Interaction, Insensitivity and Thermal Conductivity of CL-20/TNT-Based Polymer-Bonded Explosives through Molecular Dynamics Simulation.

Binders mixed with explosives to form polymer-bonded explosives (PBXs) can reduce the sensitivity of the base explosive by improving interfacial interactions. The interface formed between the binder and matrix explosive also affects the thermal conductivity. Low thermal conductivity may result in localized heat concentration inside the PBXs, causing the detonation of the explosive. To investigate the binder-explosive interfacial interactions and thermal conductivity, PBXs with polyurethane as the binder and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-trinitrotoluene (CL-20/TNT) co-crystal as the matrix explosive were investigated through molecular dynamics (MD) simulations and reverse non-equilibrium molecular dynamics (rNEMD) simulation. The analysis of the pair correlation function revealed that there are hydrogen bonding interactions between Estane5703 and CL-20/TNT. The length of the trigger bonds was adopted as a theoretical criterion of sensitivity, and the effect of polymer binders on the sensibility of PBXs was correlated by analyzing the interfacial trigger bonds and internal trigger bonds of PBXs for the first time. The results indicated that the decrease in sensitivity of CL-20/TNT mainly comes from the CL-20/TNT contact with Estane5703. Therefore, the sensitivity of CL-20/TNT-based PBXs can be further reduced by increasing the contact area between CL-20/TNT and Estane5703. The thermal conductivity of PBXs composed of Estane5703 and CL-20/TNT (0 0 1), (0 1 0) and (1 0 0) crystal planes, respectively, were calculated through rNEMD simulations, and the results showed that only the addition of Estane5703 to the (1 0 0) crystal plane can improve the thermal conductivity of PBX100.

An Ultrasound-Fenton Process for the Degradation of 2,4,6-Trinitrotoluene.

2,4,6-Trinitrotoluene (TNT), one of the main compounds in ammunition wastewater, is harmful to the environment. In this study, the treatment efficiency of 2,4,6-TNT by different treatment processes, including ferrous ion (Fe2+), hydrogen peroxide (H2O2), Fenton, ultrasound (US) irradiation, US + Fe2+, US + H2O2 and US-Fenton process, was compared. The results showed that US-Fenton was the most effective among all methods studied. The effects of initial pH, reaction time and H2O2 to Fe2+ molar ratio were investigated. The results showed that the removal of TNT, TOC and COD was maximum at an initial pH of 3.0 and H2O2 to Fe2+ molar ratio of 10:1. TNT, TOC and COD removal was fast in the first 30 min, reaching 83%, 57% and 50%, then increased gradually to 99%, 67% and 87% until 300 min, respectively. Semi-batch mode operation increased the removal of TNT and TOC by approximately 5% and 10% at 60 min, respectively. The average carbon oxidation number (ACON) was increased from -1.7 at 30 min to a steady-state value of 0.4, indicating the mineralization of TNT. Based on GC-MS analysis, 1,3,5-trinitrobenzene, 2,4,6-trinitrobenzene acid, 3,5-dinitrobenznamine and 3,5-dinitro-p-toluidine were the major byproducts from the US-Fenton process. The TNT degradation pathway was proposed, which involved methyl group oxidation, decarboxylation, aromatic ring cleavage and hydrolysis.

Tuning solvent-solute interactions enable visual colorimetric detection of nitro-aromatic explosives.

The Janowski reaction is a critical reaction for visual colorimetric detection of nitro-aromatic explosives. However, the solvent effect is still not well explored. Herein, we report the solvent-dependent activity of the Janowski reaction between 2,4-dinitrotoluene (DNT)/2,4,6-trinitrotoluene (TNT) and NaOH. Four common solvents are studied. It is found that acetone with high donor number and low polarity is able to readily dissolve the product of Janowski reaction (Meisenheimer complexes) via Lewis acid-base interactions and solvation rules, facilitating the Janowski reactions between DNT/TNT and NaOH. Based on the color change of the Janowski reactions within acetone, a visual colorimetric assay is established. The present assay can detect DNT and TNT with a detection limit of 1.4 µM and 1.2 µM, which allows for naked-eye detection. In addition, this assay is highly selective and applicable to DNT/TNT detection in soil samples. Our work reveals the solvent effect on the Janowski reaction, providing a simple and rapid method for detection of nitro-aromatic explosives.

Comparative Genomic Analysis of Antarctic Pseudomonas Isolates with 2,4,6-Trinitrotoluene Transformation Capabilities Reveals Their Unique Features for Xenobiotics Degradation.

The nitroaromatic explosive 2,4,6-trinitrotoluene (TNT) is a highly toxic and persistent environmental pollutant. Since physicochemical methods for remediation are poorly effective, the use of microorganisms has gained interest as an alternative to restore TNT-contaminated sites. We previously demonstrated the high TNT-transforming capability of three novel Pseudomonas spp. isolated from Deception Island, Antarctica, which exceeded that of the well-characterized TNT-degrading bacterium Pseudomonas putida KT2440. In this study, a comparative genomic analysis was performed to search for the metabolic functions encoded in the genomes of these isolates that might explain their TNT-transforming phenotype, and also to look for differences with 21 other selected pseudomonads, including xenobiotics-degrading species. Comparative analysis of xenobiotic degradation pathways revealed that our isolates have the highest abundance of key enzymes related to the degradation of fluorobenzoate, TNT, and bisphenol A. Further comparisons considering only TNT-transforming pseudomonads revealed the presence of unique genes in these isolates that would likely participate directly in TNT-transformation, and others involved in the ß-ketoadipate pathway for aromatic compound degradation. Lastly, the phylogenomic analysis suggested that these Antarctic isolates likely represent novel species of the genus Pseudomonas, which emphasizes their relevance as potential agents for the bioremediation of TNT and other xenobiotics.

Integration of heterogeneous photocatalysis (TiO2/UV) and activated sludge system operated in air lift reactor for the treatment of industrial effluent red water.

In the industrial production of the explosive 2,4,6-trinitrotoluene (TNT), purification steps are required to ensure the quality of the product, procedures that generate wastewater of a complex nature and with eco-toxicological potential, called red water, which consists of soluble sulfonates, TNT isomers, and other typical nitro aromatic compounds. The present work aimed to study the effects of integrating heterogeneous photocatalysis based on commercial TiO2, with a biological process, based on activated sludge, for red water treatment. For the photocatalytic treatment, a 72% reduction in the typical absorption of nitro aromatic compounds (the region between 195 - 275 nm), a 36% reduction in chemical oxygen demand (COD), and a 68% reduction in total phenols were obtained. In the biological treatment, there was a 60% reduction in absorbance in the typical nitro aromatics region (NA), 10% reduction in COD, and 36% reduction in total phenols (FT). The integration of photocatalytic and biological treatments showed promising results compared to the individual processes. Having 94% reduction in NA absorbance, 72% reduction in FT, and 89% reduction in COD with an association of photocatalytic pretreatment followed by biological, and reductions of 88% in NA absorbance, 62% in FT, and 87% in COD for a biological pretreatment followed by the photocatalytic process. In general, when comparing the chemical and biological processes, isolated and integrated, both types of integration showed significantly superior results. They were able to remove the main nitro aromatic constituents of the Red Water effluent.

Development of an environmental hazard-based rating assessment for defence-related chemical compounds in ecological soil systems.

Environmental hazard-based methods are commonly used to categorise the severity of chemical contamination to ecological soil systems, although a traffic-light approach (green, amber, red) has never been used to assess these consequences. A traffic light approach is an easy to interpretate data as it has a clear visual display which can provide an early warning approach for stakeholders to identify areas that require further investigation. This approach should be underpinned by extensive research data and systematic methods of development. However, the extent of reliable data available for specific chemicals can be limited and therefore decision making may rely on expert judgement. Therefore, in this study, an environmental hazard-based rating methodology was developed by combining the guidelines from the European Chemical Agency (ECHA) and the USEPA for Predicted Non-effect Concentration (PNEC) and Ecological Soil Screening Levels (Eco-SSL) for defence-related chemicals (2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), cypermethrin, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS)). The developed hazard-based rating assessment was design to categorise the chemicals into low, medium and high environmental hazards priority to inform and ease the decision-making process for contaminated areas to ensure that sustainable operations are carried out.

Protamine gold nanoclusters - based fluorescence turn-on sensor for rapid determination of Trinitrotoluene (TNT).

Determination of trace residues of 2,4,6-trinitrotoluene (TNT) is an analytical challenge as it is widely used in military, mining industry, civilian and counter-terrorism purposes. In this study, a gold nanocluster - based turn-on fluorescence sensor was developed for TNT determination. A one-pot approach was used to synthesize the fluorescent protamine - stabilized gold nanoclusters (PRT-AuNC). The proposed turn-on fluorometric sensor relies on the aggregation-induced emission enhancement mechanism. As a result of the donor-acceptor interaction between the non-fluorescent Meisenheimer anion formed from TNT and the amino groups of weakly fluorescent protamine, the PRT-AuNCs aggregate and an accompanying enhancement in fluorescence intensity is observed with a large Stokes shift (λex = 300 nm, λem = 600 nm). The fluorescence enhancement increased linearly with TNT with an LOD of 12.44 µg/L. Similar energetic materials, common soil ions and explosive camouflage materials did not affect the proposed fluorometric sensing method. TNT in artificially contaminated soil was determined, and the results were comparable to those obtained by the HPLC-DAD system. The proposed turn-on sensor is an important tool for simple, fast, rapid and sensitive TNT determination, and has a potential to be converted to a kit format.

Ab initio neural network MD simulation of thermal decomposition of a high energy material CL-20/TNT.

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, also known as HNIW) is one of the most powerful energetic materials. However, its high sensitivity to environmental stimuli greatly reduces its safety and severely limits its application. In this work, ab initio based neural network potential (NNP) energy surfaces for both ß-CL-20 and CL-20/TNT co-crystals were constructed. To accurately simulate the thermal decomposition processes of these two crystal systems, reactive molecular dynamics simulations based on the NNPs were performed. Many important intermediate species and their associated reaction paths during the decomposition had been identified in the simulations and the direct results on detonation temperatures of both systems were provided. The simulations also showed clearly that 2,4,6-trinitrotoluene (TNT) molecules in the co-crystal act as a buffer to slow down the chain reactions triggered by nitrogen dioxide and this effect is more significant at lower temperatures. Specifically, the addition of TNT molecules in the CL-20/TNT co-crystal introduces intermolecular hydrogen bonds between CL-20 and TNT molecules in the system, thereby increasing the thermal stability of the co-crystal. The current reactive molecular dynamics simulation is performed based on the NNP which helps in accelerating the speed of ab initio molecular dynamics (AIMD) simulation by more than 3 orders of magnitude while preserving the accuracy of density functional theory (DFT) calculations. This enabled us to perform longer-time simulations at more realistic temperatures that traditional AIMD methods cannot achieve. With the advantage of the NNP in its powerful fitting ability and transferability, the NNP-based MD simulation can be widely applied to energetic material systems.

Intermolecular Vibration Energy Transfer Process in Two CL-20-Based Cocrystals Theoretically Revealed by Two-Dimensional Infrared Spectra.

Inspired by the recent cocrystallization and theory of energetic materials, we theoretically investigated the intermolecular vibrational energy transfer process and the non-covalent intermolecular interactions between explosive compounds. The intermolecular interactions between 2,4,6-trinitrotoluene (TNT) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and between 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) and CL-20 were studied using calculated two-dimensional infrared (2D IR) spectra and the independent gradient model based on the Hirshfeld partition (IGMH) method, respectively. Based on the comparison of the theoretical infrared spectra and optimized geometries with experimental results, the theoretical models can effectively reproduce the experimental geometries. By analyzing cross-peaks in the 2D IR spectra of TNT/CL-20, the intermolecular vibrational energy transfer process between TNT and CL-20 was calculated, and the conclusion was made that the vibrational energy transfer process between CL-20 and TNTII (TNTIII) is relatively slower than between CL-20 and TNTI. As the vibration energy transfer is the bridge of the intermolecular interactions, the weak intermolecular interactions were visualized using the IGMH method, and the results demonstrate that the intermolecular non-covalent interactions of TNT/CL-20 include van der Waals (vdW) interactions and hydrogen bonds, while the intermolecular non-covalent interactions of HMX/CL-20 are mainly comprised of vdW interactions. Further, we determined that the intermolecular interaction can stabilize the trigger bond in TNT/CL-20 and HMX/CL-20 based on Mayer bond order density, and stronger intermolecular interactions generally indicate lower impact sensitivity of energetic materials. We believe that the results obtained in this work are important for a better understanding of the cocrystal mechanism and its application in the field of energetic materials.

Structural Factors That Determine the Activity of the Xenobiotic Reductase B Enzyme from Pseudomonas putida on Nitroaromatic Compounds.

Xenobiotic reductase B (XenB) catalyzes the reduction of the aromatic ring or nitro groups of nitroaromatic compounds with methyl, amino or hydroxyl radicals. This reaction is of biotechnological interest for bioremediation, the reuse of industrial waste or the activation of prodrugs. However, the structural factors that explain the binding of XenB to different substrates are unknown. Molecular dynamics simulations and quantum mechanical calculations were performed to identify the residues involved in the formation and stabilization of the enzyme/substrate complex and to explain the use of different substrates by this enzyme. Our results show that Tyr65 and Tyr335 residues stabilize the ligands through hydrophobic interactions mediated by the aromatic rings of these aminoacids. The higher XenB activity determined with the substrates 1,3,5-trinitrobenzene and 2,4,6-trinitrotoluene is consistent with the lower energy of the highest occupied molecular orbital (LUMO) orbitals and a lower energy of the homo orbital (LUMO), which favors electrophile and nucleophilic activity, respectively. The electrostatic potential maps of these compounds suggest that the bonding requires a large hydrophobic region in the aromatic ring, which is promoted by substituents in ortho and para positions. These results are consistent with experimental data and could be used to propose point mutations that allow this enzyme to process new molecules of biotechnological interest.

CL-20-Based Cocrystal Energetic Materials: Simulation, Preparation and Performance.

The cocrystallization of high-energy explosives has attracted great interests since it can alleviate to a certain extent the power-safety contradiction. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (CL-20), one of the most powerful explosives, has attracted much attention for researchers worldwide. However, the disadvantage of CL-20 has increased sensitivity to mechanical stimuli and cocrystallization of CL-20 with other compounds may provide a way to decrease its sensitivity. The intermolecular interaction of five types of CL-20-based cocrystal (CL-20/TNT, CL-20/HMX, CL-20/FOX-7, CL-20/TKX-50 and CL-20/DNB) by using molecular dynamic simulation was reviewed. The preparation methods and thermal decomposition properties of CL-20-based cocrystal are emphatically analyzed. Special emphasis is focused on the improved mechanical performances of CL-20-based cocrystal, which are compared with those of CL-20. The existing problems and challenges for the future work on CL-20-based cocrystal are discussed.

Synthesis of 2,4,6-Trinitrotoluene (TNT) Using Flow Chemistry.

This paper describes the nitration of 2,4-dinitrotoluene (DNT) and its conversion to 2,4,6-trinitrotoluene (TNT) at a gram scale with the use of a fully automated flow chemistry system. The conversion of DNT to TNT traditionally requires the use of highly hazardous reagents like fuming sulfuric acid (oleum), fuming nitric acid (90-100%), and elevated temperatures. Flow chemistry offers advantages compared to conventional syntheses including a high degree of safety and simpler multistep automation. The configuration and development of this automated process based on a commercially available flow chemistry system is described. A high conversion rate (>99%) was achieved. Unlike established synthetic methods, ordinary nitrating mixture (65% HNO3/98% H2SO4) and shorter reaction times (10-30 min) were applied. The viability of flow nitration as a means of safe and continuous synthesis of TNT was investigated. The method was optimized using an experimental design approach, and the resulting process is safer, faster, and more efficient than previously reported TNT synthesis procedures. We compared the flow chemistry and batch approaches, including a provisional cost calculation for laboratory-scale production (a thorough economic analysis is, however, beyond the scope of this article). The method is considered fit for purpose for the safe production of high-purity explosives standards at a gram scale, which are used to verify that the performance of explosive trace detection equipment complies with EU regulatory requirements.

Peptide-Functionalized Quantum Dots for Rapid Label-Free Sensing of 2,4,6-Trinitrotoluene.

Explosive compounds, such as 2,4,6-trinitrotoluene (TNT), pose a great concern in terms of both global public security and environmental protection. There are estimated to be hundreds of TNT contaminated sites all over the world, which will affect the health of humans, wildlife, and the ecosystem. Clearly, the ability to detect TNT in soils, water supplies, and wastewater is important for environmental studies but also important for security, such as in ports and boarders. However, conventional spectroscopic detection is not practical for on-site sensing because it requires sophisticated equipment and trained personnel. We report a rapid and simple chemical sensor for TNT by using TNT binding peptides which are conjugated to fluorescent CdTe/CdS quantum dots (QDs). QDs were synthesized in the aqueous phase, and the peptide was attached directly to the surface of the QDs by using thiol groups. The fluorescent emission from the QDs was quenched in response to the addition of TNT. The response could even be observed by the naked eye. The limit of detection from fluorescence spectroscopic measurement was estimated to be approximately 375 nM. In addition to the rapid response (within a few seconds), selective detection was demonstrated. We believe this label-free chemical sensor contributes to progress for the on-site explosive sensing.

Bioremediation of Explosive TNT by Trichoderma viride.

Nitroaromatic and nitroamine compounds such as 2,4,6-trinitrotoluene (TNT) are teratogenic, cytotoxic, and may cause cellular mutations in humans, animals, plants, and microorganisms. Microbial-based bioremediation technologies have been shown to offer several advantages against the cellular toxicity of nitro-organic compounds. Thus, the current study was designed to evaluate the ability of Trichoderma viride to degrade nitrogenous explosives, such as TNT, by microbiological assay and Gas chromatography-mass spectrometry (GC-MS) analysis. In this study, T. viride fungus was shown to have the ability to decompose, and TNT explosives were used at doses of 50 and 100 ppm on the respective growth media as a nitrogenous source needed for normal growth. The GC/MS analysis confirmed the biodegradable efficiency of TNT, whereas the initial retention peak of the TNT compounds disappeared, and another two peaks appeared at the retention times of 9.31 and 13.14 min. Mass spectrum analysis identified 5-(hydroxymethyl)-2-furancarboxaldehyde with the molecular formula C6H6O3 and a molecular weight of 126 g·mol-1 as the major compound, and 4-propyl benzaldehyde with a formula of C10H12O and a molecular weight of 148 g mol-1 as the minor compound, both resulting from the biodegradation of TNT by T. viride. In conclusion, T. viride could be used in microbial-based bioremediation technologies as a biological agent to eradicate the toxicity of the TNT explosive. In addition, future molecular-based studies should be conducted to clearly identify the enzymes and the corresponding genes that give T. viride the ability to degrade and remediate TNT explosives. This could help in the eradication of soils contaminated with explosives or other toxic biohazards.

Application of Ti/IrO2 electrode in the electrochemical oxidation of the TNT red water.

Via the thermal sintering, a nanocrystalline IrO2 coating was formed on the Ti substrate to successfully prepare a Ti/IrO2 electrode. Based on the electrochemical analysis, the prepared Ti/IrO2 electrode was found to have powerful oxidation effect on the organics in the TNT red water, where the nitro compound was oxidized through an irreversible electrochemical process at 0.6 V vs. SCE. According to the analysis of the nitro compound content, the UV-vis spectra, and the FTIR spectra of 2,4,6-trinitrotoluene (TNT) red water with electrolytic periods, the degradation mechanism of the dinitrotoluene sulfonate (DNTS) was developed. And the intermediates were characterized by UPLC-HRMS. The DNTS mainly occurred one electron transfer reaction on the Ti/IrO2 electrode. At the early stage of the electrolysis, the polymerization of DNTS was mainly dominated. The generated polymer did not form a polymer film on the electrode surface, but instead it promoted a further reduction. After electrolyzing for 30 h, all NO2 function group in the TNT red water was degraded completely.

13C and 15N NMR identification of product compound classes from aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene.

Photolysis is one of the main transformation pathways for 2,4,6-trinitrotoluene (TNT) released into the environment. Upon exposure to sunlight, TNT is known to undergo both oxidation and reduction reactions with release of nitrite, nitrate, and ammonium ions, followed by condensation reactions of the oxidation and reduction products. In this study, compound classes of transformation products from the aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene (TNT) have been identified by liquid and solid state 13C and 15N NMR. Aqueous phase experiments were performed on saturated solutions of T15NT in deionized water, natural pond water (pH = 8.3, DOC = 3.0 mg/L), pH 8.0 buffer solution, and in the presence of Suwannee River Natural Organic Matter (SRNOM; pH = 3.7), using a Pyrex-filtered medium pressure mercury lamp. Natural sunlight irradiations were performed on TNT in the solid phase and dissolved in the pond water. In deionized water, carboxylic acid, aldehyde, aromatic amine, primary amide, azoxy, nitrosophenol, and azo compounds were formed. 15N NMR spectra exhibited major peaks centered at 128 to 138 ppm, which are in the range of phenylhydroxylamine and secondary amide nitrogens. The secondary amides are proposed to represent benzanilides, which would arise from photochemical rearrangement of nitrones formed from the condensation of benzaldehyde and phenylhydroxylamine derivatives of TNT. The same compound classes were formed from sunlight irradiation of TNT in the solid phase. Whereas carboxylic acids, aldehydes, aromatic amines, phenylhydroxylamines, and amides were also formed from irradiation of TNT in pond water and in pH 8 buffer solution, azoxy and azo compound formation was inhibited. Solid state 15N NMR spectra of photolysates from the lamp irradiation of unlabeled 2,6-dinitrotoluene in deionized water also demonstrated the formation of aromatic amine, phenylhydroxylamine/ 2° amide, azoxy, and azo nitrogens.

Molecular Simulation Studies on the Interactions of 2,4,6-Trinitrotoluene and Its Metabolites with Lipid Membranes.

The penetration of chemicals into biological membranes is a key factor in the determination of their possible effects on organisms; this complex process involves mainly the interaction between chemicals and membranes. Here, we reported the interaction between a highly toxic class of explosives [2,4,6-trinitrotoluene (TNT) and its metabolites] and lipid membranes using molecular dynamics simulations. We calculated the permeability coefficient, transmembrane time, and liposome-water partition coefficient by integrating free-energy curves for all species. The results showed that TNT had a lower transmembrane capacity than its metabolites. Based on the liposome-water partition coefficient, we demonstrated that the membrane affinity of TNT is larger than that of its diamino metabolites but less than that of its monoamino metabolites. This result can qualitatively explain the difference of bioconcentration factors in experiments. The accumulation of TNT and metabolites in membranes can change the membrane structure, such as the area per lipid, the thickness of lipid bilayers, and the order of lipid tails and, further, the penetration of water. All of these are closely related to the interactions (mainly hydrogen bonds) of TNT and metabolites with lipid and water molecules. This work has a certain significance for understanding the toxicity of TNT and its metabolites.

Investigation of Size-Dependent Sublimation Kinetics of 2,4,6-Trinitrotoluene (TNT) Micro-Islands Using In Situ Atomic Force Microscopy.

Kinetic thermal analysis was conducted using in situ atomic force microscopy (AFM) at a temperature range of 15-25 °C to calculate the activation energy of the sublimation of 2,4,6-trinitrotoluene (TNT) islands. The decay of different diameter ranges (600-1600 nm) of TNT islands was imaged at various temperatures isothermally such that an activation energy could be obtained. The activation energy of the sublimation of TNT increases as the diameter of islands increases. It was found that the coarsening and the sublimation rate of TNT islands can be determined by the local environment of the TNT surface. This result demonstrates that a diffusion model cannot be simply applied to "real world" systems for explaining the sublimation behavior and for estimating the coarsening of TNT.

Experimental and numerical evaluation of a genetically engineered M13 bacteriophage with high sensitivity and selectivity for 2,4,6-trinitrotoluene.

Selective and sensitive detection of desired targets is very critical in sensor design. Here, we report a genetically engineered M13 bacteriophage-based sensor system evaluated by quantum mechanics (QM) calculations. Phage display is a facile way to develop the desired peptide sequences, but the resulting sequences can be imperfect peptides for binding of target molecules. A TNT binding peptide (WHW) carrying phage was self-assembled to fabricate thin films and tested for the sensitive and selective surface plasmon resonance-based detection of TNT molecules at the 500 femtomole level. SPR studies performed with the WHW peptide and control peptides (WAW, WHA, AHW) were well-matched with those of the QM calculations. Our combined method between phage engineering and QM calculation will significantly enhance our ability to design selective and sensitive sensors.

Non-Isothermal Sublimation Kinetics of 2,4,6-Trinitrotoluene (TNT) Nanofilms.

Non-isothermal sublimation kinetics of low-volatile materials is more favorable over isothermal data when time is a crucial factor to be considered, especially in the subject of detecting explosives. In this article, we report on the in-situ measurements of the sublimation activation energy for 2,4,6-trinitrotoluene (TNT) continuous nanofilms in air using rising-temperature UV-Vis absorbance spectroscopy at different heating rates. The TNT films were prepared by the spin coating deposition technique. For the first time, the most widely used procedure to determine sublimation rates using thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) was followed in this work using UV-Vis absorbance spectroscopy. The sublimation kinetics were analyzed using three well-established calculating techniques. The non-isothermal based activation energy values using the Ozawa, Flynn⁻Wall, and Kissinger models were 105.9 ± 1.4 kJ mol-1, 102.1 ± 2.7 kJ mol-1, and 105.8 ± 1.6 kJ mol-1, respectively. The calculated activation energy agreed well with our previously reported isothermally-measured value for TNT nanofilms using UV-Vis absorbance spectroscopy. The results show that the well-established non-isothermal analytical techniques can be successfully applied at a nanoscale to determine sublimation kinetics using absorbance spectroscopy.