfaces
    Yu, Nanfang; Capasso, Federico
    Nature Materials (2014), 13 (2), 139-150CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    A review. Conventional optical components such as lenses, waveplates and holograms rely on light propagation over distances much larger than the wavelength to shape wavefronts. In this way, substantial changes of the amplitude, phase or polarization of light waves are gradually accumulated along the optical path. This review focuses on recent developments on flat, ultrathin optical components dubbed 'metasurfaces' that produce abrupt changes over the scale of the free-space wavelength in the phase, amplitude and/or polarization of a light beam. Metasurfaces are generally created by assembling arrays of miniature, anisotropic light scatterers (i.e., resonators such as optical antennas). The spacing between antennas and their dimensions are much smaller than the wavelength. As a result the metasurfaces, on account of Huygens principle, are able to mold optical wavefronts into arbitrary shapes with subwavelength resoln. by introducing spatial variations in the optical response of the light scatterers. Such gradient metasurfaces go beyond the well-established technol. of frequency selective surfaces made of periodic structures and are extending to new spectral regions the functionalities of conventional microwave and millimeter-wave transmit-arrays and reflect-arrays. Metasurfaces can also be created by using ultrathin films of materials with large optical losses. By using the controllable abrupt phase shifts assocd. with reflection or transmission of light waves at the interface between lossy materials, such metasurfaces operate like optically thin cavities that strongly modify the light spectrum. Technol. opportunities in various spectral regions and their potential advantages in replacing existing optical components are discussed.
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  36. 36
    Pileni, M.-P. Light Interactions with Supracrystals either Deposited on a Substrate or Dispersed in Water. Inorg. Chem. Front. 2020, 7, 3796,  DOI: 10.1039/D0QI00353K
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    Light interactions with supracrystals either deposited on a substrate or dispersed in water
    Pileni, Marie Paule
    Inorganic Chemistry Frontiers (2020), 7 (20), 3796-3804CODEN: ICFNAW; ISSN:2052-1553. (Royal Society of Chemistry)
    Nanocrystals with low size distribution are able to self-assemble into a 3D cryst. structure called colloidal crystals or super/supracrystals. A rather large no. of supracrystal specific properties have been achieved showing promising potential applications. Here, we compared intrinsic properties induced by light interacting with fcc supracrystals of hydrophobic metal nanocrystals either deposited on a substrate or dispersed in aq. soln. We first describe the formation of a dried supracrystal film grown via a heterogeneous process with cracks formed due to the shrinking of the film caused by restriction of its adhesion on the surface. We also describe the method to fabricate hydrophobic supracrystals dispersed in aq. soln. The optical properties of the thick dried supracrystal film are detd. from the wetting layers formed at the bottom of the cracks whereas, for water dispersed suprastructures, both the collective optical photonic mode and absorption of dispersed nanocrystals used as build blocks are obsd. Ag nanocrystals used as building blocks in a dried supracrystal film vibrate coherently as atoms in a nanocrystal. However, it is impossible to det. the oscillation period of the whole assembly. Conversely from a dynamic study, the breathing period of the assemblies dispersed in aq. soln. is found to be around 300 ps. Whatever exptl. conditions, nanocrystals exposed to light breath coherently in a supracrystal. In aq. soln., supracrystals behave as nanoheaters.
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  37. 37
    Zhou, L.; Tan, Y.; Wang, J.; Xu, W.; Yuan, Y.; Cai, W.; Zhu, S.; Zhu, J. 3D Self-Assembly of Aluminium Nanoparticles for Plasmon-Enhanced Solar Desalination. Nat. Photonics 2016, 10, 393– 398,  DOI: 10.1038/nphoton.2016.75
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    3D self-assembly of aluminum nanoparticles for plasmon-enhanced solar desalination
    Zhou, Lin; Tan, Yingling; Wang, Jingyang; Xu, Weichao; Yuan, Ye; Cai, Wenshan; Zhu, Shining; Zhu, Jia
    Nature Photonics (2016), 10 (6), 393-398CODEN: NPAHBY; ISSN:1749-4885. (Nature Publishing Group)
    Plasmonics has generated tremendous excitement because of its unique capability to focus light into subwavelength vols., beneficial for various applications such as light harvesting, photodetection, sensing, catalysis and so on. Here we demonstrate a plasmon-enhanced solar desalination device, fabricated by the self-assembly of aluminum nanoparticles into a three-dimensional porous membrane. The formed porous plasmonic absorber can float naturally on water surface, efficiently absorb a broad solar spectrum (>96%) and focus the absorbed energy at the surface of the water to enable efficient (∼90%) and effective desalination (a decrease of four orders of magnitude). The durability of the devices has also been examd., indicating a stable performance over 25 cycles under various illumination conditions. The combination of the significant desalination effect, the abundance and low cost of the materials, and the scalable prodn. processes suggest that this type of plasmon-enhanced solar desalination device could provide a portable desalination soln.
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  38. 38
    Zhou, L.; Tan, Y.; Ji, D.; Zhu, B.; Zhang, P.; Xu, J.; Gan, Q.; Yu, Z.; Zhu, J. Self-Assembly of Highly Efficient, Broadband Plasmonic Absorbers for Solar Steam Generation. Sci. Adv. 2016, 2, e1501227  DOI: 10.1126/sciadv.1501227
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    Self-assembly of highly efficient, broadband plasmonic absorbers for solar steam generation
    Zhou, Lin; Tan, Yingling; Ji, Dengxin; Zhu, Bin; Zhang, Pei; Xu, Jun; Gan, Qiaoqiang; Yu, Zongfu; Zhu, Jia
    Science Advances (2016), 2 (4), e1501227/1-e1501227/8CODEN: SACDAF; ISSN:2375-2548. (American Association for the Advancement of Science)
    The study of ideal absorbers, which can efficiently absorb light over a broad range of wavelengths, is of fundamental importance, as well as crit. for many applications from solar steam generation and thermophotovoltaics to light/thermal detectors. As a result of recent advances in plasmonics, plasmonic absorbers have attracted a lot of attention. However, the performance and scalability of these absorbers, predominantly fabricated by the top-down approach, need to be further improved to enable widespread applications. We report a plasmonic absorber which can enable an av. measured absorbance of ∼99% across the wavelengths from 400 nm to 10 μm, the most efficient and broadband plasmonic absorber reported to date. The absorber is fabricated through self-assembly of metallic nanoparticles onto a nanoporous template by a one-step deposition process. Because of its efficient light absorption, strong field enhancement, and porous structures, which together enable not only efficient solar absorption but also significant local heating and continuous stream flow, plasmonic absorber-based solar steam generation has over 90% efficiency under solar irradn. of only 4-sun intensity (4 kW m-2). The pronounced light absorption effect coupled with the high-throughput self-assembly process could lead toward large-scale manufg. of other nanophotonic structures and devices.
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  39. 39
    Mazzanti, A.; Yang, Z.; Silva, M. G.; Yang, N.; Rizza, G.; Coulon, P.-E.; Manzoni, C.; de Paula, A. M.; Cerullo, G.; Della Valle, G.; Pileni, M.-P. Light-Heat Conversion Dynamics in Highly Diversified Water-Dispersed Hydrophobic Nanocrystal Assemblies. Proc. Natl. Acad. Sci. U.S.A. 2019, 116, 8161– 8166,  DOI: 10.1073/pnas.1817850116
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    Light-heat conversion dynamics in highly diversified water-dispersed hydrophobic nanocrystal assemblies
    Mazzanti, Andrea; Yang, Zhijie; Silva, Mychel G.; Yang, Nailiang; Rizza, Giancarlo; Coulon, Pierre-EugA ne; Manzoni, Cristian; de Paula, Ana Maria; Cerullo, Giulio; Della Valle, Giuseppe; Pileni, Marie-Paule
    Proceedings of the National Academy of Sciences of the United States of America (2019), 116 (17), 8161-8166CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
    The authors study, with a combination of ultrafast optical spectroscopy and semiclassical modeling, the photothermal properties of various water-sol. nanocrystal assemblies. Broadband pump-probe expts. with ~100 fs time resoln. in the visible and near IR reveal a complex scenario for their transient optical response that is dictated by their hybrid compn. at the nanoscale, comprising metallic (Au) or semiconducting (Fe3O4) nanostructures and a matrix of org. ligands. The authors track the whole chain of energy flow that starts from light absorption by the individual nanocrystals and subsequent excitation of out-of-equil. carriers followed by the electron-phonon equilibration, occurring in a few picoseconds, and then by the heat release to the matrix on the 100-ps timescale. Two-dimensional finite-element method electromagnetic simulations of the composite nanostructure and multi-temp. modeling of the energy flow dynamics enable the authors to identify the key mechanism presiding over the light-heat conversion in these kinds of nanomaterials. Hybrid (org.-inorg.) nanocrystal assemblies can operate as efficient nanoheaters by exploiting the high absorption from the individual nanocrystals, enabled by the diln. of the inorg. phase that is followed by a relatively fast heating of the embedding org. matrix, occurring on the 100-ps timescale.
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  40. 40
    Moretti, L.; Mazzanti, A.; Rossetti, A.; Schirato, A.; Polito, L.; Pizzetti, F.; Sacchetti, A.; Cerullo, G.; Della Valle, G.; Rossi, F.; Maiuri, M. Plasmonic Control of Drug Release Efficiency in Agarose Gel Loaded with Gold Nanoparticle Assemblies. Nanophoton 2020, 10, 247,  DOI: 10.1515/nanoph-2020-0418
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    Yang, N.; Deeb, C.; Pelouard, J.-L.; Felidj, N.; Pileni, M.-P. Water-Dispersed Hybrophobic Au Nanocrystal Assemblies with a Plasmon Fingerprint. ACS Nano 2017, 11, 7797– 7806,  DOI: 10.1021/acsnano.7b01605
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    Water-Dispersed Hydrophobic Au Nanocrystal Assemblies with a Plasmon Fingerprint
    Yang, Nailiang; Deeb, Claire; Pelouard, Jean-Luc; Felidj, Nordin; Pileni, Marie-Paule
    ACS Nano (2017), 11 (8), 7797-7806CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
    Hydrophobic Au nanocrystal assemblies (both ordered and amorphous) were dispersed in aq. soln. via the assistance of lipid vesicles. The intertwine between vesicles and Au assemblies was made possible through a careful selection of the length of alkyl chains on Au nanocrystals. Extinction spectra of Au assemblies showed 2 peaks that were assigned to a scattering mode that red shifted with increasing the assembly size and an absorption mode assocd. with localized surface plasmon that was independent of their size. This plasmon fingerprint could be used as a probe for studying the optical properties of such assemblies. The H2O-sol. assemblies enable exploring a variety of potential applications including solar energy and biomedicine.
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    Boles, A. M.; Engel, M.; Talapin, D. V. Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials. Chem. Rev. 2016, 116, 11220– 11289,  DOI: 10.1021/acs.chemrev.6b00196
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    Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials
    Boles, Michael A.; Engel, Michael; Talapin, Dmitri V.
    Chemical Reviews (Washington, DC, United States) (2016), 116 (18), 11220-11289CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Chem. methods developed over the past two decades enable prepn. of colloidal nanocrystals with uniform size and shape. These Brownian objects readily order into superlattices. Recently, the range of accessible inorg. cores and tunable surface chemistries dramatically increased, expanding the set of nanocrystal arrangements exptl. attainable. In this review, we discuss efforts to create next-generation materials via bottom-up organization of nanocrystals with preprogrammed functionality and self-assembly instructions. This process is often driven by both interparticle interactions and the influence of the assembly environment. The introduction provides the reader with a practical overview of nanocrystal synthesis, self-assembly, and superlattice characterization. We then summarize the theory of nanocrystal interactions and examine fundamental principles governing nanocrystal self-assembly from hard and soft particle perspectives borrowed from the comparatively established fields of micrometer colloids and block copolymer assembly. We outline the extensive catalog of superlattices prepd. to date using hydrocarbon-capped nanocrystals with spherical, polyhedral, rod, plate, and branched inorg. core shapes, as well as those obtained by mixing combinations thereof. We also provide an overview of structural defects in nanocrystal superlattices. We then explore the unique possibilities offered by leveraging nontraditional surface chemistries and assembly environments to control superlattice structure and produce nonbulk assemblies. We end with a discussion of the unique optical, magnetic, electronic, and catalytic properties of ordered nanocrystal superlattices, and the coming advances required to make use of this new class of solids.
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    Hao, J.; Yang, Y.; Zhang, F.; Yang, Z.; Wei, J. Faceted Colloidal Au/Fe3O4 Binary Supracrystals Dictated by Intrinsic Lattice Structures and Their Collective Optical Properties. J. Phys. Chem. C 2020, 124, 14775– 14786,  DOI: 10.1021/acs.jpcc.0c02984
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    Faceted Colloidal Au/Fe3O4 Binary Supracrystals Dictated by Intrinsic Lattice Structures and Their Collective Optical Properties
    Hao, Jinjie; Yang, Yanzhao; Zhang, Fenghua; Yang, Zhijie; Wei, Jingjing
    Journal of Physical Chemistry C (2020), 124 (27), 14775-14786CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Although self-assembly of binary nanocrystal mixts. into long-range ordered cryst. films with tunable lattice structures are well-known, it would be interesting to shape these binary nanocrystal supracrystals into faceted assemblies because it potentially provides the shape-dependent optical, electronic, and catalytic properties. Herein, we report the self-assembly of binary nanocrystal supracrystals with faceted morphologies from Fe3O4 and Au binary mixts. The asym. crystal parameters in AlB2-type structure, a = b > c, favors one-dimensional (1D) self-assembly along the 〈001〉 direction, resulting in the formation of supraspindles and suprarods with 20 facets. For the sym. cubic lattice system, like NaCl-type and NaZn13-type structures, truncated cube/octahedron with preferential exposed facets of (100) and (111) are produced. By contrast, for another cubic lattice of bcc.-AB6, in which large nanocrystals are ordered into body-centered-cubic (bcc.) structure, truncated rhombic dodecahedra enclosed with (110) and (100) are made. The shape-controlled assembly of binary nanocrystal supracrystals composed of plasmonic Au nanocrystals enables engineering the plasmonic near field coupling in binary nanocrystal supracrystals dispersed in water.
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  44. 44
    Nicolas-Boluda, A.; Yang, Z.; Dobryden, I.; Carn, F.; Winckelmans, N.; Péchoux, C.; Bonville, P.; Bals, S.; Claesson, P. M.; Gazeau, F.; Pileni, M.-P. Intracellular Fate of Hydrophobic Nanocrystal Self-Assemblies in Tumor Cells. Adv. Funct. Mater. 2020, 30, 2004274,  DOI: 10.1002/adfm.202004274
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    Intracellular Fate of Hydrophobic Nanocrystal Self-Assemblies in Tumor Cells
    Nicolas-Boluda, Alba; Yang, Zhijie; Dobryden, Illia; Carn, Florent; Winckelmans, Naomi; Pechoux, Christine; Bonville, Pierre; Bals, Sara; Claesson, Per Martin; Gazeau, Florence; Pileni, Marie Paule
    Advanced Functional Materials (2020), 30 (40), 2004274CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water-dispersible architectures of self-assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self-assemblies display increased cellular uptake by tumor cells compared to dispersions of the water-sol. NC building blocks. Moreover, the self-assembly structures increase the NCs d. in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mech. properties. Flexible and soft colloidosomes deform and spread along the biol. membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mech. and topol. properties of the self-assemblies direct their intracellular fate allowing the control intralysosomal d., ordering, and localization of NCs.
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    Zhang, F.; Yang, F.; Gong, Y.; Wei, Y.; Yang, Y.; Wei, J.; Yang, Z.; Pileni, M.-P. Anisotropic Assembly of Nanocrystal/Molecular Hierarchical Supralattices Decoding from Tris-Amide Triarylamines Supramolecular Networks. Small 2020, 16, 2005701,  DOI: 10.1002/smll.202005701
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    Anisotropic Assembly of Nanocrystal/Molecular Hierarchical Superlattices Decoding from Tris-Amide Triarylamines Supramolecular Networks
    Zhang, Fenghua; Yang, Fei; Gong, Yanjun; Wei, Yanze; Yang, Yanzhao; Wei, Jingjing; Yang, Zhijie; Pileni, Marie-Paule
    Small (2020), 16 (48), 2005701CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Directed assembly of nanocrystals from conventional templates suffers from poor control over the periodicity of the nanocrystal assembly, which is largely due to the fact that the template exists prior to the assembly and is not generally adaptive. Herein, small org. mols. (tris-amide triarylamines, TATA) are demonstrated as conceptual templates from self-assembly through noncovalent interactions. The as-formed supramol. structures with terminated alkyl chains, resembling the structure of as-synthesized nanocrystals capped with alkyl chains, are able to interact with nanocrystals through van der Waals attractive forces, thereby enabling directed assembly of nanocrystals into ordered superlattices. Specifically, it is found that, as detd. by the substituted alkyl chains of TATA, either H or J-aggregates of TATA can be achieved, which eventually produce several distinct supramol. structures, from rods to spindles, to rings, and to spheres, serving as on-pathway intermediate that directs the assembly of nanocrystals into diverse nanocrystal superlattices. The approach described can be applicable to produce ordered nanocrystal assemblies of a wide range of nanocrystals, independent of size and shape and without ligand exchange process. Strikingly, a helical TATA stacking can direct assembly of binary nanocrystal mixts. into NaZn13 binary superhelix.
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    Nicolas-Boluda, A.; Yang, Z.; Guilbert, T.; Fouassier, L.; Carn, F.; Gazeau, F.; Pileni, M.-P. Self-Assemblies of Fe3O4 Nanocrystals: Toward Nanoscale Precision of Photothermal Effects in the Tumor Microenvironment. Adv. Funct. Mater. 2021, 31, 2006824,  DOI: 10.1002/adfm.202006824
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    46
    Self-Assemblies of Fe3O4 Nanocrystals: Toward Nanoscale Precision of Photothermal Effects in the Tumor Microenvironment
    Nicolas-Boluda, Alba; Yang, Zhijie; Guilbert, Thomas; Fouassier, Laura; Carn, Florent; Gazeau, Florence; Pileni, Marie Paule
    Advanced Functional Materials (2021), 31 (4), 2006824CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Fe3O4 nanocrystals are self-assembled into two different conformations: colloidosome and supraball that confer them with distinct properties detg. their photo-induced heating capacities. These self-assemblies are assessed for photothermal therapy, an adjuvant strategy for tumor therapy. The tumor microenvironment is a heterogeneous ecosystem including immune cells and the extracellular matrix. The interactions between photothermal therapy agents and the different components of the tumor microenvironment det. the outcome of this therapy. In this study, the fate of both colloidosomes and supraballs within the tumor microenvironment in comparison to their Fe3O4 nanocrystal building blocks is revealed. This study highlights how these two hybrid self-assemblies target different compartments of the tumor microenvironment and trigger local photothermal damages that are inaccessible for isolated nanocrystals and not predicted by global temp. measurements.
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    Here, the authors report the design of a new system called "supracryst. colloidal eggs" formed by controlled assembly of nanocrystals into complex colloidal supracrystals through superlattice-matched epitaxial overgrowth along the existing colloidosomes. Then, with this concept, the authors extend the supracryst. growth to lattice-mismatched binary nanocrystal superlattices, in order to reach anisotropic superlattice growths, yielding freestanding binary nanocrystal supracrystals that could not be produced previously.
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    The development of nanocrystals has been intensively pursued, not only for their fundamental scientific interest, but also for many technol. applications. The synthesis of monodisperse nanocrystals (size variation <5%) is of key importance, because the properties of these nanocrystals depend strongly on their dimensions. For example, the color sharpness of semiconductor nanocrystal-based optical devices is strongly dependent on the uniformity of the nanocrystals, and monodisperse magnetic nanocrystals are crit. for the next-generation multiterabit magnetic storage media. For these monodisperse nanocrystals to be used, an economical mass prodn. method needs to be developed. Unfortunately, however, in most syntheses reported so far, only subgram quantities of monodisperse nanocrystals were produced. Uniform-sized nanocrystals of CdSe and Au have been produced using colloidal chem. synthetic procedures. In addn., monodisperse magnetic nanocrystals such as Fe, Co, γ-Fe2O3, and Fe3O4 have been synthesized by using various synthetic methods. Here, we report on the ultralarge-scale synthesis of monodisperse nanocrystals using inexpensive and nontoxic metal salts as reactants. We were able to synthesize as much as 40 g of monodisperse nanocrystals in a single reaction, without a size sorting process. Moreover, the particle size could be controlled simply by varying the exptl. conditions. The current synthetic procedure is very general and nanocrystals of many transition metal oxides were successfully synthesized using a very similar procedure.
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  1. Nuo Chen, Yueliang Wang, Zhaoxiang Deng. DNA-Condensed Plasmonic Supraballs Transparent to Molecules. Langmuir 2023, 39 (39) , 14053-14062. https://doi.org/10.1021/acs.langmuir.3c01860
  2. Yi Chen, Yu Bai, Xi Wang, Heng Zhang, Haoran Zheng, Ning Gu. Plasmonic/magnetic nanoarchitectures: From controllable design to biosensing and bioelectronic interfaces. Biosensors and Bioelectronics 2023, 219 , 114744. https://doi.org/10.1016/j.bios.2022.114744
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  • Abstract

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    Figure 1

    Figure 1. Static optical response of plasmonic suprastructures. (a) Transmission electron microscopy (TEM) images of the samples. Top labels refer to the Au concentration ratio cr, of 0.1, 0.3, and 1 from left to right, respectively. (b, c) Measured (b) and simulated (c) absorbance of the nanoeggs with cr = 0.1 (red curves), 0.3 (green curves), and 1 (blue curves), respectively. The inset shows a schematic of the geometry used in the simulation with the corresponding normalized spatial pattern of absorption at 400 nm.

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    Figure 2

    Figure 2. Transient optical response of plasmonic suprastructures for varying Au concentration. (a–d) Experimental (a, b) and simulated (c, d) 2D maps of the ultrafast transient differential transmittance from the suprastructure sample with 0.1 Au concentration, excited at λ = 400 nm pump wavelength and Fp ∼ 340 μJ/cm2 pulse fluence, shown at short (a, c) and long (b, d) pump–probe time delays. (e–h) Same as (a)–(d) for the sample with a concentration of 0.3. (i–l) Same as (a)–(d) for the 1 concentration sample.

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    Figure 3

    Figure 3. Optical dynamics of suprastructure vs coated nanoparticle. (a, b) Experimental time traces selected at specific probe wavelengths λ of the transient signal of the differential transmittance at short (a) and long (b) pump–probe time delays for the sample with Au relative concentration cr = 1. (c, d) Simulated time sections of the optical signal at short (c) and long (d) pump–probe time delays for the same sample. (e, f) Simulated time sections of differential transmittance of a fictitious homogeneous (unstructured) system with equivalent Au volume.

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    Figure 4

    Figure 4. Thermal dynamics of suprastructure vs coated nanoparticles. (a, b) The average temperature increase ΔΘO in the organic coating of a conventional plasmonic nanoparticle (a) is compared with the average temperature achieved in the organic matrix of plasmonic suprastructures (b) under the same excitation conditions, for the Au:Fe3O4 relative concentration analyzed, that is, cr = 0.1 (red curves), 0.3 (green curves), and 1 (blue curves). Colored dots highlight the maximum value of the temperature change reached. (c) Absorption cross-section normalized to the Au volume for suprastructures (solid) and corresponding coated nanoparticles (dashed). All simulations are performed in a 2D configuration.

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      Mukherjee, S.; Zhou, L.; Goodman, A. M.; Large, N.; Ayala-Orozco, C.; Zhang, Y.; Nordlander, P.; Halas, N. J. Hot-Electron-Induced Dissociation of H2 on Gold Nanoparticles Supported on SiO2. J. Am. Chem. Soc. 2014, 136, 64– 47,  DOI: 10.1021/ja411017b
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      5
      Hot-Electron-Induced Dissociation of H2 on Gold Nanoparticles Supported on SiO2
      Mukherjee, Shaunak; Zhou, Linan; Goodman, Amanda M.; Large, Nicolas; Ayala-Orozco, Ciceron; Zhang, Yu; Nordlander, Peter; Halas, Naomi J.
      Journal of the American Chemical Society (2014), 136 (1), 64-67CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Hot-electron-induced photodissocn. of H2 was demonstrated on small Au nanoparticles (AuNPs) supported on SiO2. The rate of dissocn. of H2 was found to be almost 2 orders of magnitude higher than that obsd. on equivalently prepd. AuNPs on TiO2. The rate of H2 dissocn. was found to be linearly dependent on illumination intensity with a wavelength dependence resembling the absorption spectrum of the plasmon of the AuNPs. This result provides strong addnl. support for the hot-electron-induced mechanism for H2 dissocn. in this photocatalytic system.
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    6. 6
      Ardo, S. Pathways to Electrochemical Solar-Hydrogen Technologies. Energy Environ. Sci. 2018, 11, 2768– 2783,  DOI: 10.1039/C7EE03639F
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      6
      Pathways to electrochemical solar-hydrogen technologies
      Ardo, Shane; Fernandez Rivas, David; Modestino, Miguel A.; Schulze Greiving, Verena; Abdi, Fatwa F.; Alarcon Llado, Esther; Artero, Vincent; Ayers, Katherine; Battaglia, Corsin; Becker, Jan-Philipp; Bederak, Dmytro; Berger, Alan; Buda, Francesco; Chinello, Enrico; Dam, Bernard; Di Palma, Valerio; Edvinsson, Tomas; Fujii, Katsushi; Gardeniers, Han; Geerlings, Hans; H. Hashemi, S. Mohammad; Haussener, Sophia; Houle, Frances; Huskens, Jurriaan; James, Brian D.; Konrad, Kornelia; Kudo, Akihiko; Kunturu, Pramod Patil; Lohse, Detlef; Mei, Bastian; Miller, Eric L.; Moore, Gary F.; Muller, Jiri; Orchard, Katherine L.; Rosser, Timothy E.; Saadi, Fadl H.; Schuttauf, Jan-Willem; Seger, Brian; Sheehan, Stafford W.; Smith, Wilson A.; Spurgeon, Joshua; Tang, Maureen H.; van de Krol, Roel; Vesborg, Peter C. K.; Westerik, Pieter
      Energy & Environmental Science (2018), 11 (10), 2768-2783CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      Solar-powered electrochem. prodn. of hydrogen through water electrolysis is an active and important research endeavor. However, technologies and roadmaps for implementation of this process do not exist. In this perspective paper, we describe potential pathways for solar-hydrogen technologies into the marketplace in the form of photoelectrochem. or photovoltaic-driven electrolysis devices and systems. We detail tech. approaches for device and system architectures, economic drivers, societal perceptions, political impacts, technol. challenges, and research opportunities. Implementation scenarios are broken down into short-term and long-term markets, and a specific technol. roadmap is defined. In the short term, the only plausible economical option will be photovoltaic-driven electrolysis systems for niche applications. In the long term, electrochem. solar-hydrogen technologies could be deployed more broadly in energy markets but will require advances in the technol., significant cost redns., and/or policy changes. Ultimately, a transition to a society that significantly relies on solar-hydrogen technologies will benefit from continued creativity and influence from the scientific community.
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    7. 7
      Roberts, A. T.; Yang, J.; Reish, M. E.; Alabastri, A.; Halas, N. J.; Nordlander, P.; Everitt, H. O. Plasmonic Nanoparticle-Based Epoxy Photocuring: a Deeper Look. Mater. Today 2019, 27, 14– 20,  DOI: 10.1016/j.mattod.2018.09.005
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      7
      Plasmonic nanoparticle-based epoxy photocuring: A deeper look
      Roberts, Adam T.; Yang, Jian; Reish, Matthew E.; Alabastri, Alessandro; Halas, Naomi J.; Nordlander, Peter; Everitt, Henry O.
      Materials Today (Oxford, United Kingdom) (2019), 27 (), 14-20CODEN: MTOUAN; ISSN:1369-7021. (Elsevier Ltd.)
      Many epoxy adhesives require high temps. to bond composite materials. However, oven heating severely restricts what may be attached or enclosed within composite material-based structures and greatly limits the possibilities for repair. Inspired by initial reports of photothermal epoxy curing using plasmonic nanoparticles, we examine how laser-illuminated Au nanoparticles embedded within high-temp. epoxy films convert the conventional thermal curing process into a photothermally driven one. Our theor. investigations reveal that plasmonic nanoparticle-based epoxy photocuring proceeds through a four-stage process: a rapid, plasmon-induced temp. increase, a slow localized initialization of the curing chem. that increases the optical absorption of the epoxy film, a subsequent temp. increase as the epoxy absorbs the laser radiation directly, and a final stage that completes the chem. transformation of the epoxy film to its cured state. Our exptl. studies validate this model, and also reveal that highly local photocuring can create a stronger bond between composite materials than thermal curing without nanoparticles, at times even stronger than the composite material itself, substantially reducing the time needed for the curing process. Our findings support key advances in our understanding of this approach to the rapid, highly efficient bonding and repair of composite materials.
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    8. 8
      Carretero-Palacios, S.; Jiménez-Solano, A.; Míguez, H. Plasmonic Nanoparticles as Light-Harvesting Enhancers in Perovskite Solar Cells: a User’s Guide. ACS Enery Lett. 2016, 1, 323– 331,  DOI: 10.1021/acsenergylett.6b00138
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      8
      Plasmonic Nanoparticles as Light-Harvesting Enhancers in Perovskite Solar Cells: A User's Guide
      Carretero-Palacios, S.; Jimenez-Solano, A.; Miguez, H.
      ACS Energy Letters (2016), 1 (1), 323-331CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      In this review the authors discuss the implications of employing metal particles of different shape, size, and compn. as absorption enhancers in methylammonium lead iodide perovskite solar cells, with the aim of establishing some guidelines for the future development of plasmonic resonance-based photovoltaic devices. Hybrid perovskites present an extraordinarily high absorption coeff. which, as we show here, makes it difficult to extrapolate concepts and designs that are applied to other soln.-processed photovoltaic materials. In addn., the variability of the optical consts. attained from perovskite films of seemingly similar compn. further complicates the anal. We demonstrate that, by means of rigorous design, it is possible to provide a realistic prediction of the magnitude of the absorption enhancement that can be reached for perovskite films embedding metal particles. On the basis of this, we foresee that localized surface plasmon effects will provide a means to attain highly efficient perovskite solar cells using films that are thinner than those usually employed, hence facilitating collection of photocarriers and significantly reducing the amt. of potentially toxic lead present in the device.
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    9. 9
      Dang, X.; Qi, J.; Klug, M. T.; Chen, P.-Y.; Yun, D. S.; Fang, N. X.; Hammond, P. T.; Belcher, A. M. Tunable Localized Surface Plasmon-Enabled Broadband Light-Harvesting Enhancement for High-Efficiency Panchromatic Dye-Sensitized Solar Cells. Nano Lett. 2013, 13, 637– 342,  DOI: 10.1021/nl3043823
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      9
      Tunable Localized Surface Plasmon-Enabled Broadband Light-Harvesting Enhancement for High-Efficiency Panchromatic Dye-Sensitized Solar Cells
      Dang, Xiangnan; Qi, Jifa; Klug, Matthew T.; Chen, Po-Yen; Yun, Dong Soo; Fang, Nicholas X.; Hammond, Paula T.; Belcher, Angela M.
      Nano Letters (2013), 13 (2), 637-642CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      In photovoltaic devices, light harvesting (LH) and carrier collection have opposite relations with the thickness of the photoactive layer, which imposes a fundamental compromise for the power conversion efficiency (PCE). Unbalanced LH at different wavelengths further reduces the achievable PCE. Here, a novel approach is reported to broadband balanced LH and panchromatic solar energy conversion using multiple-core-shell structured oxide-metal-oxide plasmonic nanoparticles. These nanoparticles feature tunable localized surface plasmon resonance frequencies and the required thermal stability during device fabrication. By simply blending the plasmonic nanoparticles with available photoactive materials, the broadband LH of practical photovoltaic devices can be significantly enhanced. A panchromatic dye-sensitized solar cell is demonstrated with an increased PCE from 8.3-10.8%, mainly through plasmon-enhanced photoabsorption in the otherwise less harvested region of solar spectrum. This general and simple strategy also highlights easy fabrication, and may benefit solar cells using other photoabsorbers or other types of solar-harvesting devices.
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    10. 10
      Linic, S.; Aslam, U.; Boerigter, C.; Morabito, M. Photochemical Transformations on Plasmonic Metal Nanoparticles. Nat. Mater. 2015, 14, 567– 576,  DOI: 10.1038/nmat4281
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      10
      Photochemical transformations on plasmonic metal nanoparticles
      Linic, Suljo; Aslam, Umar; Boerigter, Calvin; Morabito, Matthew
      Nature Materials (2015), 14 (6), 567-576CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      A review. The strong interaction of electromagnetic fields with plasmonic nanomaterials offers opportunities in various technologies that take advantage of photophys. processes amplified by this light-matter interaction. Recently, it has been shown that in addn. to photophys. processes, optically excited plasmonic nanoparticles can also activate chem. transformations directly on their surfaces. This potentially offers a no. of opportunities in the field of selective chem. synthesis. In this Review we summarize recent progress in the field of photochem. catalysis on plasmonic metallic nanostructures. We discuss the underlying phys. mechanisms responsible for the obsd. chem. activity, and the issues that must be better understood to see progress in the field of plasmon-mediated photocatalysis.
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    11. 11
      Swearer, D. F.; Robatjazi, H.; Martirez, J. M. P.; Zhang, M.; Zhou, L.; Carter, E. A.; Nordlander, P.; Halas, N. J. Plasmonic Photocatalysis of Nitrous Oxide into N2 and O2 Using Aluminum–Iridium Antenna–Reactor Nanoparticles. ACS Nano 2019, 13, 8076– 8086,  DOI: 10.1021/acsnano.9b02924
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      11
      Plasmonic Photocatalysis of Nitrous Oxide into N2 and O2 Using Aluminum-Iridium Antenna-Reactor Nanoparticles
      Swearer, Dayne F.; Robatjazi, Hossein; Martirez, John Mark P.; Zhang, Ming; Zhou, Linan; Carter, Emily A.; Nordlander, Peter; Halas, Naomi J.
      ACS Nano (2019), 13 (7), 8076-8086CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      Photocatalysis with optically active plasmonic nanoparticles is a growing field in heterogeneous catalysis, with the potential for substantially increasing efficiencies and selectivities of chem. reactions. Here, the decompn. of nitrous oxide (N2O), a potent anthropogenic greenhouse gas, on illuminated Al-Ir (Al-Ir) antenna-reactor plasmonic photocatalysts is reported. Under resonant illumination conditions, N2 and O2 are the only observable decompn. products, avoiding the problematic generation of NOx species obsd. using other approaches. Because no appreciable change to the apparent activation energy was obsd. under illumination, the primary reaction enhancement mechanism for Al-Ir is likely due to photothermal heating rather than plasmon-induced hot-carrier contributions. This light-based approach can induce autocatalysis for rapid N2O conversion, a process with highly promising potential for applications in N2O abatement technologies, satellite propulsion, or emergency life-support systems in space stations and submarines.
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    12. 12
      Cortés, E.; Besteiro, L. V.; Alabastri, A.; Baldi, A.; Tagliabue, G.; Demetriadou, A.; Narang, P. Challenges in Plasmonic Catalysis. ACS Nano 2020, 14, 16202– 16219,  DOI: 10.1021/acsnano.0c08773
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      12
      Challenges in Plasmonic Catalysis
      Cortes, Emiliano; Besteiro, Lucas V.; Alabastri, Alessandro; Baldi, Andrea; Tagliabue, Giulia; Demetriadou, Angela; Narang, Prineha
      ACS Nano (2020), 14 (12), 16202-16219CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      A review. The use of nanoplasmonics to control light and heat close to the thermodn. limit enables exciting opportunities in the field of plasmonic catalysis. The decay of plasmonic excitations creates highly nonequil. distributions of hot carriers that can initiate or catalyze reactions through both thermal and nonthermal pathways. In this Perspective, we present the current understanding in the field of plasmonic catalysis, capturing vibrant debates in the literature, and discuss future avenues of exploration to overcome crit. bottlenecks. Our Perspective spans first-principles theory and computation of correlated and far-from-equil. light-matter interactions, synthesis of new nanoplasmonic hybrids, and new steady-state and ultrafast spectroscopic probes of interactions in plasmonic catalysis, recognizing the key contributions of each discipline in realizing the promise of plasmonic catalysis. We conclude with our vision for fundamental and technol. advances in the field of plasmon-driven chem. reactions in the coming years.
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    13. 13
      Tao, P.; Ni, G.; Song, C.; Shang, W.; Wu, J.; Zhu, J.; Chen, G.; Deng, T. Solar-Driven Interfacial Evaporation. Nat. Ener. 2018, 3, 1031– 1041,  DOI: 10.1038/s41560-018-0260-7
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    14. 14
      Liu, H.; Huang, Z.; Liu, K.; Hu, X.; Zhou, J. Interfacial Solar-to-Heat Conversion for Desalination. Adv. Energy Mater. 2019, 9, 1900310,  DOI: 10.1002/aenm.201900310
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      There is no corresponding record for this reference.
    15. 15
      Mascaretti, L.; Schirato, A.; Zboril, R.; Kment, S.; Schmuki, P.; Alabastri, A.; Naldoni, A. Solar Steam Generation on Scalable Ultrathin TiN Nanocavity arrays. Nano Energy 2021, 83, 105828,  DOI: 10.1016/j.nanoen.2021.105828
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      15
      Solar steam generation on scalable ultrathin thermoplasmonic TiN nanocavity arrays
      Mascaretti, Luca; Schirato, Andrea; Zboril, Radek; Kment, Stepan; Schmuki, Patrik; Alabastri, Alessandro; Naldoni, Alberto
      Nano Energy (2021), 83 (), 105828CODEN: NEANCA; ISSN:2211-2855. (Elsevier Ltd.)
      Plasmonic-based solar absorbers exhibit complete light absorption in a sub-Μm thickness, representing an alternative to mm-thick carbon-based materials most typically employed for solar-driven steam generation. In this work, we present the scalable fabrication of ultrathin plasmonic titanium nitride (TiN) nanocavity arrays that exhibit 90% broadband solar light absorption within ∼ 250 nm from the illuminated surface and show a fast non-linear increase of performance with light intensity. At 14 Suns TiN nanocavities reach ∼ 15 kg h-1 m-2 evapn. rate and ∼ 76% thermal efficiency, a steep increase from ∼ 0.4 kg h-1 m-2 and ∼ 20% under 1.4 Suns. Electromagnetic, thermal and diffusion modeling of our system reveals the contribution of each material and reactor component to heat dissipation and shows that a quasi-two-dimensional heat dissipation regime significantly accelerates water evapn. Our approach to ultrathin plasmonic absorbers can boost the performance of devices for evapn./desalination and holds promise for a broader range of phase sepn. processes.
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    16. 16
      Dongare, P. D.; Alabastri, A.; Pedersen, S.; Zodrow, K. R.; Hogan, N. J.; Neumann, O.; Wu, J.; Wang, T.; Deshmukh, A.; Elimelech, M.; Li, Q.; Nordlander, P.; Halas, N. J. Nanophotonics-Enabled Solar Membrane Distillation for Off-Grid Water Purification. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 6936– 6941,  DOI: 10.1073/pnas.1701835114
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      16
      Nanophotonics-enabled solar membrane distillation for off-grid water purification
      Dongare, Pratiksha D.; Alabastri, Alessandro; Pedersen, Seth; Zodrow, Katherine R.; Hogan, Nathaniel J.; Neumann, Oara; Wu, Jinjian; Wang, Tianxiao; Deshmukh, Akshay; Elimelech, Menachem; Li, Qilin; Nordlander, Peter; Halas, Naomi J.
      Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (27), 6936-6941CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      With more than a billion people lacking accessible drinking water, there is a crit. need to convert nonpotable sources such as seawater to water suitable for human use. However, energy requirements of desalination plants account for half their operating costs, so alternative, lower energy approaches are equally crit. Membrane distn. (MD) has shown potential due to its low operating temp. and pressure requirements, but the requirement of heating the input water makes it energy intensive. Here, we demonstrate nanophotonics-enabled solar membrane distn. (NESMD), where highly localized photothermal heating induced by solar illumination alone drives the distn. process, entirely eliminating the requirement of heating the input water. Unlike MD, NESMD can be scaled to larger systems and shows increased efficiencies with decreased input flow velocities. Along with its increased efficiency at higher ambient temps., these properties all point to NESMD as a promising soln. for household- or community-scale desalination.
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    17. 17
      Kaur, M.; Ishii, S.; Shinde, S. L.; Nagao, T. All-Ceramic Solar-Driven Water Purifier Based on Anodized Aluminum Oxide and Plasmonic Titanium Nitride. Adv. Sustain. Syst. 2019, 3, 1800112,  DOI: 10.1002/adsu.201800112
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      There is no corresponding record for this reference.
    18. 18
      Jans, H.; Huo, Q. Gold Nanoparticle-Enabled Biological and Chemical Detection and Analysis. Chem. Soc. Rev. 2012, 41, 2849– 2866,  DOI: 10.1039/C1CS15280G
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      18
      Gold nanoparticle-enabled biological and chemical detection and analysis
      Jans, Hilde; Huo, Qun
      Chemical Society Reviews (2012), 41 (7), 2849-2866CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Gold nanoparticles (AuNPs) are some of the most extensively studied nanomaterials. Because of their unique optical, chem., elec., and catalytic properties, AuNPs have attracted enormous amt. of interest for applications in biol. and chem. detection and anal. The purpose of this crit. review is to provide the readers with an update on the recent developments in the field of AuNPs for sensing applications based on their optical properties. An overview of the optical properties of AuNPs is presented first, followed by a more detailed literature survey. As the last part of this review, we compare the advantages and disadvantages of each technique, briefly discuss their commercialization status, and some tech. issues that remain to be solved in order to move the technique forward (151 refs.).
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    19. 19
      Wang, C.; Yu, C. Detection of Chemical Polluants in Water Using Gold Nanoparticles as Sensors: a Review. Rev. Anal. Chem. 2013, 32, 1– 14,  DOI: 10.1515/revac-2012-0023
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      19
      Detection of chemical pollutants in water using gold nanoparticles as sensors: a review
      Wang, Chao; Yu, Chenxu
      Reviews in Analytical Chemistry (2013), 32 (1), 1-14CODEN: RACYAX; ISSN:0793-0135. (Walter de Gruyter GmbH)
      A review. Rapid and accurate evaluation of pollutant contamination in water is one of the key tasks of environmental monitoring. To make on-site assessment feasible, the anal. tools should be easy to operate, with minimal sample prepn. needs. Gold nanoparticle (AuNP)-based sensors have the potential to detect toxins, heavy metals, and inorg. and org. pollutants in water rapidly with high sensitivity, and they are expected to play an increasingly important role in environmental monitoring. In this article, the synthesis, fabrication and functionalization of AuNPs are discussed, and the recent advances in the development and application of AuNP-based sensors for the detn. of various pollutants contamination in water are reviewed.
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    20. 20
      Wang, Y.; Kohane, D. S. External Triggering and Triggered Targeting Strategies for Drug Delivery. Nat. Rev. Mater. 2017, 2, 17020,  DOI: 10.1038/natrevmats.2017.20
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      20
      External triggering and triggered targeting strategies for drug delivery
      Wang, Yanfei; Kohane, Daniel S.
      Nature Reviews Materials (2017), 2 (2), 17020CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)
      A review. Drug delivery systems that are externally triggered to release drugs and/or target tissues hold considerable promise for improving the treatment of many diseases by minimizing nonspecific toxicity and enhancing the efficacy of therapy. These drug delivery systems are constructed from materials that are sensitive to a wide range of external stimuli, including light, ultrasound, elec. and magnetic fields, and specific mols. The responsiveness conferred by these materials allows the release of therapeutics to be triggered on demand and remotely by a physician or patient. In this Review, we describe the rationales for such systems and the types of stimuli that can be deployed, and provide an outlook for the field.
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    21. 21
      Goodman, A. M.; Neumann, O.; Nørregaard, K.; Henderson, L.; Choi, M. R.; Clare, S. E.; Halas, N. J. Near-Infrared Remotely Triggered Drug-Release Strategies for Cancer Treatment. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 12419– 12424,  DOI: 10.1073/pnas.1713137114
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      21
      Near-infrared remotely triggered drug-release strategies for cancer treatment
      Goodman, Amanda M.; Neumann, Oara; Noerregaard, Kamilla; Henderson, Luke; Choi, Mi-Ran; Clare, Susan E.; Halas, Naomi J.
      Proceedings of the National Academy of Sciences of the United States of America (2017), 114 (47), 12419-12424CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      Remotely controlled, localized drug delivery is highly desirable for potentially minimizing the systemic toxicity induced by the administration of typically hydrophobic chemotherapy drugs by conventional means. Nanoparticle-based drug delivery systems provide a highly promising approach for localized drug delivery, and are an emerging field of interest in cancer treatment. Here, we demonstrate near-IR light-triggered release of two drug mols. from both DNA-based and protein-based hosts that have been conjugated to near-IR-absorbing Au nanoshells (SiO2 core, Au shell), each forming a light-responsive drug delivery complex. We show that, depending upon the drug mol., the type of host mol., and the laser illumination method (continuous wave or pulsed laser), in vitro light-triggered release can be achieved with both types of nanoparticle-based complexes. Two breast cancer drugs, docetaxel and HER2-targeted lapatinib, were delivered to MDA-MB-231 and SKBR3 (overexpressing HER2) breast cancer cells and compared with release in noncancerous RAW 264.7 macrophage cells. Continuous wave laser-induced release of docetaxel from a nanoshell-based DNA host complex showed increased cell death, which also coincided with nonspecific cell death from photothermal heating. Using a femtosecond pulsed laser, lapatinib release from a nanoshell-based human serum albumin protein host complex resulted in increased cancerous cell death while noncancerous control cells were unaffected. Both methods provide spatially and temporally localized drug-release strategies that can facilitate high local concns. of chemotherapy drugs deliverable at a specific treatment site over a specific time window, with the potential for greatly minimized side effects.
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    22. 22
      Jaque, D.; Martinez Maestro, L.; del Rosal, B.; Haro-Gonzalez, P.; Benayas, A.; Plaza, J. L.; Martin Rodriguez, E.; Garcia Sole, J. Nanoparticles for Photothermal Therapies. Nanoscale 2014, 6, 9494– 9530,  DOI: 10.1039/C4NR00708E
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      22
      Nanoparticles for photothermal therapies
      Jaque, D.; Martinez Maestro, L.; del Rosal, B.; Haro-Gonzalez, P.; Benayas, A.; Plaza, J. L.; Martin Rodriguez, E.; Garcia Sole, J.
      Nanoscale (2014), 6 (16), 9494-9530CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)
      A review. The current status of the use of nanoparticles for photothermal treatments is reviewed in detail. The different families of heating nanoparticles are described paying special attention to the phys. mechanisms at the root of the light-to-heat conversion processes. The heating efficiencies and spectral working ranges are listed and compared. The most important results obtained in both in vivo and in vitro nanoparticle assisted photothermal treatments are summarized. The advantages and disadvantages of the different heating nanoparticles are discussed.
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    23. 23
      Abadeer, N. S.; Murphy, C. J. Recent Progress in Cancer Thermal Therapy Using Gold Nanoparticles. J. Phys. Chem. C 2016, 120, 4691– 4716,  DOI: 10.1021/acs.jpcc.5b11232
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      Recent Progress in Cancer Thermal Therapy Using Gold Nanoparticles
      Abadeer, Nardine S.; Murphy, Catherine J.
      Journal of Physical Chemistry C (2016), 120 (9), 4691-4716CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      In recent years, there has been a great deal of interest in the prepn. and application of nanoparticles for cancer therapy. Gold nanoparticles are esp. suited to thermal destruction of cancer due to their ease of surface functionalization and photothermal heating ability. Here, we review recent progress in gold nanoparticle-mediated thermal cancer therapies. We begin with an introduction to the properties of gold nanoparticles and heat-generating mechanisms which have been established. The pioneering work in photothermal therapy is discussed along with the effects of photothermal heating on cells in vitro. Addnl., radiofrequency-mediated thermal therapy is reviewed. We focus our discussion on the developments and progress in nanoparticle design for photothermal cancer therapy since 2010. This includes in vitro and in vivo studies and the recent progression of gold nanoparticle photothermal therapy toward clin. cancer treatment.
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    24. 24
      Richardson, H. H.; Carlson, M. T.; Tandler, P. J.; Hernandez, P.; Govorov, A. O. Experimental and Theoretical Studies of Light-to-Heat Conversion and Collective Heating Effects in Metal Nanoparticle Solutions. Nano Lett. 2009, 9, 1139– 1146,  DOI: 10.1021/nl8036905
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      24
      Experimental and Theoretical Studies of Light-to-Heat Conversion and Collective Heating Effects in Metal Nanoparticle Solutions
      Richardson, Hugh H.; Carlson, Michael T.; Tandler, Peter J.; Hernandez, Pedro; Govorov, Alexander O.
      Nano Letters (2009), 9 (3), 1139-1146CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      The authors perform a set of expts. on photoheating in a H2O droplet contg. Au nanoparticles (NPs). Using photocalorimetric methods, the authors det. efficiency of light-to-heat conversion (η) which turns out to be remarkably close to 1, (0.97 < η < 1.03). Detailed studies reveal a complex character of heat transfer in an optically stimulated droplet. The main mechanism of equilibration is due to convectional flow. Theor. modeling is performed to describe thermal effects at both nano- and millimeter scales. Theory shows that the collective photoheating is the main mechanism. For a large concn. of NPs and small laser intensity, an averaged temp. increase (at the millimeter scale) is significant (∼7°), whereas on the nanometer scale the temp. increase at the surface of a single NP is small (∼0.02°). In the opposite regime, i.e., a small NP concn. and intense laser irradn., an opposite picture: a temp. increase at the millimeter scale is small (∼0.1°) but a local, nanoscale temp. has strong local spikes at the surfaces of NPs (∼3°) were found. These studies are crucial for the understanding of photothermal effects in NPs and for their potential and current applications in nano- and biotechnologies.
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    25. 25
      Schuller, J. A.; Barnard, E. S.; Cai, W.; Chul Jun, Y.; White, J. S.; Brongersma, M. L. Plasmonics for Extreme Light Concentration and Manipulation. Nat. Mater. 2010, 9, 193– 204,  DOI: 10.1038/nmat2630
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      Plasmonics for extreme light concentration and manipulation
      Schuller, Jon A.; Barnard, Edward S.; Cai, Wenshan; Jun, Young Chul; White, Justin S.; Brongersma, Mark L.
      Nature Materials (2010), 9 (3), 193-204CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      A review. The unprecedented ability of nanometallic (i.e., plasmonic) structures to conc. light into deep-subwavelength vols. has propelled their use in a vast array of nanophotonics technols. and research endeavours. Plasmonic light concentrators can elegantly interface diffraction-limited dielec. optical components with nanophotonic structures. Passive and active plasmonic devices provide new pathways to generate, guide, modulate and detect light with structures that are similar in size to state-of-the-art electronic devices. With the ability to produce highly confined optical fields, the conventional rules for light-matter interactions need to be reexamd., and researchers are venturing into new regimes of optical physics. The authors will discuss the basic concepts behind plasmonics-enabled light concn. and manipulation, make an attempt to capture the wide range of activities and excitement in this area, and speculate on possible future directions.
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    26. 26
      Brongersma, M. L.; Halas, N. J.; Nordlander, P. Plasmon-Induced Hot Carrier Science and Technology. Nat. Nanotechnol. 2015, 10, 25– 34,  DOI: 10.1038/nnano.2014.311
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      26
      Plasmon-induced hot carrier science and technology
      Brongersma, Mark L.; Halas, Naomi J.; Nordlander, Peter
      Nature Nanotechnology (2015), 10 (1), 25-34CODEN: NNAABX; ISSN:1748-3387. (Nature Publishing Group)
      A review. The discovery of the photoelec. effect by Heinrich Hertz in 1887 set the foundation for over 125 years of hot carrier science and technol. In the early 1900s it played a crit. role in the development of quantum mechanics, but even today the unique properties of these energetic, hot carriers offer new and exciting opportunities for fundamental research and applications. Measurement of the kinetic energy and momentum of photoejected hot electrons can provide valuable information on the electronic structure of materials. The heat generated by hot carriers can be harvested to drive a wide range of phys. and chem. processes. Their kinetic energy can be used to harvest solar energy or create sensitive photodetectors and spectrometers. Photoejected charges can also be used to elec. dope two-dimensional materials. Plasmon excitations in metallic nanostructures can be engineered to enhance and provide valuable control over the emission of hot carriers. This Review discusses recent advances in the understanding and application of plasmon-induced hot carrier generation and highlights some of the exciting new directions for the field.
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    27. 27
      Rashidi-Huyeh, M.; Palpant, B. Thermal Response of Nanocomposite Materials under Pulsed Laser Excitation. J. Appl. Phys. 2004, 96, 4475,  DOI: 10.1063/1.1794894
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      27
      Thermal response of nanocomposite materials under pulsed laser excitation
      Rashidi-Huyeh, Majid; Palpant, Bruno
      Journal of Applied Physics (2004), 96 (8), 4475-4482CODEN: JAPIAU; ISSN:0021-8979. (American Institute of Physics)
      The optical properties of nanocomposite materials made of matrix-embedded noble metal nanoparticles strongly depend on thermal effects from different origins. We propose a classical model describing the energy exchanges within the nanoparticles and between the latter and the surrounding dielec. host subsequent to a light pulse absorption. This model, which accounts for the thermal interactions between neighboring particles, allows us to calc. numerically the temp. dynamics of the electrons, metal lattice and matrix as functions of particle size, and metal concn. of the medium, whatever be the pulsed excitation temporal regime. It is illustrated in the case of Au:SiO2 materials under femtosecond and nanosecond pulse excitation. It is shown that, in the femtosecond regime, the heat transfer to the matrix cannot be neglected beyond a few picosecond delay from which particle size and metal concn. play a significant role in the electron relaxation. In the nanosecond regime, these morphol. parameters influence crucially the material thermal behavior with the possibility of generating a thermal lens effect. The implications in the anal. of exptl. results regarding both the electron relaxation dynamics and the nonlinear optical properties are also discussed. Finally, a method to adapt the model to the case of thin nanocomposite film is proposed.
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      Hartland, G. V. Optical Studies of Dynamics in Noble Metal Nanostructures. Chem. Rev. 2011, 111, 3858– 3887,  DOI: 10.1021/cr1002547
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      28
      Optical studies of dynamics in noble metal nanostructures
      Hartland, Gregory V.
      Chemical Reviews (Washington, DC, United States) (2011), 111 (6), 3858-3887CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review.
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    29. 29
      Baffou, G.; Quidant, R.; García de Abajo, F. J. Nanoscale Control of Optical Heating in Complex Plasmonic Systems. ACS Nano 2010, 4, 709– 716,  DOI: 10.1021/nn901144d
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      Nanoscale Control of Optical Heating in Complex Plasmonic Systems
      Baffou, Guillaume; Quidant, Romain; Garcia de Abajo, F. Javier
      ACS Nano (2010), 4 (2), 709-716CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      The authors introduce a numerical technique to study the temp. distribution in arbitrarily complex plasmonic systems subject to external illumination. The authors perform both electromagnetic and thermodn. calcns. based upon a time-efficient boundary element method. Two kinds of plasmonic systems are studied to illustrate the potential of such a technique. First, the authors focus on individual particles with various morphologies. In analogy with electrostatics, the authors introduce the concept of thermal capacitance. This geometry-dependent quantity allows one to assess the temp. increase inside a plasmonic particle from the sole knowledge of its absorption cross section. The authors present universal thermal-capacitance curves for ellipsoids, rods, disks, and rings. Addnl., the authors study assemblies of nanoparticles in close proximity and show that, despite its diffusive nature, the temp. distribution can be made highly nonuniform even at the nanoscale using plasmonic systems. A significant degree of nanoscale control over the individual temps. of neighboring particles is demonstrated, depending on the external light wavelength and direction of incidence. The authors illustrate this concept with simulations of Au sphere dimers and chains in H2O. Work opens new possibilities for selectively controlling processes such as local melting for dynamic patterning of textured materials, chem. and metabolic thermal activation, and heat delivery for producing mech. motion with spatial precision in the nanoscale.
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    30. 30
      Berry, K. R.; Dunklin, J. R.; Blake, P. A.; Roper, D. K. Thermal Dynamics of Plasmonic Nanoparticle Composites. J. Phys. Chem. C 2015, 119, 10550– 10557,  DOI: 10.1021/jp512701v
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      30
      Thermal Dynamics of Plasmonic Nanoparticle Composites
      Berry, Keith R.; Dunklin, Jeremy R.; Blake, Phillip A.; Roper, D. Keith
      Journal of Physical Chemistry C (2015), 119 (19), 10550-10557CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Thermal response rates of plasmonic nanocomposite materials limit their capacity for adaptive control and scalable implementation. This work examines thermal dynamics in insulating and conductive dielecs. contg. two- and three-dimensional disordered distributions of plasmonic gold nanoparticles (AuNP). It is shown that a balance of micro- and macroscale internal and external dissipation rates can model overall thermal dynamics and dissipation rates measured for widely varying composite materials to within a few percent using independent geometric and thermodn. parameters. The independent ests. are within 2.6% of values measured for isolated colloid AuNP suspensions, between 0.15 to 13.4% for randomly sized AuNP embedded in polymer films, and within 5.4 to 30.0% for AuNP deposited on conductive ceramics. Estd. thermal dynamics for AuNP embedded in thin polymer film are higher than AuNP in fluid or on ceramic substrates. This modeling approach could guide design and deployment of thermally responsive plasmonic energy materials, sensors, and therapeutics for heat-sensitive applications.
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    31. 31
      Govorov, A. O.; Zhang, W.; Skeini, T.; Richardson, H.; Lee, J.; Kotov, N. A. Gold Nanoparticle Ensembles as Heaters and Actuators: Melting and Collective Plasmon Resonances. Nanoscale Res. Lett. 2006, 1, 84– 90,  DOI: 10.1007/s11671-006-9015-7
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      Palpant, B.; Guillet, Y.; Rashidi-Huyeh, M.; Prot, D. Gold Nanoparticle Assemblies: Thermal Behaviour under Optical Excitation. Gold Bull. 2008, 41, 105– 115,  DOI: 10.1007/BF03216588
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      32
      Gold nanoparticle assemblies: Thermal behaviour under optical excitation
      Palpant, Bruno; Guillet, Yannick; Rashidi-Huyeh, Majid; Prot, Dominique
      Gold Bulletin (London, United Kingdom) (2008), 41 (2), 105-115CODEN: GOBUFW; ISSN:1027-8591. (World Gold Council)
      The optical response of materials based on gold nanoparticle assemblies depends on many parameters connected to both material morphol. and light excitation characteristics. The optical energy absorbed is then converted into heat through different nanoscale energy exchange mechanisms. This heating subsequently modifies itself the optical properties. We investigate the interplay between the optical and thermal responses of nanocomposite media under its theor. aspect. In this first paper, the thermal response of gold nanoparticle assemblies under pulsed optical excitation is considered. Both conventional and original modeling approaches are presented. We first underline the role of electromagnetic interactions between particles in a dense assembly in its linear optical response. We then show how the interaction of light with matrix-embedded gold nanoparticles can result in the generation of thermal excitations through different energy exchange mechanisms. Finally, we demonstrate the possible significant influence of the heat carrier ballistic regime and phonon rarefaction in the cooling dynamics of an embedded gold nanoparticle subsequent to ultrafast pulsed laser excitation.
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    33. 33
      Baffou, G.; Berto, P.; Bermúdez Ureña, E.; Quidant, R.; Monneret, S.; Polleux, J.; Rigneault, H. Photoinduced Heating of Nanoparticle Arrays. ACS Nano 2013, 7, 6478– 6488,  DOI: 10.1021/nn401924n
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      Photoinduced Heating of Nanoparticle Arrays
      Baffou, Guillaume; Berto, Pascal; Bermudez Urena, Esteban; Quidant, Romain; Monneret, Serge; Polleux, Julien; Rigneault, Herve
      ACS Nano (2013), 7 (8), 6478-6488CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      The temp. distribution throughout arrays of illuminated metal nanoparticles is studied numerically and exptl. The 2 cases of continuous and femtosecond-pulsed illumination are addressed. In the case of continuous illumination, 2 distinct regimes are evidenced: a temp. confinement regime, where the temp. increase remains confined at the vicinity of each nanosource of heat, and a temp. delocalization regime, where the temp. is uniform throughout the whole nanoparticle assembly despite the heat sources' nanometric size. The occurrence of 1 regime or another simply depends on the geometry of the nanoparticle distribution. In particular, the authors derived (i) simple expressions of dimensionless parameters aimed at predicting the degree of temp. confinement and (ii) anal. expressions aimed at estg. the actual temp. increase at the center of an assembly of nanoparticles under illumination, preventing heavy numerical simulations. All these theor. results are supported by exptl. measurements of the temp. distribution on regular arrays of Au nanoparticles under illumination. In the case of femtosecond-pulsed illumination, the authors explain the 2 conditions that must be fulfilled to observe a further enhanced temp. spatial confinement.
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      Kildishev, A. V.; Boltasseva, A.; Shalaev, V. M. Planar Photonics with Metasurfaces. Science 2013, 339, 1289,  DOI: 10.1126/science.1232009
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      Yu, N.; Capasso, F. Flat Optics with Designer Metasurfaces. Nat. Mater. 2014, 13, 139,  DOI: 10.1038/nmat3839
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      Flat optics with designer metasurfaces
      Yu, Nanfang; Capasso, Federico
      Nature Materials (2014), 13 (2), 139-150CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      A review. Conventional optical components such as lenses, waveplates and holograms rely on light propagation over distances much larger than the wavelength to shape wavefronts. In this way, substantial changes of the amplitude, phase or polarization of light waves are gradually accumulated along the optical path. This review focuses on recent developments on flat, ultrathin optical components dubbed 'metasurfaces' that produce abrupt changes over the scale of the free-space wavelength in the phase, amplitude and/or polarization of a light beam. Metasurfaces are generally created by assembling arrays of miniature, anisotropic light scatterers (i.e., resonators such as optical antennas). The spacing between antennas and their dimensions are much smaller than the wavelength. As a result the metasurfaces, on account of Huygens principle, are able to mold optical wavefronts into arbitrary shapes with subwavelength resoln. by introducing spatial variations in the optical response of the light scatterers. Such gradient metasurfaces go beyond the well-established technol. of frequency selective surfaces made of periodic structures and are extending to new spectral regions the functionalities of conventional microwave and millimeter-wave transmit-arrays and reflect-arrays. Metasurfaces can also be created by using ultrathin films of materials with large optical losses. By using the controllable abrupt phase shifts assocd. with reflection or transmission of light waves at the interface between lossy materials, such metasurfaces operate like optically thin cavities that strongly modify the light spectrum. Technol. opportunities in various spectral regions and their potential advantages in replacing existing optical components are discussed.
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    36. 36
      Pileni, M.-P. Light Interactions with Supracrystals either Deposited on a Substrate or Dispersed in Water. Inorg. Chem. Front. 2020, 7, 3796,  DOI: 10.1039/D0QI00353K
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      Light interactions with supracrystals either deposited on a substrate or dispersed in water
      Pileni, Marie Paule
      Inorganic Chemistry Frontiers (2020), 7 (20), 3796-3804CODEN: ICFNAW; ISSN:2052-1553. (Royal Society of Chemistry)
      Nanocrystals with low size distribution are able to self-assemble into a 3D cryst. structure called colloidal crystals or super/supracrystals. A rather large no. of supracrystal specific properties have been achieved showing promising potential applications. Here, we compared intrinsic properties induced by light interacting with fcc supracrystals of hydrophobic metal nanocrystals either deposited on a substrate or dispersed in aq. soln. We first describe the formation of a dried supracrystal film grown via a heterogeneous process with cracks formed due to the shrinking of the film caused by restriction of its adhesion on the surface. We also describe the method to fabricate hydrophobic supracrystals dispersed in aq. soln. The optical properties of the thick dried supracrystal film are detd. from the wetting layers formed at the bottom of the cracks whereas, for water dispersed suprastructures, both the collective optical photonic mode and absorption of dispersed nanocrystals used as build blocks are obsd. Ag nanocrystals used as building blocks in a dried supracrystal film vibrate coherently as atoms in a nanocrystal. However, it is impossible to det. the oscillation period of the whole assembly. Conversely from a dynamic study, the breathing period of the assemblies dispersed in aq. soln. is found to be around 300 ps. Whatever exptl. conditions, nanocrystals exposed to light breath coherently in a supracrystal. In aq. soln., supracrystals behave as nanoheaters.
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    37. 37
      Zhou, L.; Tan, Y.; Wang, J.; Xu, W.; Yuan, Y.; Cai, W.; Zhu, S.; Zhu, J. 3D Self-Assembly of Aluminium Nanoparticles for Plasmon-Enhanced Solar Desalination. Nat. Photonics 2016, 10, 393– 398,  DOI: 10.1038/nphoton.2016.75
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      3D self-assembly of aluminum nanoparticles for plasmon-enhanced solar desalination
      Zhou, Lin; Tan, Yingling; Wang, Jingyang; Xu, Weichao; Yuan, Ye; Cai, Wenshan; Zhu, Shining; Zhu, Jia
      Nature Photonics (2016), 10 (6), 393-398CODEN: NPAHBY; ISSN:1749-4885. (Nature Publishing Group)
      Plasmonics has generated tremendous excitement because of its unique capability to focus light into subwavelength vols., beneficial for various applications such as light harvesting, photodetection, sensing, catalysis and so on. Here we demonstrate a plasmon-enhanced solar desalination device, fabricated by the self-assembly of aluminum nanoparticles into a three-dimensional porous membrane. The formed porous plasmonic absorber can float naturally on water surface, efficiently absorb a broad solar spectrum (>96%) and focus the absorbed energy at the surface of the water to enable efficient (∼90%) and effective desalination (a decrease of four orders of magnitude). The durability of the devices has also been examd., indicating a stable performance over 25 cycles under various illumination conditions. The combination of the significant desalination effect, the abundance and low cost of the materials, and the scalable prodn. processes suggest that this type of plasmon-enhanced solar desalination device could provide a portable desalination soln.
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    38. 38
      Zhou, L.; Tan, Y.; Ji, D.; Zhu, B.; Zhang, P.; Xu, J.; Gan, Q.; Yu, Z.; Zhu, J. Self-Assembly of Highly Efficient, Broadband Plasmonic Absorbers for Solar Steam Generation. Sci. Adv. 2016, 2, e1501227  DOI: 10.1126/sciadv.1501227
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      Self-assembly of highly efficient, broadband plasmonic absorbers for solar steam generation
      Zhou, Lin; Tan, Yingling; Ji, Dengxin; Zhu, Bin; Zhang, Pei; Xu, Jun; Gan, Qiaoqiang; Yu, Zongfu; Zhu, Jia
      Science Advances (2016), 2 (4), e1501227/1-e1501227/8CODEN: SACDAF; ISSN:2375-2548. (American Association for the Advancement of Science)
      The study of ideal absorbers, which can efficiently absorb light over a broad range of wavelengths, is of fundamental importance, as well as crit. for many applications from solar steam generation and thermophotovoltaics to light/thermal detectors. As a result of recent advances in plasmonics, plasmonic absorbers have attracted a lot of attention. However, the performance and scalability of these absorbers, predominantly fabricated by the top-down approach, need to be further improved to enable widespread applications. We report a plasmonic absorber which can enable an av. measured absorbance of ∼99% across the wavelengths from 400 nm to 10 μm, the most efficient and broadband plasmonic absorber reported to date. The absorber is fabricated through self-assembly of metallic nanoparticles onto a nanoporous template by a one-step deposition process. Because of its efficient light absorption, strong field enhancement, and porous structures, which together enable not only efficient solar absorption but also significant local heating and continuous stream flow, plasmonic absorber-based solar steam generation has over 90% efficiency under solar irradn. of only 4-sun intensity (4 kW m-2). The pronounced light absorption effect coupled with the high-throughput self-assembly process could lead toward large-scale manufg. of other nanophotonic structures and devices.
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    39. 39
      Mazzanti, A.; Yang, Z.; Silva, M. G.; Yang, N.; Rizza, G.; Coulon, P.-E.; Manzoni, C.; de Paula, A. M.; Cerullo, G.; Della Valle, G.; Pileni, M.-P. Light-Heat Conversion Dynamics in Highly Diversified Water-Dispersed Hydrophobic Nanocrystal Assemblies. Proc. Natl. Acad. Sci. U.S.A. 2019, 116, 8161– 8166,  DOI: 10.1073/pnas.1817850116
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      Light-heat conversion dynamics in highly diversified water-dispersed hydrophobic nanocrystal assemblies
      Mazzanti, Andrea; Yang, Zhijie; Silva, Mychel G.; Yang, Nailiang; Rizza, Giancarlo; Coulon, Pierre-EugA ne; Manzoni, Cristian; de Paula, Ana Maria; Cerullo, Giulio; Della Valle, Giuseppe; Pileni, Marie-Paule
      Proceedings of the National Academy of Sciences of the United States of America (2019), 116 (17), 8161-8166CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)
      The authors study, with a combination of ultrafast optical spectroscopy and semiclassical modeling, the photothermal properties of various water-sol. nanocrystal assemblies. Broadband pump-probe expts. with ~100 fs time resoln. in the visible and near IR reveal a complex scenario for their transient optical response that is dictated by their hybrid compn. at the nanoscale, comprising metallic (Au) or semiconducting (Fe3O4) nanostructures and a matrix of org. ligands. The authors track the whole chain of energy flow that starts from light absorption by the individual nanocrystals and subsequent excitation of out-of-equil. carriers followed by the electron-phonon equilibration, occurring in a few picoseconds, and then by the heat release to the matrix on the 100-ps timescale. Two-dimensional finite-element method electromagnetic simulations of the composite nanostructure and multi-temp. modeling of the energy flow dynamics enable the authors to identify the key mechanism presiding over the light-heat conversion in these kinds of nanomaterials. Hybrid (org.-inorg.) nanocrystal assemblies can operate as efficient nanoheaters by exploiting the high absorption from the individual nanocrystals, enabled by the diln. of the inorg. phase that is followed by a relatively fast heating of the embedding org. matrix, occurring on the 100-ps timescale.
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    40. 40
      Moretti, L.; Mazzanti, A.; Rossetti, A.; Schirato, A.; Polito, L.; Pizzetti, F.; Sacchetti, A.; Cerullo, G.; Della Valle, G.; Rossi, F.; Maiuri, M. Plasmonic Control of Drug Release Efficiency in Agarose Gel Loaded with Gold Nanoparticle Assemblies. Nanophoton 2020, 10, 247,  DOI: 10.1515/nanoph-2020-0418
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      Yang, N.; Deeb, C.; Pelouard, J.-L.; Felidj, N.; Pileni, M.-P. Water-Dispersed Hybrophobic Au Nanocrystal Assemblies with a Plasmon Fingerprint. ACS Nano 2017, 11, 7797– 7806,  DOI: 10.1021/acsnano.7b01605
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      Water-Dispersed Hydrophobic Au Nanocrystal Assemblies with a Plasmon Fingerprint
      Yang, Nailiang; Deeb, Claire; Pelouard, Jean-Luc; Felidj, Nordin; Pileni, Marie-Paule
      ACS Nano (2017), 11 (8), 7797-7806CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)
      Hydrophobic Au nanocrystal assemblies (both ordered and amorphous) were dispersed in aq. soln. via the assistance of lipid vesicles. The intertwine between vesicles and Au assemblies was made possible through a careful selection of the length of alkyl chains on Au nanocrystals. Extinction spectra of Au assemblies showed 2 peaks that were assigned to a scattering mode that red shifted with increasing the assembly size and an absorption mode assocd. with localized surface plasmon that was independent of their size. This plasmon fingerprint could be used as a probe for studying the optical properties of such assemblies. The H2O-sol. assemblies enable exploring a variety of potential applications including solar energy and biomedicine.
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    42. 42
      Boles, A. M.; Engel, M.; Talapin, D. V. Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials. Chem. Rev. 2016, 116, 11220– 11289,  DOI: 10.1021/acs.chemrev.6b00196
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      42
      Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials
      Boles, Michael A.; Engel, Michael; Talapin, Dmitri V.
      Chemical Reviews (Washington, DC, United States) (2016), 116 (18), 11220-11289CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Chem. methods developed over the past two decades enable prepn. of colloidal nanocrystals with uniform size and shape. These Brownian objects readily order into superlattices. Recently, the range of accessible inorg. cores and tunable surface chemistries dramatically increased, expanding the set of nanocrystal arrangements exptl. attainable. In this review, we discuss efforts to create next-generation materials via bottom-up organization of nanocrystals with preprogrammed functionality and self-assembly instructions. This process is often driven by both interparticle interactions and the influence of the assembly environment. The introduction provides the reader with a practical overview of nanocrystal synthesis, self-assembly, and superlattice characterization. We then summarize the theory of nanocrystal interactions and examine fundamental principles governing nanocrystal self-assembly from hard and soft particle perspectives borrowed from the comparatively established fields of micrometer colloids and block copolymer assembly. We outline the extensive catalog of superlattices prepd. to date using hydrocarbon-capped nanocrystals with spherical, polyhedral, rod, plate, and branched inorg. core shapes, as well as those obtained by mixing combinations thereof. We also provide an overview of structural defects in nanocrystal superlattices. We then explore the unique possibilities offered by leveraging nontraditional surface chemistries and assembly environments to control superlattice structure and produce nonbulk assemblies. We end with a discussion of the unique optical, magnetic, electronic, and catalytic properties of ordered nanocrystal superlattices, and the coming advances required to make use of this new class of solids.
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    43. 43
      Hao, J.; Yang, Y.; Zhang, F.; Yang, Z.; Wei, J. Faceted Colloidal Au/Fe3O4 Binary Supracrystals Dictated by Intrinsic Lattice Structures and Their Collective Optical Properties. J. Phys. Chem. C 2020, 124, 14775– 14786,  DOI: 10.1021/acs.jpcc.0c02984
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      43
      Faceted Colloidal Au/Fe3O4 Binary Supracrystals Dictated by Intrinsic Lattice Structures and Their Collective Optical Properties
      Hao, Jinjie; Yang, Yanzhao; Zhang, Fenghua; Yang, Zhijie; Wei, Jingjing
      Journal of Physical Chemistry C (2020), 124 (27), 14775-14786CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Although self-assembly of binary nanocrystal mixts. into long-range ordered cryst. films with tunable lattice structures are well-known, it would be interesting to shape these binary nanocrystal supracrystals into faceted assemblies because it potentially provides the shape-dependent optical, electronic, and catalytic properties. Herein, we report the self-assembly of binary nanocrystal supracrystals with faceted morphologies from Fe3O4 and Au binary mixts. The asym. crystal parameters in AlB2-type structure, a = b > c, favors one-dimensional (1D) self-assembly along the 〈001〉 direction, resulting in the formation of supraspindles and suprarods with 20 facets. For the sym. cubic lattice system, like NaCl-type and NaZn13-type structures, truncated cube/octahedron with preferential exposed facets of (100) and (111) are produced. By contrast, for another cubic lattice of bcc.-AB6, in which large nanocrystals are ordered into body-centered-cubic (bcc.) structure, truncated rhombic dodecahedra enclosed with (110) and (100) are made. The shape-controlled assembly of binary nanocrystal supracrystals composed of plasmonic Au nanocrystals enables engineering the plasmonic near field coupling in binary nanocrystal supracrystals dispersed in water.
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    44. 44
      Nicolas-Boluda, A.; Yang, Z.; Dobryden, I.; Carn, F.; Winckelmans, N.; Péchoux, C.; Bonville, P.; Bals, S.; Claesson, P. M.; Gazeau, F.; Pileni, M.-P. Intracellular Fate of Hydrophobic Nanocrystal Self-Assemblies in Tumor Cells. Adv. Funct. Mater. 2020, 30, 2004274,  DOI: 10.1002/adfm.202004274
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      44
      Intracellular Fate of Hydrophobic Nanocrystal Self-Assemblies in Tumor Cells
      Nicolas-Boluda, Alba; Yang, Zhijie; Dobryden, Illia; Carn, Florent; Winckelmans, Naomi; Pechoux, Christine; Bonville, Pierre; Bals, Sara; Claesson, Per Martin; Gazeau, Florence; Pileni, Marie Paule
      Advanced Functional Materials (2020), 30 (40), 2004274CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water-dispersible architectures of self-assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self-assemblies display increased cellular uptake by tumor cells compared to dispersions of the water-sol. NC building blocks. Moreover, the self-assembly structures increase the NCs d. in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mech. properties. Flexible and soft colloidosomes deform and spread along the biol. membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mech. and topol. properties of the self-assemblies direct their intracellular fate allowing the control intralysosomal d., ordering, and localization of NCs.
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    45. 45
      Zhang, F.; Yang, F.; Gong, Y.; Wei, Y.; Yang, Y.; Wei, J.; Yang, Z.; Pileni, M.-P. Anisotropic Assembly of Nanocrystal/Molecular Hierarchical Supralattices Decoding from Tris-Amide Triarylamines Supramolecular Networks. Small 2020, 16, 2005701,  DOI: 10.1002/smll.202005701
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      45
      Anisotropic Assembly of Nanocrystal/Molecular Hierarchical Superlattices Decoding from Tris-Amide Triarylamines Supramolecular Networks
      Zhang, Fenghua; Yang, Fei; Gong, Yanjun; Wei, Yanze; Yang, Yanzhao; Wei, Jingjing; Yang, Zhijie; Pileni, Marie-Paule
      Small (2020), 16 (48), 2005701CODEN: SMALBC; ISSN:1613-6810. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Directed assembly of nanocrystals from conventional templates suffers from poor control over the periodicity of the nanocrystal assembly, which is largely due to the fact that the template exists prior to the assembly and is not generally adaptive. Herein, small org. mols. (tris-amide triarylamines, TATA) are demonstrated as conceptual templates from self-assembly through noncovalent interactions. The as-formed supramol. structures with terminated alkyl chains, resembling the structure of as-synthesized nanocrystals capped with alkyl chains, are able to interact with nanocrystals through van der Waals attractive forces, thereby enabling directed assembly of nanocrystals into ordered superlattices. Specifically, it is found that, as detd. by the substituted alkyl chains of TATA, either H or J-aggregates of TATA can be achieved, which eventually produce several distinct supramol. structures, from rods to spindles, to rings, and to spheres, serving as on-pathway intermediate that directs the assembly of nanocrystals into diverse nanocrystal superlattices. The approach described can be applicable to produce ordered nanocrystal assemblies of a wide range of nanocrystals, independent of size and shape and without ligand exchange process. Strikingly, a helical TATA stacking can direct assembly of binary nanocrystal mixts. into NaZn13 binary superhelix.
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    46. 46
      Nicolas-Boluda, A.; Yang, Z.; Guilbert, T.; Fouassier, L.; Carn, F.; Gazeau, F.; Pileni, M.-P. Self-Assemblies of Fe3O4 Nanocrystals: Toward Nanoscale Precision of Photothermal Effects in the Tumor Microenvironment. Adv. Funct. Mater. 2021, 31, 2006824,  DOI: 10.1002/adfm.202006824
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      46
      Self-Assemblies of Fe3O4 Nanocrystals: Toward Nanoscale Precision of Photothermal Effects in the Tumor Microenvironment
      Nicolas-Boluda, Alba; Yang, Zhijie; Guilbert, Thomas; Fouassier, Laura; Carn, Florent; Gazeau, Florence; Pileni, Marie Paule
      Advanced Functional Materials (2021), 31 (4), 2006824CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Fe3O4 nanocrystals are self-assembled into two different conformations: colloidosome and supraball that confer them with distinct properties detg. their photo-induced heating capacities. These self-assemblies are assessed for photothermal therapy, an adjuvant strategy for tumor therapy. The tumor microenvironment is a heterogeneous ecosystem including immune cells and the extracellular matrix. The interactions between photothermal therapy agents and the different components of the tumor microenvironment det. the outcome of this therapy. In this study, the fate of both colloidosomes and supraballs within the tumor microenvironment in comparison to their Fe3O4 nanocrystal building blocks is revealed. This study highlights how these two hybrid self-assemblies target different compartments of the tumor microenvironment and trigger local photothermal damages that are inaccessible for isolated nanocrystals and not predicted by global temp. measurements.
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    47. 47
      Yang, Z.; Altantzis, T.; Zanaga, D.; Bals, S.; Van Tendeloo, G.; Pileni, M.-P. Supracrystalline Colloidal Eggs: Epitaxial Growth and Freestanding Three-Dimensional Supracrystals in Nanoscaled Colloidosomes. J. Am. Chem. Soc. 2016, 138, 3493– 3500,  DOI: 10.1021/jacs.5b13235
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      Supracrystalline Colloidal Eggs: Epitaxial Growth and Freestanding Three-Dimensional Supracrystals in Nanoscaled Colloidosomes
      Yang, Zhijie; Altantzis, Thomas; Zanaga, Daniele; Bals, Sara; Van Tendeloo, Gustaaf; Pileni, Marie-Paule
      Journal of the American Chemical Society (2016), 138 (10), 3493-3500CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Here, the authors report the design of a new system called "supracryst. colloidal eggs" formed by controlled assembly of nanocrystals into complex colloidal supracrystals through superlattice-matched epitaxial overgrowth along the existing colloidosomes. Then, with this concept, the authors extend the supracryst. growth to lattice-mismatched binary nanocrystal superlattices, in order to reach anisotropic superlattice growths, yielding freestanding binary nanocrystal supracrystals that could not be produced previously.
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      Park, J.; An, K.; Hwang, Y.; Park, J.-G.; Noh, H.-J.; Kim, J.-Y.; Park, J.-H.; Hwang, N.-M.; Hyeon, T. Ultra-large-scale Syntheses of Monodisperse Nanocrystals. Nat. Mater. 2004, 3, 891– 895,  DOI: 10.1038/nmat1251
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      Ultra-large-scale syntheses of monodisperse nanocrystals
      Park, Jongnam; An, Kwangjin; Hwang, Yosun; Park, Je-Geun; Noh, Han-Jin; Kim, Jae-Young; Park, Jae-Hoon; Hwang, Nong-Moon; Hyeon, Taeghwan
      Nature Materials (2004), 3 (12), 891-895CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      The development of nanocrystals has been intensively pursued, not only for their fundamental scientific interest, but also for many technol. applications. The synthesis of monodisperse nanocrystals (size variation <5%) is of key importance, because the properties of these nanocrystals depend strongly on their dimensions. For example, the color sharpness of semiconductor nanocrystal-based optical devices is strongly dependent on the uniformity of the nanocrystals, and monodisperse magnetic nanocrystals are crit. for the next-generation multiterabit magnetic storage media. For these monodisperse nanocrystals to be used, an economical mass prodn. method needs to be developed. Unfortunately, however, in most syntheses reported so far, only subgram quantities of monodisperse nanocrystals were produced. Uniform-sized nanocrystals of CdSe and Au have been produced using colloidal chem. synthetic procedures. In addn., monodisperse magnetic nanocrystals such as Fe, Co, γ-Fe2O3, and Fe3O4 have been synthesized by using various synthetic methods. Here, we report on the ultralarge-scale synthesis of monodisperse nanocrystals using inexpensive and nontoxic metal salts as reactants. We were able to synthesize as much as 40 g of monodisperse nanocrystals in a single reaction, without a size sorting process. Moreover, the particle size could be controlled simply by varying the exptl. conditions. The current synthetic procedure is very general and nanocrystals of many transition metal oxides were successfully synthesized using a very similar procedure.
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      Zheng, N.; Fan, J.; Stucky, G. D. One-Step One-Phase Synthesis of Monodisperse Noble-Metallic Nanoparticles and Their Colloidal Crystals. J. Am. Chem. Soc. 2006, 128, 6550– 6551,  DOI: 10.1021/ja0604717
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      One-Step One-Phase Synthesis of Monodisperse Noble-Metallic Nanoparticles and Their Colloidal Crystals
      Zheng, Nanfeng; Fan, Jie; Stucky, Galen D.
      Journal of the American Chemical Society (2006), 128 (20), 6550-6551CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A variety of metallic nanoparticles with a narrow size distribution have been synthesized in a facile one-phase method in which amine-borane complexes are applied as reducing agents. It is particularly striking that large colloidal crystals with sizes up to tens of micrometers can directly form from the reaction mixts. without any further treatment. By using the synthetic route described, large-scale syntheses of both mono- and alloyed metallic nanoparticles with a narrow size distribution can be easily achieved.
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      Goubet, N.; Portalès, H.; Yan, C.; Arfaoui, I.; Albouy, P.-A.; Mermet, A.; Pileni, M.-P. Simultaneous Growth of Gold Colloidal Crystals. J. Am. Chem. Soc. 2012, 134, 3714– 3719,  DOI: 10.1021/ja207941p
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      Simultaneous Growths of Gold Colloidal Crystals
      Goubet, Nicolas; Portales, Herve; Yan, Cong; Arfaoui, Imad; Albouy, Pierre-Antoine; Mermet, Alain; Pileni, Marie-Paule
      Journal of the American Chemical Society (2012), 134 (8), 3714-3719CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Natural systems give the route to design periodic arrangements with mesoscopic architecture using individual nanocrystals as building blocks forming colloidal crystals or supracrystals. The collective properties of such supracrystals are one of the main driving forces in materials research for the 21st century with potential applications in electronics or biomedical environments. Here the authors describe 2 simultaneous supracrystal growth processes from Au nanocrystal suspension, taking place in soln. and at the air-liq. interface. Also, the growth processes involve the crystallinity selection of nanocrystals and induce marked changes in the supracrystal mech. properties.
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      Crotti, G.; Schirato, A.; Proietti-Zaccaria, R.; Della Valle, G. On the Limits of Quasi-Static Theory in Plasmonic Nanostructures. J. Opt. 2022, 24, 015001,  DOI: 10.1088/2040-8986/ac3e00
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      On the limits of quasi-static theory in plasmonic nanostructures
      Crotti, Giulia; Schirato, Andrea; Zaccaria, Remo Proietti; Della Valle, Giuseppe
      Journal of Optics (Bristol, United Kingdom) (2022), 24 (1), 015001CODEN: JOOPCA; ISSN:2040-8978. (IOP Publishing Ltd.)
      The approximated anal. approach of quasi-static theory (QST) is widely used in modeling the optical response of plasmonic nanoparticles. It is well known that its accuracy is remarkable provided that the particle is much smaller than the wavelength of the interacting radiation and that the field induced inside the structure is approx. uniform. Here, we investigate the limits of QST range of validity for gold nanostructures freestanding in air. First, we compare QST predictions of scattering spectra of nanospheres and cylindrical nanowires of various sizes with the exact results provided by Mie scattering theory. We observe a non-monotonic behavior of the error of QST as a function of the characteristic length of the nanostructures, revealing a non-trivial scaling of its accuracy with the scatterer size. Second, we study nanowires with elliptical section upon different excitation conditions by performing finite element numerical anal. Comparing simulation results with QST ests. of the extinction cross-section, we find that QST accuracy is strongly dependent on the excitation conditions, yielding good results even if the field is highly inhomogeneous inside the structure.
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      Sun, C.-K.; Vallée, F.; Acioli, L. H.; Ippen, E. P.; Fujimoto, J. G. Femtosecond-Tunable Measurement of Electron Thermalization in Gold. Phys. Rev. B 1994, 50, 15337,  DOI: 10.1103/PhysRevB.50.15337
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      Femtosecond-tunable measurement of electron thermalization in gold
      Sun, C.-K.; Vallee, F.; Acioli, L. H.; Ippen, E. P.; Fujimoto, J. G.
      Physical Review B: Condensed Matter (1994), 50 (20), 15337-48CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)
      Femtosecond electron thermalization in metals was investigated using transient thermomodulation transmissivity and reflectivity. Studies were performed using a tunable multiple-wavelength femtosecond pump-probe technique in optically thin gold films in the low perturbation limit. An IR pump beam is used to heat the electron distribution and changes in electron temp. are measured with a visible probe beam at the d band to Fermi-surface transition. We show that the subpicosecond optical response of gold is dominated by delayed thermalization of the electron gas. This effect is particularly important far off the spectral peak of the reflectivity or transmissivity changes, permitting a direct and sensitive access to the internal thermalization of the electron gas. Using a simple rate-equation model, line-shape anal. of the transient reflectivity and transmissivity indicates a thermalization time of the order of 500 fs. At energies close to the Fermi surface, longer thermalization times ∼1-2 ps are obsd. These results are in agreement with a more sophisticated model based on calcns. of the electron-thermalization dynamics by numerical solns. of the Boltzmann equation. This model quant. describes the measured transient optical response during the full thermalization time of electron gas, of the order of 1.5 ps, and gives new insight into electron thermalization in metals.
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    53. 53
      Zavelani-Rossi, M.; Polli, D.; Kochtcheev, S.; Baudrion, A.-L.; Béal, J.; Kumar, V.; Molotokaite, E.; Marangoni, M.; Longhi, S.; Cerullo, G.; Adam, P. M.; Della Valle, G. Transient Optical Response of a Single Gold Nanoantenna: the Role of Plasmon Detuning. ACS Photon 2015, 2, 521– 529,  DOI: 10.1021/ph5004175
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      Gaspari, R.; Della Valle, G.; Ghosh, S.; Kriegel, I.; Scotognella, F.; Cavalli, A.; Manna, L. Quasi-Static Resonances in the Visible Spectrum for all-Dielectric Intermediate Band Semiconductor Nanocrystals. Nano Lett. 2017, 17, 7691– 7695,  DOI: 10.1021/acs.nanolett.7b03787
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      Quasi-Static Resonances in the Visible Spectrum from All-Dielectric Intermediate Band Semiconductor Nanocrystals
      Gaspari, Roberto; Della Valle, Giuseppe; Ghosh, Sandeep; Kriegel, Ilka; Scotognella, Francesco; Cavalli, Andrea; Manna, Liberato
      Nano Letters (2017), 17 (12), 7691-7695CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      Intermediate band (IB) semiconductor nanocrystals (NCs) as a class of all-dielec. nanomaterials providing quasi-static optical resonances are presented. IB NCs can display a neg. permittivity in a broad range of visible wavelengths, enabling a metal-like optical response despite the absence of free carriers in the NC ground state. Using a combination of spectroscopy measurements and ab initio calcns., the authors hereby provide a theor. model for both the linear and nonlinear optical properties of chalcopyrite CuFeS2 NCs, as a case study of IB semiconductor nanomaterials. The results rationalize the high performance of IB nanomaterials as photothermal agents and suggest the use of IB semiconductors as alternatives to noble metals for technologies based on plasmonic materials.
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      Brown, A. M.; Sundararaman, R.; Narang, P.; Schwartzberg, A. D.; Goddard, W. A., III; Atwater, H. A. Experimentally and Ab Initio Ultrafast Carriers Dynamics in Plasmonic Nanoparticles. Phys. Rev. Lett. 2017, 118, 087401,  DOI: 10.1103/PhysRevLett.118.087401
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      Experimental and ab initio ultrafast carrier dynamics in plasmonic nanoparticles
      Brown, Ana M.; Sundararaman, Ravishankar; Narang, Prineha; Schwartzberg, Adam M.; Goddard, William A., III; Atwater, Harry A.
      Physical Review Letters (2017), 118 (8), 087401/1-087401/6CODEN: PRLTAO; ISSN:1079-7114. (American Physical Society)
      Ultrafast pump-probe measurements of plasmonic nanostructures probe the nonequil. behavior of excited carriers, which involves several competing effects obscured in typical empirical analyses. Here we present pump-probe measurements of plasmonic nanoparticles along with a complete theor. description based on first-principles calcns. of carrier dynamics and optical response, free of any fitting parameters. We account for detailed electronic-structure effects in the d. of states, excited carrier distributions, electron-phonon coupling, and dielec. functions that allow us to avoid effective electron temp. approxns. Using this calcn. method, we obtain excellent quant. agreement with spectral and temporal features in transient-absorption measurements. In both our expts. and calcns., we identify the two major contributions of the initial response with distinct signatures: short-lived highly nonthermal excited carriers and longer-lived thermalizing carriers.
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      Wang, X.; Guillet, Y.; Selvakannan, P. R.; Remita, H.; Palpant, B. Broadband Spectral Signature of the Ultrafast Transient Optical Response of Gold Nanorods. J. Phys. Chem. C 2015, 119, 7416– 7427,  DOI: 10.1021/acs.jpcc.5b00131
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      Broadband Spectral Signature of the Ultrafast Transient Optical Response of Gold Nanorods
      Wang, Xiaoli; Guillet, Yannick; Selvakannan, Periasamy R.; Remita, Hynd; Palpant, Bruno
      Journal of Physical Chemistry C (2015), 119 (13), 7416-7427CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      The ultrafast transient optical response of gold nanorods presents a complex spectral signature that is very sensitive to the nanoparticle aspect ratio. This stems from the different electronic contributions to the photoinduced dynamics of the metal dielec. function, which modify the transverse and longitudinal localized plasmon modes. Here, we analyze the phys. origins of the ultrafast optical response of ensembles of nanorods over the whole visible range. Using broadband time-resolved spectroscopy, we det. within the first picoseconds after pump excitation the transient response of colloidal solns. contg. gold nanorods with different mean aspect ratios. Supported by model calcn., it is shown that the contribution of interband electron transitions dominates at ultrashort times, even for photon energies far below their threshold. At longer times, a slower intraband transition component linked with the nanoparticle heating appears. We then describe how the ensemble effect modifies the global spectral profile. The initial athermal regime for the conduction electron gas is demonstrated to affect the first instants of the dynamics. Finally, the influence of the shape distribution is exptl. evidenced and analyzed through a double selection process.
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      Della Valle, G.; Conforti, M.; Longhi, S.; Cerullo, G.; Brida, D. Real-Time Optical Mapping of the Dynamics of Nonthermal Electrons in Thin Gold Films. Phys. Rev. B 2012, 86, 155139,  DOI: 10.1103/PhysRevB.86.155139
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      Real-time optical mapping of the dynamics of nonthermal electrons in thin gold films
      Della Valle, G.; Conforti, M.; Longhi, S.; Cerullo, G.; Brida, D.
      Physical Review B: Condensed Matter and Materials Physics (2012), 86 (15), 155139/1-155139/6CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)
      We investigate the nonlinear optical response of thin gold films with an unprecedented combination of high temporal resoln. (∼15 fs) and broad spectral coverage. We quant. model the data without free parameters using an extended version of the two-temp. model. Our combined exptl. and theor. approach allows tracking the evolution from a purely nonthermal electron distribution towards a fully thermalized one. These results pose the basis for better understanding of light-matter interaction in metals on the ultrafast time scale.
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    58. 58
      Dobryden, I.; Yang, Z.; Claesson, P. M.; Pileni, M.-P. Water Dispersive Suprastructures: an Organizational Impact on Nanomechanical Properties. Adv. Mater. Interfaces 2021, 8, 2001687,  DOI: 10.1002/admi.202001687
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      There is no corresponding record for this reference.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.2c00364.

    • Notes S1: Reduced 2D geometry to model plasmonic nanoegg; S2: Model of the nanoegg optical response; S3: Dynamical model of nanoegg photoexcitation; S4: Model of the nanoegg thermal response; S5: Organic matrix temperature relaxation (PDF)


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