Determination of DNA using sodium 9,10-anthraquinone-2-sulfonate as an in situ photochemical fluorescence probe

An in situ photochemical fluorescence probe method for the determination of DNA with sodium 9,10-anthraquinone-2-sulfonate (AQS) as a photochemical fluorescence probe was developed. It was based on the conversion of AQS into an intensively fluorescent product by irradiating with UV radiation. The photochemical reaction is retarded by DNA. The determination can be carried out by measuring the fluorescence intensity at a fixed time. The calibration graph was linear in the range 0–80 ng ml⁻¹ calf thymus (CT) DNA (r = 0.9991), the limit of detection was 3.2 ng ml⁻¹ CT DNA (n = 9). The kinetic behaviour of the photochemical reaction and the effects of experimental conditions were investigated and discussed in detail. The results of absorption spectra and competitive binding experiments suggested the interaction between AQS and DNA to be intercalative.     

Photocatalytic oxidation of phenol in aqueous solutions with oxygen catalyzed by supported metallophthalocyanine catalyst

In this paper, zinc tetraaminophthalocyanine (Zn-APc) was immobilized on cellulosic fiber by covalent bond to obtain a novel cellulosic fiber supported metallophthalocyanine, named Zn-TDTAPc-F. At pH 11, upon visible light irradiation for 6 h in the presence of O2, Zn-TDTAPc-F was found to be highly effective for the degradation of phenol in aqueous solution, and the degradation rate of phenol was more than 95%. HPLC was used to confirm formic acid, fumaric acid and maleic acid as its main degradation products.     

Selective oxidation of isobutane over Mo-V-Te mixed oxide catalysts with different tellurium contents

A series of MoV_0.3Te_x (x = 0−0.3) mixed oxides were prepared and investigated for the selective oxidation of isobutane. Among them, MoV_0.3Te_0.23 showed the best methacrolein and methacrylic acid selectivity (as high as 17% and 16%, respectively), and the yield to methacrolein and methacrylic acid reached 3.6% and 3.5%, respectively, at 21.3% isobutane conversion at 440°C.     

Acid-, base-, and lewis-acid-catalyzed heterolysis of methoxide from an alpha-hydroxy-beta-methoxy radical: models for reactions catalyzed by coenzyme B12-dependent diol dehydratase

[Reaction: see text].A model for glycol radicals was employed in laser flash photolysis kinetic studies of catalysis of the fragmentation of a methoxy group adjacent to an alpha-hydroxy radical center. Photolysis of a phenylselenylmethylcyclopropane precursor gave a cyclopropylcarbinyl radical that rapidly ring opened to the target alpha-hydroxy-beta-methoxy radical (3). Heterolysis of the methoxy group in 3 gave an enolyl radical (4a) or an enol ether radical cation (4b), depending upon pH. Radicals 4 contain a 2,2-diphenylcyclopropane reporter group, and they rapidly opened to give UV-observable diphenylalkyl radicals as the final products. No heterolysis was observed for radical 3 under neutral conditions. In basic aqueous acetonitrile solutions, specific base catalysis of the heterolysis was observed; the pK(a) of radical 3 was determined to be 12.5 from kinetic titration plots, and the ketyl radical formed by deprotonation of 3 eliminated methoxide with a rate constant of 5 x 10(7) s(-1). In the presence of carboxylic acids in acetonitrile solutions, radical 3 eliminated methanol in a general acid-catalyzed reaction, and rate constants for protonation of the methoxy group in 3 by several acids were measured. Radical 3 also reacted by fragmentation of methoxide in Lewis-acid-catalyzed heterolysis reactions; ZnBr2, Sc(OTf)3, and BF3 were found to be efficient catalysts. Catalytic rate constants for the heterolysis reactions were in the range of 3 x 10(4) to 2 x 10(6) s(-1). The Lewis-acid-catalyzed heterolysis reactions are fast enough for kinetic competence in coenzyme B12 dependent enzyme-catalyzed reactions of glycols, and Lewis-acid-catalyzed cleavages of beta-ethers in radicals might be applied in synthetic reactions.     

Correlation and response functions with non-Markovian dissipation: a reduced Liouville-space theory

Based on a recently developed quantum dissipation formulation [R. X. Xu and Y. J. Yan, J. Chem. Phys. 116, 9196 (2002)], we present a reduced Liouville-space approach to evaluate the response and correlation functions of dissipative systems. The weak system-bath interaction is treated properly for its effects on the initial state, the evolution, and the correlation between coherent driving and non-Markovian dissipation. Numerical demonstration shows this correlated effect cannot be neglected even in the calculation of linear response quantities that do not explicitly depend on external fields. Highlighted in this paper is also the proper choice of theory among various formulations in the weak system-bath interaction regime.     

聚苯乙烯型阴离子交换剂的合成方法

对聚苯乙烯型阴离子交换剂的各种合成方法作了较为全面的评述。指出使用氯甲醚为原料的氯甲基化法由于毒性问题已经受到限制，分析了其它方法在实现工业化生产并最终取代氯甲基化法方面的可能性。     

Synthesis of open-ended MoS2 nanotubes and the application as the catalyst of methanation

We report the synthesis of open-ended MoS2 nanotubes and their application as the catalyst for methanation of carbon monoxide with hydrogen. Because the catalysis of the methanation reaction occurs at relatively low temperatures, such nanotubes may provide new solutions toward harnessing the environmental load caused by CO emission.     

Syntheses, structures, and magnetic properties of mixed-valent diruthenium(II,III) diphosphonates with discrete and one-dimensional structures

Four mixed-valent ruthenium diphosphonates, namely, Na(4)[Ru(2)(hedp)(2)X]x16H(2)O [X = Cl (1), Br (2)], K(3)[Ru(2)(hedp)(2)(H(2)O)(2)]x6H(2)O (3), and Na(7)[Ru(2)(hedp)(2)Fe(CN)(6)]x24H(2)O (4), where hedp represents 1-hydroxyethylidenediphosphonate [CH(3)C(OH)(PO(3))(2)](4-), were synthesized and structurally characterized. Compounds 1, 2, and 4 show linear chain structures in which the mixed-valent [Ru(2)(hedp)(2)](3-) dimers are linked by X(-) or [Fe(CN)(6)](4-) bridges. Compound 3 contains discrete species of [Ru(2)(hedp)(2)(H(2)O)(2)](3-) where the axial positions of [Ru(2)(hedp)(2)](3-) paddlewheel are terminated by water molecules. Magnetic studies show that significant antiferromagnetic exchanges are mediated between the [Ru(2)(hedp)(2)](3-) (S = 3/2) units through halide bridges in compounds 1 and 2.     

Immunosuppressive ent‐Kaurene Diterpenoids from Isodon serra

Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3).     

Photohydration and photosolvolysis of biphenyl alkenes and alcohols via biphenyl quinone methide-type intermediates and diarylmethyl carbocations

Evidence is presented for the photochemical generation of novel biphenyl quinone methide (BQM)-type intermediates on photolysis of hydroxybiphenyl alkenes 7 and 8 and hydroxybiphenyl alcohols 9 and 10. Mechanistic investigations utilizing product, fluorescence, and nanosecond laser flash photolysis (LFP) studies indicate two distinct pathways for the formation of these BQMs depending upon the functional groups of the progenitor. Formal excited-state intramolecular proton transfer (ESIPT) between the phenol and the alkene led to BQMs upon irradiation of the hydroxybiphenyl alkenes 7 and 8, while excited-state proton transfer (ESPT) to solvent followed by dehydroxylation was responsible for BQM formation from the hydroxybiphenyl alcohols 9 and 10. Photolysis of 7 and 8 in aqueous CH(3)CN gave photohydration products via attack of water on the respective BQMs, while photolysis of the analogous methyl ethers (of the phenolic moiety) gave only carbocation intermediates. Hydroxybiphenyl alcohols 9 and 10 yielded the corresponding photomethanolysis products in aqueous methanol, through attack of CH(3)OH on the respective BQMs. Although no evidence was found for BQM formation in LFP studies of 8 and 10, due to its suspected short lifetime, the respective diaryl carbocation (lambda(max) 420 nm, tau = 8.5 micros) has been observed upon irradiation of 8 in 2,2,2-trifluoroethanol. A BQM (lambda(max) 580 nm) was observed for 9 but not for 10, the latter having more complex chemistry on laser excitation, resulting in a transient that appears to mask any BQM absorption. Significant quenching of fluorescence from the hydroxybiphenyl alkenes at low water content implies that H(2)O is directly involved in reaction from the singlet excited state. The decrease in fluorescence intensity of 8 was found to depend on [H(2)O](3); however, the distance required for ESIPT in these systems is too large to be bridged by a water trimer. The nonlinear quenching has been attributed to deprotonation of the phenol by two water molecules, with concerted protonation at the alkene by another molecule of water. Fluorescence quenching of the hydroxybiphenyl alcohols required much higher water content, implying a different mechanism of reaction, consistent with the proposal of ESPT (to solvent water) followed by dehydroxylation.