Theoretical studies on the unimolecular decomposition of nitroglycerin

To improve the understanding of the unimolecular decomposition mechanism of nitroglycerin (NG) in the gas phase, density functional theory calculations were performed to determine various decomposition channels at the B3LYP/6-311G** level. For the unimolecular decomposition mechanism of NG, we find two main mechanisms: (I) homolytic cleavage of O-NO₂ to form ?NO₂ and CH₂ONO₂CHONO₂CH₂O?, which subsequently decomposes to form ?CHO, ?NO₂, and 2CH₂O; (II) successive HONO eliminations to form HONO and CHO-CO-CHO, which subsequently decomposes to form CH₂O?+?2CO₂ and ?CHO?+?CO. We also find that the former channel has slightly smaller activation energy than the latter one. In addition, the rate constants of the initial process of the two decomposition channels were calculated. The results show that the O-NO₂ cleavage pathway occurs more easily than the HONO elimination.     

Adsorption and decomposition mechanism of hexogen (RDX) on Al(111) surface by periodic DFT calculations

The adsorption of hexogen (RDX) molecule on the Al(111) surface was investigated by the generalized gradient approximation (GGA) of density functional theory (DFT). The calculations employ a supercell (4×4×3) slab model and three-dimensional periodic boundary conditions. The strong attractive forces between RDX molecule and aluminum atoms induce the N?O and N?N bond breaking of the RDX. Subsequently, the dissociated oxygen atoms, NO₂ group and radical fragment of RDX oxidize the Al surface. The largest adsorption energy is ?835.7 kJ mol^–1. We also investigated the adsorption and decomposition mechanism of RDX molecule on the Al(111) surface. The activation energy for the dissociation steps of V4 configuration is as large as 353.1 kJ mol^–1, while activation energies of other configurations are much smaller, in the range of 70.5–202.9 kJ mol^–1. The N?O is even easier than the N?NO₂ bond to decompose on the Al(111) surface.     

Simulating the evolution of signal transduction pathways

We use a generic model of a network of proteins that can activate or deactivate each other to explore the emergence and evolution of signal transduction networks and to gain a basic understanding of their general properties. Starting with a set of non-interacting proteins, we evolve a signal transduction network by random mutation and selection to fulfill a complex biological task. In order to validate this approach we base selection on a fitness function that captures the essential features of chemotactic behavior as seen in bacteria. We find that a system of as few as three proteins can evolve into a network mediating chemotaxis-like behavior by acting as a "derivative sensor". Furthermore, we find that the dynamics and topology of such networks show many similarities to the natural chemotaxis pathway, that the response magnitude can increase with increasing network size and that network behavior shows robustness towards variations in some of the internal parameters. We conclude that simulating the evolution of signal transduction networks to mediate a certain behavior may be a promising approach for understanding the general properties of the natural pathway for that behavior.     

Reaction pathways in the decomposition of hydrogen peroxide catalyzed by copper(II)

The kinetics of the decomposition of H(2)O(2) catalyzed by Cu(II) has been studied by the initial-rate method in aqueous phosphate media at near physiological pH. The activity of the catalyst is increased by [Fe(CN)(6)](3-) and decreased by VO(3)(-), CrO(4)(2-) and Zn(II). Three reaction pathways are involved in the Cu(II)-H(2)O(2) reaction, the kinetic orders of the catalyst being 1 (rate constant k1), 2 (rate constant k2) and 3 (rate constant k3). The three pathways present fractional apparent orders (>1) in H(2)O(2) and base catalysis. The apparent activation energies associated to rate constants k1, k2 and k3 are 102+/-4, 65+/-8 and 61+/-5 kJ mol(-1). Free-radical chain mechanisms are proposed for the three pathways.     

Theoretical study of the decomposition mechanisms and kinetics of the ingredients RDX in composition B

RDX as a component in composition B (TNT + RDX) was first studied by us on its mechanism and kinetics of decomposition reactions in this paper. We have pointed out three possible pathways and found a new low-energy process of its decomposition. The N-N bond cleavage in composition B has higher dissociation energies than the monomer, but it is also the initial step. The optimized structures and the frequencies of all the stationary points were calculated at the B3LYP/6-31G(d) level. The minimum-energy paths were obtained by using the intrinsic reaction coordinate (IRC) theory, and the reaction potential energy curve was corrected with zero-point energy. Finally, the rate constants were calculated in a wide temperature region from 200 to 2500 K using TST, TST/Eckart theories. The obtained results also indicate that the tunneling effects are remarkable at low temperature (200 K 相似文献   

Fungal interactions with the explosive RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine)

The bacterially mediated, anaerobic biodegradation of the explosive RDX (hexahydro 1,3,5 trinitro-1,3,5-triazine) is well established. Reports of successful mineralization of RDX by white rot fungi, and the enhanced transformation of RDX in stirred as compared to static composts, led us to study the possible aerobic role of several filamentous fungi in RDX biodegradation.Cladosporium resinae, Cunninghamella echinulata varelegans, Cyathus pallidus andPhanerochaete chrysosporium were grown in the presence of 50 and 100 g ml^–1 of RDX on a vegetable juice agar. Little inhibition of radial growth was observed, while control cultures with TNT exhibited substantial inhibition. When 100 g ml^–1 of RDX was added to pre-grown mycelia in a nonlignolytic liquid medium, between 12 and 31% was lost after 3 days. In similar experiments using¹⁴C-RDX, most of the label remained in the organic fraction, and little or none was found in the aqueous fraction, the volatile fraction or incorporated into cell walls. Although disappearance of RDX was observed for all four species tested, there was no evidence of mineralization. Mixed cultures of microorganisms, including both bacteria and fungi, merit further study as agents for the decontamination of munitions-contaminated soils.     

Cationic ligands for Ag(I): Organometallic polymers versus unimolecular complexes

We have prepared and characterized two cationic ligands and their Ag(I) coordination compounds. For the bidentate ligand 2, 2,2-bis-pyridin-2-ylmethyl-2,3-dihydro-1H-isoindolium bromide, we obtained the organometallic polymer [AgL]_x[CF₃SO₃]_2x (4), and the unimolecular complex [AgL₂][PF₆]₃ (5). Compound 4 exists as an organometallic linear polymer with triflate anions either bonded to Ag(I) or non-bonded and sandwiched between the polymer chains. Complex 5 is the only unimolecular example in this series due to the non-interaction of anions with Ag(I) or with the cationic portion of the ligand. In the case of the tridentate cationic ligand 3-(3-pyridin-2-yl-2-pyridin-2-ylmethy-propyl)-benzyl-triethylammonium bromide (3), two dimeric Ag(I) complexes are formed, [Ag₂L₂][CF₃SO₃]₄ (6), and [Ag₂(CH₃CN₂)₂L₂][PF₆]₄ (7). Both of these dimers have essentially similar structures, with a closed-shell Ag(I)?Ag(I) interaction of approximately 3.00 Å in both cases; the pyridyl moieties of the ligands are forced into an electronically unfavourable face-to-face arrangement. The coordination spheres of the Ag(I) cations are completed by in the case of 6, and by CH₃CN solvent in the case of 7. In the extended packing diagrams, the arrangements of 6 and 7 are driven by intermolecular π-stacking and cation-anion interactions.     

Molecular simulations of adsorption of RDX and TATP on IRMOF-1(Be)

The influence of different sorption sites of isoreticular metal-organic frameworks (IRMOFs) on interactions with explosive molecules is investigated. Different connector effects are taken into account by choosing IRMOF-1(Be) (IRMOF-1 with Zn replaced by Be), and two high explosive molecules: 1,3,5-trinitro-s-triazine (RDX) and triacetone triperoxide (TATP). The key interaction features (structural, electronic and energetic) of selected contaminants were analyzed by means of density functional calculations. The interaction of RDX and TATP with different IRMOF-1(Be) fragments is studied. The results show that physisorption is favored and occurs due to hydrogen bonding, which involves the C-H groups of both molecules and the carbonyl oxygen atoms of IRMOF-1(Be). Additional stabilization of RDX and TATP arises from weak electrostatic interactions. Interaction with IRMOF-1(Be) fragments leads to polarization of the target molecules. Of the molecular configurations we have studied, the Be-O-C cluster connected with six benzene linkers (1,4-benzenedicarboxylate, BDC), possesses the highest binding energy for the studied explosives (-16.4 kcal mol(-1) for RDX and -12.9 kcal mol(-1) for TATP). The main difference was discovered to be in the preferable adsorption site for adsorbates (RDX above the small and TATP placed above the big cage). Based on these results, IRMOF-1 can be suggested as an effective material for storage and also for separation of similar explosives. Hydration destabilizes most of the studied adsorption systems by 1-3 kcal mol(-1) but it leads to the same trend in the binding strength as found for the non-hydrated complexes.     

Lateral Transfer of Genes for Hexahydro-1,3,5-Trinitro-1,3,5-Triazine (RDX) Degradation

Recent studies demonstrated that degradation of the military explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by species of Rhodococcus, Gordonia, and Williamsia is mediated by a novel cytochrome P450 with a fused flavodoxin reductase domain (XplA) in conjunction with a flavodoxin reductase (XplB). Pulse field gel analysis was used to localize xplA to extrachromosomal elements in a Rhodococcus sp. and distantly related Microbacterium sp. strain MA1. Comparison of Rhodococcus rhodochrous 11Y and Microbacterium plasmid sequences in the vicinity of xplB and xplA showed near identity (6,710 of 6,721 bp). Sequencing of the associated 52.2-kb region of the Microbacterium plasmid pMA1 revealed flanking insertion sequence elements and additional genes implicated in RDX uptake and degradation.Past practices of production, application, and disposal of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) have resulted in widespread contamination. Environmental contamination is aggravated by its high mobility, contributing to more-widespread contamination of groundwater than by other commonly used explosives (27). Ingestion or inhalation of RDX is associated with neurological disorders and organ failure (38), and exposed wildlife show behavioral changes and suffer liver and reproductive damage (38). The U.S. Environmental Protection Agency (EPA) has classified RDX as a possible human carcinogen (37). These adverse effects have provided motivation to better understand the microbiology and biochemistry of RDX degradation.As yet there is relatively limited information concerning natural rates of microbial RDX degradation or degradation mechanisms; such information is needed to predict or control rates of degradation in the environment. Of the three general pathways for RDX degradation or transformation based on metabolite analysis outlined in the review by Crocker and associates (6), aerobic degradation initiated by XplA is among the better-characterized systems. This enzyme, a novel cytochrome P450 with a fused flavodoxin reductive domain (18, 33), was first identified by Seth-Smith et al. in Rhodococcus rhodochrous 11Y as being encoded by xplA (33). This gene has been identified in 24 bacterial isolates of the Corynebacterineae capable of utilizing RDX as a sole nitrogen source (4, 25, 32-34). While mammalian nitric oxide synthase family enzymes are known to be P450-like enzymes with fused flavodoxin domains, there are very few identified examples of this type of protein fusion among characterized microbial species (2, 15, 18, 24). Subsequent studies by Jackson and associates (18) demonstrated that XplA, in association with an electron-transferring flavodoxin reductase (XplB), functions to efficiently denitrate RDX aerobically to the aliphatic nitramine 4-nitro-2,4-diazabutanal (NDAB) (18). NDAB has been shown to serve as a viable nitrogen source for Methylobacterium sp. strain JS178 (13) and to be degraded by Phanerochaete chrysosporium (11). Thus, complete mineralization often appears to be mediated by multiple microbial populations.The capacity for microbial degradation of recalcitrant organics, many of which are apparently new to the biosphere as a result of chemical manufacture, is often determined by plasmids and associated mobile genetic elements (36, 39). Plasmids both serve as a reservoir of genetic information and promote metabolic innovation, since their replication is independent of the chromosome and they do not generally encode essential functions. Although it was earlier suggested that genes in Rhodococcus sp. strain DN22 associated with initial steps of RDX degradation are carried by plasmids (5), no direct evidence for an extrachromosomal location was provided. We now show that nearly identical genes for XplA and XplB are carried on plasmids in two phylogenetically and geographically distinct bacterial isolates: Microbacterium sp. strain MA1, isolated from North America (Milan, TN), and Rhodococcus rhodochrous 11Y, isolated from England (33). Thus, these genes are more broadly distributed within the Actinomycetales than previously recognized, and the near identity of gene sequence (6,710 of 6,721 bp) in these divergent genera is indicative of recent plasmid-mediated transfer. Analysis of approximately 52 kbp of sequence near xplA and xplB in strain MA1 revealed closely linked genes for transport and degradation that are flanked by transposable elements, suggesting that plasmid-carried xplA and xplB are part of a larger class I transposable element encoding both transport and degradation of RDX.     

RDX degrading microbial communities and the prediction of microorganisms responsible for RDX bioremediation

The explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) has caused significant soil and groundwater contamination. To remediate these sites, there is a need to determine which microorganisms are responsible for in situ biodegradation of RDX to enable the appropriate planning of bioremediation efforts. Here, studies are examined that have reported on the microbial communities linked with RDX biodegradation. Dominant microorganisms across samples are discussed and summarized. This information is then compared to current knowledge on RDX degrading isolates to predict which organisms may be responsible for RDX degradation in soils and groundwater. From the phyla with known RDX degrading isolates, Firmicutes and Proteobacteria (particularly Gammaproteobacteria) were the most dominant organisms in many contaminated site derived samples. Organisms in the phyla Deltaproteobacteria, Alphaproteobacteria and Actinobacteria were dominant in these studies less frequently. Notably, organisms within the class Betaproteobacteria were dominant in many samples and yet this class does not appear to contain any known RDX degraders. This analysis is valuable for the future development of molecular techniques to track the occurrence and abundance of RDX degraders at contaminated sites.     

Characterization ofClostridium bifermentans and its biotransformation of 2,4,6-trinitrotoluene (TNT) and 1,3,5-triaza-1,3,5-trinitrocyclohexane (RDX)

Summary We have determined that an organism able to degrade both RDX and TNT in a pure culture is a strain ofClostridium bifermentans. The consortium from which this organism is derived also degrades these compounds, and we suspect thatC. bifermentans is also the responsible organism within that consortium. The bioconversion of RDX and TNT occurs under anaerobic conditions both in the consortium and in pure culture without the need of an added reductant. The presence of co-metabolites speeded these biotransformations.     

Ovine Ruminal Microbes Are Capable of Biotransforming Hexahydro-1,3,5-Trinitro-1,3,5-Triazine (RDX)

Bioremediation is of great interest in the detoxification of soil contaminated with residues from explosives such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Although there are numerous forms of in situ and ex situ bioremediation, ruminants would provide the option of an in situ bioreactor that could be transported to the site of contamination. Bovine rumen fluid has been previously shown to transform 2,4,6-trinitrotoluene (TNT), a similar compound, in 4 h. In this study, RDX incubated in whole ovine rumen fluid was nearly eliminated within 4 h. Whole ovine rumen fluid was then inoculated into five different types of media to select for archaeal and bacterial organisms capable of RDX biotransformation. Cultures containing 30 μg mL⁻¹ RDX were transferred each time the RDX concentration decreased to 5 μg mL⁻¹ or less. Time point samples were analyzed for RDX biotransformation by HPLC. The two fastest transforming enrichments were in methanogenic and low nitrogen basal media. After 21 days, DNA was extracted from all enrichments able to partially or completely transform RDX in 7 days or less. To understand microbial diversity, 16S rRNA-gene-targeted denaturing gradient gel electrophoresis (DGGE) fingerprinting was conducted. Cloning and sequencing of partial 16S rRNA fragments were performed on both low nitrogen basal and methanogenic media enrichments. Phylogenetic analysis revealed similar homologies to eight different bacterial and one archaeal genera classified under the phyla Firmicutes, Actinobacteria, and Euryarchaeota. After continuing enrichment for RDX degraders for 1 year, two consortia remained: one that transformed RDX in 4 days and one which had slowed after 2 months of transfers without RDX. DGGE comparison of the slower transforming consortium to the faster one showed identical banding patterns except one band. Homology matches to clones from the two consortia identified the same uncultured Clostridia genus in both; Sporanaerobacter acetigenes was identified only in the consortia able to completely transform RDX. This is the first study to examine the rumen as a potential bioremediation tool for soils contaminated with RDX, as well as to discover S. acetigenes in the rumen and its potential ability to metabolize this energetic compound.     

Trace level detection of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by microimmunosensor.

Reported in this paper is the development and characterization of a highly sensitive microcapillary immunosensor for the detection of the explosive, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The immunosensor exploits antibodies as recognition elements for target antigens, fluorescence dye conjugates for reporter molecules and fused silica microcapillaries for its high surface-to-volume ratio. Detection of RDX with the microcapillary immunosensor requires covalent immobilization of anti-RDX antibodies on the inner core of the microcapillaries via heterobifunctional cross-linker chemistry. Subsequent saturation of all antibody binding domains follows with a synthetically prepared fluorescent analog of RDX. Displacement immunoassays were performed with the microcapillary immunosensor with the injection of unlabeled RDX at concentration levels from 1 part-per-trillion (pptr) to 1000 part-per-billion (ppb). As unlabeled RDX reaches the binding domain of the antibody, fluorescent RDX analog is displaced from the antibody, flows downstream and is measured by a spectrofluorometer. Fluorescence measurements of the displaced fluorescent RDX analog were equated to a standard calibration curve to quantify sample concentration. Complete evaluation of the RDX microcapillary immunosensor for selectivity and sensitivity was performed based on the following criteria: variable flow rates, antibody cross-reactivity, reproducibility and cross-linker (carbon spacer) comparison. Results indicate the lowest detectable limit (LDL) for RDX is 10 pptr (ng/l) with a linear dynamic range from 0.1 to 1000 ppb (ug/l).     

Effective connectivity of dorsal and ventral visual pathways in chunk decomposition

Chunk decomposition is defined as a cognitive process which breaks up familiar items into several parts to reorganize them in an alternative approach. The present study investigated the effective connectivity of visual streams in chunk decomposition through dynamic causal modeling (DCM). The results revealed that chunk familiarity and perceptual tightness made a combined contribution to highlight not only the “what” and the “where” streams, but also the effective connectivity from the left inferior temporal gyrus to the left superior parietal lobule.     

Crystal structure and exchange pathways of the complex l-(trypthophyl-glycinato)copper(II)

The crystal structure and the EPR characterization of the compound Cu [C₁₃H₁₃N₃O₃] is reported. It crystallizes in the P2₁2₁2₁ space group, with a=8.2829(5), b=9.347(2), c=16.499(2) Å and Z=4. The copper ion is in a distorted square planar coordination, bonded to two nitrogen and one oxygen atoms from one dipeptide and to an oxygen atom from a symmetry-related molecule. Thus, neighbor copper atoms at 5.14 Å are connected by equatorial syn–anti carboxylate bridges giving rise to a chain structure along the b-axis. The chains are connected via hydrogen bonds and cation–π interactions, the latter being provided by the ‘sandwich’ structure involving each copper atom and two tryptophan residues from neighbor molecules. The EPR spectra of polycrystalline sample imply an essentially d_x2−y2 ground state orbital for the Cu(II) ions. The g-values reflect a slightly distorted axial symmetry around the Cu(II) ions as expected from the structural results. No hyperfine interaction is observed, which is indicative of the presence of exchange interactions between the copper atoms as suggested by the X-ray results as well.     

Thermal decomposition studies of cis-bis(1-alkenyl)platinum(II) complexes

Thermal decomposition studies of bis(1-alkenyl)platinum(II) complexes of the type Pt(L₂)R₂ (where L = PPh₃ or L₂ = dppe or dppp; R = 1-alkenyl) are reported. The results revealed interesting organic product distributions depending on the length of the alkenyl chains, the nature of the supporting ligands and the metal centers. It is believed that the major decomposition pathways for the title complexes involve β-hydride elimination and/or reductive elimination as well as alkene isomerization. Mechanisms for the major and minor decomposition pathways are proposed. The amount of isomeric products obtained, i.e., 2-alkenes and 1,(n ? 2)-diene, increases with increasing chain length.     

Nutrient limitation to the decomposition of water hyacinth ( Eichhornia crassipes)

The responses of decomposition to N and P supply were investigated in three leaf types of water hyacinth (Eichhornia crassipes (Mart.) Solms): dead green leaves collected from Donghu Lake; green, and brown leaves collected from outdoor tanks. The ratios of C:N, C:P, lignin:N and lignin:P were lowest in the green leaves collected from Donghu Lake, and highest in the brown leaves collected from outdoor tanks. Decomposition constant (k) of water hyacinth varied greatly, ranged from 0.006 to 0.099 d^–1. Leaf litters decayed most quickly within the initial two weeks during the experimental period, but decomposition rate decreased significantly in the following days. Decomposition and nutrient (N and P) release were fastest in the green leaves collected from Donghu Lake, intermediate in the green leaves collected from outdoor tanks, slowest in the brown leaves collected from outdoor tanks. Statistical analyses revealed that the effects of P-availability on decomposition rate and N, P release rate of the three litter types were significant, whereas the impacts of N-availability was insignificant (p > 0.05) except for the brown leaves collected from outdoor tanks. These results suggest that decomposition rate and nutrient content dynamics of water hyacinth differ with their growth habitats, and could partly be regulated by nutrient availability, especially by P-availability, in the environments.