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1.
Trinitrotoluene, known as TNT, is a widely used powerful explosive. It is a poisonous material, which injures almost all cells, especially those of liver, bone marrow, and kidney. Estrone is a sex hormone having an electron rich aromatic (phenolic) ring that is capable of forming a π complex with molecules containing an electron deficient π system. This study has focused on investigating the tendency of the complex formation of TNT with estrone. It has been thought that the formation of estrone‐TNT π complex might take place in a human body exposed to acute or prolong period of this hazardous chemical and consequently estrone activities might be impaired. The complex formation reaction was investigated mainly using DFT method with B3LYP/6‐31G(d, p) basis set in gas phase. The existence of π interaction between estrone and TNT was demonstrated by computational spectroscopic analyses (UV/Vis, IR, and 1H NMR techniques). The frontier molecular orbital (HOMO and LUMO) analyses have shown that the considered π complex is very resistant to oxidation with respect to its components, estrone and TNT.  相似文献   

2.
影响TiO2纳米管光电催化还原Cr(VI)的因素探讨   总被引:1,自引:0,他引:1  
汪青  尚静  宋寒 《催化学报》2011,32(9):1525-1530
采用阳极氧化法在Ti基底上生长TiO2纳米管(TNT)阵列薄膜,利用扫描电镜和X射线衍射对样品的形貌和结构进行了表征.以TNT薄膜为光阳极、Ti网为光阴极,在酸性条件下进行紫外光光电催化还原Cr(VI),探讨了外加偏压、NaCl浓度、柠檬酸浓度以及Cr(VI)初始浓度对反应性能的影响.结果表明,外加电压有效地促进了电子...  相似文献   

3.
Silica xerogels incorporated with trinitrotoluene (TNT) and pentaerythritoltetranitrate (PETN) were synthesized using sol–gel method. Tetramethoxysilane was used as precursor for silica. TNT and PETN content in the resulted explosive/silica xerogel was varied ranging from 50 to 90%. Infra red spectra showed that explosives were retained in the silica xerogel matrix. Transmission electron microscopy (TEM) reveal that explosives particles were uniformly distributed in xerogel matrix and the size of the PETN and TNT particles are in the range 15–18 nm. Small angle x-ray scattering showed that the sizes of the pores in the silica matrix are in the range 25–13 nm. The particles of TNT and PETN occupy the pores in the matrix resulting in gradual reduction of pore-size affecting the surface characteristics of the pore-matrix interface. Understanding of the structure of aggregates of small particles thus produced could be useful to explain the properties shown by the fine explosives. Our study suggests that particle size of explosives in the nanometer range can be achieved using the sol–gel method.  相似文献   

4.
This article describes a rapid and reliable electrochemical/enzymatic method of verifying the presence of nitroaromatic explosives. The new technique leverages both conventional voltammetric analysis and biocatalytic conversion of TNT. The simultaneous use of independent measurement schemes, based on two distinct processes, dramatically increases the information content and offers substantially improved reliability while minimizing the occurrence of false alarms. This has been accomplished by coupling direct voltammetric analysis with the biocatalytic conversion of the TNT substrate via nitroreductase (NR), which reduces a nitro group of TNT using NADH as an electron donor. This chemical reduction (30 s timescale) can then be observed using square‐wave voltammetry by examination of the reductive and oxidative features. This novel protocol was found to be selective for TNT, not only when compared to DNT and NT, but also to other explosive species such as RDX and PETN. This unique dual‐mode detection strategy for measuring TNT at a single device holds considerable promise for improving the probability of explosive detection and hence for diverse security screening applications.  相似文献   

5.
Contaminated land and groundwater remediation in military waste dumping sites often necessitates the use of simple, cost-effective, and rapid tests for detecting trinitrotoluene (TNT) residues in the field along with their dinitro-analogues. A simple, rapid, low-cost, and field-adaptable (on-site) colorimetric method was developed for quantifying TNT in the presence of RDX, PETN, picric acid, 2,4-DNT (dinitrotoluene), dinitrophenol, and dinitroaniline. Most commercialized methods for TNT assay-with the exception of Cold Regions Research and Engineering Laboratory of the U.S. Army (CRREL) method-use proprietary chemicals, and the color stability and intensity are highly dependent on the composition of the organic solution comprised of acetone or methanol. The developed colorimetric method is based on the extraction of TNT from water-acetone solution into an organic solvent mixture of dicyclohexylamine (DCHA)-isobutyl methyl ketone (IBMK) (10:1, v/v), filtration through a filter paper into a stoppered optical cell containing anhydrous sodium sulfate, and measurement of the absorbance of the organic extract at 531 nm after 5 min. The red-violet color of the extract was due to intermolecular charge-transfer (CT) between the electron attracting TNT and electron-donating DCHA, and the molar absorptivity for TNT in final organic solution was (1.16 ± 0.02) × 104 L mol−1 cm−1.The R.S.D. of the slope of calibration line was 0.7%. The LOD of the method in the final organic phase was 0.38 μM TNT, and LOD values expressed on the basis of original soil TNT content were 0.5, 1.3, and 1.5 ppm (μg g−1) for clay, loamy clay, and sandy soils, respectively. Unlike other spectrophotometric methods, the developed assay was basically tolerant to common cations and anions found in soil and water at 100-fold weight ratios, and to soil humic acids. Among a number of compounds that may be encountered in polynitro-explosive storage and waste reclaimation sites such as picric acid, dinitrophenol, 2,4-dinitrotoluene, dinitroaniline, RDX, PETN, and tetryl, only tetryl interfered with the developed TNT assay. Water tolerance and exploitability over a wide pH range were other superiorities over the CRREL method. The CT-complex was relatively stable, as the absorbance of the organic extract was not significantly influenced from the dilution of the water-acetone phase. Aside from the extractive-photometric procedure established for aqueous solutions, a simulated field colorimetric assay for TNT directly applicable to soil was also devised, based on direct color development in a 4:1 (v/v) acetone-dicyclohexylamine organic extract of soil at a liquid-to-solid ratio of 5 mL g−1.  相似文献   

6.
2,4,6‐Trinitrotoluene (TNT) is a widely used nitroaromatic explosive with significant detrimental effects on the environment and human health. Its detection is of great importance. In this study, both electrochemiluminescence (ECL)‐based detection of TNT through the formation of a TNT–amine complex and the detection of TNT through electrochemiluminescence resonance energy transfer (ECRET) are developed for the first time. 3‐Aminopropyltriethoxysilane (APTES)‐modified [Ru(phen)3]2+ (phen=1,10‐phenanthroline)‐doped silica nanoparticles (RuSiNPs) with uniform sizes of (73±3) nm were synthesized. TNT can interact with APTES‐modified RuSiNPs through charge transfer from electron‐rich amines in the RuSiNPs to the electron‐deficient aromatic ring of TNT to form a red TNT–amine complex. The absorption spectrum of this complex overlaps with the ECL spectrum of the APTES‐modified RuSiNPs/triethylamine system. As a result, ECL signals of the APTES‐modified RuSiNPs/triethylamine system are turned off in the presence of TNT owing to resonance energy transfer from electrochemically excited RuSiNPs to the TNT–amine complex. This ECRET method has been successfully applied for the sensitive determination of TNT with a linear range from 1×10?9 to 1×10?6 M with a fast response time within 1 min. The limit of detection is 0.3 nM . The method exhibits good selectivity towards 2,4‐dinitrotoluene, p‐nitrotoluene, nitrobenzene, phenol, p‐quinone, 8‐hydroxyquinoline, p‐phenylenediamine, K3[Fe(CN)6], Fe3+, NO3?, NO2?, Cr3+, Fe2+, Pb2+, SO32?, formaldehyde, oxalate, proline, and glycine.  相似文献   

7.
The unimolecular decomposition reaction of TNT can in principle be used to design ways to either detect or remove TNT from the environment. Here, we report the results of a density functional theory study of possible ways to lower the reaction barrier for this decomposition process by ionization, so that decomposition and/or detection can occur at room temperature. We find that ionizing TNT lowers the reaction barrier for the initial step of this decomposition. We further show that a similar effect can occur if a positive moiety is bound to the TNT molecule. The positive charge produces a pronounced electron redistribution and dipole formation in TNT with minimal charge transfer from TNT to the positive moiety.  相似文献   

8.
This paper reports an inverted opal fluorescence chemosensor for the ultrasensitive detection of explosive nitroaromatic vapors through resonance‐energy‐transfer‐amplified fluorescence quenching. The inverted opal silica film with amino ligands was first fabricated by the acid–base interaction between 3‐aminopropyltriethoxysilane and surface sulfonic groups on polystyrene microsphere templates. The fluorescent dye was then chemically anchored onto the interconnected porous surface to form a hybrid monolayer of amino ligands and dye molecules. The amino ligands can efficiently capture vapor molecules of nitroaromatics such as 2,4,6‐trinitrotoluene (TNT) through the charge‐transfer complexing interaction between electron‐rich amino ligands and electron‐deficient aromatic rings. Meanwhile, the resultant TNT–amine complexes can strongly suppress the fluorescence emission of the chosen dye by the fluorescent resonance energy transfer (FRET) from the dye donor to the irradiative TNT–amino acceptor through intermolecular polar–polar resonance at spatial proximity. The quenching response of the highly ordered porous films with TNT is greatly amplified by at least 10‐fold that of the amorphous silica films, due to the interconnected porous structure and large surface‐to‐volume ratio. The inverted opal film with a stable fluorescence brightness and strong analyte affinity has lead to an ultrasensitive detection of several ppb of TNT vapor in air.  相似文献   

9.
A sensitive electrochemical sensor has been fabricated to detect ultratrace nitroaromatic explosives using ordered mesoporus carbon (OMC). OMC was synthesized and characterized by scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption measurements. Glassy carbon electrodes functionalized with OMC show high sensitivity of 62.7 μA cm−2 per ppb towards 2,4,6-trinitrotoluene (TNT). By comparison with other materials such as carbon nanotubes and ordered mesoporous silica, it is found that the high performance of OMC toward sensing TNT is attributed to its large specific surface area and fast electron transfer capability. As low as 0.2 ppb TNT, 1 ppb 2,4-dinitrotoluene and 1 ppb 1,3-dinitrobenzene can be detected on OMC based electrodes. This work renders new opportunities to detect ultratrace explosives for applications of environment protections and home securities against chemical warfare agents.  相似文献   

10.
报道了一种基于TiO2纳米管(TNT)阵列正面透光型光阳极的高效染料敏化太阳能电池.将TNTs在450°C烧结后能避免其有序结构在HF处理过程中被破坏,使膜内高速电子传输通道被保留,有利于染料敏化太阳能电池(DSSC)实现高速电荷传输.再用HF、TiCl4、HF和TiCl4混合等溶剂对TNTs进行处理,提高其表面粗糙度以吸附更多染料.染料吸附量的增加能提高光阳极在300-570 nm波段光子捕获效率,该波段是染料吸收光子的主要区域.然而,在染料吸收光子较弱的长波段区域(570-800 nm)光子捕获效率的增加主要源于光阳极光散射率的提高.光阳极光子捕获效率的提高使DSSC的内外量子效率在全波段(300-800 nm)均有所增加,从而使短路电流明显提高.从电化学阻抗数据可知,与电子传输性能密切相关的电化学参数如电荷传输电阻、界面电荷复合电阻、电容、电子寿命、电子扩散长度和电子收集效率等在含处理过的TNTs光阳极DSSC中均有所改善,从而提高电池光电转换效率.含HF和TiCl4混合溶剂处理TNTs光阳极的DSSC最高光电转换效率能达到7.30%,比未处理的DSSC(5.38%)提高35.69%.  相似文献   

11.
TNT (2,4,6-trinitrotoluene) formed deep red 1:1 CT complexes with chromogenic agents like isopropylamine, ethylenediamine, bis(3-aminopropyl)amine and tetraethylenepentamine in DMSO. The complexes were also observed in solvents like methanol, acetone, etc. when the amines were present in large excess. The isopropylamine, complex showed three absorption peaks (at 378, 532 and 629 nm) whereas higher amines showed four peaks (at 370, 463, 532 and 629 nm). The peak at 463 nm vanished rapidly. The peak of the complexes near 530 nm required about 8-10 min to develop and the complexes were stable for about an hour but the peak slowly shifted towards 500 nm and the complexes were found to be stable for more than 24 h. The evidence of complex formation was obtained from distinct spots in HPTLC plates and from the shifts in frequencies and formation of new peaks in FTIR spectra. The peaks near 460 nm (transient) and 530 nm may be due to Janovsky reaction but could not be established. The extinction coefficients of the complexes were determined directly which enabled the accurate determination of the association constants KDA with TNT and amines in stoichiometric ratios. The results were verified using iterative method. The quantification of TNT was made using epsilon value of the complex with ethylenediamine. The vertical electron affinity (EA) of TNT was calculated using the method suggested by Mulliken.  相似文献   

12.
In this paper, the capture of radiocadmium (Cd(II)) by adsorption onto the titanate nanotube/iron oxide (TNT/IOM) magnetic composite as a function of contact time, pH, ionic strength, foreign cation and anion ions, humic acid (HA) and fulvic acid (FA) was studied using batch technique. The results indicated that the adsorption of Cd(II) onto the TNT/IOM magnetic composite was dependent on ionic strength at pH <9.0, but was independent of ionic strength at pH >9.0. Outer-sphere surface complexation were the main mechanism of Cd(II) adsorption onto the TNT/IOM magnetic composite at low pH values, whereas the adsorption was mainly dominated via inner-sphere surface complexation at high pH values. The adsorption of Cd(II) onto the TNT/IOM magnetic composite was dependent on foreign cation and anion ions at low pH values, but was independent of foreign cation and anion ions at high pH values. A positive effect of HA/FA on Cd(II) adsorption onto the TNT/IOM magnetic composite was found at low pH values, while a negative effect was observed at high pH values. From the results of Cd(II) removal by the TNT/IOM magnetic composite, the optimum reaction conditions can be obtained for the maximum removal of Cd(II) from water. It is clear that the best pH values of the system to remove Cd(II) from solution by using the TNT/IOM magnetic composite are 7.0–8.0. Considering the low cost and effective disposal of Cd(II)-contaminated wastewaters, the best condition for Cd(II) capture by the TNT/IOM magnetic composite is at room temperature and solid content of 0.5 g L?1. These results are quite important for estimating and optimizing the removal of Cd(II) and related metal ions by the TNT-based magnetic composite.  相似文献   

13.
Titanate nanotubes (TNT) were proven to be efficient support for the immobilization of methylene blue (MB). UV–vis absorption and Fourier transform infrared spectra showed that the effect of MB absorbed on TNT was better than nanocrystalline anatase TiO2 (TNP). The quantity of MB absorbed onto TNT was found to be greater than that of TNP and the electrode modified with the MB–TNT film was more stable due to the strong interaction between TNT and MB as well. The absorption of MB on TNT was impacted by the pH value of the reaction solution for the change of surface charge. Electrochemical oxidation of dopamine (DA) at different electrodes was studied. The result showed that the MB–TNT composite film exhibited excellent catalytic activities to DA compared to those of pure TNT, which is a result of the great promotion of the electron-transfer rate between DA and the electrode surface by the MB–TNT film. Furthermore, the layer-by-layer self-assembly behavior of the electrochemically functional MB–TNT nanocomposite was also discussed after obtaining the stable colloid suspension of MB–TNT. The excellent electrochemical ability and the easy fabrication of layered nanocomposite make the MB–TNT nanocomposite very promising in electrochemistry study and new nanotube-based devices.  相似文献   

14.
In this work, we report the absorption and confinement of 2,4,6-trinitrotoluene (TNT) in porous metals (Ag, Ag/Al, and Ag/Cu), and the effect of the physical properties of the metal on the calorimetric properties of TNT using thermogravimetric analysis and differential scanning calorimetry. The surface area and pore size distribution of the confiners were calculated to determine their effect on both the onset temperature and the rate at which TNT volatilizes. Confinement of TNT into the mixed metal sponges was confirmed by scanning electron microscopy. Overall, this study provides an insight into the fundamental factors influencing the properties of energetic materials under confinement that could potentially allow for more controlled and reliable degradation techniques depending on the characteristics of the porous material.  相似文献   

15.
This paper demonstrates a new electrochemical method for the detection of ultratrace amount of 2,4,6-trinitrotoluene (TNT) with synthetic copolypeptide-doped polyaniline nanofibers. The copolypeptide, comprising of glutamic acid (Glu) and lysine (Lys) units, is in situ doped into polyaniline through the protonation of the imine nitrogen atoms of polyaniline by the free carboxylic groups of Glu segments, resulting in the formation of polyaniline nanofibers of emeraldine salt. The free amino groups of Lys segments at the surface of nanofibers provide the receptor sites of TNT through the formation of charge-transfer complex between the electron-rich amino groups and the electron-deficient aromatic rings. Adsorptive stripping voltammetry results demonstrate that the poly(Glu-Lys)-doped nanofibers confined onto glassy carbon electrodes exhibit a remarkable enriching effect and thus sensitive electrochemical response to TNT with a linear dynamic range of 0.5-10 μM and a detection limit down to 100 nM. Moreover, other kinds of nitro compounds show different redox behaviors from TNT at the doped nanofibers, and thus do not interfere with the electrochemical detection of TNT. This study essentially offers a new and simple method for electrochemical detection of ultratrace TNT.  相似文献   

16.
Erol Erça? 《Talanta》2009,78(3):772-90
Because of the extremely heterogeneous distribution of explosives in contaminated soils, on-site colorimetric methods are efficient tools to assess the nature and extent of contamination. To meet the need for rapid and low-cost chemical sensing of explosive traces or residues in soil and post-blast debris, a colorimetric absorption-based sensor for trinitrotoluene (TNT) determination has been developed. The charge-transfer (CT) reagent (dicyclohexylamine, DCHA) is entrapped in a polyvinylchloride (PVC) polymer matrix plasticised with dioctylphtalate (DOP), and moulded into a transparent sensor membrane sliced into test strips capable of sensing TNT showing an absorption maximum at 530 nm when placed in a 1-mm spectrophotometer cell. The sensor gave a linear absorption response to 5-50 mg L−1 TNT solutions in 30% aqueous acetone with limit of detection (LOD): 3 mg L−1. The sensor is only affected by tetryl, but not by RDX, pentaerythritoltetranitrate (PETN), dinitrotoluene (DNT), and picric acid. The proposed method was statistically validated for TNT assay against high performance liquid chromatography (HPLC) using a standard sample of Comp B. The developed sensor was relatively resistant to air and water, was of low-cost and high specificity, gave a rapid and reproducible response, and was suitable for field use of TNT determination in both dry and humid soil and groundwater with a portable colorimeter.  相似文献   

17.
The reduction and oxidation properties of four nitrocompounds (trinitrotoluene [TNT], 2,4‐dinitrotoluene, 2,4‐dinitroanisole, and 5‐nitro‐2,4‐dihydro‐3H‐1,2,4‐triazol‐3‐one [NTO]) dissolved in water as compared with the same properties for compounds adsorbed on a silica surface were studied. To consider the influence of adsorption, cluster models were developed at the M05/tzvp level. A hydroxylated silica (001) surface was chosen to represent a key component of soil. The PCM(Pauling) and SMD solvation models were used to model water bulk influence. The following properties were analyzed: electron affinity, ionization potential, reduction Gibbs free energy, oxidation Gibbs free energy, and reduction and oxidation potentials. It was found that adsorption and solvation decrease gas phase electron affinity, ionization potential, and Gibbs free energy of reduction and oxidation, and thus, promote redox transformation of nitrocompounds. However, in case of solvation, the changes are more significant than for adsorption. This means that nitrocompounds dissolved in water are easier to transform by reduction or oxidation than adsorbed ones. Among the considered compounds, TNT was found to be the most reactive in an electron attachment process and the least reactive for an electron detachment transformation. During ionization, a deprotonation of adsorbed NTO was found to occur. © 2015 Wiley Periodicals, Inc.  相似文献   

18.
Three new electron‐rich metal–organic frameworks ( MOF‐1 – MOF‐3 ) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3 , on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (KS) as well as collisional constants (KC) has revealed that MOF‐1 and MOF‐2 have higher KS values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.  相似文献   

19.
Titanate nanotubes (TNT) were prepared via a hydrothermal treatment of TiO(2) powders (P25) in a 10 M NaOH solution at 150 degrees C for 24 h and subsequently washed with HCl aqueous solution of different concentrations (0.1, 0.01, and 0.001 N). Samples with different contents of remnant sodium in nanotubes were characterized, as synthesized and after heat-treatment, by transmission electron microscopy, X-ray diffraction, and nitrogen adsorption-desorption isotherms. The photocatalytic activity of TNT was evaluated by photocatalytic oxidation of basic dye (basic violet 10 (BV10)) in water solution. It was found that if the sodium was not completely exchanged with proton, the removal of sodium increased the specific surface area (and pore volume), while the thermal stability was reduced. When the sodium content of TNT was approximately 0 wt% (nearly complete proton exchange), the nanotubular structure of titanates might be destroyed. The effects of the alterations of microstructures induced by the exchange of sodium and heat-treatment on the photocatalytic activity of TNT were discussed with the variations of specific surface area, pore volume, and the amounts of anatase phase in TNT.  相似文献   

20.
We have developed a new immunosensor based on self-assembly chemistry for highly sensitive and label-free detection of 2,4,6-trinitrotoluene (TNT) using surface plasmon resonance (SPR). A monolayer of amine terminated poly(ethylene glycol) hydrazinehydrochloride (PEG-NH2) thiolate was constructed on an activated gold surface and immobilized with trinitrophenyl-β-alanine (TNPh-β-alanine) by amide coupling method. The binding interaction of a monoclonal anti-TNT Ab (M-TNT Ab) with TNPh-β-alanine immobilized thiolate monolayer surface was monitored and evaluated for detection of TNT based on the principle of indirect competitive immunoreaction. Here, the competition between the self-assembled TNT derivative and the TNT in solution for binding with antibody yields in the response signal that is inversely proportional to the concentration of TNT in the linear detection range. With the present immunoassay format, TNT could be detected in the concentration range from 0.008 ng/ml (8 ppt) to 30 ng/ml (30 ppb). The response time for an immunoreaction was 2 min and one immunocycle could be done with in 4 min including surface regeneration. Bound antibodies could be easily eluted from the self-assembled immunosurface at high recoveries (more than 100 cycles) using pepsin solution without any damage to the TNT derivatives immobilized on the surface. The compact self-assembled monolayer was highly stable and prevented the non-specific adsorption of proteins on the surface favoring error free measurement.  相似文献   

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