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The [M(NO)n]+cation complexes (M = Au and Ag) are studiedfor exploring the coordination and bonding between nitric oxide andnoble metal cations. These species are produced in a laser vaporizationsupersonic ion source and probed by infrared photodissociation spectroscopyin the NO stretching frequency region using a collinear tandem time-of-flightmass spectrometer. The geometric and electronic structures of thesecomplexes are determined by comparison of the distinctive experimentalspectra with simulated spectra derived from density functional theorycalculations. All of these noble metal nitrosyl cation complexes arecharacterized to have bent NO ligands serving as one-electron donors.The spectrum of [Au(NO)2Ar]+is consistent with2-fold coordination with a near linear N–Au–N arrangementfor this ion. The [Au(NO)n]+(n= 3–4) cations are determined to be amixture of 2-fold coordinated form and 3- or 4-fold coordinated form.In contrast, the spectra of [Ag(NO)n]+(n= 3–6) provide evidence for thecompletion of the first coordination shell at n=5. The high [Au(NO)n]+and[Ag(NO)n]+(n≥ 3 for Au, n≥ 4 for Ag) complexeseach involve one or more (NO)2dimer ligands, as observedin the copper nitrosyl cation complexes, indicating that ligand–ligandcoupling plays an important role in the structure and bonding of noblemetal nitrosyl cation complexes. [ABSTRACT FROM AUTHOR]

Gold cation–water complexes with attached argonatoms areproduced via a laser vaporization supersonic cluster source. The [Au(H2O)nArx]+(n= 1–8; x= 1 or 2) complexes are each mass selected and studied by infraredphotodissociation spectroscopy in the OH stretching frequency regionto explore the coordination and solvation structures of the Au+cation. Density functional calculations have been performed,and the calculated vibrational spectra are compared to the experimentalspectra to identify the gas-phase structures of the Au(H2O)n+complexes. Confirmingprevious theoretical predications, the first coordination shell ofthe Au+cation contains two water molecules forming a linearO–Au+–O arrangement; subsequent water moleculesbind to the two H2O ligands of the Au(H2O)2+core ion via hydrogen bond forming of the secondhydration shell, which is complete at n= 6. Forthe complexes with n≤ 7, the experimentalspectrum can in general be assigned to the predicted global minimumstructure. However, the spectrum suggests that two or more conformerscoexist for the n= 8 complex, indicating that theidentification of a single global minimum becomes less important uponincreasing the number of solvating water molecules. [ABSTRACT FROM AUTHOR]

The reactions of beryllium atoms with dioxygen A were renvestigated by matrix isolation infrared absorption spectroscopy. Besides the previously reported linear OBeO and cyclic Be2O2 molecules, two interconvertible beryllium iA annealing ozonide complexes were prepared and characterized. The BeOBe (π2O3)complex was formed on annealing, which is characterized to be a side-on bonded ozonide complex with a planar C2n structure. The BeOBe (π2O3) complex isomerized to the BeOBe (π1O3) isomer under visible light excitation, which is an end- on bonded ozonide complex with planar Q symmetry. These two isomers are interconvertible; that is, visible light induces the conversion of the side-on bonded complex to the end-on bonded isomer, and vice versa on annealing. In addition, evidence is also presented for the linear BeOBeOBe duster. [ABSTRACT FROM AUTHOR]

In response to the growing demand for global health monitoring, we report a nonintrusive health detection method using a compact, conformal wearable ultraviolet (UV)-assisted gas-sensing system based on an intrinsically flexible porous polydimethylsiloxane (PDMS)-zinc oxide (ZnO) composite layer (PPZL) for the breath acetone (BrAce) detection and breath event analysis. The enhanced acetone response is attributed to the synergistic effect of UV irradiation and the high surface area of the porous structure, which also improves the mechanical robustness. The UV-assisted wearable sensor reliably detects acetone concentrations ranging from 1 to 100 ppm at room temperature under 4.05 mW/cm 2 UV intensity, even under mechanical strains such as a bending radius of 5 mm and 60% tensile strain. It accurately analyzes different breathing patterns (12-20 breaths per minute) and BrAce concentrations, maintaining a stable performance over 20 days with less than 5% signal degradation. The sensor exhibits response and recovery times of average 110-150 and 130-180 s, respectively, and maintains a consistent 3 ppm BrAce response under varying humidity levels up to 70% relative humidity, ensuring accurate detection of BrAce concentrations during real-world breath tests. Additionally, the sensor targets only specific gases, and the sensor's selectivity is not a key concern. This flexible acetone gas sensor offers a portable solution for health management and a fabrication method for designing flexible metal oxide materials.

Bacterial sensing and inactivating is one of the key steps to prevent bacterial propagation and transfer. Here, using Ag nanoparticle-grafted tungsten oxide films (WO 3 /Ag), we developed a multifunctional platform that may act as a surface-enhanced Raman spectroscopy substrate for sensitively capturing and counting bacteria. Moreover, we demonstrated that the use of photon-triggered surface plasmon resonance of Ag on the WO 3 surface resulted in a significantly improved photocatalytic activity under visible light (638 nm). The photogenerated reactive oxygen species have been shown to be efficient in the inactivation of bacteria, and the bacteria inactivation process could be monitored in situ by Raman spectroscopy. On the basis of the obtained Raman results and fluorescence measurements of green fluorescence protein expressing bacteria, the active species triggered by hot spots was demonstrated to account for broken cell walls. The bacterial cell contents subsequently leaked out, leading to cell degradation. Potentially, our work may provide a promising strategy for capturing and monitoring the bactericidal process at low concentration and, specifically, may help in the investigation of related inactivation approaches and mechanisms.

Synthetic biology involves reprogramming and engineering of regulatory genes in innovative ways for the implementation of novel tasks. Transcriptional gene regulation systems induced by small molecules in prokaryotes provide a rich source for logic gates. Cross-regulation, whereby a promoter is activated by different molecules or different promoters are activated by one molecule, can be used to design an OR-gate and achieve cross-talk between gene networks in cells. Acinetobacter baylyi ADP1 is naturally transformable, readily editing its chromosomal DNA, which makes it a convenient chassis for synthetic biology. The catabolic genes for salicylate, benzoate, and catechol metabolism are located within a supraoperonic cluster (-sal-are-ben-cat-) in the chromosome of A. baylyi ADP1, which are separately regulated by LysR-type transcriptional regulators (LTTRs). ADP1-based biosensors were constructed in which salA, benA, and catB were fused with a reporter gene cassette luxCDABE under the separate control of SalR, BenM, and CatM regulators. Salicylate, benzoate, catechol, and associated metabolites were found to mediate cross-regulation among sal, ben, and cat operons. A new mathematical model was developed by considering regulator-inducer binding and promoter activation as two separate steps. This model fits the experimental data well and is shown to predict cross-regulation performance.

The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H(+) and OH(-) make the decomposition in gaseous state energetically favorable. However, the effect of H(+) is much different from that of OH(-) in aqueous solution: OH(-) can accelerate the decomposition but H(+) cannot. The difference is mainly caused by the large aqueous solvation energy difference between H(+) and OH(-). The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H(+) and OH(-).

The reactions of beryllium atoms with dioxygen were reinvestigated by matrix isolation infrared absorption spectroscopy. Besides the previously reported linear OBeO and cyclic Be(2)O(2) molecules, two interconvertible beryllium ozonide complexes were prepared and characterized. The BeOBe(η(2)-O(3)) complex was formed on annealing, which is characterized to be a side-on bonded ozonide complex with a planar C(2v) structure. The BeOBe(η(2)-O(3)) complex isomerized to the BeOBe(η(1)-O(3)) isomer under visible light excitation, which is an end-on bonded ozonide complex with planar C(s) symmetry. These two isomers are interconvertible; that is, visible light induces the conversion of the side-on bonded complex to the end-on bonded isomer, and vice versa on annealing. In addition, evidence is also presented for the linear BeOBeOBe cluster.

The photoelectron images of Ag(-)(H(2)O)(x) (x=1,2) and AgOH(-)(H(2)O)(y) (y=0-4) are reported. The Ag(-)(H(2)O)(1,2) anionic complexes have similar characteristics to the other two coinage metal-water complexes that can be characterized as metal atomic anion solvated by water molecules with the electron mainly localized on the metal. The vibrationally well-resolved photoelectron spectrum allows the adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of AgOH(-) to be determined as 1.18(2) and 1.24(2) eV, respectively. The AgOH(-) anion interacts more strongly with water molecules than the Ag(-) anion. The photoelectron spectra of Ag(-)(H(2)O)(x) and AgOH(-)(H(2)O)(y) show a gradual increase in ADE and VDE with increasing x and y due to the solvent stabilization., (© 2011 American Chemical Society)

Mechanisms and kinetics of the reaction of atomic oxygen with acetone have been investigated using ab initio quantum chemistry methods and transition state theory. The structures of the stationary points along the possible reaction pathways were obtained using the second-order Møller-Plesset theory and the coupled-cluster theory with single and double excitations with the triple-zeta quality basis sets. The energetics of the reaction pathways were calculated at the reduced second-order Gaussian-3 level and the extrapolated full coupled-cluster/complete basis set limit. The rate coefficients were calculated in the temperature range 200-3000 K, with the detailed consideration of the hindered internal rotation and the tunneling effect using Eckart and the semiclassical WKB approximations. It is shown that the predominant mechanism is the direct hydrogen abstraction producing hydroxyl and acetonyl radicals. Although the nucleophilic OC addition/elimination channel leading to CH3 and CO2 involves comparable barrier with the direct hydrogen abstraction channel, kinetically it cannot play any role in the overall reaction. It is predicted that the rate coefficients show positive temperature dependence in the range 200-3000 K and strong non-Arrhenius behavior. The tunneling effect plays a significant role. Moreover, the reaction has strong kinetic isotope effect. The calculated results are in good agreement with the available experimental data. The present rigorous theoretical work is helpful for the understanding of the characteristics of the reaction of atomic oxygen with acetone.

Eight exothermic product channels of the reaction of chlorinated vinyl radical (C2Cl3) with molecular oxygen (O2) have been investigated using ab initio quantum chemistry methods. The energetics of the reaction pathways were calculated at the second-order Moller-Plesset Gaussian-3 level of theory (G3MP2) using the B3LYP/6-311G(d) optimized geometries. It has been shown that the C2Cl3 + O2 reaction takes place via a barrierless addition to form the chlorinated vinylperoxy radical complex, which can decompose or isomerize to various products via the complicated mechanisms. Two major reaction routes were revealed, i.e., the three-member-ring reaction mechanism leading to ClCO + CCl2O, CO + CCl3O, CO2 + CCl3, Cl + (ClCO)2, etc., and the OO bond cleavage mechanism leading to O(3P) + C2Cl3O. The other mechanisms are shown to be unimportant. The results are validated by the calculations using the restricted coupled cluster theory [RCCSD(T)] with the complete basis set extrapolation. Variational transition state theory was employed to calculate the individual and total rate coefficients as a function of temperature and pressure (helium). The theoretical rate coefficients are in good agreement with the available experimental data. It was found that the total rate coefficients show strong negative temperature dependence in the range 200-2000 K. At room temperature (297 K), the total rate coefficients are shown to be nearly pressure independent over a wide range of helium pressures (1-10(9) Torr). The deactivation of the initial adduct, C2Cl3O2, is only significant at pressures higher than 1000 Torr. The three-member-ring reaction mechanism is always predominant over the OO bond cleavage.

The reaction of F(2P) with acetone has been studied theoretically using ab initio quantum chemistry methods and transition state theory. The potential energy surface was calculated at the G3MP2 level using the MP2/6-311G(d,p) optimized structures. Additionally, to ensure the accuracy of the calculations, optimizations with either larger basis set (e.g., MP2/G3MP2Large) or higher level electron correlation [e.g., CCSD/ 6-311G(d,p)] were also performed. It has been revealed that the F + CH3C(O)CH3 reaction proceeds via two pathways: (1) the direct hydrogen abstraction of acetone by F gives the major products HF + CH3C(O)CH2; (2) the addition of F atom to the >C=O double bond of acetone and the subsequent C-C bond cleavage gives the minor products CH3 + CH3C(O)F. All other product channels are of no importance due to the occurrence of significant barriers. Both abstraction and addition appear to be barrierless processes. Variational transition state model and multichannel RRKM theory were employed to calculate the temperature- and pressure-dependent rate constants and branching ratios. The predicted rate constants for the abstraction channel and the yields of HF + CH3C(O)CH3 and CH3 + CH3C(O)F are both in good agreement with the experimental data at 295 K and 700 Torr. A negative temperature dependence of the overall rate constants was predicted at temperatures below 500 K.