Silica Nanoparticle/Fluorescent Dye Assembly Capable of Ultrasensitively Detecting Airborne Triacetone Triperoxide: Proof-of-Concept Detection of Improvised Explosive Devices in the WorkroomClick to copy article linkArticle link copied!
- Andrea Revilla-CuestaAndrea Revilla-CuestaDepartment of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by Andrea Revilla-Cuesta
- Irene Abajo-CuadradoIrene Abajo-CuadradoDepartment of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by Irene Abajo-Cuadrado
- María MedranoMaría MedranoDepartment of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by María Medrano
- Mateo M. SalgadoMateo M. SalgadoDepartment of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by Mateo M. Salgado
- Manuel AvellaManuel AvellaElectron Microscopy Lab, IMDEA Materials Institute, Eric Kandel, 2, Tecnogetafe, 28906 Getafe, Madrid, SpainMore by Manuel Avella
- María Teresa RodríguezMaría Teresa RodríguezDepartment of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by María Teresa Rodríguez
- José García-CalvoJosé García-CalvoDepartment of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by José García-Calvo
- Tomás Torroba*Tomás Torroba*Email: [email protected]Department of Chemistry, Faculty of Science, University of Burgos, 09001 Burgos, SpainMore by Tomás Torroba
Abstract
We describe the proof of concept of a portable testing setup for the detection of triacetone triperoxide (TATP), a common component in improvised explosive devices. The system allows for field testing and generation of real-time results to test for TATP vapor traces in air by simply using circulation of the air samples through the sensing mechanism under the air conditioning system of an ordinary room. In this way, the controlled trapping of the analyte in the chemical sensor gives reliable results at extremely low concentrations of TATP in air under real-life conditions, suitable for daily use in luggage storage for airlines or a locker room for a major sporting event. The reported fluorescent methodology is very sensitive and selective, allowing for the trapping of triacetone triperoxide in the chemical sensor to give reliable results at very low concentrations in air under ambient conditions, by comparing the fluorescence of the material before and after exposition to TATP traces in air.
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License Summary*
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License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
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Introduction
Results and Discussion
Preparation of Materials
Figure 1
Figure 1. (a) Structure of chemical probes used for the study. (b) Model of the chemical probe AR82s on silica. (c, e) Structural and (d) elemental TEM images of the AR82s@SiO2 nanoparticles. (f) Elemental composition of the AR82s@SiO2 nanoparticles and high-resolution TEM images.
Titration under Increasing Concentration of TATP Using a Recirculation System for TATP Vapors
Figure 2
Figure 2. (a) Microfluidic device dimensions: Eppendorf: outer top diameter: 11 mm, inner top diameter: 9 mm, outer bottom diameter: 5 mm, inner bottom diameter: 3 mm, volume: 1.5 mL, height (with lid): 40 mm, height (without lid): 38 mm; tubing: outer diameter: 3 mm, inner diameter: 1.5 mm, length (flow tube): 25 mm, length (return tube:): 35 mm. (b) The actual aspect of the system; reproduced from ref (48) with permission from the Chinese Chemical Society (CCS), Institute of Chemistry of Chinese Academy of Sciences (IC), and the Royal Society of Chemistry. (c) Fluorescence changes with TATP gas. (d) Titration curves of AR82s@SiO2 and TATP vapor. (e) Fluorescent profile at 535 nm and (f) calibration for the limit of detection of AR82s@SiO2 nanoparticles under increasing concentrations of TATP vapor. λexc = 370 nm, λem = 535 nm.
Validation in Real-Life Scenarios
Figure 3
Figure 3. (a) Distribution of TATP sample (yellow arrow) and sensor samples (red arrows) in the room. (b) Close view of the arrangement of the TATP sample (yellow arrow) in front of the airflow outlet and the sensing material samples (red arrows). (c) Histogram plotting the differences in intensity emission in all cases before and after exposure to TATP vapors as a function of distance from the TATP source and temperature of the room, normalized to the top and reference signals. (d) A sample of sensing material showing the modified nanoparticles.
Figure 4
Figure 4. Summary of experiments 7–12. (a) Arrangement of the TATP in front of the airflow outlet. (b) Distribution of sensing nanoparticles in the room. (c) 3D representation of the variation of the normalized emission intensity as a function of the distance to the TATP source. (d) Assembly of the nanoparticles for measurements. (e) Details of one sample of AR82@SiO2.
Figure 5
Figure 5. Average and standard deviation of normalized emission variation as a function of the distance to the TATP source.
Mobile Phone Application
Figure 6
Figure 6. (a) View of the room for the experiment, (b) the TATP sample and the sensing material at different distances from the TATP, (c) picture of the sensing material placed at 25 cm from the TATP source, under a UV lamp, before (up) and after (down) being exposed to TATP, (d) picture (down) captured by the mobile phone app, and (e) the app assigned a positive value after comparing the RGB values in the selected point with the customized database.
Experimental Methods
Figure 7
Figure 7. (a) Titration curves, TATP titration. (b) Fluorescence profile at 500 nm, TATP titration. (c) Calibration plot for the limit of detection of 2.5 μM GC2 solutions in DCM under increasing concentrations of TATP. (d) Image of solutions before and after TATP titration. (e) Titration curves, m-CPBA titration. (f) Fluorescence profile at 500 nm, m-CPBA titration. (g) Calibration plot for the limit of detection. (h) Fluorescence profile at the corresponding working curves of the ratiometric probe in the presence of m-CPBA.
1H NMR Titration of AR82s with TATP in the Presence of Amberlite
Figure 8
Figure 8. 1H NMR (CDCl3, 500 MHz) titration of AR82s with increasing amounts of TATP in the presence of amberlite, 3 mg of AR82s in 0.5 mL of CDCl3, and TATP amounts: (1) 0 μg, (2) 5 μg, (3) 10 μg, (4) 15 μg, (5) 20 μg, (6) 30 μg, (7) 40 μg, (8) 60 μg, (9) 90 μg, (10) 150 μg, (11) 300 μg, (12) 500 μg, (13) 800 μg, (14) 1400 μg, (15) 3200 μg, (16) 6800 μg, (17) 10 400 μg, (18) 15 800 μg as total added TATP after each addition, (a) 2.8–4.0 ppm region, (b) 7.5–8.7 ppm region.
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c05931.
Complete characterization for all compounds, additional experimental details, materials, and methods (PDF)
Fluorometer measurements with nanoparticles in a fixed position (MP4)
Fluorometer measurements with nanoparticles in a fixed position (MP4)
Photographs of experimental setup (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
This research was funded by the NATO Science for Peace and Security Programme (Grant SPS G5536) and the Ministerio de Ciencia e Innovación (Grants PID2019-111215RB-I00 and PDC2022-133955-I00). A.R.-C. thanks Secretaría General de Universidades for a FPU18/03225 Grant. The authors thank J. Rafael Santana-Tejada, from Movilmatica (www.movilmatica.com) for technical assistance with the preparation of the app.
TATP | triacetone triperoxide |
IED | improvised explosive devices |
TNT | trinitrotoluene |
HMTD | hexamethylene triperoxide diamine |
AIE | aggregation-induced emission |
PDMS | poly(dimethylsiloxane) |
GC2@SiO2 | C2-supported silica nanoparticles |
TEM | transmission electron microscopy |
LOD | limit of detection |
MCH | methylcyclohexane |
m-CPBA | meta-chloroperbenzoic acid |
TNB | trinitrobenzene |
IR | infrared |
NMR | nuclear magnetic resonance |
HRMS | high-resolution mass spectrometry |
MALDI | matrix-assisted laser desorption/ionization |
ESI | electrospray ionization |
UV–Vis | ultraviolet–visible |
FL | fluorescence |
Ø | quantum yield |
τ | lifetime |
References
This article references 68 other publications.
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- 9Forbes, T. P.; Krauss, S. T.; Gillen, G. Trace Detection and Chemical Analysis of Homemade Fuel-Oxidizer Mixture Explosives: Emerging Challenges and Perspectives. TrAC, Trends Anal. Chem. 2020, 131, 116023 DOI: 10.1016/j.trac.2020.116023Google Scholar9Trace detection and chemical analysis of homemade fuel-oxidizer mixture explosives: Emerging challenges and perspectivesForbes, Thomas P.; Krauss, Shannon T.; Gillen, GregTrAC, Trends in Analytical Chemistry (2020), 131 (), 116023CODEN: TTAEDJ; ISSN:0165-9936. (Elsevier B.V.)The chem. anal. of homemade explosives (HMEs) and improvised explosive devices (IEDs) remains challenging for fieldable anal. instrumentation and sensors. Complex explosive fuel-oxidizer mixts., black and smokeless powders, flash powders, and pyrotechnics often include an array of potential org. and inorg. components that present unique interference and matrix effect difficulties. The widely varying physicochem. properties of these components as well as external environmental interferents and background challenge many sampling and sensing modalities. This review provides perspective on these emerging challenges, critically discusses developments in sampling, sensors, and instrumentation, and showcases advancements for the trace detection of inorg.-based explosives.
- 10Liu, R.; Li, Z.; Huang, Z.; Li, K.; Lv, Y. Biosensors for Explosives: State of Art and Future Trends. TrAC, Trends Anal. Chem. 2019, 118, 123– 137, DOI: 10.1016/j.trac.2019.05.034Google Scholar10Biosensors for explosives: State of art and future trendsLiu, Rui; Li, Ziyan; Huang, Zili; Li, Kun; Lv, YiTrAC, Trends in Analytical Chemistry (2019), 118 (), 123-137CODEN: TTAEDJ; ISSN:0165-9936. (Elsevier B.V.)A review. Explosives sensing is currently one of the most pressing and significant concerns in homeland security, antiterrorism, and environmental protection. Biosensors can often provide an outstanding specificity and sensitivity for explosives, utilizing biol. or bio-mimic recognition components such as antibodies, aptamers, and molecularly imprinted polymers. Despite intriguing properties and fast development, the biosensors-based explosive detection has not been reviewed in the past decade. Herein, the focus of this review is towards advances of biosensors of explosive, emphasizing quant. biosensors in the past ten years, with the readers being referred to earlier or other technique related reviews. The basics of explosives, the qual. biosensing (based on animals, electronic noses, and genetically engineered microorganisms), the quant. biosensing (based on antibody, peptide aptamer, and molecularly imprinted polymers), and future perspectives are discussed in detail.
- 11Apak, R.; Çekiç, S. D.; Uzer, A.; Çapanoglu, E.; Çelik, S. E.; Bener, M.; Can, Z.; Durmazel, S. Colorimetric Sensors and Nanoprobes for Characterizing Antioxidant and Energetic Substances. Anal. Methods 2020, 12, 5266– 5321, DOI: 10.1039/D0AY01521KGoogle Scholar11Colorimetric sensors and nanoprobes for characterizing antioxidant and energetic substancesApak, Resat; Cekic, Sema Demirci; Uzer, Aysem; Capanoglu, Esra; Celik, Saliha Esin; Bener, Mustafa; Can, Ziya; Durmazel, SelenAnalytical Methods (2020), 12 (44), 5266-5321CODEN: AMNEGX; ISSN:1759-9679. (Royal Society of Chemistry)A review. The development of anal. techniques for antioxidant compds. is important, because antioxidants that can inactivate reactive species and radicals are health-beneficial compds., also used in the preservation of food and protection of almost every kind of org. substance from oxidn. Energetic substances include explosives, pyrotechnics, propellants and fuels, and their detn. at bulk/trace levels is important for the safety and well-being of modern societies exposed to various security threats. Most of the time, in field/on site detection of these important analytes necessitates the use of colorimetric sensors and probes enabling naked-eye detection, or low-cost and easy-to-use fluorometric sensors. The use of nanosensors brings important advantages to this field of anal. chem. due to their various physico-chem. advantages of increased surface area, surface plasmon resonance absorption of noble metal nanoparticles, and superior enzyme-mimic catalytic properties. Thus, this crit. review focuses on the design strategies for colorimetric sensors and nanoprobes in characterizing antioxidant and energetic substances. In this regard, the main themes and properties in optical sensor design are defined and classified. Nanomaterial-based optical sensors/probes are discussed with respect to their mechanisms of operation, namely formation and growth of noble metal nanoparticles, their aggregation and disaggregation, displacement of active constituents by complexation or electrostatic interaction, misc. mechanisms, and the choice of metallic oxide nanoparticles taking part in such formulations.
- 12Ostrinskaya, A.; Kunz, R. R.; Clark, M.; Kingsborough, R. P.; Ong, T.-H.; Deneault, S. Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow-Injection Analysis Tandem Mass Spectrometry. J. Forensic Sci. 2019, 64, 223– 230, DOI: 10.1111/1556-4029.13827Google Scholar12Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow-Injection Analysis Tandem Mass SpectrometryOstrinskaya, Alla; Kunz, Roderick R.; Clark, Michelle; Kingsborough, Richard P.; Ong, Ta-Hsuan; Deneault, SandraJournal of Forensic Sciences (2019), 64 (1), 223-230CODEN: JFSCAS; ISSN:0022-1198. (John Wiley & Sons, Inc.)A review. A flow-injection anal. tandem mass spectrometry (FIA MSMS) method was developed for rapid quant. anal. of 10 different inorg. and org. explosives. Performance is optimized by tailoring the ionization method (APCI/ESI), de-clustering potentials, and collision energies for each specific analyte. In doing so, a single instrument can be used to detect urea nitrate, potassium chlorate, 2,4,6-trinitrotoluene, 2,4,6-trinitrophenylmethylnitramine, triacetone triperoxide, hexamethylene triperoxide diamine, pentaerythritol tetranitrate, 1,3,5-trinitroperhydro-1,3,5-triazine, nitroglycerin, and octohy-dro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with sensitivities all in the picogram per mL range. In conclusion, FIA APCI/ESI MSMS is a fast (<1 min/sample), sensitive (∼pg/mL LOQ), and precise (intraday RSD < 10%) method for trace explosive detection that can play an important role in criminal and attributional forensics, counterterrorism, and environmental protection areas, and has the potential to augment or replace several of the existing explosive detection methods.
- 13Glackin, J. M. E.; Gillanders, R. N.; Eriksson, F.; Fjällgren, M.; Engblom, J.; Mohammed, S.; Samuel, I. D. W.; Turnbull, G. A. Explosives Detection by Swabbing for Improvised Explosive Devices. Analyst 2020, 145, 7956– 7963, DOI: 10.1039/D0AN01312AGoogle Scholar13Explosives detection by swabbing for improvised explosive devicesGlackin, James M. E.; Gillanders, Ross N.; Eriksson, Frans; Fjallgren, Marcus; Engblom, Joachim; Mohammed, Salam; Samuel, Ifor D. W.; Turnbull, Graham A.Analyst (Cambridge, United Kingdom) (2020), 145 (24), 7956-7963CODEN: ANALAO; ISSN:0003-2654. (Royal Society of Chemistry)Swabs taken from the surface of a suspicious object are a std. method of identifying a concealed explosive device in security-conscious locations like airports. In this paper a sensitive method is demonstrated to collect and detect trace explosive residues from improvised explosive devices using swabs and an optical sensor element. Swabs coated with a com. fluoropolymer are used to collect material and are subsequently heated to thermally desorb the explosives, causing the quenching of light emission from a thin film luminescent sensor. The sorption and desorption characteristics are reported of swabs loaded with 2,4-DNT tested with Super Yellow fluorescent sensors in a lab. setting, with detection that is up to three orders of magnitude more sensitive than std. colorimetric tests. The method was then applied in field tests with raw military-grade explosives TNT, PETN, and RDX, on various objects contg. the explosives, and post-blast craters. It is shown for the first time results using org. semiconductors to detect sub-milligram amts. of explosive sorbed onto a substrate from real explosives in the field, giving a promising new approach for IED detection.
- 14Ong, T.-H.; Mendum, T.; Geurtsen, G.; Kelley, J.; Ostrinskaya, A.; Kunz, R. Use of Mass Spectrometric Vapor Analysis to Improve Canine Explosive Detection Efficiency. Anal. Chem. 2017, 89, 6482– 6490, DOI: 10.1021/acs.analchem.7b00451Google Scholar14Use of Mass Spectrometric Vapor Analysis To Improve Canine Explosive Detection EfficiencyOng, Ta-Hsuan; Mendum, Ted; Geurtsen, Geoff; Kelley, Jude; Ostrinskaya, Alla; Kunz, RoderickAnalytical Chemistry (Washington, DC, United States) (2017), 89 (12), 6482-6490CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Canines remain the gold std. for explosives detection in many situations, and there is an ongoing desire for them to perform at the highest level. This goal requires canine training to be approached similarly to scientific sensor design. Developing a canine training regimen is made challenging by a lack of understanding of the canine's odor environment, which is dynamic and typically contains multiple odorants. Existing methodol. assumes that the handler's intention is an adequate surrogate for actual knowledge of the odors cuing the canine, but canines are easily exposed to unintentional explosive odors through training material cross-contamination. A sensitive, real-time (∼1 s) vapor anal. mass spectrometer was developed to provide tools, techniques, and knowledge to better understand, train, and utilize canines. The instrument has a detection library of nine explosives and explosive-related materials consisting of 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), pentaerythritol tetranitrate (PETN), triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), and cyclohexanone, with detection limits in the parts-per-trillion to parts-per-quadrillion range by vol. The instrument can illustrate aspects of vapor plume dynamics, such as detecting plume filaments at a distance. The instrument was deployed to support canine training in the field, detecting cross-contamination among training materials, and developing an evaluation method based on the odor environment. Support for training material prodn. and handling was provided by studying the dynamic headspace of a nonexplosive HMTD training aid that is in development. These results supported existing canine training and identified certain areas that may be improved.
- 15Li, Z.; Askim, J. R.; Suslick, K. S. The Optoelectronic Nose: Colorimetric and Fluorometric Sensor Arrays. Chem. Rev. 2019, 119, 231– 292, DOI: 10.1021/acs.chemrev.8b00226Google Scholar15The Optoelectronic Nose: Colorimetric and Fluorometric Sensor ArraysLi, Zheng; Askim, Jon R.; Suslick, Kenneth S.Chemical Reviews (Washington, DC, United States) (2019), 119 (1), 231-292CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. A comprehensive review on the development and state of the art of colorimetric and fluorometric sensor arrays is presented. Chem. sensing aims to detect subtle changes in the chem. environment by transforming relevant chem. or phys. properties of mol. or ionic species (i.e., analytes) into an anal. useful output. Optical arrays based on chemoresponsive colorants (dyes and nanoporous pigments) probe the chem. reactivity of analytes, rather than their phys. properties (e.g., mass). The chem. specificity of the olfactory system does not come from specific receptors for specific analytes (e.g., the traditional lock-and-key model of substrate-enzyme interactions), but rather olfaction makes use of pattern recognition of the combined response of several hundred olfactory receptors. In a similar fashion, arrays of chemoresponsive colorants provide high-dimensional data from the color or fluorescence changes of the dyes in these arrays as they are exposed to analytes. This provides chem. sensing with high sensitivity (often down to ppb levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixts. over a wide range of analyte types, in both the gas and liq. phases. Design of both sensor arrays and instrumentation for their anal. are discussed. In addn., the various chemometric and statistical analyses of high-dimensional data (including hierarchical cluster anal. (HCA), principal component anal. (PCA), linear discriminant anal. (LDA), support vector machines (SVMs), and artificial neural networks (ANNs)) are presented and critiqued in ref. to their use in chem. sensing. A variety of applications are also discussed, including personal dosimetry of toxic industrial chem., detection of explosives or accelerants, quality control of foods and beverages, biosensing intracellularly, identification of bacteria and fungi, and detection of cancer and disease biomarkers.
- 16Li, Z.; Suslick, K. S. The Optoelectronic Nose. Acc. Chem. Res. 2021, 54, 950– 960, DOI: 10.1021/acs.accounts.0c00671Google Scholar16The Optoelectronic NoseLi, Zheng; Suslick, Kenneth S.Accounts of Chemical Research (2021), 54 (4), 950-960CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Conspectus: How does one tell the difference between one mol. or mixt. of mols. from another. Chem. sensing seeks to probe phys. or chem. properties of mol. or ionic species (i.e., analytes) and transform that information into a useful and distinguishable output. The olfactory system of animals is the prototype of chem. sensing. Even for human beings (who are generally more visual than olfactory creatures), the sense of smell is one of our most basic capabilities, and we can discriminate among many thousands, and possibly even billions, of different odors. The chem. specificity of the olfactory system does not come from specific receptors for specific analytes (i.e., the traditional lock-and-key model of enzyme-substrate interactions), but rather olfaction uses pattern recognition of the combined responses of several hundred olfactory receptors. In analogy to olfaction, colorimetric sensor arrays provide high dimensional data from the color changes of chem. responsive colorants as they are exposed to analytes. These colorants include pH responsive dyes, Lewis acid/base indicators, redox dyes, vapochromics, and surface-modified silver nanoparticles. The color difference maps so created provide chem. sensing with high sensitivity (often down to ppb levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixts. over a wide range of analyte types, both in the gas and liq. phases. Such colorimetric arrays probe a wide range of the chem. reactivity of analytes, rather than the limited dimensionality of phys. properties (e.g., mass) or physisorption (e.g., traditional electronic noses). Our sensor arrays are disposable and simple to produce by either inkjet or robotic dip-pen printing onto the surface of porous polymer membranes or even paper. Design of both sensor arrays and optical readers for their anal. has advanced to a fully self-contained pocket-sized instrument, the optoelectronic nose. Quant. anal. requires appropriate chemometric methods for pattern recognition of data with inherently high dimensionality, e.g., hierarchical cluster anal. and support vector machines. A wide range of applications for the colorimetric sensor arrays has been developed, including personal dosimetry of toxic industrial chems., detection of explosives or fire accelerants, monitoring pollutants for artwork and cultural heritage preservation, quality control of foods and beverages, rapid identification of bacteria and fungi, and detection of disease biomarkers in breath or urine. The development of portable, high-accuracy instrumentation using std. imaging devices with the capability of onboard, real-time anal. has had substantial progress and increasingly meets the expectations for real-world use.
- 17Härtel, M. A. C.; Klapötke, T. M.; Stiasny, B.; Stierstorfer, J. Gas-phase Concentration of Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP). Propellants Explos. Pyrotech. 2017, 42, 623– 634, DOI: 10.1002/prep.201700034Google ScholarThere is no corresponding record for this reference.
- 18Dubnikova, F.; Kosloff, R.; Almog, J.; Zeiri, Y.; Boese, R.; Itzhaky, H.; Alt, A.; Keinan, E. Decomposition of Triacetone Triperoxide Is an Entropic Explosion. J. Am. Chem. Soc. 2005, 127, 1146– 1159, DOI: 10.1021/ja0464903Google Scholar18Decomposition of Triacetone Triperoxide Is an Entropic ExplosionDubnikova, Faina; Kosloff, Ronnie; Almog, Joseph; Zeiri, Yehuda; Boese, Roland; Itzhaky, Harel; Alt, Aaron; Keinan, EhudJournal of the American Chemical Society (2005), 127 (4), 1146-1159CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Both X-ray crystallog. and electronic structure calcns. using the cc-pVDZ basis set at the DFT B3LYP level were employed to study the explosive properties of triacetone triperoxide (TATP) and diacetone diperoxide (DADP). The thermal decompn. pathway of TATP was investigated by a series of calcns. that identified transition states, intermediates, and the final products. Counterintuitively, these calcns. predict that the explosion of TATP is not a thermochem. highly favored event. It rather involves entropy burst, which is the result of formation of one ozone and three acetone mols. from every mol. of TATP in the solid state.
- 19Romero, D. C.; Calvo-Gredilla, P.; García-Calvo, J.; Diez-Varga, A.; Cuevas, J. V.; Revilla-Cuesta, A.; Busto, N.; Abajo, I.; Aullón, G.; Torroba, T. Self-Assembly Hydrosoluble Coronenes: A Rich Source of Supramolecular Turn-On Fluorogenic Sensing Materials in Aqueous Media. Org. Lett. 2021, 23, 8727– 8732, DOI: 10.1021/acs.orglett.1c03175Google Scholar19Self-Assembly Hydrosoluble Coronenes: A Rich Source of Supramolecular Turn-On Fluorogenic Sensing Materials in Aqueous MediaRomero, Daisy C.; Calvo-Gredilla, Patricia; Garcia-Calvo, Jose; Diez-Varga, Alberto; Cuevas, Jose Vicente; Revilla-Cuesta, Andrea; Busto, Natalia; Abajo, Irene; Aullon, Gabriel; Torroba, TomasOrganic Letters (2021), 23 (22), 8727-8732CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)Water-sol. coronenes, that form nanoparticles by self-assocn., work as new fluorescent materials by complexation with cucurbit[7]uril, as well as selective turn-on fluorogenic sensors for nitroarom. explosives with remarkable selectivity, by using only water as solvent.
- 20Wan, W.-M.; Tian, D.; Jing, Y.-N.; Zhang, X.-Y.; Wu, W.; Ren, H.; Bao, H.-L. NBN-Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives. Angew. Chem., Int. Ed. 2018, 57, 15510– 15516, DOI: 10.1002/anie.201809844Google Scholar20NBN-Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of ExplosivesWan, Wen-Ming; Tian, Di; Jing, Ya-Nan; Zhang, Xiao-Yun; Wu, Wei; Ren, Hao; Bao, Hong-LiAngewandte Chemie, International Edition (2018), 57 (47), 15510-15516CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A simple and efficient synthesis of NBN-doped conjugated polycyclic arom. hydrocarbons (such as diazaborinines) has been accomplished by a catalyst-free intermol. dehydration reaction at room temp. between boronic acid and diamine moieties with yields up to 99 %. Polycyclic arom. hydrocarbons with a six-membered NBN ring are a new class of aggregation-induced emissive luminogens. Extremely sensitive detection of ppb levels of TNT by Ph naphthodiazaborinine is straightforward. Visual detection of TNT is illustrated by fabrication of TNT test strips, which can detect as little as 100 ng of TNT powder. This simple and sensitive detection of TNT has potential applications in the area of public safety and security against terrorist activities.
- 21Kim, S.; Kim, H.; Qiao, T.; Cha, C.; Lee, S. K.; Lee, K.; Ro, H. J.; Kim, Y.; Lee, W.; Lee, H. Fluorescence Enhancement from Nitro-Compound-Sensitive Bacteria within Spherical Hydrogel Scaffolds. ACS Appl. Mater. Interfaces 2019, 11, 14354– 14361, DOI: 10.1021/acsami.9b02262Google Scholar21Fluorescence Enhancement from Nitro-Compound-Sensitive Bacteria within Spherical Hydrogel ScaffoldsKim, Soohyun; Kim, Hyunji; Qiao, Tian; Cha, Chaenyung; Lee, Sung Kuk; Lee, Kangseok; Ro, Hyun Ji; Kim, Youngkyun; Lee, Wonmok; Lee, HyunjungACS Applied Materials & Interfaces (2019), 11 (15), 14354-14361CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)For the safety of both prodn. and life, it is a very significant issue to detect explosive nitro-compds. in a remote way or over a long distance. Here, we report that nitro-compds. were detected by the bacterial sensor based on hydrogel micro-beads as a platform. A green fluorescent protein(GFP)-producing Escherichia coli which was genetically engineered in order to be sensitive to nitro-compds. was loaded within poly(2-hydroxyethyl methacrylate) (poly(HEMA)) based hydrogel beads, in which fluorescent signals from bacteria were concd. and strong enough to be easily detected. For efficient loading of neg. charged bacteria, a surface charge of poly(HEMA) based beads was controlled by copolymn. with 2-(methacryloyloxy) Et trimethylammonium chloride (MAETC) as a cationic monomer. With the addn. of MAETC, the cell affinity was nine times enhanced by an interaction between the pos. charged poly(HEMA-co-MAETC) beads and neg. charged bacteria. These increased cell affinity resulted in an enhancement of a sensing signal. After exposure to 2,4,6-trinitrotoluene (TNT), typical explosive nitro-compds., the fluorescence intensity of bacteria sensors using poly(HEMA-co MAETC) bead having 80 wt% of MAETC was five times increased compared to those based on poly(HEMA) beads. This amplification of the fluorescent signal enables easier detection of explosives efficiently by a remote detection, even over a long distance.
- 22Zhang, Z.; Chen, S.; Shi, R.; Ji, J.; Wang, D.; Jin, S.; Han, T.; Zhou, C.; Shu, Q. A Single Molecular Fluorescent Probe for Selective and Sensitive Detection of Nitroaromatic Explosives: A New Strategy for The Mask-Free Discrimination of TNT and TNP Within Same Sample. Talanta 2017, 166, 228– 233, DOI: 10.1016/j.talanta.2017.01.046Google Scholar22A single molecular fluorescent probe for selective and sensitive detection of nitroaromatic explosives: A new strategy for the mask-free discrimination of TNT and TNP within same sampleZhang, Zhe; Chen, Shusen; Shi, Rui; Ji, Jiawen; Wang, Dequan; Jin, Shaohua; Han, Tongyu; Zhou, Chenxiao; Shu, QinghaiTalanta (2017), 166 (), 228-233CODEN: TLNTA2; ISSN:0039-9140. (Elsevier B.V.)A simple naphthalene based fluorescent probe was first time reported as dual sensing of 2,4,6-trinitrotolune (TNT) and 2,4,6-trinitrophenol (TNP) by distinguishable changes in both soln. color change and fluorescence within same sample without any mask agent. Upon addn. of TNT and TNP, the strong emission quenching at 412 nm and a new emission band at 530 nm was obsd., resp. In addn., the sensing mechanism was evaluated by DFT calcns. by Gaussian 09 software.
- 23Tripathi, N.; Kumar, R.; Singh, P.; Kumar, S. Ratiometric Fluorescence “Turn On” Probe for Fast and Selective Detection of TNT in Solution, Solid and Vapour. Sens. Actuators, B 2017, 246, 1001– 1010, DOI: 10.1016/j.snb.2017.02.174Google Scholar23Ratiometric fluorescence "Turn On" probe for fast and selective detection of TNT in solution, solid and vapourTripathi, Neetu; Kumar, Rahul; Singh, Prabhpreet; Kumar, SubodhSensors and Actuators, B: Chemical (2017), 246 (), 1001-1010CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)A review. Fluorescent probe UREA-TP undergoes nearly 600% increase in emission intensity at 310 nm on addn. of 1 equiv of TNT, but the emission band centered at 440 nm remains unchanged. UREA-TP acts as a ratiometric fluorescence "turn-on" probe and can detect TNT between 10-9 to 10-5 M with limit of detection as low as 100 pM. Paper strips coated with UREA-TP on interaction with TNT become fluorescent purple under 365 nm light and can det. both qual. and quant. as low as 10μl soln. of 10-13 M TNT, which accounts for 2.27 × 10-16 g cm-2 TNT, significantly lower than the TNT concn. allowed in drinking water by EPA. The common nitroarom. derivs. 2,4-DNT, 2,6-DNT, picric acid and 2,4-DNP, the pain killers, food supplements and inorg. anions show insignificant interference in the detn. of TNT using UREA-TP. The aggregate size detn. using dynamic light scattering anal. and morphol. studies using TEM investigations reveals that UREA-TP in H2O-DMSO (98:2) remains in aggregate state with av. size of 200 nm, which undergo further aggregation to larger size aggregates with increasing amts. of TNT.
- 24Colizza, K.; Yevdokimov, A.; McLennan, L.; Smith, J. L.; Oxley, J. C. Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2018, 29, 675– 684, DOI: 10.1007/s13361-017-1879-5Google Scholar24Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass SpectrometryColizza, Kevin; Yevdokimov, Alexander; McLennan, Lindsay; Smith, James L.; Oxley, Jimmie C.Journal of the American Society for Mass Spectrometry (2018), 29 (4), 675-684CODEN: JAMSEF; ISSN:1044-0305. (Springer)The authors' efforts to lower the detection limits of hexamethylene triperoxide diamine (HMTD) have uncovered previously unreported gas-phase reactions of primary and secondary amines with one of the six methylene carbons. The reaction occurs primarily in the atm. pressure chem. ionization (APCI) source and is similar to the behavior of alcs. with HMTD [1]. However, unlike alcs., the amine reaction conserves the hydrogen peroxide on the intact product. Furthermore, with or without amines, HMTD is oxidized to tetramethylene diperoxide diamine dialdehyde (TMDDD) in a temp.-dependent fashion in the APCI source. Synthesized TMDDD forms very strong adducts (not products) to ammonium and amine ions in the electrospray ionization (ESI) source. Attempts to improve HMTD detection by generating TMDDD in the APCI source with post-column addn. of amines were not successful. Signal intensity of the solvent related HMTD product in methanol, [HMTD+MeOH2-H2O2]+ (m/z 207.0975), was understandably related to the amt. of methanol in the HMTD environment as it elutes into the source. With conditions optimized for this product, the detection of 100 pg on column was accomplished with a robust anal. of 300 pg (1.44 pmol) routinely performed on the Orbitrap mass spectrometers.
- 25Mäkinen, M.; Nousiainen, M.; Sillanpaa, M. Ion Spectrometric Detection Technologies for Ultra-Traces of Explosives: A Review. Mass Spectrom. Rev. 2011, 30, 940– 973, DOI: 10.1002/mas.20308Google Scholar25Ion spectrometric detection technologies for ultra-traces of explosives: a reviewMakinen Marko; Nousiainen Marjaana; Sillanpaa MikaMass spectrometry reviews (2011), 30 (5), 940-73 ISSN:.In recent years, explosive materials have been widely employed for various military applications and civilian conflicts; their use for hostile purposes has increased considerably. The detection of different kind of explosive agents has become crucially important for protection of human lives, infrastructures, and properties. Moreover, both the environmental aspects such as the risk of soil and water contamination and health risks related to the release of explosive particles need to be taken into account. For these reasons, there is a growing need to develop analyzing methods which are faster and more sensitive for detecting explosives. The detection techniques of the explosive materials should ideally serve fast real-time analysis in high accuracy and resolution from a minimal quantity of explosive without involving complicated sample preparation. The performance of the in-field analysis of extremely hazardous material has to be user-friendly and safe for operators. The two closely related ion spectrometric methods used in explosive analyses include mass spectrometry (MS) and ion mobility spectrometry (IMS). The four requirements-speed, selectivity, sensitivity, and sampling-are fulfilled with both of these methods.
- 26Jiang, D.; Peng, L.; Wen, M.; Zhou, Q.; Chen, C.; Wang, X.; Chen, W.; Li, H. Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex Matrices. Anal. Chem. 2016, 88, 4391– 4399, DOI: 10.1021/acs.analchem.5b04830Google Scholar26Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex MatricesJiang, Dandan; Peng, Liying; Wen, Meng; Zhou, Qinghua; Chen, Chuang; Wang, Xin; Chen, Wendong; Li, HaiyangAnalytical Chemistry (Washington, DC, United States) (2016), 88 (8), 4391-4399CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Peroxide explosives, such as triacetone triperoxide (TATP) and hexamethylene trioxide diamine (HMTD), were often used in the terrorist attacks due to their easy synthesis from readily starting materials. Therefore, an on-site detection method for TATP and HMTD is urgently needed. Herein, we developed a stand-alone dopant-assisted pos. photoionization ion mobility spectrometry (DAPP-IMS) coupled with time-resolved thermal desorption introduction for rapid and sensitive detection of TATP and HMTD in complex matrixes, such as white solids, soft drinks, and cosmetics. Acetone was chosen as the optimal dopant for better sepn. between reactant ion peaks and product ion peaks as well as higher sensitivity, and the limits of detection (LODs) of TATP and HMTD std. samples were 23.3 and 0.2 ng, resp. Explosives on the sampling swab were thermally desorbed and carried into the ionization region dynamically within 10 s, and the max. released concn. of TATP or HMTD could be time-resolved from the matrix interference owing to the different volatility. Furthermore, with the combination of the fast response thermal desorber (within 0.8 s) and the quick data acquisition software to DAPP-IMS, two-dimensional data related to drift time (TATP: 6.98 ms, K0 = 2.05 cm2 V-1 s-1; HMTD: 9.36 ms, K0 = 1.53 cm2 V-1 s-1) and desorption time was obtained for TATP and HMTD, which is beneficial for their identification in complex matrixes.
- 27Correa, D. N.; Melendez-Perez, J. J.; Zacca, J. J.; Borges, R.; Schmidt, E. M.; Eberlin, M. N.; Meurer, E. C. Direct Detection of Triacetone Triperoxide (TATP) in Real Banknotes from ATM Explosion by EASI-MS. Propellants Explos. Pyrotech. 2017, 42, 370– 375, DOI: 10.1002/prep.201600046Google ScholarThere is no corresponding record for this reference.
- 28Hagenhoff, S.; Franzke, J.; Hayen, H. Determination of Peroxide Explosive TATP and Related Compounds by Dielectric Barrier Discharge Ionization-Mass Spectrometry (DBDI-MS). Anal. Chem. 2017, 89, 4210– 4215, DOI: 10.1021/acs.analchem.7b00233Google Scholar28Determination of Peroxide Explosive TATP and Related Compounds by Dielectric Barrier Discharge Ionization-Mass Spectrometry (DBDI-MS)Hagenhoff, Sebastian; Franzke, Joachim; Hayen, HeikoAnalytical Chemistry (Washington, DC, United States) (2017), 89 (7), 4210-4215CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Dielec. barrier discharge ionization-mass spectrometry (DBDI-MS), which is based on the use of a low temp. helium plasma as ionization source, is used for the detn. of trace amts. of triacetone triperoxide (TATP) and its homolog diacetone diperoxide (DADP) from surfaces. TATP is obsd. as [M+NH4]+ adduct, whereas DADP is obsd. as [M+O+NH4]+. Measurement of DADP with varying deuteration degrees (DADP, DADP-d6, and DADP-d12) indicates that DADP undergoes oxidn. when ionized by DBDI. If acetonitrile is used as deposition solvent, TATP tends to show fragmentation and is not only detected as [M+NH4]+ but as [M-CH4+NH4]+ and [M-C2H4+NH4]+ as well. Quantification of TATP solns. from glass surfaces by DBDI-MS, using TATP-3,6,9-13C as internal std., was done and validated using an LC/APCI-MS method. Achievable limits of detection (LOD) for TATP are equiv. to the deposition of 15 ng TATP and are comparable with other ambient desorption/ionization mass spectrometric techniques like desorption electrospray ionization (DESI).
- 29Tang, S.; Vinerot, N.; Fisher, D.; Bulatov, V.; Yavetz-Chen, Y.; Schechter, I. Detection and Mapping of Trace Explosives on Surfaces Under Ambient Conditions Using Multiphoton Electron Extraction Spectroscopy (MEES). Talanta 2016, 155, 235– 244, DOI: 10.1016/j.talanta.2016.04.027Google Scholar29Detection and mapping of trace explosives on surfaces under ambient conditions using multiphoton electron extraction spectroscopy (MEES)Tang, Shisong; Vinerot, Nataly; Fisher, Danny; Bulatov, Valery; Yavetz-Chen, Yehuda; Schechter, IsraelTalanta (2016), 155 (), 235-244CODEN: TLNTA2; ISSN:0039-9140. (Elsevier B.V.)Multiphoton electron extn. spectroscopy (MEES) is an anal. method in which UV laser pulses are utilized for extg. electrons from solid surfaces in multiphoton processes under ambient conditions. Counting the emitted electrons as a function of laser wavelength results in detailed spectral features, which can be used for material identification. The method has been applied to detection of trace explosives on a variety of surfaces. Detection was possible on dusty swabs spiked with explosives and also in the std. dry-transfer contamination procedure. Plastic explosives could also be detected. The anal. limits of detection (LODs) are in the sub pmole range, which indicates that MEES is one of the most sensitive detection methods for solid surface under ambient conditions. Scanning the surface with the laser allows for its imaging, such that explosives (as well as other materials) can be located. The imaging mode is also useful in forensic applications, such as detection of explosives in human fingerprints.
- 30Lichtenstein, A.; Havivi, E.; Shacham, R.; Hahamy, E.; Leibovich, R.; Pevzner, A.; Krivitsky, V.; Davivi, G.; Presman, I.; Elnathan, R.; Engel, Y.; Flaxer, E.; Patolsky, F. Supersensitive Fingerprinting of Explosives by Chemically Modified Nanosensors Arrays. Nat. Commun. 2014, 5, 4195 DOI: 10.1038/ncomms5195Google Scholar30Supersensitive fingerprinting of explosives by chemically modified nanosensors arraysLichtenstein, Amir; Havivi, Ehud; Shacham, Ronen; Hahamy, Ehud; Leibovich, Ronit; Pevzner, Alexander; Krivitsky, Vadim; Davivi, Guy; Presman, Igor; Elnathan, Roey; Engel, Yoni; Flaxer, Eli; Patolsky, FernandoNature Communications (2014), 5 (), 4195CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)The capability to detect traces of explosives sensitively, selectively and rapidly could be of great benefit for applications relating to civilian national security and military needs. Here, we show that, when chem. modified in a multiplexed mode, nanoelec. devices arrays enable the supersensitive discriminative detection of explosive species. The fingerprinting of explosives is achieved by pattern recognizing the inherent kinetics, and thermodn., of interaction between the chem. modified nanosensors array and the mol. analytes under test. This platform allows for the rapid detection of explosives, from air collected samples, down to the parts-per-quadrillion concn. range, and represents the first nanotechnol.-inspired demonstration on the selective supersensitive detection of explosives, including the nitro- and peroxide-derivs., on a single electronic platform. Furthermore, the ultrahigh sensitivity displayed by our platform may allow the remote detection of various explosives, a task unachieved by existing detection technologies.
- 31Lin, H.; Suslick, K. S. A Colorimetric Sensor Array for Detection of Triacetone Triperoxide Vapor. J. Am. Chem. Soc. 2010, 132, 15519– 15521, DOI: 10.1021/ja107419tGoogle Scholar31A Colorimetric Sensor Array for Detection of Triacetone Triperoxide VaporLin, Hengwei; Suslick, Kenneth S.Journal of the American Chemical Society (2010), 132 (44), 15519-15521CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Triacetone triperoxide (TATP), one of the most dangerous primary explosives, has emerged as an explosive of choice for terrorists in recent years. Owing to the lack of UV absorbance, fluorescence, or facile ionization, TATP is extremely difficult to detect directly. Techniques that are able to detect generally require expensive instrumentation, need extensive sample prepn., or cannot detect TATP in the gas phase. Here we report a simple and highly sensitive colorimetric sensor for the detection of TATP vapor with semiquant. anal. from 50 ppb to 10 ppm. By using a solid acid catalyst to pretreat a gas stream, we have discovered that a colorimetric sensor array of redox sensitive dyes can detect even very low levels of TATP vapor from its acid decompn. products (e.g., H2O2) with limits of detection (LOD) below 2 ppb (i.e., <0.02% of its satn. vapor pressure). Common potential interferences (e.g., humidity, personal hygiene products, perfume, laundry supplies, volatile org. compds., etc.) do not generate an array response, and the array can also differentiate TATP from other chem. oxidants (e.g., hydrogen peroxide, bleach, tert-butylhydroperoxide, peracetic acid).
- 32Li, Z.; Bassett, W. P.; Askim, J. R.; Suslick, K. S. Differentiation Among Peroxide Explosives with an Optoelectronic Nose. Chem. Commun. 2015, 51, 15312– 15315, DOI: 10.1039/C5CC06221GGoogle Scholar32Differentiation among peroxide explosives with an optoelectronic noseLi, Zheng; Bassett, Will P.; Askim, Jon R.; Suslick, Kenneth S.Chemical Communications (Cambridge, United Kingdom) (2015), 51 (83), 15312-15315CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)Forensic identification of batches of homemade explosives (HME) poses a difficult anal. challenge. Differentiation among peroxide explosives is reported herein using a colorimetric sensor array and handheld scanner with a field-appropriate sampling protocol. Clear discrimination was demonstrated among twelve peroxide samples prepd. from different reagents, with a classification accuracy > 98%.
- 33Askim, J. R.; Li, Z.; LaGasse, M. K.; Rankin, J. M.; Suslick, K. S. An Optoelectronic Nose for Identification of Explosives. Chem. Sci. 2016, 7, 199– 206, DOI: 10.1039/C5SC02632FGoogle Scholar33An optoelectronic nose for identification of explosivesAskim, Jon R.; Li, Zheng; La Gasse, Maria K.; Rankin, Jaqueline M.; Suslick, Kenneth S.Chemical Science (2016), 7 (1), 199-206CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)Compact and portable methods for identification of explosives are increasingly needed for both civilian and military applications. A portable optoelectronic nose for the gas-phase identification of explosive materials is described that uses a highly cross-reactive colorimetric sensor array and a handheld scanner. The array probes a wide range of chem. reactivities using 40 chem. responsive colorimetric indicators, including pH sensors, metal-dye salts, redox-sensitive chromogenic compds., solvatochromic dyes, and other chromogenic indicators. Sixteen sep. analytes including common explosives, homemade explosives, and characteristic explosive components were differentiated into fourteen sep. classes with a classification error rate of <1%. Portable colorimetric array sensing could represent an important, complementary part of the toolbox used in practical applications of explosives detection and identification.
- 34Xu, M.; Han, J.-M.; Wang, C.; Yang, X.; Pei, J.; Zang, L. Fluorescence Ratiometric Sensor for Trace Vapor Detection of Hydrogen Peroxide. ACS Appl. Mater. Interfaces 2014, 6, 8708– 8714, DOI: 10.1021/am501502vGoogle Scholar34Fluorescence Ratiometric Sensor for Trace Vapor Detection of Hydrogen PeroxideXu, Miao; Han, Ji-Min; Wang, Chen; Yang, Xiaomei; Pei, Jian; Zang, LingACS Applied Materials & Interfaces (2014), 6 (11), 8708-8714CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Trace vapor detection of hydrogen peroxide (H2O2) represents a practical approach to nondestructive detection of peroxide-based explosives, including liq. mixts. of H2O2 and fuels and energetic peroxide derivs., such as triacetone triperoxide (TATP), diacetone diperoxide (DADP), and hexamethylene triperoxide diamine (HMTD). Development of a simple chem. sensor system that responds to H2O2 vapor with high reliability and sufficient sensitivity (reactivity) remains a challenge. We report a fluorescence ratiometric sensor mol., di-Et 2,5-bis((((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)carbonyl)amino)terephthalate (DAT-B), for H2O2 that can be fabricated into an expedient, reliable, and sensitive sensor system suitable for trace vapor detection of H2O2. DAT-B is fluorescent in the blue region, with an emission max. at 500 nm in the solid state. Upon reaction with H2O2, DAT-B is converted to an electronic "push-pull" structure, di-Et 2,5-diaminoterephthalate (DAT-N), which has an emission peak at a longer wavelength centered at 574 nm. Such H2O2-mediated oxidn. of aryl boronates can be accelerated through the addn. of an org. base such as tetrabutylammonium hydroxide (TBAH), resulting in a response time of less than 0.5 s under 1 ppm of H2O2 vapor. The strong overlap between the absorption band of DAT-N and the emission band of DAT-B enables efficient Forster resonance energy transfer (FRET), thus allowing further enhancement of the sensing efficiency of H2O2 vapor. The detection limit of a drop-cast DAT-B/TBAH film was projected to be 7.7 ppb. By combining high sensitivity and selectivity, the reported sensor system may find broad application in vapor detection of peroxide-based explosives and relevant chem. reagents through its fabrication into easy-to-use, cost-effective kits.
- 35Zhu, Q.-H.; Zhang, G.-H.; Yuan, W.-L.; Wang, S.-L.; He, L.; Yong, F.; Tao, G.-H. Handy Fluorescent Paper Device Based on a Curcumin Derivative for Ultrafast Detection of Peroxide-Based Explosives. Chem. Commun. 2019, 55, 13661– 13664, DOI: 10.1039/C9CC06737JGoogle Scholar35Handy fluorescent paper device based on a curcumin derivative for ultrafast detection of peroxide-based explosivesZhu, Qiu-Hong; Zhang, Guo-Hao; Yuan, Wen-Li; Wang, Shuang-Long; He, Ling; Yong, Fang; Tao, Guo-HongChemical Communications (Cambridge, United Kingdom) (2019), 55 (91), 13661-13664CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)A handy, simple and inexpensive paper device is reported for extremely sensitive detection of peroxide-based explosives. The sensing device fabricated using a curcumin deriv. was capable of ultrafast sensing of triacetone triperoxide. The detection time was < 5 s. Moreover, the sensor retained full function under storage at ambient temp. for at least 120 days.
- 36Yu, X.; Gong, Y.; Xiong, W.; Li, M.; Zhao, J.; Che, Y. Turn-on Fluorescent Detection of Hydrogen Peroxide and Triacetone Triperoxide via Enhancing Interfacial Interactions of a Blended System. Anal. Chem. 2019, 91, 6967– 6970, DOI: 10.1021/acs.analchem.9b01255Google Scholar36Turn-on Fluorescent Detection of Hydrogen Peroxide and Triacetone Triperoxide via Enhancing Interfacial Interactions of a Blended SystemYu, Xinting; Gong, Yanjun; Xiong, Wei; Li, Mei; Zhao, Jincai; Che, YankeAnalytical Chemistry (Washington, DC, United States) (2019), 91 (11), 6967-6970CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)In this work, we report the fabrication of a blend consisting of fluorescent 1 nanofibers and amberlyst-15 particles as a turn-on fluorescence sensor for trace TATP vapors. Fluorescence imaging and lifetime anal. reveal that the interface between 1 nanofibers and amberlyst-15 particles exhibits stronger photoluminescence than the unblended areas because of the formed strong hydrogen bonding between. Furthermore, the interfacial adhesion between 1 nanofibers and amberlyst-15 particles can be amplified by H2O2, which in turn gives rise to rapid and remarkable fluorescence enhancement. When exposed to TATP vapors, the amberlyst-15 component can rapidly decomp. TATP into H2O2 that gives sensitive fluorescence enhancement responses of the blend. On the basis of this detection mechanism, fluorescence detection of TATP with rapid response (ca. 5 s) and high sensitivity (ca. 0.1 ppm) is achieved. Here, the resulting blend combines the pretreatment of TATP and detection responses and thereby simplifies the sensor fabrication for the practical application.
- 37Qi, Y.; Xu, W.; Ding, N.; Chang, X.; Shang, C.; Peng, H.; Liu, T.; Fang, Y. A Film-Based Fluorescent Device for Vapor Phase Detection of Acetone and Related Peroxide Explosives. Mater. Chem. Front. 2019, 3, 1218– 1224, DOI: 10.1039/C9QM00095JGoogle Scholar37A film-based fluorescent device for vapor phase detection of acetone and related peroxide explosivesQi, Yanyu; Xu, Wenjun; Ding, Nannan; Chang, Xingmao; Shang, Congdi; Peng, Haonan; Liu, Taihong; Fang, YuMaterials Chemistry Frontiers (2019), 3 (6), 1218-1224CODEN: MCFAC5; ISSN:2052-1537. (Royal Society of Chemistry)On site, sensitive and selective detection of acetone vapor at room temp. is of great importance for health, and in particular for in air detection of triacetone triperoxide (TATP) and diacetone diperoxide (DADP), two improvised explosives commonly used by terrorists in suicide attacks. This paper reports a relevant high-performance film-based fluorescent device, where a newly synthesized perylene monoimide modified non-planar organoboron deriv. (PMI-BQ) was adopted as the sensing fluorophore. The performance of the device is excellent as evidenced by less than 2 s response time, no more than 10 s recovery time, nearly perfect reversibility, and lower than 50 ppm exptl. detection limit (DL) for acetone. In addn., the presence of potential interferences showed little effect upon the sensing. Notably, more than 30 days sensing tests showed no observable degrdn. in the performance of the film device. Further tests revealed that the film-based device can be further used for the detection of TATP and DADP. The exptl. DLs for the two explosives are lower than 30 and 50 μg, resp. The superior performance of the device was ascribed to the non-planar structure of the sensing fluorophore as it may produce micro-channels in the film. Meanwhile, solvation may also play a crucial role in the process. We believe our contribution not only realizes reversible fluorescence sensing of acetone vapor and the related explosives, but also demonstrates that the combination of solvent effect and non-planar structure could be an effective way to develop high performance fluorescent sensing films.
- 38An, Y.; Xu, X.; Liu, K.; An, X.; Shang, C.; Wang, G.; Liu, T.; Li, H.; Peng, H.; Fang, Y. Fast, Sensitive, Selective and Reversible Fluorescence Monitoring of TATP in a Vapor Phase. Chem. Commun. 2019, 55, 941– 944, DOI: 10.1039/C8CC08399AGoogle Scholar38Fast, sensitive, selective and reversible fluorescence monitoring of TATP in a vapor phaseAn, Yanqin; Xu, Xiaojie; Liu, Ke; An, Xuan; Shang, Congdi; Wang, Gang; Liu, Taihong; Li, Hong; Peng, Haonan; Fang, YuChemical Communications (Cambridge, United Kingdom) (2019), 55 (7), 941-944CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)The development of sensors for the detection of triacetone triperoxide (TATP) has attracted great attention. Here, we constructed a low-cost, portable, reusable, visible paper-based fluorescent sensor for the sensitive detection of TATP via vapor sampling. Under optimized conditions, the fluorescent film showed a high sensitivity to TATP with a detection limit of lower than 0.5μg mL-1 in air. The linear range of the response is from 0.5 to 8.0μg mL-1. In addn., the paper-based sensor exhibited high selectivity to TATP. The presence of potential interferents showed little effect on sensing. Moreover, sensing is fully reversible. Fortunately, the test can also be conducted in a visualized way.
- 39Rao, M. R.; Fang, Y.; De Feyter, S.; Perepichka, D. F. Conjugated Covalent Organic Frameworks via Michael Addition–Elimination. J. Am. Chem. Soc. 2017, 139, 2421– 2427, DOI: 10.1021/jacs.6b12005Google Scholar39Conjugated Covalent Organic Frameworks via Michael Addition-EliminationRao, M. Rajeswara; Fang, Yuan; De Feyter, Steven; Perepichka, Dmitrii F.Journal of the American Chemical Society (2017), 139 (6), 2421-2427CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Dynamic covalent chem. enables self-assembly of reactive building blocks into structurally complex yet robust materials, such as Covalent Org. Frameworks (COFs). However, the synthetic toolbox used to prep. such materials, and thus the spectrum of attainable properties, is limited. For π-conjugated COFs, the Schiff base condensation of aldehydes and amines is the only general dynamic reaction, but the resulting imine-linked COFs display only a moderate electron delocalization and are susceptible to hydrolysis, particularly in acidic conditions. Here we report a new dynamic polymn. based on Michael addn.-elimination reaction of structurally diverse β-ketoenols with amines, and use it to prep. novel two dimensional (2D) π-conjugated COFs, as cryst. powders and exfoliated micron-size sheets. π-Conjugation is manifested in these COFs in significantly reduced band gap (1.8-2.2 eV), solid state luminescence and reversible electrochem. doping creating mid-gap (NIR absorbing) polaronic states. The β-ketoenamine moiety enables protonation control of electron delocalization through the 2D COF sheets. It also gives rise to direct sensing of triacetone triperoxide (TATP) explosive through fluorescence quenching.
- 40Liu, K.; Wang, Z.; Shang, C.; Li, X.; Peng, H.; Miao, R.; Ding, L.; Liu, J.; Liu, T.; Fang, Y. Unambiguous Discrimination and Detection of Controlled Chemical Vapors by a Film-Based Fluorescent Sensor Array. Adv. Mater. Technol. 2019, 4, 1800644 DOI: 10.1002/admt.201800644Google Scholar40Unambiguous Discrimination and Detection of Controlled Chemical Vapors by a Film-Based Fluorescent Sensor ArrayLiu, Ke; Wang, Zhaolong; Shang, Congdi; Li, Xiao; Peng, Haonan; Miao, Rong; Ding, Liping; Liu, Jing; Liu, Taihong; Fang, YuAdvanced Materials Technologies (Weinheim, Germany) (2019), 4 (7), 1800644CODEN: AMTDCM; ISSN:2365-709X. (Wiley-VCH Verlag GmbH & Co. KGaA)In situ, online, fast, and sensitive detection and discrimination of explosives, illicit drugs, and volatile org. compds. via vapor sampling is a challenge for many years. The highly efficient and noncontact detection of 15 types of chems. mentioned above using a film-based fluorescent sensor array is reported herein. Importantly, the presence of water, toiletries, fruit, dirty clothes, and other interferences has little effect upon detection. Discrimination of the controlled chems. is realized using a pattern recognition strategy. Meanwhile, a conceptual detector based on a sensor array is constructed and successfully used for simulated field tests. It is strongly believed that the present work not only provides a powerful fluorescent technique for efficient detection and discrimination of controlled chems. with remarkably different properties but also demonstrates that arraying a single sensor is a promising strategy to mitigate the limitations of conventional film-based fluorescent sensors.
- 41OSAC. Analysis of Explosives Reference List, 2020. https://www.nist.gov/topics/organization-scientific-area-committees-forensic-science/fire-debris-explosives-subcommittee (accessed May 20, 2022).Google ScholarThere is no corresponding record for this reference.
- 42EU-SENSE. Characteristics of Improvised Explosive Devices Containing Chemical Substances in the Context of the International Airports Protection, 2021. https://eu-sense.eu/characteristics-of-improvised-explosive-devices-containing-chemical-substances-in-the-context-of-the-international-airports-protection/ (accessed May 20, 2022).Google ScholarThere is no corresponding record for this reference.
- 43González-Calabuig, A.; Cetó, X.; del Valle, M. Electronic Tongue for Nitro and Peroxide Explosive Sensing. Talanta 2016, 153, 340– 346, DOI: 10.1016/j.talanta.2016.03.009Google Scholar43Electronic tongue for nitro and peroxide explosive sensingGonzalez-Calabuig, Andreu; Ceto, Xavier; del Valle, ManelTalanta (2016), 153 (), 340-346CODEN: TLNTA2; ISSN:0039-9140. (Elsevier B.V.)This work reports the application of a voltammetric electronic tongue (ET) towards the simultaneous detn. of both nitro-contg. and peroxide-based explosive compds., two families that represent the vast majority of compds. employed either in com. mixts. or in improvised explosive devices. The multielectrode array was formed by graphite, gold and platinum electrodes, which exhibited marked mix-responses towards the compds. examd.; namely, 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT), N-methyl-N,2,4,6-tetranitroaniline (Tetryl) and triacetone triperoxide (TATP). Departure information was the set of voltammograms, which were first analyzed by principal component anal. (PCA) allowing the discrimination of the different individual compds., while artificial neural networks (ANNs) were used for the resoln. and individual quantification of some of their mixts. (total normalized root mean square error for the external test set of 0.108 and correlation of the obtained vs. expected concns. comparison graphs r>0.929).
- 44Krivitsky, V.; Filanovsky, B.; Naddaka, V.; Patolsky, F. Direct and Selective Electrochemical Vapor Trace Detection of Organic Peroxide Explosives via Surface Decoration. Anal. Chem. 2019, 91, 5323– 5330, DOI: 10.1021/acs.analchem.9b00257Google Scholar44Direct and Selective Electrochemical Vapor Trace Detection of Organic Peroxide Explosives via Surface DecorationKrivitsky, Vadim; Filanovsky, Boris; Naddaka, Vladimir; Patolsky, FernandoAnalytical Chemistry (Washington, DC, United States) (2019), 91 (8), 5323-5330CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The ability to detect traces of highly energetic explosive materials sensitively, selectively, accurately, and rapidly could be of enormous benefit to civilian national security, military applications, and environmental monitoring. Unfortunately, the detection of explosives still poses a largely unmet arduous anal. problem, making their detection an issue of burning immediacy and a massive current challenge in terms of research and development. Although numerous explosive detection approaches have been developed, these methods are usually time-consuming, require bulky equipment, tedious sample prepn., a trained operator, cannot be miniaturized, and lack the ability to perform automated real-time high-throughput anal., strongly handicapping their mass deployment. Here, we present the first demonstration of the "direct" electrochem. approach for the sensitive, selective, and rapid vapor trace detection of TATP and HMTD, under ambient conditions, unaffected by the presence of oxygen and hydrogen peroxide species, down to concns. lower than 10 ppb. The method is based on the use of Ag-nanoparticles-decorated carbon microfibers air-collecting electrodes (μCF), which allow for the selective direct detection of the org. peroxide explosives, through opening multiple redox routes, not existent in the undecorated carbon electrodes. Finally, we demonstrate the direct and rapid detection of TATP and HMTD explosive species from real-world air samples.
- 45Calvo-Gredilla, P.; García-Calvo, J.; Cuevas, J. V.; Torroba, T.; Pablos, J.-L.; García, F. C.; García, J.-M.; Zink-Lorre, N.; Font-Sanchis, E.; Sastre-Santos, A.; Fernández-Lázaro, F. Solvent-Free Off–On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic Materials. Chem. – Eur. J. 2017, 23, 13973– 13979, DOI: 10.1002/chem.201702412Google Scholar45Solvent-Free Off-On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic MaterialsCalvo-Gredilla, Patricia; Garcia-Calvo, Jose; Cuevas, Jose V.; Torroba, Tomas; Pablos, Jesus-Luis; Garcia, Felix C.; Garcia, Jose-Miguel; Zink-Lorre, Nathalie; Font-Sanchis, Enrique; Sastre-Santos, Angela; Fernandez-Lazaro, FernandoChemistry - A European Journal (2017), 23 (56), 13973-13979CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A fluorogenic perylenediimide-functionalized polyacrylate capable of generating color and fluorescence changes in the presence of triacetone triperoxide (TATP), an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions has been developed. The material works by accumulating volatile TATP until it reaches a threshold; therefore, triggering colorimetric and fluorescent responses.
- 46García-Calvo, J.; Calvo-Gredilla, P.; Ibáñez-Llorente, M.; Romero, D. C.; Cuevas, J. V.; García-Herbosa, G.; Avella, M.; Torroba, T. Surface Functionalized Silica Nanoparticles for the Off–On Fluorogenic Detection of an Improvised Explosive, TATP, in a Vapour Flow. J. Mater. Chem. A 2018, 6, 4416– 4423, DOI: 10.1039/C7TA10792GGoogle Scholar46Surface functionalized silica nanoparticles for the off-on fluorogenic detection of an improvised explosive, TATP, in a vapor flowGarcia-Calvo, Jose; Calvo-Gredilla, Patricia; Ibanez-Llorente, Marcos; Romero, Daisy C.; Cuevas, Jose V.; Garcia-Herbosa, Gabriel; Avella, Manuel; Torroba, TomasJournal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (10), 4416-4423CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The development is reported of new fluorogenic silica nanomaterials that were able to generate fluorescence in the presence of vapors of triacetone triperoxide, TATP, an improvised explosive used in terrorist attacks. The materials worked in a vapor flow of TATP, giving a permanent and strongly fluorescent response.
- 47Blanco, S.; Macario, A.; García-Calvo, J.; Revilla-Cuesta, A.; Torroba, T.; López, J. C. Microwave Detection of Wet Triacetone Triperoxide (TATP): Non-Covalent Forces and Water Dynamics. Chem. – Eur. J. 2021, 27, 1680– 1687, DOI: 10.1002/chem.202003499Google Scholar47Microwave Detection of Wet Triacetone Triperoxide (TATP): Non-Covalent Forces and Water DynamicsBlanco, Susana; Macario, Alberto; Garcia-Calvo, Jose; Revilla-Cuesta, Andrea; Torroba, Tomas; Lopez, Juan CarlosChemistry - A European Journal (2021), 27 (5), 1680-1687CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)The water adducts of triacetone triperoxide (TATP) have been obsd. by using broadband rotational spectroscopy. This work opens a new way for the gas-phase detection of this improvised explosive. The obsd. clusters exhibit unusual water dynamics and rarely obsd. multicenter interactions. TATP-H2O is formed from the D3 symmetry conformer of TATP with water lying close to the C3 axis. Water rotation around this axis with a very low barrier gives rise to the rotational spectrum of a sym. top. The main interaction of the monohydrate is a four-center trifurcated donor Ow-H···O hydrogen bond, not obsd. previously in the gas phase, reinforced by a weak four-center trifurcated acceptor C-H···Ow interaction. Surprisingly, all structural signatures show the weakness of these interactions. The complex TATP-(H2O)2 is formed from the monohydrated TATP by the self-assocn. of water.
- 48Lapcinska, S.; Revilla-Cuesta, A.; Abajo-Cuadrado, I.; Cuevas, J. V.; Avella, M.; Arsenyan, P.; Torroba, T. Dye-Modified Silica-Anatase Nanoparticles for the Ultrasensitive Fluorogenic Detection of the Improvised Explosive TATP in an Air Microfluidic Device. Mater. Chem. Front. 2021, 5, 8097– 8107, DOI: 10.1039/D1QM01041GGoogle Scholar48Dye-modified silica-anatase nanoparticles for the ultrasensitive fluorogenic detection of the improvised explosive TATP in an air microfluidic deviceLapcinska, Sindija; Revilla-Cuesta, Andrea; Abajo-Cuadrado, Irene; Cuevas, Jose V.; Avella, Manuel; Arsenyan, Pavel; Torroba, TomasMaterials Chemistry Frontiers (2021), 5 (23), 8097-8107CODEN: MCFAC5; ISSN:2052-1537. (Royal Society of Chemistry)We describe the proof of concept of a portable testing setup for the detection of triacetone triperoxide (TATP), a common component in improvised explosive devices. The system will allow field-testing and generation of real-time results to test for TATP vapor traces in a no. of different environments. It will work by recirculating the gas samples in connection to the sensing mechanism in a suitable microfluidic portable device. In this way, the system will allow controlled trapping of the analyte in the chem. sensor to afford reliable results at very low concns. in air.
- 49Torroba, T.; Schechter, I.; Calvo, J. G.; Revilla-Cuesta, A. Explosives Detection, Sensors, Electronic Systems and Data Processing; Capineri, L.; Turmus, E. K., Eds.; Springer: The Netherlands, 2019; pp 208– 247.Google ScholarThere is no corresponding record for this reference.
- 50Gopikrishna, P.; Meher, N.; Iyer, P. K. Functional 1,8-Naphthalimide AIE/AIEEgens: Recent Advances and Prospects. ACS Appl. Mater. Interfaces 2018, 10, 12081– 12111, DOI: 10.1021/acsami.7b14473Google Scholar50Functional 1,8-Naphthalimide AIE/AIEEgens: Recent Advances and ProspectsGopikrishna, Peddaboodi; Meher, Niranjan; Iyer, Parameswar KrishnanACS Applied Materials & Interfaces (2018), 10 (15), 12081-12111CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A review. A survey is given of the up-to-date development of aggregation-induced emission/aggregation-induced emission enhancement (AIE/AIEE) active naphthalimide (NI)-based smart materials with potential for wide and real-world applications and that serves as a highly versatile building block with tunable absorption and emission in the complete visible region. The review article commences with a precise description of the importance of NI moiety and its several restricted area of applications owing to its aggregation caused quenching (ACQ) properties, followed by the discovery and importance of AIE/AIEE-active NIs. The introduction section tracked an overview of the state of the art in NI luminogens in multiple applications. It also includes a few mechanistic studies on the structure-property correlation of NIs and provides more insights into the condensed-state photophys. properties of small aggregation-prone systems. The review aims to ultimately accomplish current and forthcoming views comprising the use of the NIs for the detection of biol. active mols., such as amino acids and proteins, recognition of toxic analytes, fabrication of light emitting diodes, and their potential in therapeutics and diagnostics.
- 51de Greñu, B. D.; Moreno, D.; Torroba, T.; Berg, A.; Gunnars, J.; Nilsson, T.; Nyman, R.; Persson, M.; Pettersson, J.; Eklind, I.; Wästerby, P. Fluorescent Discrimination between Traces of Chemical Warfare Agents and Their Mimics. J. Am. Chem. Soc. 2014, 136, 4125– 4128, DOI: 10.1021/ja500710mGoogle ScholarThere is no corresponding record for this reference.
- 52de Greñu, B. D.; García-Calvo, J.; Cuevas, J.; García-Herbosa, G.; García, B.; Busto, N.; Ibeas, S.; Torroba, T.; Torroba, B.; Herrera, A.; Pons, S. Chemical Speciation of MeHg+ and Hg2+ in Aqueous Solution and HEK Cells Nuclei by means of DNA Interacting Fluorogenic Probes. Chem. Sci. 2015, 6, 3757– 3764, DOI: 10.1039/C5SC00718FGoogle ScholarThere is no corresponding record for this reference.
- 53García-Calvo, J.; Vallejos, S.; García, F. C.; Rojo, J.; García, J. M.; Torroba, T. A Smart Material for the in Situ Detection of Mercury in Fish. Chem. Commun. 2016, 52, 11915– 11918, DOI: 10.1039/C6CC05977EGoogle Scholar53A smart material for the in situ detection of mercury in fishGarcia-Calvo, Jose; Vallejos, Saul; Garcia, Felix C.; Rojo, Josefa; Garcia, Jose M.; Torroba, TomasChemical Communications (Cambridge, United Kingdom) (2016), 52 (80), 11915-11918CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)We have developed a new fluorogenic polymer capable of detecting the presence of mercury contamination in fish samples. The modified polymer emits blue light when irradiated with UV light proportional to the quantity of mercury, as MeHg+ or Hg2+, present in fish. The quant. relation between the concn. of mercury in fish and the increase of fluorescence in the polymer in contact with fish samples was confirmed, giving rise to quick and reliable results in the measurements of the presence of mercury in fish using a portable fluorogenic polymeric probe.
- 54García-Calvo, J.; Calvo-Gredilla, P.; Ibáñez-Llorente, M.; Rodríguez, T.; Torroba, T. Detection of Contaminants of High Environmental Impact by Means of Fluorogenic Probes. Chem. Rec. 2016, 16, 810– 824, DOI: 10.1002/tcr.201500253Google Scholar54Detection of Contaminants of High Environmental Impact by Means of Fluorogenic ProbesGarcia-Calvo, Jose; Calvo-Gredilla, Patricia; Ibanez-Llorente, Marcos; Rodriguez, Teresa; Torroba, TomasChemical Record (2016), 16 (2), 810-824CODEN: CRHEAK; ISSN:1528-0691. (Wiley-VCH Verlag GmbH & Co. KGaA)This personal account describes our contribution to the design of selective fluorogenic probes for contaminants of high environmental impact. For this purpose, we have developed a new family of highly versatile fluorogenic reagents that were able to show large differences in their fluorescence in the presence of selected analytes. They were used in the prepn. of fluorogenic probes for the detection of contaminants of high environmental impact which currently have no good solns.: phosphorylating agents, such as chem. weapons; Me mercury(II); the cyanide anion; amino-acid metabolites, such as doping substances; and biogenic amine mimics, such as drugs of abuse and recreational drugs. The development of new materials for specific sensing was achieved by anchoring selected probes to silica nanomaterials, suitable for the selective detection of org. analytes in water for immediate application to toxicol. or environmental purposes.
- 55García-Calvo, J.; Robson, J. A.; Torroba, T.; Wilton-Ely, J. D. E. T. Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and Gases. Chem. – Eur. J. 2019, 25, 14214– 14222, DOI: 10.1002/chem.201903303Google Scholar55Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and GasesGarcia-Calvo, Jose; Robson, Jonathan A.; Torroba, Tomas; Wilton-Ely, James D. E. T.Chemistry - A European Journal (2019), 25 (62), 14214-14222CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A series of new ruthenium(II) vinyl complexes has been prepd. incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalized with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or through the pyridyl nitrogen. The inherent low soly. of the perylene compds. was improved through the design of poly-PEGylated (PEG = polyethylene glycol) units bearing a terminal alkyne or a pyridyl group. By absorbing the compds. on silica, vapors and gases could be detected in the solid state. The reaction of the complexes [Ru(CH:CH-PerIm)Cl(CO)(py-3PEG)(PPh3)2] and [Ru(CH:CH-3PEG)Cl(CO)(py-PerIm)(PPh3)2] with carbon monoxide, isonitrile or cyanide was found to result in modulation of the fluorescence behavior. The complexes were obsd. to display solvatochromic effects and the interaction of the complexes with a wide range of other species was also studied. The study suggests that such complexes have potential for the detection of gases or vapors that are toxic to humans.
- 56García-Calvo, V.; Cuevas, J. V.; Barbero, H.; Ferrero, S.; Álvarez, C. M.; González, J. A.; Díaz de Greñu, B.; García-Calvo, J.; Torroba, T. Synthesis of a Tetracorannulene-perylenediimide That Acts as a Selective Receptor for C60 over C70. Org. Lett. 2019, 21, 5803– 5807, DOI: 10.1021/acs.orglett.9b01729Google Scholar56Synthesis of a Tetracorannulene-perylenediimide That Acts as a Selective Receptor for C60 over C70Garcia-Calvo, Victor; Cuevas, Jose V.; Barbero, Hector; Ferrero, Sergio; Alvarez, Celedonio M.; Gonzalez, Jesus A.; Diaz de Grenu, Borja; Garcia-Calvo, Jose; Torroba, TomasOrganic Letters (2019), 21 (15), 5803-5807CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)The authors report the use of a tetraborylated perylenediimide as starting material for the prepn. of a tetracorannulene-perylenediimide that is able to bind up to two fullerene-C60 mols. by host-guest mol. recognition with preference over C70. Titrn. with fullerene-C60 is followed by a dramatic shift of the arom. signals in 1H NMR and an initial increase in the fluorescence of the system. By this simple mechanism, fluorogenic sensing of fullerene-C60 is easily accomplished by an unprecedented fluorescent turn-on mechanism.
- 57Busto, N.; Calvo, P.; Santolaya, J.; Leal, J. M.; Guédin, A.; Barone, G.; Torroba, T.; Mergny, J.-L.; García, B. Fishing for G-Quadruplexes in Solution with a Perylene Diimide Derivative Labeled with Biotins. Chem. – Eur. J. 2018, 24, 11292– 11296, DOI: 10.1002/chem.201802365Google Scholar57Fishing for G-Quadruplexes in Solution with a Perylene Diimide Derivative Labeled with BiotinsBusto, Natalia; Calvo, Patricia; Santolaya, Javier; Leal, Jose M.; Guedin, Aurore; Barone, Giampaolo; Torroba, Tomas; Mergny, Jean-Louis; Garcia, BegonaChemistry - A European Journal (2018), 24 (44), 11292-11296CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A new fluorescent, noncytotoxic perylene diimide deriv. with two biotins at the peri position, PDI2B, has been synthesized. This mol. is able to interact selectively with G-quadruplexes with scarce or no affinity towards single- or double-stranded DNA. These features have made it possible to design a simple, effective, safe, cheap, and selective method for fishing G-quadruplex structures in soln. by use of PDI2B and streptavidin coated magnetic beads. The new cyclic method reported leads to the recovery of more than 80% of G-quadruplex structures from soln., even in the presence of an excess of single-stranded or duplex DNA as competitors. Moreover, PDI2B is a G4 ligand that can display higher thermal stabilization and greater affinity for 2- over 3-tetrad quadruplexes, which constitutes a novel type of behavior.
- 58García-Calvo, J.; Torroba, T.; Brañas-Fresnillo, V.; Perdomo, G.; Cózar-Castellano, I.; Li, Y.-H.; Legrand, Y.-M.; Barboiu, M. Manipulation of Transmembrane Transport by Synthetic K+ Ionophore Depsipeptides and Its Implications in Glucose-Stimulated Insulin Secretion in β-Cells. Chem. – Eur. J. 2019, 25, 9287– 9294, DOI: 10.1002/chem.201901372Google Scholar58Manipulation of transmembrane transport by synthetic K+ ionophore depsipeptides and its implications in glucose-stimulated insulin secretion in β-cellsGarcia-Calvo, Jose; Torroba, Tomas; Branas-Fresnillo, Virginia; Perdomo, German; Cozar-Castellano, Irene; Li, Yu-Hao; Legrand, Yves-Marie; Barboiu, MihailChemistry - A European Journal (2019), 25 (39), 9287-9294CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)The cyclic depsipeptide cereulide toxin it is a very well-known potassium electrogenic ionophore particularly sensitive to pancreatic beta cells. The mechanistic details of its specific activity are unknown. Here, we describe a series of synthetic substituted cereulide potassium ionophores that cause impressive selective activation of glucose-induced insulin secretion in a constitutive manner in rat insulinoma INS1E cells. Our study demonstrates that the different electroneutral K+ transport mechanism exhibited by the anionic mutant depsipeptides when compared with classical electrogenic cereulides can have an important impact of pharmacol. value on glucose-stimulated insulin secretion.
- 59Busto, N.; García-Calvo, J.; Cuevas, J. V.; Herrera, A.; Mergny, J.-L.; Pons, S.; Torroba, T.; García, B. Influence of Core Extension and Side Chain Nature in Targeting G-Quadruplex Structures with Perylene Monoimide Derivatives. Bioorg. Chem. 2021, 108, 104660 DOI: 10.1016/j.bioorg.2021.104660Google Scholar59Influence of core extension and side chain nature in targeting G-quadruplex structures with perylene monoimide derivativesBusto, Natalia; Garcia-Calvo, Jose; Cuevas, Jose Vicente; Herrera, Antonio; Mergny, Jean-Louis; Pons, Sebastian; Torroba, Tomas; Garcia, BegonaBioorganic Chemistry (2021), 108 (), 104660CODEN: BOCMBM; ISSN:0045-2068. (Elsevier B.V.)A structure-activity relationship (SAR) study in terms of G-quadruplex binding ability and antiproliferative activity of six fluorescent perylenemonoimide (PMIs) derivs. is reported. A pos. charge seems to be the key to target G4. This study also reveals the importance of the element substitution in the potential biol. activity of PMIs, being the polyethylene glycol (PEG) chains in the peri position responsible for their antiproliferative activity. Among them, the cationic PMI6 with two PEG chains is the most promising compd. since its fluorescence is enhanced in the presence of G-quadruplex structures. Moreover, PMI6 binds to the human telomeric G-quadruplex hTelo with high affinity and displays a high antiproliferative potential towards HeLa (cervical adenocarcinoma), A549 (lung adenocarcinoma) and A2780 (ovarian adenocarcinoma) cells. Its fate can be followed inside cells thanks to its fluorescent properties: the compd. is found to accumulate in the mitochondria.
- 60Tajima, K.; Fukui, N.; Shinokubo, H. Aggregation-Induced Emission of Nitrogen-Bridged Naphthalene Monoimide Dimers. Org. Lett. 2019, 21, 9516– 9520, DOI: 10.1021/acs.orglett.9b03699Google Scholar60Aggregation-Induced Emission of Nitrogen-Bridged Naphthalene Monoimide DimersTajima, Keita; Fukui, Norihito; Shinokubo, HiroshiOrganic Letters (2019), 21 (23), 9516-9520CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)We have prepd. four 4-aminonaphthalene monoimide derivs. and examd. the aggregation-induced emission (AIE) properties. A nitrogen-bridged dimer is AIE-active and exhibits bright green emission with a high quantum yield in the solid state. The X-ray diffraction anal. suggests that key to the bright luminescence is the favorable crystal packing dominated by CH/π interaction. The late-stage cyanation of the dimer tuned its AIE color from green to orange.
- 61Wang, Y.; Teng, Y.; Yang, H.; Li, X.; Yin, D.; Tian, Y. Bioorthogonally Applicable Multicolor Fluorogenic Naphthalimide–Tetrazine Probes with Aggregation-Induced Emission Characters. Chem. Commun. 2022, 58, 949– 952, DOI: 10.1039/D1CC05204GGoogle Scholar61Bioorthogonally applicable multicolor fluorogenic naphthalimide-tetrazine probes with aggregation-induced emission charactersWang, Yongcheng; Teng, Yu; Yang, Hong; Li, Xiang; Yin, Dali; Tian, YulinChemical Communications (Cambridge, United Kingdom) (2022), 58 (7), 949-952CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)A series of naphthalimide-tetrazines were developed as bioorthogonal fluorogenic probes, which could produce significant fluorescence enhancement, notable aggregation-induced emission (AIE) characters and multicolor emissions after bioorthogonal reaction with strained dienophiles. Manipulating the π-bridge in the fluorophore skeleton allows fine-tuning of the emission wavelength and influences the AIE-active properties. With these probes, we succeeded in no-wash fluorogenic protein labeling and mitochondria-selective bioorthogonal imaging in live cells.
- 62García-Calvo, J.; Calvo-Gredilla, P.; Vallejos, S.; García, J. M.; Cuevas-Vicario, J. V.; García-Herbosa, G.; Avella, M.; Torroba, T. Palladium Nanodendrites Uniformly Deposited on the Surface of Polymers as an Efficient and Recyclable Catalyst for Direct Drug Modification Via Z-Selective Semihydrogenation of Alkynes. Green Chem. 2018, 20, 3875– 3883, DOI: 10.1039/C8GC01522HGoogle Scholar62Palladium nanodendrites uniformly deposited on the surface of polymers as an efficient and recyclable catalyst for direct drug modification via Z-selective semihydrogenation of alkynesGarcia-Calvo, Jose; Calvo-Gredilla, Patricia; Vallejos, Saul; Garcia, Jose Miguel; Cuevas-Vicario, Jose Vicente; Garcia-Herbosa, Gabriel; Avella, Manuel; Torroba, TomasGreen Chemistry (2018), 20 (16), 3875-3883CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)The prepn. of new monodisperse polycryst. palladium nanoparticles uniformly distributed on the surface of polymers, by simply adding a palladium(II) soln. in water to the polymers, is described. The polymer supported palladium nanoparticles material was used as an efficient portable and reusable catalyst for the stereoselective semihydrogenation reaction of internal alkynes to (Z)-alkenes in green solvents.
- 63García-Calvo, J.; García-Calvo, V.; Vallejos, S.; García, F. C.; Avella, M.; García, J.-M.; Torroba, T. Surface Coating by Gold Nanoparticles on Functional Polymers: On-Demand Portable Catalysts for Suzuki Reactions. ACS Appl. Mater. Interfaces 2016, 8, 24999– 25004, DOI: 10.1021/acsami.6b07746Google Scholar63Surface Coating by Gold Nanoparticles on Functional Polymers: On-Demand Portable Catalysts for Suzuki ReactionsGarcia-Calvo, Jose; Garcia-Calvo, Victor; Vallejos, Saul; Garcia, Felix C.; Avella, Manuel; Garcia, Jose-Miguel; Torroba, TomasACS Applied Materials & Interfaces (2016), 8 (38), 24999-25004CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)We have developed new functionalized polymers capable of being easily coated by gold nanoparticles, uniformly distributed on the surface of the polymers, by simply adding a gold(III) soln. in water to the polymers. The polymer-supported gold nanoparticle material was used as an efficient portable and reusable catalyst for Suzuki reactions in mixed org.-aq. solvents.
- 64Sanluis-Verdes, A.; Colomer-Vidal, P.; Rodriguez-Ventura, F.; Bello-Villarino, M.; Spinola-Amilibia, M.; Ruiz-Lopez, E.; Illanes-Vicioso, R.; Castroviejo, P.; Aiese Cigliano, R.; Montoya, M.; Falabella, P.; Pesquera, C.; Gonzalez-Legarreta, L.; Arias-Palomo, E.; Solà, M.; Torroba, T.; Arias, C. F.; Bertocchini, F. Wax Worm Saliva and the Enzymes therein Are the Key to Polyethylene Degradation by Galleria mellonella. Nat. Commun. 2022, 13, 5568 DOI: 10.1038/s41467-022-33127-wGoogle Scholar64Wax worm saliva and the enzymes therein are the key to polyethylene degradation by Galleria mellonellaSanluis-Verdes, A.; Colomer-Vidal, P.; Rodriguez-Ventura, F.; Bello-Villarino, M.; Spinola-Amilibia, M.; Ruiz-Lopez, E.; Illanes-Vicioso, R.; Castroviejo, P.; Aiese Cigliano, R.; Montoya, M.; Falabella, P.; Pesquera, C.; Gonzalez-Legarreta, L.; Arias-Palomo, E.; Sola, M.; Torroba, T.; Arias, C. F.; Bertocchini, F.Nature Communications (2022), 13 (1), 5568CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Plastic degrdn. by biol. systems with re-utilization of the byproducts could be a future soln. to the global threat of plastic waste accumulation. Here, we report that the saliva of Galleria mellonella larvae (wax worms) is capable of oxidizing and depolymg. polyethylene (PE), one of the most produced and sturdy polyolefin-derived plastics. This effect is achieved after a few hours' exposure at room temp. under physiol. conditions (neutral pH). The wax worm saliva can overcome the bottleneck step in PE biodegrdn., namely the initial oxidn. step. Within the saliva, we identify two enzymes, belonging to the phenol oxidase family, that can reproduce the same effect. To the best of our knowledge, these enzymes are the first animal enzymes with this capability, opening the way to potential solns. for plastic waste management through bio-recycling/up-cycling.
- 65Allegrini, F.; Olivieri, A. C. IUPAC-Consistent Approach to the Limit of Detection in Partial Least-Squares Calibration. Anal. Chem. 2014, 86, 7858– 7866, DOI: 10.1021/ac501786uGoogle Scholar65IUPAC-Consistent Approach to the Limit of Detection in Partial Least-Squares CalibrationAllegrini, Franco; Olivieri, Alejandro C.Analytical Chemistry (Washington, DC, United States) (2014), 86 (15), 7858-7866CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)There is currently no well-defined procedure for providing the limit of detection (LOD) in multivariate calibration. Defining an estimator for the LOD in this scenario showed to be more complex than intuitively extending the traditional univariate definition. For these reasons, although many attempts were made to arrive at a reasonable convention, addnl. effort is required to achieve full agreement between the univariate and multivariate LOD definitions. A novel approach is presented to est. the LOD in partial least-squares (PLS) calibration. Instead of a single LOD value, an interval of LODs is provided, which depends on the variation of the background compn. in the calibration space. This is in contrast with previously proposed univariate extensions of the LOD concept. With the present definition, the LOD interval becomes a parameter characterizing the overall PLS calibration model, and not each test sample in particular, as was proposed in the past. The new approach takes into account IUPAC official recommendations, and also the latest developments in error-in-variables theory for PLS calibration. Both simulated and real anal. systems were studied for illustrating the properties of the new LOD concept.
- 66Ortiz, M. C.; Sarabia, L. A.; Sánchez, M. S. Tutorial on Evaluation of Type I and Type II Errors in Chemical Analyses: From the Analytical Detection to Authentication of Products and Process Control. Anal. Chim. Acta 2010, 674, 123– 142, DOI: 10.1016/j.aca.2010.06.026Google Scholar66Tutorial on evaluation of type I and type II errors in chemical analyses: From the analytical detection to authentication of products and process controlOrtiz, M. C.; Sarabia, L. A.; Sanchez, M. S.Analytica Chimica Acta (2010), 674 (2), 123-142CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)A review. Uncertainty is inherent in all exptl. detns. Nevertheless, these measurements were used to make decisions including the performance of the own measurement systems. The link between the decision and the true implicit system that generates the data (measurement system, prodn. process, category of samples, etc.) is a representation of this uncertainty as a probability distribution. This representation leads to the probabilistic formalization of the possibility of making errors. In the context of regulations established by official agencies, it is important to use these statistical decision methods in some cases because the own norm makes them mandatory and, in general, because this is the way of reasonably evaluating whether a working hypothesis is rejected from the exptl. data. The aim of the present tutorial is to introduce some ideas and basic methods for the crit. anal. of exptl. data. With this goal, the basic elements of the Neyman-Pearson theory of hypothesis testing are formally introduced in connection with the common problems in chem. anal. and, if this is the case, their relation to the norms of regulatory agencies. The notion of decision with enough quality' is modeled when explicitly considering: (1) the null, H 0, and alternative, H 1, hypotheses. (2) The significance level of the test, which is the probability, α, of rejecting H 0 when it is true, and the power of the test, 1 - β, β being the probability of accepting H 0 when it is false. (3) The difference between H 0 and H 1 that has to be detected with exptl. data. (4) The needed sample size. These four concepts should be explicitly defined for each problem and, under the usual assumption of normal distribution of the data, the math. relations among these concepts are shown, which allow the analyst to design a decision rule with pre-set values of α and β. To illustrate the unifying character of this inferential methodol., several situations are exposed along the tutorial: the design of a hypothesis test to decide on the performance characteristics of anal. methods, the capability of detection of both quant. and qual. anal. methods (including its generalization to the case of multivariate and/or multiway signals), the anal. sensitivity with multivariate signals, the class-modeling and the process control.
- 67RStudio, Version 1.4.1103; RStudio: Boston, MA, 2009–2021.Google ScholarThere is no corresponding record for this reference.
- 68Fujiyama-Novak, J. H.; Gaddam, C. K.; Das, D.; Wal, R. L. V.; Ward, B. Detection of Explosives by Plasma Optical Emission Spectroscopy. Sens. Actuators, B 2013, 176, 985– 993, DOI: 10.1016/j.snb.2012.08.063Google Scholar68Detection of explosives by plasma optical emission spectroscopyFujiyama-Novak, Jane H.; Gaddam, Chethan Kumar; Das, Debanjan; Vander Wal, Randall L.; Ward, BenjaminSensors and Actuators, B: Chemical (2013), 176 (), 985-993CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)A new pre-concn./sepn. system coupled to a micro-hollow glow discharge plasma detector is demonstrated for the anal. of explosives. The detector and spectrometer are miniaturized and field-portable. Sepn. eliminated air interferences while pre-concn. improved detection limits for TATP (triacetone triperoxide) and DNT (dinitrotoluene). In the anal. step, a temp. ramp desorbed the 2 explosives into an entraining Ar flow. Optical emission spectroscopy was applied to detect the plasma generated at. and diat. radicals using a spectrometer at atm. pressure. For both test species, the detection limits reached values <5 ppb. The effect of an at-sea environment was also evaluated. Such a detector system is very promising for the detection of explosives due its small size, high sensitivity, and selectivity.
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Abstract
Figure 1
Figure 1. (a) Structure of chemical probes used for the study. (b) Model of the chemical probe AR82s on silica. (c, e) Structural and (d) elemental TEM images of the AR82s@SiO2 nanoparticles. (f) Elemental composition of the AR82s@SiO2 nanoparticles and high-resolution TEM images.
Figure 2
Figure 2. (a) Microfluidic device dimensions: Eppendorf: outer top diameter: 11 mm, inner top diameter: 9 mm, outer bottom diameter: 5 mm, inner bottom diameter: 3 mm, volume: 1.5 mL, height (with lid): 40 mm, height (without lid): 38 mm; tubing: outer diameter: 3 mm, inner diameter: 1.5 mm, length (flow tube): 25 mm, length (return tube:): 35 mm. (b) The actual aspect of the system; reproduced from ref (48) with permission from the Chinese Chemical Society (CCS), Institute of Chemistry of Chinese Academy of Sciences (IC), and the Royal Society of Chemistry. (c) Fluorescence changes with TATP gas. (d) Titration curves of AR82s@SiO2 and TATP vapor. (e) Fluorescent profile at 535 nm and (f) calibration for the limit of detection of AR82s@SiO2 nanoparticles under increasing concentrations of TATP vapor. λexc = 370 nm, λem = 535 nm.
Figure 3
Figure 3. (a) Distribution of TATP sample (yellow arrow) and sensor samples (red arrows) in the room. (b) Close view of the arrangement of the TATP sample (yellow arrow) in front of the airflow outlet and the sensing material samples (red arrows). (c) Histogram plotting the differences in intensity emission in all cases before and after exposure to TATP vapors as a function of distance from the TATP source and temperature of the room, normalized to the top and reference signals. (d) A sample of sensing material showing the modified nanoparticles.
Figure 4
Figure 4. Summary of experiments 7–12. (a) Arrangement of the TATP in front of the airflow outlet. (b) Distribution of sensing nanoparticles in the room. (c) 3D representation of the variation of the normalized emission intensity as a function of the distance to the TATP source. (d) Assembly of the nanoparticles for measurements. (e) Details of one sample of AR82@SiO2.
Figure 5
Figure 5. Average and standard deviation of normalized emission variation as a function of the distance to the TATP source.
Figure 6
Figure 6. (a) View of the room for the experiment, (b) the TATP sample and the sensing material at different distances from the TATP, (c) picture of the sensing material placed at 25 cm from the TATP source, under a UV lamp, before (up) and after (down) being exposed to TATP, (d) picture (down) captured by the mobile phone app, and (e) the app assigned a positive value after comparing the RGB values in the selected point with the customized database.
Figure 7
Figure 7. (a) Titration curves, TATP titration. (b) Fluorescence profile at 500 nm, TATP titration. (c) Calibration plot for the limit of detection of 2.5 μM GC2 solutions in DCM under increasing concentrations of TATP. (d) Image of solutions before and after TATP titration. (e) Titration curves, m-CPBA titration. (f) Fluorescence profile at 500 nm, m-CPBA titration. (g) Calibration plot for the limit of detection. (h) Fluorescence profile at the corresponding working curves of the ratiometric probe in the presence of m-CPBA.
Figure 8
Figure 8. 1H NMR (CDCl3, 500 MHz) titration of AR82s with increasing amounts of TATP in the presence of amberlite, 3 mg of AR82s in 0.5 mL of CDCl3, and TATP amounts: (1) 0 μg, (2) 5 μg, (3) 10 μg, (4) 15 μg, (5) 20 μg, (6) 30 μg, (7) 40 μg, (8) 60 μg, (9) 90 μg, (10) 150 μg, (11) 300 μg, (12) 500 μg, (13) 800 μg, (14) 1400 μg, (15) 3200 μg, (16) 6800 μg, (17) 10 400 μg, (18) 15 800 μg as total added TATP after each addition, (a) 2.8–4.0 ppm region, (b) 7.5–8.7 ppm region.
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- 7To, K. C.; Ben-Jaber, S.; Parkin, I. P. Recent Developments in the Field of Explosive Trace Detection. ACS Nano 2020, 14, 10804– 10833, DOI: 10.1021/acsnano.0c015797Recent Developments in the Field of Explosive Trace DetectionTo, Ka Chuen; Ben-Jaber, Sultan; Parkin, Ivan P.ACS Nano (2020), 14 (9), 10804-10833CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)A review. Explosive trace detection (ETD) technologies play a vital role in maintaining national security. ETD remains an active research area with many anal. techniques in operational use. This review details the latest advances in animal olfactory, ion mobility spectrometry (IMS), and Raman and colorimetric detection methods. Developments in optical, biol., electrochem., mass, and thermal sensors are also covered in addn. to the use of nanomaterials technol. Com. available systems are presented as examples of current detection capabilities and as benchmarks for improvement. Attention is also drawn to recent collaborative projects involving government, academia, and industry to highlight the emergence of multimodal screening approaches and applications. The objective of the review is to provide a comprehensive overview of ETD by highlighting challenges in ETD and providing an understanding of the principles, advantages, and limitations of each technol. and relating this to current systems.
- 8Wasilewski, T.; Gębicki, J. Emerging Strategies for Enhancing Detection of Explosives by Artificial Olfaction. Microchem. J. 2021, 164, 106025 DOI: 10.1016/j.microc.2021.1060258Emerging strategies for enhancing detection of explosives by artificial olfactionWasilewski, Tomasz; Gebicki, JacekMicrochemical Journal (2021), 164 (), 106025CODEN: MICJAN; ISSN:0026-265X. (Elsevier B.V.)A review. Explosives detection systems need to be able to reliably detect a wide range of explosive materials and their vapors. The continued development and improvement of artificial olfaction techniques, including electronic nose (EN), remains important to overcome existing challenges and meet requirements posed by new improvements in the field of explosives. There is an increasingly popular trend aimed at improvement of fundamental metrol. parameters of sensors for the construction of sensor arrays for the detection of ultralow target analytes. Even after decades of developments, applications of artificial olfaction instruments aimed at selective and sensitive detection of trace quantities of explosives constitute still a difficult and challenging problem. Essential aspects of artificial olfaction were theor. discussed with an emphasis on evaluation of enhancing sensors parameters in the detection of explosives. Progress in nanotechnol. and prospects in mimicking biol. sense of smell successively remove the boundaries of artificial olfaction technologies. A tendency towards improved selectivity and specificity of the sensors is evident. Elaboration of novel sensing materials, data processing systems and sampling procedures are the main approaches to increase sensors major metrol. parameters. Implementation of designed construction solns. in practice and meeting particular requirements are still a bottleneck in the commercialization process. The demonstration of achievements in artificial olfaction technol. during the last couple of years is reviewed and different strategies to enhance their properties are suggested. Moreover, recent technol. advancement including bio-inspired strategies, robots, drones and smartphones were described. Finally, we discuss emerging approaches to solve problems accompanied with direct and discriminative detection of explosives and outline future perspectives related to this topic.
- 9Forbes, T. P.; Krauss, S. T.; Gillen, G. Trace Detection and Chemical Analysis of Homemade Fuel-Oxidizer Mixture Explosives: Emerging Challenges and Perspectives. TrAC, Trends Anal. Chem. 2020, 131, 116023 DOI: 10.1016/j.trac.2020.1160239Trace detection and chemical analysis of homemade fuel-oxidizer mixture explosives: Emerging challenges and perspectivesForbes, Thomas P.; Krauss, Shannon T.; Gillen, GregTrAC, Trends in Analytical Chemistry (2020), 131 (), 116023CODEN: TTAEDJ; ISSN:0165-9936. (Elsevier B.V.)The chem. anal. of homemade explosives (HMEs) and improvised explosive devices (IEDs) remains challenging for fieldable anal. instrumentation and sensors. Complex explosive fuel-oxidizer mixts., black and smokeless powders, flash powders, and pyrotechnics often include an array of potential org. and inorg. components that present unique interference and matrix effect difficulties. The widely varying physicochem. properties of these components as well as external environmental interferents and background challenge many sampling and sensing modalities. This review provides perspective on these emerging challenges, critically discusses developments in sampling, sensors, and instrumentation, and showcases advancements for the trace detection of inorg.-based explosives.
- 10Liu, R.; Li, Z.; Huang, Z.; Li, K.; Lv, Y. Biosensors for Explosives: State of Art and Future Trends. TrAC, Trends Anal. Chem. 2019, 118, 123– 137, DOI: 10.1016/j.trac.2019.05.03410Biosensors for explosives: State of art and future trendsLiu, Rui; Li, Ziyan; Huang, Zili; Li, Kun; Lv, YiTrAC, Trends in Analytical Chemistry (2019), 118 (), 123-137CODEN: TTAEDJ; ISSN:0165-9936. (Elsevier B.V.)A review. Explosives sensing is currently one of the most pressing and significant concerns in homeland security, antiterrorism, and environmental protection. Biosensors can often provide an outstanding specificity and sensitivity for explosives, utilizing biol. or bio-mimic recognition components such as antibodies, aptamers, and molecularly imprinted polymers. Despite intriguing properties and fast development, the biosensors-based explosive detection has not been reviewed in the past decade. Herein, the focus of this review is towards advances of biosensors of explosive, emphasizing quant. biosensors in the past ten years, with the readers being referred to earlier or other technique related reviews. The basics of explosives, the qual. biosensing (based on animals, electronic noses, and genetically engineered microorganisms), the quant. biosensing (based on antibody, peptide aptamer, and molecularly imprinted polymers), and future perspectives are discussed in detail.
- 11Apak, R.; Çekiç, S. D.; Uzer, A.; Çapanoglu, E.; Çelik, S. E.; Bener, M.; Can, Z.; Durmazel, S. Colorimetric Sensors and Nanoprobes for Characterizing Antioxidant and Energetic Substances. Anal. Methods 2020, 12, 5266– 5321, DOI: 10.1039/D0AY01521K11Colorimetric sensors and nanoprobes for characterizing antioxidant and energetic substancesApak, Resat; Cekic, Sema Demirci; Uzer, Aysem; Capanoglu, Esra; Celik, Saliha Esin; Bener, Mustafa; Can, Ziya; Durmazel, SelenAnalytical Methods (2020), 12 (44), 5266-5321CODEN: AMNEGX; ISSN:1759-9679. (Royal Society of Chemistry)A review. The development of anal. techniques for antioxidant compds. is important, because antioxidants that can inactivate reactive species and radicals are health-beneficial compds., also used in the preservation of food and protection of almost every kind of org. substance from oxidn. Energetic substances include explosives, pyrotechnics, propellants and fuels, and their detn. at bulk/trace levels is important for the safety and well-being of modern societies exposed to various security threats. Most of the time, in field/on site detection of these important analytes necessitates the use of colorimetric sensors and probes enabling naked-eye detection, or low-cost and easy-to-use fluorometric sensors. The use of nanosensors brings important advantages to this field of anal. chem. due to their various physico-chem. advantages of increased surface area, surface plasmon resonance absorption of noble metal nanoparticles, and superior enzyme-mimic catalytic properties. Thus, this crit. review focuses on the design strategies for colorimetric sensors and nanoprobes in characterizing antioxidant and energetic substances. In this regard, the main themes and properties in optical sensor design are defined and classified. Nanomaterial-based optical sensors/probes are discussed with respect to their mechanisms of operation, namely formation and growth of noble metal nanoparticles, their aggregation and disaggregation, displacement of active constituents by complexation or electrostatic interaction, misc. mechanisms, and the choice of metallic oxide nanoparticles taking part in such formulations.
- 12Ostrinskaya, A.; Kunz, R. R.; Clark, M.; Kingsborough, R. P.; Ong, T.-H.; Deneault, S. Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow-Injection Analysis Tandem Mass Spectrometry. J. Forensic Sci. 2019, 64, 223– 230, DOI: 10.1111/1556-4029.1382712Rapid Quantitative Analysis of Multiple Explosive Compound Classes on a Single Instrument via Flow-Injection Analysis Tandem Mass SpectrometryOstrinskaya, Alla; Kunz, Roderick R.; Clark, Michelle; Kingsborough, Richard P.; Ong, Ta-Hsuan; Deneault, SandraJournal of Forensic Sciences (2019), 64 (1), 223-230CODEN: JFSCAS; ISSN:0022-1198. (John Wiley & Sons, Inc.)A review. A flow-injection anal. tandem mass spectrometry (FIA MSMS) method was developed for rapid quant. anal. of 10 different inorg. and org. explosives. Performance is optimized by tailoring the ionization method (APCI/ESI), de-clustering potentials, and collision energies for each specific analyte. In doing so, a single instrument can be used to detect urea nitrate, potassium chlorate, 2,4,6-trinitrotoluene, 2,4,6-trinitrophenylmethylnitramine, triacetone triperoxide, hexamethylene triperoxide diamine, pentaerythritol tetranitrate, 1,3,5-trinitroperhydro-1,3,5-triazine, nitroglycerin, and octohy-dro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with sensitivities all in the picogram per mL range. In conclusion, FIA APCI/ESI MSMS is a fast (<1 min/sample), sensitive (∼pg/mL LOQ), and precise (intraday RSD < 10%) method for trace explosive detection that can play an important role in criminal and attributional forensics, counterterrorism, and environmental protection areas, and has the potential to augment or replace several of the existing explosive detection methods.
- 13Glackin, J. M. E.; Gillanders, R. N.; Eriksson, F.; Fjällgren, M.; Engblom, J.; Mohammed, S.; Samuel, I. D. W.; Turnbull, G. A. Explosives Detection by Swabbing for Improvised Explosive Devices. Analyst 2020, 145, 7956– 7963, DOI: 10.1039/D0AN01312A13Explosives detection by swabbing for improvised explosive devicesGlackin, James M. E.; Gillanders, Ross N.; Eriksson, Frans; Fjallgren, Marcus; Engblom, Joachim; Mohammed, Salam; Samuel, Ifor D. W.; Turnbull, Graham A.Analyst (Cambridge, United Kingdom) (2020), 145 (24), 7956-7963CODEN: ANALAO; ISSN:0003-2654. (Royal Society of Chemistry)Swabs taken from the surface of a suspicious object are a std. method of identifying a concealed explosive device in security-conscious locations like airports. In this paper a sensitive method is demonstrated to collect and detect trace explosive residues from improvised explosive devices using swabs and an optical sensor element. Swabs coated with a com. fluoropolymer are used to collect material and are subsequently heated to thermally desorb the explosives, causing the quenching of light emission from a thin film luminescent sensor. The sorption and desorption characteristics are reported of swabs loaded with 2,4-DNT tested with Super Yellow fluorescent sensors in a lab. setting, with detection that is up to three orders of magnitude more sensitive than std. colorimetric tests. The method was then applied in field tests with raw military-grade explosives TNT, PETN, and RDX, on various objects contg. the explosives, and post-blast craters. It is shown for the first time results using org. semiconductors to detect sub-milligram amts. of explosive sorbed onto a substrate from real explosives in the field, giving a promising new approach for IED detection.
- 14Ong, T.-H.; Mendum, T.; Geurtsen, G.; Kelley, J.; Ostrinskaya, A.; Kunz, R. Use of Mass Spectrometric Vapor Analysis to Improve Canine Explosive Detection Efficiency. Anal. Chem. 2017, 89, 6482– 6490, DOI: 10.1021/acs.analchem.7b0045114Use of Mass Spectrometric Vapor Analysis To Improve Canine Explosive Detection EfficiencyOng, Ta-Hsuan; Mendum, Ted; Geurtsen, Geoff; Kelley, Jude; Ostrinskaya, Alla; Kunz, RoderickAnalytical Chemistry (Washington, DC, United States) (2017), 89 (12), 6482-6490CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Canines remain the gold std. for explosives detection in many situations, and there is an ongoing desire for them to perform at the highest level. This goal requires canine training to be approached similarly to scientific sensor design. Developing a canine training regimen is made challenging by a lack of understanding of the canine's odor environment, which is dynamic and typically contains multiple odorants. Existing methodol. assumes that the handler's intention is an adequate surrogate for actual knowledge of the odors cuing the canine, but canines are easily exposed to unintentional explosive odors through training material cross-contamination. A sensitive, real-time (∼1 s) vapor anal. mass spectrometer was developed to provide tools, techniques, and knowledge to better understand, train, and utilize canines. The instrument has a detection library of nine explosives and explosive-related materials consisting of 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), pentaerythritol tetranitrate (PETN), triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), and cyclohexanone, with detection limits in the parts-per-trillion to parts-per-quadrillion range by vol. The instrument can illustrate aspects of vapor plume dynamics, such as detecting plume filaments at a distance. The instrument was deployed to support canine training in the field, detecting cross-contamination among training materials, and developing an evaluation method based on the odor environment. Support for training material prodn. and handling was provided by studying the dynamic headspace of a nonexplosive HMTD training aid that is in development. These results supported existing canine training and identified certain areas that may be improved.
- 15Li, Z.; Askim, J. R.; Suslick, K. S. The Optoelectronic Nose: Colorimetric and Fluorometric Sensor Arrays. Chem. Rev. 2019, 119, 231– 292, DOI: 10.1021/acs.chemrev.8b0022615The Optoelectronic Nose: Colorimetric and Fluorometric Sensor ArraysLi, Zheng; Askim, Jon R.; Suslick, Kenneth S.Chemical Reviews (Washington, DC, United States) (2019), 119 (1), 231-292CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. A comprehensive review on the development and state of the art of colorimetric and fluorometric sensor arrays is presented. Chem. sensing aims to detect subtle changes in the chem. environment by transforming relevant chem. or phys. properties of mol. or ionic species (i.e., analytes) into an anal. useful output. Optical arrays based on chemoresponsive colorants (dyes and nanoporous pigments) probe the chem. reactivity of analytes, rather than their phys. properties (e.g., mass). The chem. specificity of the olfactory system does not come from specific receptors for specific analytes (e.g., the traditional lock-and-key model of substrate-enzyme interactions), but rather olfaction makes use of pattern recognition of the combined response of several hundred olfactory receptors. In a similar fashion, arrays of chemoresponsive colorants provide high-dimensional data from the color or fluorescence changes of the dyes in these arrays as they are exposed to analytes. This provides chem. sensing with high sensitivity (often down to ppb levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixts. over a wide range of analyte types, in both the gas and liq. phases. Design of both sensor arrays and instrumentation for their anal. are discussed. In addn., the various chemometric and statistical analyses of high-dimensional data (including hierarchical cluster anal. (HCA), principal component anal. (PCA), linear discriminant anal. (LDA), support vector machines (SVMs), and artificial neural networks (ANNs)) are presented and critiqued in ref. to their use in chem. sensing. A variety of applications are also discussed, including personal dosimetry of toxic industrial chem., detection of explosives or accelerants, quality control of foods and beverages, biosensing intracellularly, identification of bacteria and fungi, and detection of cancer and disease biomarkers.
- 16Li, Z.; Suslick, K. S. The Optoelectronic Nose. Acc. Chem. Res. 2021, 54, 950– 960, DOI: 10.1021/acs.accounts.0c0067116The Optoelectronic NoseLi, Zheng; Suslick, Kenneth S.Accounts of Chemical Research (2021), 54 (4), 950-960CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Conspectus: How does one tell the difference between one mol. or mixt. of mols. from another. Chem. sensing seeks to probe phys. or chem. properties of mol. or ionic species (i.e., analytes) and transform that information into a useful and distinguishable output. The olfactory system of animals is the prototype of chem. sensing. Even for human beings (who are generally more visual than olfactory creatures), the sense of smell is one of our most basic capabilities, and we can discriminate among many thousands, and possibly even billions, of different odors. The chem. specificity of the olfactory system does not come from specific receptors for specific analytes (i.e., the traditional lock-and-key model of enzyme-substrate interactions), but rather olfaction uses pattern recognition of the combined responses of several hundred olfactory receptors. In analogy to olfaction, colorimetric sensor arrays provide high dimensional data from the color changes of chem. responsive colorants as they are exposed to analytes. These colorants include pH responsive dyes, Lewis acid/base indicators, redox dyes, vapochromics, and surface-modified silver nanoparticles. The color difference maps so created provide chem. sensing with high sensitivity (often down to ppb levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixts. over a wide range of analyte types, both in the gas and liq. phases. Such colorimetric arrays probe a wide range of the chem. reactivity of analytes, rather than the limited dimensionality of phys. properties (e.g., mass) or physisorption (e.g., traditional electronic noses). Our sensor arrays are disposable and simple to produce by either inkjet or robotic dip-pen printing onto the surface of porous polymer membranes or even paper. Design of both sensor arrays and optical readers for their anal. has advanced to a fully self-contained pocket-sized instrument, the optoelectronic nose. Quant. anal. requires appropriate chemometric methods for pattern recognition of data with inherently high dimensionality, e.g., hierarchical cluster anal. and support vector machines. A wide range of applications for the colorimetric sensor arrays has been developed, including personal dosimetry of toxic industrial chems., detection of explosives or fire accelerants, monitoring pollutants for artwork and cultural heritage preservation, quality control of foods and beverages, rapid identification of bacteria and fungi, and detection of disease biomarkers in breath or urine. The development of portable, high-accuracy instrumentation using std. imaging devices with the capability of onboard, real-time anal. has had substantial progress and increasingly meets the expectations for real-world use.
- 17Härtel, M. A. C.; Klapötke, T. M.; Stiasny, B.; Stierstorfer, J. Gas-phase Concentration of Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP). Propellants Explos. Pyrotech. 2017, 42, 623– 634, DOI: 10.1002/prep.201700034There is no corresponding record for this reference.
- 18Dubnikova, F.; Kosloff, R.; Almog, J.; Zeiri, Y.; Boese, R.; Itzhaky, H.; Alt, A.; Keinan, E. Decomposition of Triacetone Triperoxide Is an Entropic Explosion. J. Am. Chem. Soc. 2005, 127, 1146– 1159, DOI: 10.1021/ja046490318Decomposition of Triacetone Triperoxide Is an Entropic ExplosionDubnikova, Faina; Kosloff, Ronnie; Almog, Joseph; Zeiri, Yehuda; Boese, Roland; Itzhaky, Harel; Alt, Aaron; Keinan, EhudJournal of the American Chemical Society (2005), 127 (4), 1146-1159CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Both X-ray crystallog. and electronic structure calcns. using the cc-pVDZ basis set at the DFT B3LYP level were employed to study the explosive properties of triacetone triperoxide (TATP) and diacetone diperoxide (DADP). The thermal decompn. pathway of TATP was investigated by a series of calcns. that identified transition states, intermediates, and the final products. Counterintuitively, these calcns. predict that the explosion of TATP is not a thermochem. highly favored event. It rather involves entropy burst, which is the result of formation of one ozone and three acetone mols. from every mol. of TATP in the solid state.
- 19Romero, D. C.; Calvo-Gredilla, P.; García-Calvo, J.; Diez-Varga, A.; Cuevas, J. V.; Revilla-Cuesta, A.; Busto, N.; Abajo, I.; Aullón, G.; Torroba, T. Self-Assembly Hydrosoluble Coronenes: A Rich Source of Supramolecular Turn-On Fluorogenic Sensing Materials in Aqueous Media. Org. Lett. 2021, 23, 8727– 8732, DOI: 10.1021/acs.orglett.1c0317519Self-Assembly Hydrosoluble Coronenes: A Rich Source of Supramolecular Turn-On Fluorogenic Sensing Materials in Aqueous MediaRomero, Daisy C.; Calvo-Gredilla, Patricia; Garcia-Calvo, Jose; Diez-Varga, Alberto; Cuevas, Jose Vicente; Revilla-Cuesta, Andrea; Busto, Natalia; Abajo, Irene; Aullon, Gabriel; Torroba, TomasOrganic Letters (2021), 23 (22), 8727-8732CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)Water-sol. coronenes, that form nanoparticles by self-assocn., work as new fluorescent materials by complexation with cucurbit[7]uril, as well as selective turn-on fluorogenic sensors for nitroarom. explosives with remarkable selectivity, by using only water as solvent.
- 20Wan, W.-M.; Tian, D.; Jing, Y.-N.; Zhang, X.-Y.; Wu, W.; Ren, H.; Bao, H.-L. NBN-Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives. Angew. Chem., Int. Ed. 2018, 57, 15510– 15516, DOI: 10.1002/anie.20180984420NBN-Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of ExplosivesWan, Wen-Ming; Tian, Di; Jing, Ya-Nan; Zhang, Xiao-Yun; Wu, Wei; Ren, Hao; Bao, Hong-LiAngewandte Chemie, International Edition (2018), 57 (47), 15510-15516CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A simple and efficient synthesis of NBN-doped conjugated polycyclic arom. hydrocarbons (such as diazaborinines) has been accomplished by a catalyst-free intermol. dehydration reaction at room temp. between boronic acid and diamine moieties with yields up to 99 %. Polycyclic arom. hydrocarbons with a six-membered NBN ring are a new class of aggregation-induced emissive luminogens. Extremely sensitive detection of ppb levels of TNT by Ph naphthodiazaborinine is straightforward. Visual detection of TNT is illustrated by fabrication of TNT test strips, which can detect as little as 100 ng of TNT powder. This simple and sensitive detection of TNT has potential applications in the area of public safety and security against terrorist activities.
- 21Kim, S.; Kim, H.; Qiao, T.; Cha, C.; Lee, S. K.; Lee, K.; Ro, H. J.; Kim, Y.; Lee, W.; Lee, H. Fluorescence Enhancement from Nitro-Compound-Sensitive Bacteria within Spherical Hydrogel Scaffolds. ACS Appl. Mater. Interfaces 2019, 11, 14354– 14361, DOI: 10.1021/acsami.9b0226221Fluorescence Enhancement from Nitro-Compound-Sensitive Bacteria within Spherical Hydrogel ScaffoldsKim, Soohyun; Kim, Hyunji; Qiao, Tian; Cha, Chaenyung; Lee, Sung Kuk; Lee, Kangseok; Ro, Hyun Ji; Kim, Youngkyun; Lee, Wonmok; Lee, HyunjungACS Applied Materials & Interfaces (2019), 11 (15), 14354-14361CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)For the safety of both prodn. and life, it is a very significant issue to detect explosive nitro-compds. in a remote way or over a long distance. Here, we report that nitro-compds. were detected by the bacterial sensor based on hydrogel micro-beads as a platform. A green fluorescent protein(GFP)-producing Escherichia coli which was genetically engineered in order to be sensitive to nitro-compds. was loaded within poly(2-hydroxyethyl methacrylate) (poly(HEMA)) based hydrogel beads, in which fluorescent signals from bacteria were concd. and strong enough to be easily detected. For efficient loading of neg. charged bacteria, a surface charge of poly(HEMA) based beads was controlled by copolymn. with 2-(methacryloyloxy) Et trimethylammonium chloride (MAETC) as a cationic monomer. With the addn. of MAETC, the cell affinity was nine times enhanced by an interaction between the pos. charged poly(HEMA-co-MAETC) beads and neg. charged bacteria. These increased cell affinity resulted in an enhancement of a sensing signal. After exposure to 2,4,6-trinitrotoluene (TNT), typical explosive nitro-compds., the fluorescence intensity of bacteria sensors using poly(HEMA-co MAETC) bead having 80 wt% of MAETC was five times increased compared to those based on poly(HEMA) beads. This amplification of the fluorescent signal enables easier detection of explosives efficiently by a remote detection, even over a long distance.
- 22Zhang, Z.; Chen, S.; Shi, R.; Ji, J.; Wang, D.; Jin, S.; Han, T.; Zhou, C.; Shu, Q. A Single Molecular Fluorescent Probe for Selective and Sensitive Detection of Nitroaromatic Explosives: A New Strategy for The Mask-Free Discrimination of TNT and TNP Within Same Sample. Talanta 2017, 166, 228– 233, DOI: 10.1016/j.talanta.2017.01.04622A single molecular fluorescent probe for selective and sensitive detection of nitroaromatic explosives: A new strategy for the mask-free discrimination of TNT and TNP within same sampleZhang, Zhe; Chen, Shusen; Shi, Rui; Ji, Jiawen; Wang, Dequan; Jin, Shaohua; Han, Tongyu; Zhou, Chenxiao; Shu, QinghaiTalanta (2017), 166 (), 228-233CODEN: TLNTA2; ISSN:0039-9140. (Elsevier B.V.)A simple naphthalene based fluorescent probe was first time reported as dual sensing of 2,4,6-trinitrotolune (TNT) and 2,4,6-trinitrophenol (TNP) by distinguishable changes in both soln. color change and fluorescence within same sample without any mask agent. Upon addn. of TNT and TNP, the strong emission quenching at 412 nm and a new emission band at 530 nm was obsd., resp. In addn., the sensing mechanism was evaluated by DFT calcns. by Gaussian 09 software.
- 23Tripathi, N.; Kumar, R.; Singh, P.; Kumar, S. Ratiometric Fluorescence “Turn On” Probe for Fast and Selective Detection of TNT in Solution, Solid and Vapour. Sens. Actuators, B 2017, 246, 1001– 1010, DOI: 10.1016/j.snb.2017.02.17423Ratiometric fluorescence "Turn On" probe for fast and selective detection of TNT in solution, solid and vapourTripathi, Neetu; Kumar, Rahul; Singh, Prabhpreet; Kumar, SubodhSensors and Actuators, B: Chemical (2017), 246 (), 1001-1010CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)A review. Fluorescent probe UREA-TP undergoes nearly 600% increase in emission intensity at 310 nm on addn. of 1 equiv of TNT, but the emission band centered at 440 nm remains unchanged. UREA-TP acts as a ratiometric fluorescence "turn-on" probe and can detect TNT between 10-9 to 10-5 M with limit of detection as low as 100 pM. Paper strips coated with UREA-TP on interaction with TNT become fluorescent purple under 365 nm light and can det. both qual. and quant. as low as 10μl soln. of 10-13 M TNT, which accounts for 2.27 × 10-16 g cm-2 TNT, significantly lower than the TNT concn. allowed in drinking water by EPA. The common nitroarom. derivs. 2,4-DNT, 2,6-DNT, picric acid and 2,4-DNP, the pain killers, food supplements and inorg. anions show insignificant interference in the detn. of TNT using UREA-TP. The aggregate size detn. using dynamic light scattering anal. and morphol. studies using TEM investigations reveals that UREA-TP in H2O-DMSO (98:2) remains in aggregate state with av. size of 200 nm, which undergo further aggregation to larger size aggregates with increasing amts. of TNT.
- 24Colizza, K.; Yevdokimov, A.; McLennan, L.; Smith, J. L.; Oxley, J. C. Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2018, 29, 675– 684, DOI: 10.1007/s13361-017-1879-524Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass SpectrometryColizza, Kevin; Yevdokimov, Alexander; McLennan, Lindsay; Smith, James L.; Oxley, Jimmie C.Journal of the American Society for Mass Spectrometry (2018), 29 (4), 675-684CODEN: JAMSEF; ISSN:1044-0305. (Springer)The authors' efforts to lower the detection limits of hexamethylene triperoxide diamine (HMTD) have uncovered previously unreported gas-phase reactions of primary and secondary amines with one of the six methylene carbons. The reaction occurs primarily in the atm. pressure chem. ionization (APCI) source and is similar to the behavior of alcs. with HMTD [1]. However, unlike alcs., the amine reaction conserves the hydrogen peroxide on the intact product. Furthermore, with or without amines, HMTD is oxidized to tetramethylene diperoxide diamine dialdehyde (TMDDD) in a temp.-dependent fashion in the APCI source. Synthesized TMDDD forms very strong adducts (not products) to ammonium and amine ions in the electrospray ionization (ESI) source. Attempts to improve HMTD detection by generating TMDDD in the APCI source with post-column addn. of amines were not successful. Signal intensity of the solvent related HMTD product in methanol, [HMTD+MeOH2-H2O2]+ (m/z 207.0975), was understandably related to the amt. of methanol in the HMTD environment as it elutes into the source. With conditions optimized for this product, the detection of 100 pg on column was accomplished with a robust anal. of 300 pg (1.44 pmol) routinely performed on the Orbitrap mass spectrometers.
- 25Mäkinen, M.; Nousiainen, M.; Sillanpaa, M. Ion Spectrometric Detection Technologies for Ultra-Traces of Explosives: A Review. Mass Spectrom. Rev. 2011, 30, 940– 973, DOI: 10.1002/mas.2030825Ion spectrometric detection technologies for ultra-traces of explosives: a reviewMakinen Marko; Nousiainen Marjaana; Sillanpaa MikaMass spectrometry reviews (2011), 30 (5), 940-73 ISSN:.In recent years, explosive materials have been widely employed for various military applications and civilian conflicts; their use for hostile purposes has increased considerably. The detection of different kind of explosive agents has become crucially important for protection of human lives, infrastructures, and properties. Moreover, both the environmental aspects such as the risk of soil and water contamination and health risks related to the release of explosive particles need to be taken into account. For these reasons, there is a growing need to develop analyzing methods which are faster and more sensitive for detecting explosives. The detection techniques of the explosive materials should ideally serve fast real-time analysis in high accuracy and resolution from a minimal quantity of explosive without involving complicated sample preparation. The performance of the in-field analysis of extremely hazardous material has to be user-friendly and safe for operators. The two closely related ion spectrometric methods used in explosive analyses include mass spectrometry (MS) and ion mobility spectrometry (IMS). The four requirements-speed, selectivity, sensitivity, and sampling-are fulfilled with both of these methods.
- 26Jiang, D.; Peng, L.; Wen, M.; Zhou, Q.; Chen, C.; Wang, X.; Chen, W.; Li, H. Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex Matrices. Anal. Chem. 2016, 88, 4391– 4399, DOI: 10.1021/acs.analchem.5b0483026Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex MatricesJiang, Dandan; Peng, Liying; Wen, Meng; Zhou, Qinghua; Chen, Chuang; Wang, Xin; Chen, Wendong; Li, HaiyangAnalytical Chemistry (Washington, DC, United States) (2016), 88 (8), 4391-4399CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Peroxide explosives, such as triacetone triperoxide (TATP) and hexamethylene trioxide diamine (HMTD), were often used in the terrorist attacks due to their easy synthesis from readily starting materials. Therefore, an on-site detection method for TATP and HMTD is urgently needed. Herein, we developed a stand-alone dopant-assisted pos. photoionization ion mobility spectrometry (DAPP-IMS) coupled with time-resolved thermal desorption introduction for rapid and sensitive detection of TATP and HMTD in complex matrixes, such as white solids, soft drinks, and cosmetics. Acetone was chosen as the optimal dopant for better sepn. between reactant ion peaks and product ion peaks as well as higher sensitivity, and the limits of detection (LODs) of TATP and HMTD std. samples were 23.3 and 0.2 ng, resp. Explosives on the sampling swab were thermally desorbed and carried into the ionization region dynamically within 10 s, and the max. released concn. of TATP or HMTD could be time-resolved from the matrix interference owing to the different volatility. Furthermore, with the combination of the fast response thermal desorber (within 0.8 s) and the quick data acquisition software to DAPP-IMS, two-dimensional data related to drift time (TATP: 6.98 ms, K0 = 2.05 cm2 V-1 s-1; HMTD: 9.36 ms, K0 = 1.53 cm2 V-1 s-1) and desorption time was obtained for TATP and HMTD, which is beneficial for their identification in complex matrixes.
- 27Correa, D. N.; Melendez-Perez, J. J.; Zacca, J. J.; Borges, R.; Schmidt, E. M.; Eberlin, M. N.; Meurer, E. C. Direct Detection of Triacetone Triperoxide (TATP) in Real Banknotes from ATM Explosion by EASI-MS. Propellants Explos. Pyrotech. 2017, 42, 370– 375, DOI: 10.1002/prep.201600046There is no corresponding record for this reference.
- 28Hagenhoff, S.; Franzke, J.; Hayen, H. Determination of Peroxide Explosive TATP and Related Compounds by Dielectric Barrier Discharge Ionization-Mass Spectrometry (DBDI-MS). Anal. Chem. 2017, 89, 4210– 4215, DOI: 10.1021/acs.analchem.7b0023328Determination of Peroxide Explosive TATP and Related Compounds by Dielectric Barrier Discharge Ionization-Mass Spectrometry (DBDI-MS)Hagenhoff, Sebastian; Franzke, Joachim; Hayen, HeikoAnalytical Chemistry (Washington, DC, United States) (2017), 89 (7), 4210-4215CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Dielec. barrier discharge ionization-mass spectrometry (DBDI-MS), which is based on the use of a low temp. helium plasma as ionization source, is used for the detn. of trace amts. of triacetone triperoxide (TATP) and its homolog diacetone diperoxide (DADP) from surfaces. TATP is obsd. as [M+NH4]+ adduct, whereas DADP is obsd. as [M+O+NH4]+. Measurement of DADP with varying deuteration degrees (DADP, DADP-d6, and DADP-d12) indicates that DADP undergoes oxidn. when ionized by DBDI. If acetonitrile is used as deposition solvent, TATP tends to show fragmentation and is not only detected as [M+NH4]+ but as [M-CH4+NH4]+ and [M-C2H4+NH4]+ as well. Quantification of TATP solns. from glass surfaces by DBDI-MS, using TATP-3,6,9-13C as internal std., was done and validated using an LC/APCI-MS method. Achievable limits of detection (LOD) for TATP are equiv. to the deposition of 15 ng TATP and are comparable with other ambient desorption/ionization mass spectrometric techniques like desorption electrospray ionization (DESI).
- 29Tang, S.; Vinerot, N.; Fisher, D.; Bulatov, V.; Yavetz-Chen, Y.; Schechter, I. Detection and Mapping of Trace Explosives on Surfaces Under Ambient Conditions Using Multiphoton Electron Extraction Spectroscopy (MEES). Talanta 2016, 155, 235– 244, DOI: 10.1016/j.talanta.2016.04.02729Detection and mapping of trace explosives on surfaces under ambient conditions using multiphoton electron extraction spectroscopy (MEES)Tang, Shisong; Vinerot, Nataly; Fisher, Danny; Bulatov, Valery; Yavetz-Chen, Yehuda; Schechter, IsraelTalanta (2016), 155 (), 235-244CODEN: TLNTA2; ISSN:0039-9140. (Elsevier B.V.)Multiphoton electron extn. spectroscopy (MEES) is an anal. method in which UV laser pulses are utilized for extg. electrons from solid surfaces in multiphoton processes under ambient conditions. Counting the emitted electrons as a function of laser wavelength results in detailed spectral features, which can be used for material identification. The method has been applied to detection of trace explosives on a variety of surfaces. Detection was possible on dusty swabs spiked with explosives and also in the std. dry-transfer contamination procedure. Plastic explosives could also be detected. The anal. limits of detection (LODs) are in the sub pmole range, which indicates that MEES is one of the most sensitive detection methods for solid surface under ambient conditions. Scanning the surface with the laser allows for its imaging, such that explosives (as well as other materials) can be located. The imaging mode is also useful in forensic applications, such as detection of explosives in human fingerprints.
- 30Lichtenstein, A.; Havivi, E.; Shacham, R.; Hahamy, E.; Leibovich, R.; Pevzner, A.; Krivitsky, V.; Davivi, G.; Presman, I.; Elnathan, R.; Engel, Y.; Flaxer, E.; Patolsky, F. Supersensitive Fingerprinting of Explosives by Chemically Modified Nanosensors Arrays. Nat. Commun. 2014, 5, 4195 DOI: 10.1038/ncomms519530Supersensitive fingerprinting of explosives by chemically modified nanosensors arraysLichtenstein, Amir; Havivi, Ehud; Shacham, Ronen; Hahamy, Ehud; Leibovich, Ronit; Pevzner, Alexander; Krivitsky, Vadim; Davivi, Guy; Presman, Igor; Elnathan, Roey; Engel, Yoni; Flaxer, Eli; Patolsky, FernandoNature Communications (2014), 5 (), 4195CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)The capability to detect traces of explosives sensitively, selectively and rapidly could be of great benefit for applications relating to civilian national security and military needs. Here, we show that, when chem. modified in a multiplexed mode, nanoelec. devices arrays enable the supersensitive discriminative detection of explosive species. The fingerprinting of explosives is achieved by pattern recognizing the inherent kinetics, and thermodn., of interaction between the chem. modified nanosensors array and the mol. analytes under test. This platform allows for the rapid detection of explosives, from air collected samples, down to the parts-per-quadrillion concn. range, and represents the first nanotechnol.-inspired demonstration on the selective supersensitive detection of explosives, including the nitro- and peroxide-derivs., on a single electronic platform. Furthermore, the ultrahigh sensitivity displayed by our platform may allow the remote detection of various explosives, a task unachieved by existing detection technologies.
- 31Lin, H.; Suslick, K. S. A Colorimetric Sensor Array for Detection of Triacetone Triperoxide Vapor. J. Am. Chem. Soc. 2010, 132, 15519– 15521, DOI: 10.1021/ja107419t31A Colorimetric Sensor Array for Detection of Triacetone Triperoxide VaporLin, Hengwei; Suslick, Kenneth S.Journal of the American Chemical Society (2010), 132 (44), 15519-15521CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Triacetone triperoxide (TATP), one of the most dangerous primary explosives, has emerged as an explosive of choice for terrorists in recent years. Owing to the lack of UV absorbance, fluorescence, or facile ionization, TATP is extremely difficult to detect directly. Techniques that are able to detect generally require expensive instrumentation, need extensive sample prepn., or cannot detect TATP in the gas phase. Here we report a simple and highly sensitive colorimetric sensor for the detection of TATP vapor with semiquant. anal. from 50 ppb to 10 ppm. By using a solid acid catalyst to pretreat a gas stream, we have discovered that a colorimetric sensor array of redox sensitive dyes can detect even very low levels of TATP vapor from its acid decompn. products (e.g., H2O2) with limits of detection (LOD) below 2 ppb (i.e., <0.02% of its satn. vapor pressure). Common potential interferences (e.g., humidity, personal hygiene products, perfume, laundry supplies, volatile org. compds., etc.) do not generate an array response, and the array can also differentiate TATP from other chem. oxidants (e.g., hydrogen peroxide, bleach, tert-butylhydroperoxide, peracetic acid).
- 32Li, Z.; Bassett, W. P.; Askim, J. R.; Suslick, K. S. Differentiation Among Peroxide Explosives with an Optoelectronic Nose. Chem. Commun. 2015, 51, 15312– 15315, DOI: 10.1039/C5CC06221G32Differentiation among peroxide explosives with an optoelectronic noseLi, Zheng; Bassett, Will P.; Askim, Jon R.; Suslick, Kenneth S.Chemical Communications (Cambridge, United Kingdom) (2015), 51 (83), 15312-15315CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)Forensic identification of batches of homemade explosives (HME) poses a difficult anal. challenge. Differentiation among peroxide explosives is reported herein using a colorimetric sensor array and handheld scanner with a field-appropriate sampling protocol. Clear discrimination was demonstrated among twelve peroxide samples prepd. from different reagents, with a classification accuracy > 98%.
- 33Askim, J. R.; Li, Z.; LaGasse, M. K.; Rankin, J. M.; Suslick, K. S. An Optoelectronic Nose for Identification of Explosives. Chem. Sci. 2016, 7, 199– 206, DOI: 10.1039/C5SC02632F33An optoelectronic nose for identification of explosivesAskim, Jon R.; Li, Zheng; La Gasse, Maria K.; Rankin, Jaqueline M.; Suslick, Kenneth S.Chemical Science (2016), 7 (1), 199-206CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)Compact and portable methods for identification of explosives are increasingly needed for both civilian and military applications. A portable optoelectronic nose for the gas-phase identification of explosive materials is described that uses a highly cross-reactive colorimetric sensor array and a handheld scanner. The array probes a wide range of chem. reactivities using 40 chem. responsive colorimetric indicators, including pH sensors, metal-dye salts, redox-sensitive chromogenic compds., solvatochromic dyes, and other chromogenic indicators. Sixteen sep. analytes including common explosives, homemade explosives, and characteristic explosive components were differentiated into fourteen sep. classes with a classification error rate of <1%. Portable colorimetric array sensing could represent an important, complementary part of the toolbox used in practical applications of explosives detection and identification.
- 34Xu, M.; Han, J.-M.; Wang, C.; Yang, X.; Pei, J.; Zang, L. Fluorescence Ratiometric Sensor for Trace Vapor Detection of Hydrogen Peroxide. ACS Appl. Mater. Interfaces 2014, 6, 8708– 8714, DOI: 10.1021/am501502v34Fluorescence Ratiometric Sensor for Trace Vapor Detection of Hydrogen PeroxideXu, Miao; Han, Ji-Min; Wang, Chen; Yang, Xiaomei; Pei, Jian; Zang, LingACS Applied Materials & Interfaces (2014), 6 (11), 8708-8714CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Trace vapor detection of hydrogen peroxide (H2O2) represents a practical approach to nondestructive detection of peroxide-based explosives, including liq. mixts. of H2O2 and fuels and energetic peroxide derivs., such as triacetone triperoxide (TATP), diacetone diperoxide (DADP), and hexamethylene triperoxide diamine (HMTD). Development of a simple chem. sensor system that responds to H2O2 vapor with high reliability and sufficient sensitivity (reactivity) remains a challenge. We report a fluorescence ratiometric sensor mol., di-Et 2,5-bis((((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)carbonyl)amino)terephthalate (DAT-B), for H2O2 that can be fabricated into an expedient, reliable, and sensitive sensor system suitable for trace vapor detection of H2O2. DAT-B is fluorescent in the blue region, with an emission max. at 500 nm in the solid state. Upon reaction with H2O2, DAT-B is converted to an electronic "push-pull" structure, di-Et 2,5-diaminoterephthalate (DAT-N), which has an emission peak at a longer wavelength centered at 574 nm. Such H2O2-mediated oxidn. of aryl boronates can be accelerated through the addn. of an org. base such as tetrabutylammonium hydroxide (TBAH), resulting in a response time of less than 0.5 s under 1 ppm of H2O2 vapor. The strong overlap between the absorption band of DAT-N and the emission band of DAT-B enables efficient Forster resonance energy transfer (FRET), thus allowing further enhancement of the sensing efficiency of H2O2 vapor. The detection limit of a drop-cast DAT-B/TBAH film was projected to be 7.7 ppb. By combining high sensitivity and selectivity, the reported sensor system may find broad application in vapor detection of peroxide-based explosives and relevant chem. reagents through its fabrication into easy-to-use, cost-effective kits.
- 35Zhu, Q.-H.; Zhang, G.-H.; Yuan, W.-L.; Wang, S.-L.; He, L.; Yong, F.; Tao, G.-H. Handy Fluorescent Paper Device Based on a Curcumin Derivative for Ultrafast Detection of Peroxide-Based Explosives. Chem. Commun. 2019, 55, 13661– 13664, DOI: 10.1039/C9CC06737J35Handy fluorescent paper device based on a curcumin derivative for ultrafast detection of peroxide-based explosivesZhu, Qiu-Hong; Zhang, Guo-Hao; Yuan, Wen-Li; Wang, Shuang-Long; He, Ling; Yong, Fang; Tao, Guo-HongChemical Communications (Cambridge, United Kingdom) (2019), 55 (91), 13661-13664CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)A handy, simple and inexpensive paper device is reported for extremely sensitive detection of peroxide-based explosives. The sensing device fabricated using a curcumin deriv. was capable of ultrafast sensing of triacetone triperoxide. The detection time was < 5 s. Moreover, the sensor retained full function under storage at ambient temp. for at least 120 days.
- 36Yu, X.; Gong, Y.; Xiong, W.; Li, M.; Zhao, J.; Che, Y. Turn-on Fluorescent Detection of Hydrogen Peroxide and Triacetone Triperoxide via Enhancing Interfacial Interactions of a Blended System. Anal. Chem. 2019, 91, 6967– 6970, DOI: 10.1021/acs.analchem.9b0125536Turn-on Fluorescent Detection of Hydrogen Peroxide and Triacetone Triperoxide via Enhancing Interfacial Interactions of a Blended SystemYu, Xinting; Gong, Yanjun; Xiong, Wei; Li, Mei; Zhao, Jincai; Che, YankeAnalytical Chemistry (Washington, DC, United States) (2019), 91 (11), 6967-6970CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)In this work, we report the fabrication of a blend consisting of fluorescent 1 nanofibers and amberlyst-15 particles as a turn-on fluorescence sensor for trace TATP vapors. Fluorescence imaging and lifetime anal. reveal that the interface between 1 nanofibers and amberlyst-15 particles exhibits stronger photoluminescence than the unblended areas because of the formed strong hydrogen bonding between. Furthermore, the interfacial adhesion between 1 nanofibers and amberlyst-15 particles can be amplified by H2O2, which in turn gives rise to rapid and remarkable fluorescence enhancement. When exposed to TATP vapors, the amberlyst-15 component can rapidly decomp. TATP into H2O2 that gives sensitive fluorescence enhancement responses of the blend. On the basis of this detection mechanism, fluorescence detection of TATP with rapid response (ca. 5 s) and high sensitivity (ca. 0.1 ppm) is achieved. Here, the resulting blend combines the pretreatment of TATP and detection responses and thereby simplifies the sensor fabrication for the practical application.
- 37Qi, Y.; Xu, W.; Ding, N.; Chang, X.; Shang, C.; Peng, H.; Liu, T.; Fang, Y. A Film-Based Fluorescent Device for Vapor Phase Detection of Acetone and Related Peroxide Explosives. Mater. Chem. Front. 2019, 3, 1218– 1224, DOI: 10.1039/C9QM00095J37A film-based fluorescent device for vapor phase detection of acetone and related peroxide explosivesQi, Yanyu; Xu, Wenjun; Ding, Nannan; Chang, Xingmao; Shang, Congdi; Peng, Haonan; Liu, Taihong; Fang, YuMaterials Chemistry Frontiers (2019), 3 (6), 1218-1224CODEN: MCFAC5; ISSN:2052-1537. (Royal Society of Chemistry)On site, sensitive and selective detection of acetone vapor at room temp. is of great importance for health, and in particular for in air detection of triacetone triperoxide (TATP) and diacetone diperoxide (DADP), two improvised explosives commonly used by terrorists in suicide attacks. This paper reports a relevant high-performance film-based fluorescent device, where a newly synthesized perylene monoimide modified non-planar organoboron deriv. (PMI-BQ) was adopted as the sensing fluorophore. The performance of the device is excellent as evidenced by less than 2 s response time, no more than 10 s recovery time, nearly perfect reversibility, and lower than 50 ppm exptl. detection limit (DL) for acetone. In addn., the presence of potential interferences showed little effect upon the sensing. Notably, more than 30 days sensing tests showed no observable degrdn. in the performance of the film device. Further tests revealed that the film-based device can be further used for the detection of TATP and DADP. The exptl. DLs for the two explosives are lower than 30 and 50 μg, resp. The superior performance of the device was ascribed to the non-planar structure of the sensing fluorophore as it may produce micro-channels in the film. Meanwhile, solvation may also play a crucial role in the process. We believe our contribution not only realizes reversible fluorescence sensing of acetone vapor and the related explosives, but also demonstrates that the combination of solvent effect and non-planar structure could be an effective way to develop high performance fluorescent sensing films.
- 38An, Y.; Xu, X.; Liu, K.; An, X.; Shang, C.; Wang, G.; Liu, T.; Li, H.; Peng, H.; Fang, Y. Fast, Sensitive, Selective and Reversible Fluorescence Monitoring of TATP in a Vapor Phase. Chem. Commun. 2019, 55, 941– 944, DOI: 10.1039/C8CC08399A38Fast, sensitive, selective and reversible fluorescence monitoring of TATP in a vapor phaseAn, Yanqin; Xu, Xiaojie; Liu, Ke; An, Xuan; Shang, Congdi; Wang, Gang; Liu, Taihong; Li, Hong; Peng, Haonan; Fang, YuChemical Communications (Cambridge, United Kingdom) (2019), 55 (7), 941-944CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)The development of sensors for the detection of triacetone triperoxide (TATP) has attracted great attention. Here, we constructed a low-cost, portable, reusable, visible paper-based fluorescent sensor for the sensitive detection of TATP via vapor sampling. Under optimized conditions, the fluorescent film showed a high sensitivity to TATP with a detection limit of lower than 0.5μg mL-1 in air. The linear range of the response is from 0.5 to 8.0μg mL-1. In addn., the paper-based sensor exhibited high selectivity to TATP. The presence of potential interferents showed little effect on sensing. Moreover, sensing is fully reversible. Fortunately, the test can also be conducted in a visualized way.
- 39Rao, M. R.; Fang, Y.; De Feyter, S.; Perepichka, D. F. Conjugated Covalent Organic Frameworks via Michael Addition–Elimination. J. Am. Chem. Soc. 2017, 139, 2421– 2427, DOI: 10.1021/jacs.6b1200539Conjugated Covalent Organic Frameworks via Michael Addition-EliminationRao, M. Rajeswara; Fang, Yuan; De Feyter, Steven; Perepichka, Dmitrii F.Journal of the American Chemical Society (2017), 139 (6), 2421-2427CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Dynamic covalent chem. enables self-assembly of reactive building blocks into structurally complex yet robust materials, such as Covalent Org. Frameworks (COFs). However, the synthetic toolbox used to prep. such materials, and thus the spectrum of attainable properties, is limited. For π-conjugated COFs, the Schiff base condensation of aldehydes and amines is the only general dynamic reaction, but the resulting imine-linked COFs display only a moderate electron delocalization and are susceptible to hydrolysis, particularly in acidic conditions. Here we report a new dynamic polymn. based on Michael addn.-elimination reaction of structurally diverse β-ketoenols with amines, and use it to prep. novel two dimensional (2D) π-conjugated COFs, as cryst. powders and exfoliated micron-size sheets. π-Conjugation is manifested in these COFs in significantly reduced band gap (1.8-2.2 eV), solid state luminescence and reversible electrochem. doping creating mid-gap (NIR absorbing) polaronic states. The β-ketoenamine moiety enables protonation control of electron delocalization through the 2D COF sheets. It also gives rise to direct sensing of triacetone triperoxide (TATP) explosive through fluorescence quenching.
- 40Liu, K.; Wang, Z.; Shang, C.; Li, X.; Peng, H.; Miao, R.; Ding, L.; Liu, J.; Liu, T.; Fang, Y. Unambiguous Discrimination and Detection of Controlled Chemical Vapors by a Film-Based Fluorescent Sensor Array. Adv. Mater. Technol. 2019, 4, 1800644 DOI: 10.1002/admt.20180064440Unambiguous Discrimination and Detection of Controlled Chemical Vapors by a Film-Based Fluorescent Sensor ArrayLiu, Ke; Wang, Zhaolong; Shang, Congdi; Li, Xiao; Peng, Haonan; Miao, Rong; Ding, Liping; Liu, Jing; Liu, Taihong; Fang, YuAdvanced Materials Technologies (Weinheim, Germany) (2019), 4 (7), 1800644CODEN: AMTDCM; ISSN:2365-709X. (Wiley-VCH Verlag GmbH & Co. KGaA)In situ, online, fast, and sensitive detection and discrimination of explosives, illicit drugs, and volatile org. compds. via vapor sampling is a challenge for many years. The highly efficient and noncontact detection of 15 types of chems. mentioned above using a film-based fluorescent sensor array is reported herein. Importantly, the presence of water, toiletries, fruit, dirty clothes, and other interferences has little effect upon detection. Discrimination of the controlled chems. is realized using a pattern recognition strategy. Meanwhile, a conceptual detector based on a sensor array is constructed and successfully used for simulated field tests. It is strongly believed that the present work not only provides a powerful fluorescent technique for efficient detection and discrimination of controlled chems. with remarkably different properties but also demonstrates that arraying a single sensor is a promising strategy to mitigate the limitations of conventional film-based fluorescent sensors.
- 41OSAC. Analysis of Explosives Reference List, 2020. https://www.nist.gov/topics/organization-scientific-area-committees-forensic-science/fire-debris-explosives-subcommittee (accessed May 20, 2022).There is no corresponding record for this reference.
- 42EU-SENSE. Characteristics of Improvised Explosive Devices Containing Chemical Substances in the Context of the International Airports Protection, 2021. https://eu-sense.eu/characteristics-of-improvised-explosive-devices-containing-chemical-substances-in-the-context-of-the-international-airports-protection/ (accessed May 20, 2022).There is no corresponding record for this reference.
- 43González-Calabuig, A.; Cetó, X.; del Valle, M. Electronic Tongue for Nitro and Peroxide Explosive Sensing. Talanta 2016, 153, 340– 346, DOI: 10.1016/j.talanta.2016.03.00943Electronic tongue for nitro and peroxide explosive sensingGonzalez-Calabuig, Andreu; Ceto, Xavier; del Valle, ManelTalanta (2016), 153 (), 340-346CODEN: TLNTA2; ISSN:0039-9140. (Elsevier B.V.)This work reports the application of a voltammetric electronic tongue (ET) towards the simultaneous detn. of both nitro-contg. and peroxide-based explosive compds., two families that represent the vast majority of compds. employed either in com. mixts. or in improvised explosive devices. The multielectrode array was formed by graphite, gold and platinum electrodes, which exhibited marked mix-responses towards the compds. examd.; namely, 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), pentaerythritol tetranitrate (PETN), 2,4,6-trinitrotoluene (TNT), N-methyl-N,2,4,6-tetranitroaniline (Tetryl) and triacetone triperoxide (TATP). Departure information was the set of voltammograms, which were first analyzed by principal component anal. (PCA) allowing the discrimination of the different individual compds., while artificial neural networks (ANNs) were used for the resoln. and individual quantification of some of their mixts. (total normalized root mean square error for the external test set of 0.108 and correlation of the obtained vs. expected concns. comparison graphs r>0.929).
- 44Krivitsky, V.; Filanovsky, B.; Naddaka, V.; Patolsky, F. Direct and Selective Electrochemical Vapor Trace Detection of Organic Peroxide Explosives via Surface Decoration. Anal. Chem. 2019, 91, 5323– 5330, DOI: 10.1021/acs.analchem.9b0025744Direct and Selective Electrochemical Vapor Trace Detection of Organic Peroxide Explosives via Surface DecorationKrivitsky, Vadim; Filanovsky, Boris; Naddaka, Vladimir; Patolsky, FernandoAnalytical Chemistry (Washington, DC, United States) (2019), 91 (8), 5323-5330CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The ability to detect traces of highly energetic explosive materials sensitively, selectively, accurately, and rapidly could be of enormous benefit to civilian national security, military applications, and environmental monitoring. Unfortunately, the detection of explosives still poses a largely unmet arduous anal. problem, making their detection an issue of burning immediacy and a massive current challenge in terms of research and development. Although numerous explosive detection approaches have been developed, these methods are usually time-consuming, require bulky equipment, tedious sample prepn., a trained operator, cannot be miniaturized, and lack the ability to perform automated real-time high-throughput anal., strongly handicapping their mass deployment. Here, we present the first demonstration of the "direct" electrochem. approach for the sensitive, selective, and rapid vapor trace detection of TATP and HMTD, under ambient conditions, unaffected by the presence of oxygen and hydrogen peroxide species, down to concns. lower than 10 ppb. The method is based on the use of Ag-nanoparticles-decorated carbon microfibers air-collecting electrodes (μCF), which allow for the selective direct detection of the org. peroxide explosives, through opening multiple redox routes, not existent in the undecorated carbon electrodes. Finally, we demonstrate the direct and rapid detection of TATP and HMTD explosive species from real-world air samples.
- 45Calvo-Gredilla, P.; García-Calvo, J.; Cuevas, J. V.; Torroba, T.; Pablos, J.-L.; García, F. C.; García, J.-M.; Zink-Lorre, N.; Font-Sanchis, E.; Sastre-Santos, A.; Fernández-Lázaro, F. Solvent-Free Off–On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic Materials. Chem. – Eur. J. 2017, 23, 13973– 13979, DOI: 10.1002/chem.20170241245Solvent-Free Off-On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic MaterialsCalvo-Gredilla, Patricia; Garcia-Calvo, Jose; Cuevas, Jose V.; Torroba, Tomas; Pablos, Jesus-Luis; Garcia, Felix C.; Garcia, Jose-Miguel; Zink-Lorre, Nathalie; Font-Sanchis, Enrique; Sastre-Santos, Angela; Fernandez-Lazaro, FernandoChemistry - A European Journal (2017), 23 (56), 13973-13979CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A fluorogenic perylenediimide-functionalized polyacrylate capable of generating color and fluorescence changes in the presence of triacetone triperoxide (TATP), an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions has been developed. The material works by accumulating volatile TATP until it reaches a threshold; therefore, triggering colorimetric and fluorescent responses.
- 46García-Calvo, J.; Calvo-Gredilla, P.; Ibáñez-Llorente, M.; Romero, D. C.; Cuevas, J. V.; García-Herbosa, G.; Avella, M.; Torroba, T. Surface Functionalized Silica Nanoparticles for the Off–On Fluorogenic Detection of an Improvised Explosive, TATP, in a Vapour Flow. J. Mater. Chem. A 2018, 6, 4416– 4423, DOI: 10.1039/C7TA10792G46Surface functionalized silica nanoparticles for the off-on fluorogenic detection of an improvised explosive, TATP, in a vapor flowGarcia-Calvo, Jose; Calvo-Gredilla, Patricia; Ibanez-Llorente, Marcos; Romero, Daisy C.; Cuevas, Jose V.; Garcia-Herbosa, Gabriel; Avella, Manuel; Torroba, TomasJournal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (10), 4416-4423CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The development is reported of new fluorogenic silica nanomaterials that were able to generate fluorescence in the presence of vapors of triacetone triperoxide, TATP, an improvised explosive used in terrorist attacks. The materials worked in a vapor flow of TATP, giving a permanent and strongly fluorescent response.
- 47Blanco, S.; Macario, A.; García-Calvo, J.; Revilla-Cuesta, A.; Torroba, T.; López, J. C. Microwave Detection of Wet Triacetone Triperoxide (TATP): Non-Covalent Forces and Water Dynamics. Chem. – Eur. J. 2021, 27, 1680– 1687, DOI: 10.1002/chem.20200349947Microwave Detection of Wet Triacetone Triperoxide (TATP): Non-Covalent Forces and Water DynamicsBlanco, Susana; Macario, Alberto; Garcia-Calvo, Jose; Revilla-Cuesta, Andrea; Torroba, Tomas; Lopez, Juan CarlosChemistry - A European Journal (2021), 27 (5), 1680-1687CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)The water adducts of triacetone triperoxide (TATP) have been obsd. by using broadband rotational spectroscopy. This work opens a new way for the gas-phase detection of this improvised explosive. The obsd. clusters exhibit unusual water dynamics and rarely obsd. multicenter interactions. TATP-H2O is formed from the D3 symmetry conformer of TATP with water lying close to the C3 axis. Water rotation around this axis with a very low barrier gives rise to the rotational spectrum of a sym. top. The main interaction of the monohydrate is a four-center trifurcated donor Ow-H···O hydrogen bond, not obsd. previously in the gas phase, reinforced by a weak four-center trifurcated acceptor C-H···Ow interaction. Surprisingly, all structural signatures show the weakness of these interactions. The complex TATP-(H2O)2 is formed from the monohydrated TATP by the self-assocn. of water.
- 48Lapcinska, S.; Revilla-Cuesta, A.; Abajo-Cuadrado, I.; Cuevas, J. V.; Avella, M.; Arsenyan, P.; Torroba, T. Dye-Modified Silica-Anatase Nanoparticles for the Ultrasensitive Fluorogenic Detection of the Improvised Explosive TATP in an Air Microfluidic Device. Mater. Chem. Front. 2021, 5, 8097– 8107, DOI: 10.1039/D1QM01041G48Dye-modified silica-anatase nanoparticles for the ultrasensitive fluorogenic detection of the improvised explosive TATP in an air microfluidic deviceLapcinska, Sindija; Revilla-Cuesta, Andrea; Abajo-Cuadrado, Irene; Cuevas, Jose V.; Avella, Manuel; Arsenyan, Pavel; Torroba, TomasMaterials Chemistry Frontiers (2021), 5 (23), 8097-8107CODEN: MCFAC5; ISSN:2052-1537. (Royal Society of Chemistry)We describe the proof of concept of a portable testing setup for the detection of triacetone triperoxide (TATP), a common component in improvised explosive devices. The system will allow field-testing and generation of real-time results to test for TATP vapor traces in a no. of different environments. It will work by recirculating the gas samples in connection to the sensing mechanism in a suitable microfluidic portable device. In this way, the system will allow controlled trapping of the analyte in the chem. sensor to afford reliable results at very low concns. in air.
- 49Torroba, T.; Schechter, I.; Calvo, J. G.; Revilla-Cuesta, A. Explosives Detection, Sensors, Electronic Systems and Data Processing; Capineri, L.; Turmus, E. K., Eds.; Springer: The Netherlands, 2019; pp 208– 247.There is no corresponding record for this reference.
- 50Gopikrishna, P.; Meher, N.; Iyer, P. K. Functional 1,8-Naphthalimide AIE/AIEEgens: Recent Advances and Prospects. ACS Appl. Mater. Interfaces 2018, 10, 12081– 12111, DOI: 10.1021/acsami.7b1447350Functional 1,8-Naphthalimide AIE/AIEEgens: Recent Advances and ProspectsGopikrishna, Peddaboodi; Meher, Niranjan; Iyer, Parameswar KrishnanACS Applied Materials & Interfaces (2018), 10 (15), 12081-12111CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)A review. A survey is given of the up-to-date development of aggregation-induced emission/aggregation-induced emission enhancement (AIE/AIEE) active naphthalimide (NI)-based smart materials with potential for wide and real-world applications and that serves as a highly versatile building block with tunable absorption and emission in the complete visible region. The review article commences with a precise description of the importance of NI moiety and its several restricted area of applications owing to its aggregation caused quenching (ACQ) properties, followed by the discovery and importance of AIE/AIEE-active NIs. The introduction section tracked an overview of the state of the art in NI luminogens in multiple applications. It also includes a few mechanistic studies on the structure-property correlation of NIs and provides more insights into the condensed-state photophys. properties of small aggregation-prone systems. The review aims to ultimately accomplish current and forthcoming views comprising the use of the NIs for the detection of biol. active mols., such as amino acids and proteins, recognition of toxic analytes, fabrication of light emitting diodes, and their potential in therapeutics and diagnostics.
- 51de Greñu, B. D.; Moreno, D.; Torroba, T.; Berg, A.; Gunnars, J.; Nilsson, T.; Nyman, R.; Persson, M.; Pettersson, J.; Eklind, I.; Wästerby, P. Fluorescent Discrimination between Traces of Chemical Warfare Agents and Their Mimics. J. Am. Chem. Soc. 2014, 136, 4125– 4128, DOI: 10.1021/ja500710mThere is no corresponding record for this reference.
- 52de Greñu, B. D.; García-Calvo, J.; Cuevas, J.; García-Herbosa, G.; García, B.; Busto, N.; Ibeas, S.; Torroba, T.; Torroba, B.; Herrera, A.; Pons, S. Chemical Speciation of MeHg+ and Hg2+ in Aqueous Solution and HEK Cells Nuclei by means of DNA Interacting Fluorogenic Probes. Chem. Sci. 2015, 6, 3757– 3764, DOI: 10.1039/C5SC00718FThere is no corresponding record for this reference.
- 53García-Calvo, J.; Vallejos, S.; García, F. C.; Rojo, J.; García, J. M.; Torroba, T. A Smart Material for the in Situ Detection of Mercury in Fish. Chem. Commun. 2016, 52, 11915– 11918, DOI: 10.1039/C6CC05977E53A smart material for the in situ detection of mercury in fishGarcia-Calvo, Jose; Vallejos, Saul; Garcia, Felix C.; Rojo, Josefa; Garcia, Jose M.; Torroba, TomasChemical Communications (Cambridge, United Kingdom) (2016), 52 (80), 11915-11918CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)We have developed a new fluorogenic polymer capable of detecting the presence of mercury contamination in fish samples. The modified polymer emits blue light when irradiated with UV light proportional to the quantity of mercury, as MeHg+ or Hg2+, present in fish. The quant. relation between the concn. of mercury in fish and the increase of fluorescence in the polymer in contact with fish samples was confirmed, giving rise to quick and reliable results in the measurements of the presence of mercury in fish using a portable fluorogenic polymeric probe.
- 54García-Calvo, J.; Calvo-Gredilla, P.; Ibáñez-Llorente, M.; Rodríguez, T.; Torroba, T. Detection of Contaminants of High Environmental Impact by Means of Fluorogenic Probes. Chem. Rec. 2016, 16, 810– 824, DOI: 10.1002/tcr.20150025354Detection of Contaminants of High Environmental Impact by Means of Fluorogenic ProbesGarcia-Calvo, Jose; Calvo-Gredilla, Patricia; Ibanez-Llorente, Marcos; Rodriguez, Teresa; Torroba, TomasChemical Record (2016), 16 (2), 810-824CODEN: CRHEAK; ISSN:1528-0691. (Wiley-VCH Verlag GmbH & Co. KGaA)This personal account describes our contribution to the design of selective fluorogenic probes for contaminants of high environmental impact. For this purpose, we have developed a new family of highly versatile fluorogenic reagents that were able to show large differences in their fluorescence in the presence of selected analytes. They were used in the prepn. of fluorogenic probes for the detection of contaminants of high environmental impact which currently have no good solns.: phosphorylating agents, such as chem. weapons; Me mercury(II); the cyanide anion; amino-acid metabolites, such as doping substances; and biogenic amine mimics, such as drugs of abuse and recreational drugs. The development of new materials for specific sensing was achieved by anchoring selected probes to silica nanomaterials, suitable for the selective detection of org. analytes in water for immediate application to toxicol. or environmental purposes.
- 55García-Calvo, J.; Robson, J. A.; Torroba, T.; Wilton-Ely, J. D. E. T. Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and Gases. Chem. – Eur. J. 2019, 25, 14214– 14222, DOI: 10.1002/chem.20190330355Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and GasesGarcia-Calvo, Jose; Robson, Jonathan A.; Torroba, Tomas; Wilton-Ely, James D. E. T.Chemistry - A European Journal (2019), 25 (62), 14214-14222CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A series of new ruthenium(II) vinyl complexes has been prepd. incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalized with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or through the pyridyl nitrogen. The inherent low soly. of the perylene compds. was improved through the design of poly-PEGylated (PEG = polyethylene glycol) units bearing a terminal alkyne or a pyridyl group. By absorbing the compds. on silica, vapors and gases could be detected in the solid state. The reaction of the complexes [Ru(CH:CH-PerIm)Cl(CO)(py-3PEG)(PPh3)2] and [Ru(CH:CH-3PEG)Cl(CO)(py-PerIm)(PPh3)2] with carbon monoxide, isonitrile or cyanide was found to result in modulation of the fluorescence behavior. The complexes were obsd. to display solvatochromic effects and the interaction of the complexes with a wide range of other species was also studied. The study suggests that such complexes have potential for the detection of gases or vapors that are toxic to humans.
- 56García-Calvo, V.; Cuevas, J. V.; Barbero, H.; Ferrero, S.; Álvarez, C. M.; González, J. A.; Díaz de Greñu, B.; García-Calvo, J.; Torroba, T. Synthesis of a Tetracorannulene-perylenediimide That Acts as a Selective Receptor for C60 over C70. Org. Lett. 2019, 21, 5803– 5807, DOI: 10.1021/acs.orglett.9b0172956Synthesis of a Tetracorannulene-perylenediimide That Acts as a Selective Receptor for C60 over C70Garcia-Calvo, Victor; Cuevas, Jose V.; Barbero, Hector; Ferrero, Sergio; Alvarez, Celedonio M.; Gonzalez, Jesus A.; Diaz de Grenu, Borja; Garcia-Calvo, Jose; Torroba, TomasOrganic Letters (2019), 21 (15), 5803-5807CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)The authors report the use of a tetraborylated perylenediimide as starting material for the prepn. of a tetracorannulene-perylenediimide that is able to bind up to two fullerene-C60 mols. by host-guest mol. recognition with preference over C70. Titrn. with fullerene-C60 is followed by a dramatic shift of the arom. signals in 1H NMR and an initial increase in the fluorescence of the system. By this simple mechanism, fluorogenic sensing of fullerene-C60 is easily accomplished by an unprecedented fluorescent turn-on mechanism.
- 57Busto, N.; Calvo, P.; Santolaya, J.; Leal, J. M.; Guédin, A.; Barone, G.; Torroba, T.; Mergny, J.-L.; García, B. Fishing for G-Quadruplexes in Solution with a Perylene Diimide Derivative Labeled with Biotins. Chem. – Eur. J. 2018, 24, 11292– 11296, DOI: 10.1002/chem.20180236557Fishing for G-Quadruplexes in Solution with a Perylene Diimide Derivative Labeled with BiotinsBusto, Natalia; Calvo, Patricia; Santolaya, Javier; Leal, Jose M.; Guedin, Aurore; Barone, Giampaolo; Torroba, Tomas; Mergny, Jean-Louis; Garcia, BegonaChemistry - A European Journal (2018), 24 (44), 11292-11296CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)A new fluorescent, noncytotoxic perylene diimide deriv. with two biotins at the peri position, PDI2B, has been synthesized. This mol. is able to interact selectively with G-quadruplexes with scarce or no affinity towards single- or double-stranded DNA. These features have made it possible to design a simple, effective, safe, cheap, and selective method for fishing G-quadruplex structures in soln. by use of PDI2B and streptavidin coated magnetic beads. The new cyclic method reported leads to the recovery of more than 80% of G-quadruplex structures from soln., even in the presence of an excess of single-stranded or duplex DNA as competitors. Moreover, PDI2B is a G4 ligand that can display higher thermal stabilization and greater affinity for 2- over 3-tetrad quadruplexes, which constitutes a novel type of behavior.
- 58García-Calvo, J.; Torroba, T.; Brañas-Fresnillo, V.; Perdomo, G.; Cózar-Castellano, I.; Li, Y.-H.; Legrand, Y.-M.; Barboiu, M. Manipulation of Transmembrane Transport by Synthetic K+ Ionophore Depsipeptides and Its Implications in Glucose-Stimulated Insulin Secretion in β-Cells. Chem. – Eur. J. 2019, 25, 9287– 9294, DOI: 10.1002/chem.20190137258Manipulation of transmembrane transport by synthetic K+ ionophore depsipeptides and its implications in glucose-stimulated insulin secretion in β-cellsGarcia-Calvo, Jose; Torroba, Tomas; Branas-Fresnillo, Virginia; Perdomo, German; Cozar-Castellano, Irene; Li, Yu-Hao; Legrand, Yves-Marie; Barboiu, MihailChemistry - A European Journal (2019), 25 (39), 9287-9294CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)The cyclic depsipeptide cereulide toxin it is a very well-known potassium electrogenic ionophore particularly sensitive to pancreatic beta cells. The mechanistic details of its specific activity are unknown. Here, we describe a series of synthetic substituted cereulide potassium ionophores that cause impressive selective activation of glucose-induced insulin secretion in a constitutive manner in rat insulinoma INS1E cells. Our study demonstrates that the different electroneutral K+ transport mechanism exhibited by the anionic mutant depsipeptides when compared with classical electrogenic cereulides can have an important impact of pharmacol. value on glucose-stimulated insulin secretion.
- 59Busto, N.; García-Calvo, J.; Cuevas, J. V.; Herrera, A.; Mergny, J.-L.; Pons, S.; Torroba, T.; García, B. Influence of Core Extension and Side Chain Nature in Targeting G-Quadruplex Structures with Perylene Monoimide Derivatives. Bioorg. Chem. 2021, 108, 104660 DOI: 10.1016/j.bioorg.2021.10466059Influence of core extension and side chain nature in targeting G-quadruplex structures with perylene monoimide derivativesBusto, Natalia; Garcia-Calvo, Jose; Cuevas, Jose Vicente; Herrera, Antonio; Mergny, Jean-Louis; Pons, Sebastian; Torroba, Tomas; Garcia, BegonaBioorganic Chemistry (2021), 108 (), 104660CODEN: BOCMBM; ISSN:0045-2068. (Elsevier B.V.)A structure-activity relationship (SAR) study in terms of G-quadruplex binding ability and antiproliferative activity of six fluorescent perylenemonoimide (PMIs) derivs. is reported. A pos. charge seems to be the key to target G4. This study also reveals the importance of the element substitution in the potential biol. activity of PMIs, being the polyethylene glycol (PEG) chains in the peri position responsible for their antiproliferative activity. Among them, the cationic PMI6 with two PEG chains is the most promising compd. since its fluorescence is enhanced in the presence of G-quadruplex structures. Moreover, PMI6 binds to the human telomeric G-quadruplex hTelo with high affinity and displays a high antiproliferative potential towards HeLa (cervical adenocarcinoma), A549 (lung adenocarcinoma) and A2780 (ovarian adenocarcinoma) cells. Its fate can be followed inside cells thanks to its fluorescent properties: the compd. is found to accumulate in the mitochondria.
- 60Tajima, K.; Fukui, N.; Shinokubo, H. Aggregation-Induced Emission of Nitrogen-Bridged Naphthalene Monoimide Dimers. Org. Lett. 2019, 21, 9516– 9520, DOI: 10.1021/acs.orglett.9b0369960Aggregation-Induced Emission of Nitrogen-Bridged Naphthalene Monoimide DimersTajima, Keita; Fukui, Norihito; Shinokubo, HiroshiOrganic Letters (2019), 21 (23), 9516-9520CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)We have prepd. four 4-aminonaphthalene monoimide derivs. and examd. the aggregation-induced emission (AIE) properties. A nitrogen-bridged dimer is AIE-active and exhibits bright green emission with a high quantum yield in the solid state. The X-ray diffraction anal. suggests that key to the bright luminescence is the favorable crystal packing dominated by CH/π interaction. The late-stage cyanation of the dimer tuned its AIE color from green to orange.
- 61Wang, Y.; Teng, Y.; Yang, H.; Li, X.; Yin, D.; Tian, Y. Bioorthogonally Applicable Multicolor Fluorogenic Naphthalimide–Tetrazine Probes with Aggregation-Induced Emission Characters. Chem. Commun. 2022, 58, 949– 952, DOI: 10.1039/D1CC05204G61Bioorthogonally applicable multicolor fluorogenic naphthalimide-tetrazine probes with aggregation-induced emission charactersWang, Yongcheng; Teng, Yu; Yang, Hong; Li, Xiang; Yin, Dali; Tian, YulinChemical Communications (Cambridge, United Kingdom) (2022), 58 (7), 949-952CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)A series of naphthalimide-tetrazines were developed as bioorthogonal fluorogenic probes, which could produce significant fluorescence enhancement, notable aggregation-induced emission (AIE) characters and multicolor emissions after bioorthogonal reaction with strained dienophiles. Manipulating the π-bridge in the fluorophore skeleton allows fine-tuning of the emission wavelength and influences the AIE-active properties. With these probes, we succeeded in no-wash fluorogenic protein labeling and mitochondria-selective bioorthogonal imaging in live cells.
- 62García-Calvo, J.; Calvo-Gredilla, P.; Vallejos, S.; García, J. M.; Cuevas-Vicario, J. V.; García-Herbosa, G.; Avella, M.; Torroba, T. Palladium Nanodendrites Uniformly Deposited on the Surface of Polymers as an Efficient and Recyclable Catalyst for Direct Drug Modification Via Z-Selective Semihydrogenation of Alkynes. Green Chem. 2018, 20, 3875– 3883, DOI: 10.1039/C8GC01522H62Palladium nanodendrites uniformly deposited on the surface of polymers as an efficient and recyclable catalyst for direct drug modification via Z-selective semihydrogenation of alkynesGarcia-Calvo, Jose; Calvo-Gredilla, Patricia; Vallejos, Saul; Garcia, Jose Miguel; Cuevas-Vicario, Jose Vicente; Garcia-Herbosa, Gabriel; Avella, Manuel; Torroba, TomasGreen Chemistry (2018), 20 (16), 3875-3883CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)The prepn. of new monodisperse polycryst. palladium nanoparticles uniformly distributed on the surface of polymers, by simply adding a palladium(II) soln. in water to the polymers, is described. The polymer supported palladium nanoparticles material was used as an efficient portable and reusable catalyst for the stereoselective semihydrogenation reaction of internal alkynes to (Z)-alkenes in green solvents.
- 63García-Calvo, J.; García-Calvo, V.; Vallejos, S.; García, F. C.; Avella, M.; García, J.-M.; Torroba, T. Surface Coating by Gold Nanoparticles on Functional Polymers: On-Demand Portable Catalysts for Suzuki Reactions. ACS Appl. Mater. Interfaces 2016, 8, 24999– 25004, DOI: 10.1021/acsami.6b0774663Surface Coating by Gold Nanoparticles on Functional Polymers: On-Demand Portable Catalysts for Suzuki ReactionsGarcia-Calvo, Jose; Garcia-Calvo, Victor; Vallejos, Saul; Garcia, Felix C.; Avella, Manuel; Garcia, Jose-Miguel; Torroba, TomasACS Applied Materials & Interfaces (2016), 8 (38), 24999-25004CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)We have developed new functionalized polymers capable of being easily coated by gold nanoparticles, uniformly distributed on the surface of the polymers, by simply adding a gold(III) soln. in water to the polymers. The polymer-supported gold nanoparticle material was used as an efficient portable and reusable catalyst for Suzuki reactions in mixed org.-aq. solvents.
- 64Sanluis-Verdes, A.; Colomer-Vidal, P.; Rodriguez-Ventura, F.; Bello-Villarino, M.; Spinola-Amilibia, M.; Ruiz-Lopez, E.; Illanes-Vicioso, R.; Castroviejo, P.; Aiese Cigliano, R.; Montoya, M.; Falabella, P.; Pesquera, C.; Gonzalez-Legarreta, L.; Arias-Palomo, E.; Solà, M.; Torroba, T.; Arias, C. F.; Bertocchini, F. Wax Worm Saliva and the Enzymes therein Are the Key to Polyethylene Degradation by Galleria mellonella. Nat. Commun. 2022, 13, 5568 DOI: 10.1038/s41467-022-33127-w64Wax worm saliva and the enzymes therein are the key to polyethylene degradation by Galleria mellonellaSanluis-Verdes, A.; Colomer-Vidal, P.; Rodriguez-Ventura, F.; Bello-Villarino, M.; Spinola-Amilibia, M.; Ruiz-Lopez, E.; Illanes-Vicioso, R.; Castroviejo, P.; Aiese Cigliano, R.; Montoya, M.; Falabella, P.; Pesquera, C.; Gonzalez-Legarreta, L.; Arias-Palomo, E.; Sola, M.; Torroba, T.; Arias, C. F.; Bertocchini, F.Nature Communications (2022), 13 (1), 5568CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Plastic degrdn. by biol. systems with re-utilization of the byproducts could be a future soln. to the global threat of plastic waste accumulation. Here, we report that the saliva of Galleria mellonella larvae (wax worms) is capable of oxidizing and depolymg. polyethylene (PE), one of the most produced and sturdy polyolefin-derived plastics. This effect is achieved after a few hours' exposure at room temp. under physiol. conditions (neutral pH). The wax worm saliva can overcome the bottleneck step in PE biodegrdn., namely the initial oxidn. step. Within the saliva, we identify two enzymes, belonging to the phenol oxidase family, that can reproduce the same effect. To the best of our knowledge, these enzymes are the first animal enzymes with this capability, opening the way to potential solns. for plastic waste management through bio-recycling/up-cycling.
- 65Allegrini, F.; Olivieri, A. C. IUPAC-Consistent Approach to the Limit of Detection in Partial Least-Squares Calibration. Anal. Chem. 2014, 86, 7858– 7866, DOI: 10.1021/ac501786u65IUPAC-Consistent Approach to the Limit of Detection in Partial Least-Squares CalibrationAllegrini, Franco; Olivieri, Alejandro C.Analytical Chemistry (Washington, DC, United States) (2014), 86 (15), 7858-7866CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)There is currently no well-defined procedure for providing the limit of detection (LOD) in multivariate calibration. Defining an estimator for the LOD in this scenario showed to be more complex than intuitively extending the traditional univariate definition. For these reasons, although many attempts were made to arrive at a reasonable convention, addnl. effort is required to achieve full agreement between the univariate and multivariate LOD definitions. A novel approach is presented to est. the LOD in partial least-squares (PLS) calibration. Instead of a single LOD value, an interval of LODs is provided, which depends on the variation of the background compn. in the calibration space. This is in contrast with previously proposed univariate extensions of the LOD concept. With the present definition, the LOD interval becomes a parameter characterizing the overall PLS calibration model, and not each test sample in particular, as was proposed in the past. The new approach takes into account IUPAC official recommendations, and also the latest developments in error-in-variables theory for PLS calibration. Both simulated and real anal. systems were studied for illustrating the properties of the new LOD concept.
- 66Ortiz, M. C.; Sarabia, L. A.; Sánchez, M. S. Tutorial on Evaluation of Type I and Type II Errors in Chemical Analyses: From the Analytical Detection to Authentication of Products and Process Control. Anal. Chim. Acta 2010, 674, 123– 142, DOI: 10.1016/j.aca.2010.06.02666Tutorial on evaluation of type I and type II errors in chemical analyses: From the analytical detection to authentication of products and process controlOrtiz, M. C.; Sarabia, L. A.; Sanchez, M. S.Analytica Chimica Acta (2010), 674 (2), 123-142CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)A review. Uncertainty is inherent in all exptl. detns. Nevertheless, these measurements were used to make decisions including the performance of the own measurement systems. The link between the decision and the true implicit system that generates the data (measurement system, prodn. process, category of samples, etc.) is a representation of this uncertainty as a probability distribution. This representation leads to the probabilistic formalization of the possibility of making errors. In the context of regulations established by official agencies, it is important to use these statistical decision methods in some cases because the own norm makes them mandatory and, in general, because this is the way of reasonably evaluating whether a working hypothesis is rejected from the exptl. data. The aim of the present tutorial is to introduce some ideas and basic methods for the crit. anal. of exptl. data. With this goal, the basic elements of the Neyman-Pearson theory of hypothesis testing are formally introduced in connection with the common problems in chem. anal. and, if this is the case, their relation to the norms of regulatory agencies. The notion of decision with enough quality' is modeled when explicitly considering: (1) the null, H 0, and alternative, H 1, hypotheses. (2) The significance level of the test, which is the probability, α, of rejecting H 0 when it is true, and the power of the test, 1 - β, β being the probability of accepting H 0 when it is false. (3) The difference between H 0 and H 1 that has to be detected with exptl. data. (4) The needed sample size. These four concepts should be explicitly defined for each problem and, under the usual assumption of normal distribution of the data, the math. relations among these concepts are shown, which allow the analyst to design a decision rule with pre-set values of α and β. To illustrate the unifying character of this inferential methodol., several situations are exposed along the tutorial: the design of a hypothesis test to decide on the performance characteristics of anal. methods, the capability of detection of both quant. and qual. anal. methods (including its generalization to the case of multivariate and/or multiway signals), the anal. sensitivity with multivariate signals, the class-modeling and the process control.
- 67RStudio, Version 1.4.1103; RStudio: Boston, MA, 2009–2021.There is no corresponding record for this reference.
- 68Fujiyama-Novak, J. H.; Gaddam, C. K.; Das, D.; Wal, R. L. V.; Ward, B. Detection of Explosives by Plasma Optical Emission Spectroscopy. Sens. Actuators, B 2013, 176, 985– 993, DOI: 10.1016/j.snb.2012.08.06368Detection of explosives by plasma optical emission spectroscopyFujiyama-Novak, Jane H.; Gaddam, Chethan Kumar; Das, Debanjan; Vander Wal, Randall L.; Ward, BenjaminSensors and Actuators, B: Chemical (2013), 176 (), 985-993CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)A new pre-concn./sepn. system coupled to a micro-hollow glow discharge plasma detector is demonstrated for the anal. of explosives. The detector and spectrometer are miniaturized and field-portable. Sepn. eliminated air interferences while pre-concn. improved detection limits for TATP (triacetone triperoxide) and DNT (dinitrotoluene). In the anal. step, a temp. ramp desorbed the 2 explosives into an entraining Ar flow. Optical emission spectroscopy was applied to detect the plasma generated at. and diat. radicals using a spectrometer at atm. pressure. For both test species, the detection limits reached values <5 ppb. The effect of an at-sea environment was also evaluated. Such a detector system is very promising for the detection of explosives due its small size, high sensitivity, and selectivity.
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Complete characterization for all compounds, additional experimental details, materials, and methods (PDF)
Fluorometer measurements with nanoparticles in a fixed position (MP4)
Fluorometer measurements with nanoparticles in a fixed position (MP4)
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