In situ simultaneous determination the photolysis of multi-component PAHs adsorbed on the leaf surfaces of living Kandelia candel seedlings

A fiber-optic fluorimetry for in situ simultaneous determination of fluorine (Flu), phenanthrene (Phe) and fluoranthene (Fla) adsorbed on the leaf surfaces of Kandelia candel (Kc) seedlings was developed. Experimental results showed that the linear ranges for determination of Flu, Phe and Fla adsorbed on Kc leaves were 35-700, 5-900 and 2-450 ng/spot, respectively. The detection limits for Flu, Phe and Fla were 9.11, 1.65 and 0.90 ng/spot and with the relative standard deviations less than 10.32%, 7.56% and 4.29% (n = 9), respectively. The recovery results for Flu, Phe and Fla adsorbed on Kc leaves were 83.0-91.2, 78.5-88.5 and 91.5-107.3%, respectively. Under the laboratory experimental conditions, the photolysis processes of Flu, Phe and Fla individual and in mixtures adsorbed on the leaf surfaces of living Kc seedlings were studied. Results showed that the photolysis of Flu, Phe and Fla individual and in mixtures adsorbed on the leaf surfaces of Kc seedlings followed first-order kinetics with photolysis rates in the order of Flu > Fla > Phe on the Kc leaves. An antagonistic effect was found when the three polycyclic aromatic hydrocarbons (PAHs) were co-adsorbed on living Kc seedlings. The experimental results also indicated that photolysis was the main transformation pathway for Flu, Phe and Fla both individual and in mixtures adsorbed on Kc leaves, whereas disappearance of the adsorbed Flu, Phe and Fla as a result of volatilization and leaf absorption could be negligible during the experimental period.     

Towards the catalytic formation of α,β-vinylesters and alkoxy substituted γ-lactones

A facile, one pot, high yield synthesis of α,β-vinylester (1-14) and alkoxy substituted γ-lactones (15-28) has been achieved by the photochemical reaction of terminal acetylene (ferrocenyl phenyl trimethylsillyl, hexyl and cyclohexyl) with alcohol (methanol, ethanol and isopropanol) and carbon monoxide in presence of iron pentacarbonyl as a catalyst. The selectivity of the compounds depends on the time of photolysis of the reaction as well as the solvent used. A stable reaction intermediate ferrole was isolated, and further photolysis with alcohols, resulted in the formation of α,β-vinylester. All the compounds were fully characterised by spectroscopic methods and the molecular structures of compounds 1, 16, 17 and 20 were established crystallographically.     

Metal carbonyl-promoted reactions of ferrocenylacetylene with sulfur to form thiophene, dithiine, thioketone and vinylthioketone derivatives

Photolysis of a hexane solution of ferrocenylacetylene and sulfur powder in presence of Cr(CO)₆ resulted in the formation of 2,6-diferrocenyldithiine and 2,5-diferrocenylthiophene. Similar reactions with Mo(CO)₆ or W(CO)₆ gave only the thiophene derivative. Formation of ferrocenyl-substituted thioketone complexes was observed in the reaction of ferrocenylacetylene with water and sulfur, in presence of W(CO)₆. Use of D₂O confirmed water as source of protons for the conversion of acetylenic CH to CH₃.     

热氢原子碰撞导致的CO2(v3)的高振动激发

用时间分辨-傅里叶变换红外发射光谱研究了热的氢原子与C02分子间高效率的平动—振动(T—V)能传递．热的氢原子由ArF激光光解H2S得到，这种氢原子的平动能为223kJ／mo1。实验中观察到了从2130cm^-1到2400cm^-1的红外发射谱带，它归属于高振动激发的CO2分子的非对称伸缩振动(v3)．对这一发射谱带的光谱拟合显示CO2的非对称伸缩振动被激发到了较高的振动态，振动量子数达到了v=7。并且有5580cm^-1的能量经传能过程由氢原子到达了CO2的v3模。实验条件下氢原子与C02的T—V传能效率为0.30。实验结果与Schatz等人的用3D半经典计算预测的碰撞截面符合的很好．     

关于N-苯基-萘胺的光分解过程

采用ESR方法研究了α-和β-N-苯基取代萘胺在苯溶液中的分解过程及其反应中间体.结果表明,有三种自由基被检测到,即H,C₁₀H·₇和C₆H·₅(H)N·自由基.其中值得注意的是萘自由基的生成,这意味着在一定的光解条件下,苯基萘胺分子中的C-N键可发生断裂,萘基可从氮原子上断裂下来.同时,通过调节自旋捕捉剂的浓度与添加光敏剂,可以明显地改变三种自旋捕获物的相对生成比例,借此得到三种自由基结构与光稳定性的信息.此外,本文还结合量子化学的计算讨论了此光解过程各种自由基生成的可能性.     

Synthesis, Crystal Structure, Thermal Behavior and IR Characterization of Pentacarbonyl(4-methylpyridine)chromium(0) Complex

Abstract  Pentacarbonyl(4-methylpyridine)chromium(0) complex was isolated from n-hexane solution as yellow plate-like crystals and characterized by using X-ray crystallography. It crystallizes in the orthorhombic system with the space group Cmcm and Z = 4. The unit cell parameters are a = 11.737(1) ?, b = 12.857(2) ?, c = 8.465(1) ?. The single crystal X-ray structure of the complex shows that the coordination sphere around the chromium central atom is slightly distorted octahedron, involving the 4-methylpyridine (4-mp), ligand as a monodentate N-donor ligand and five carbonyl groups. The four equatorial CO groups in the complex, with the Cr–C2 distance of 1.886 Ǻ, are slightly bent away from the 4-methylpyridine ligand with the N–Cr–C2 angle of 91.69°. The pyridine ring plane makes an angle of 135.17° with the Cr–N–CO bond axis. The thermal analysis (differential thermal analysis and thermal gravimetry) and IR spectra of the complex indicated that the compound undergoes complete decomposition to form the Cr₂O₃ as the final decomposition product. Index Abstract  The crystal structure of pentacarbonyl(4-methylpyridine)chromium(0) complex has been determined and its thermal behavior has also been studied.      

VUV photoionisation of free azabenzenes: Pyridine, pyrazine, pyrimidine, pyridazine and s-triazine

Photoionisation mass spectrometry was used to obtain the fragmentation pathways of pyridine, pyridazine, pyrimidine, pyrazine and s-triazine molecules upon absorption of 23.0, 15.7 and 13.8 eV synchrotron photons. The ionic fragments observed vary from molecule to molecule, however C₂H₂⁺, HCN⁺and HCNH⁺ are common to all five molecules at the three photon energies. Furthermore, the presence of C₂H₂N₂⁺, C₃H₃N⁺ and C₄H₄⁺ in the spectra of some of the molecules suggests dissociation pathways via loss of HCN moieties. The respective parent cations, m/q=79, 80 and 81 have a greater yield at low photon energies when compared to the most intense fragment peak in each spectra. We recorded two of the fragment cation yields, as well as the parent photoion yield curves of pyridine, pyridazine, and pyrimidine in the 8–30 eV range. The formation of abundant cation fragments show a strong propensity of the molecules for dissociation after the absorption of VUV photons higher than 14 eV. The differences in relative fragment yields from molecule to molecule, and when changing the excitation energy, suggest significant bond rearrangements and nuclear motion during the dissociation time. Thus, bond cleavage is dependent on the photon energy deposited in the molecule and on intramolecular reactivity. With the aid of photoion yield curves and energy estimations we have assigned major peaks in the spectra and discussed their fragmentation pathways.     

Photolytic decarbonylation of o-benzoquinones

It was established that photodecarbonylation of o-benzoquinones occurs by irradiation not only by UV-light, but visible light (λ>520 nm) too. Study of the series of 4,5-di-substituted 3,6-di-tert-butyl-o-benzoquinones detected that the only product of photoreaction is the corresponding 3,4-di-substituted 2,5-di-tert-butyl-cyclopentadienone, which is formed in a yield close to quantitative. NMR monitoring of reaction of photodecarbonylation of o-benzoquinones detected that this is a two-stage process. In the first stage the photoexcited molecule of quinone rearranges into bicyclo compound (bicyclo[1.3.0]hexa-3-en-2,6-dione) containing five- and three- membered cycles, which spontaneously decomposes during the following dark stage into cyclopentadienone and a molecule of CO.     

Neurotransmitter amino acid—oxobenzo[f]benzopyran conjugates: synthesis and photorelease studies

A series of fluorescent conjugates of neurotransmitter amino acids, such as β-alanine, tyrosine, 3,4-dihydroxyphenylalanine (DOPA) and glutamic acid, were prepared by reaction with a suitable fluorophore, namely 1-chloromethyl-9-methoxy-3-oxo-3H-benzo[f]benzopyran. The photophysical properties of the resulting ester bioconjugates were evaluated as well as the stability to photolysis at different wavelengths of irradiation (250, 300, 350 and 419 nm).     

Frozen matrix photolysis of Group VIII M(CO)2Cl2L2 derivatives: Direct observation of CO-loss species and photochemical isomerization

Photolysis of Group VIII complexes of the form M(CO)₂X₂L₂ and chelated ruthenium compounds, Ru(CO)₂Cl₂(κ²-L) in frozen matrices results in CO-loss. In the case of Fe(CO)₂Br₂(PMe₃)₂ evidence is presented for photochemical bromide ion elimination.