Hydrogen‐bonded nucleophile effects in ANS: the reactions of 1‐chloro and 1‐fluoro‐2,4‐dinitrobenzene with 2‐guanidinobenzimidazole, 1‐(2‐aminoethyl)piperidine and N‐(3‐aminopropyl)morpholine in aprotic solvents

The kinetics of the reactions of 2,4‐dinitrofluorobenzene (DNFB) and 2,4‐dinitrochlorobenzene (DNClB) with 2‐guanidinobenzimidazole (2‐GB) at 40 ± 0.2 °C in dimethylsulphoxide (DMSO), toluene, and in toluene–DMSO mixtures, and with 1‐(2‐aminoethyl)piperidine (2‐AEPip) and N‐(3‐aminopropyl)morpholine (3‐APMo) in toluene at 25 ± 0.2 °C were studied under pseudo first‐order conditions. For the reactions of 2‐GB carried out in pure DMSO, the second‐order rate coefficients were independent of the amine concentration. In contrast, the reactions of 2‐GB with DNFB in toluene, showed a kinetic behaviour consistent with a base‐catalysed decomposition of the zwitterionic intermediate. These results suggest an intramolecular H‐bonding of 2‐GB in toluene, which is not present in DMSO. To confirm this interpretation the reactions were studied in DMSO–toluene mixtures. Small amounts of DMSO produce significant increase in rate that is not expected on the basis of the classical effect of a dipolar aprotic medium; the effect is consistent with the formation of a nucleophile/co‐solvent mixed aggregate. For the reactions of 3‐APMo with both substrates in toluene, the second‐order rate coefficients, k_A, show a linear dependence on the [amine]. 3‐APMo is able to form a six‐membered ring by an intramolecular H‐bond which prevents the formation of self‐aggregates. In contrast, a third order was observed in the reactions with 2‐AEPip: these results can be interpreted as a H‐bonded homo‐aggregate of the amine acting as a better nucleophile than the monomer. Most of these results can be well explained within the frame of the ‘dimer nucleophile’ mechanism. Copyright © 2010 John Wiley & Sons, Ltd.     

取代基对N-H•••O=C氢键二聚体中氢键强度的影响

使用MP2方法研究了N-H•••O=C氢键二聚体的氢键强度,探讨了不同取代基对N-H•••O=C氢键强度的影响.研究发现,可以通过改变质子供体或受体分子上取代基的供电性或吸电性来调控氢键强度:乙基等供电子基团对N-H•••O=C氢键强度的调节作用不大;NO2和CN等强吸电子基团可极大地改变N-H•••O=C氢键强度;质子供体分子中的强吸电子基团如CN可使N-H•••O=C氢键强度增强多达4.6kcal/mol,质子受体分子中的强吸电子基团如NO2可使N-H•••O=C氢键强度减弱多达2.6kcal/mol.自然键轨道(NBO)分析表明,N-H•••O=C氢键强度越强,参与形成氢键的氢原子电荷越正,氧原子电荷越负,单体分子间电荷转移越多,N-H•••O=C氢键中氧原子孤对电子n(O)对N-H反键轨道σ*(N-H)的二阶稳定化能越大.     

Model liquid crystalline dimers in a slit pore: Monte Carlo simulation study

ABSTRACT

In this work, we present results from (isobaric–isothermal) Monte Carlo Simulation studies of liquid crystalline dimer systems confined in a slit pore. Liquid crystalline dimer systems of various spacer numbers have been considered. Surface-induced conformational and alignment properties of these systems at different pressures under homeotropic anchoring condition have been investigated. We have used easily manageable coarse grained force fields to model both monomer–monomer and monomer–substrate interaction potentials. According to the simulated result, the anchoring of dimers to the surface and orientation of mesogenic units with respect to the surface normal seem to depend on the spacer number for messogen attractive confinement. Dimers with lower spacer number are able be adsorbed to the surface and most of their mesogens are oriented along the surface normal even at lower pressure. Those with larger spacer number are distributed throughout the volume at lower pressure. In the case of mesogen repulsive confinement, most of the dimers are adsorbed to the surface and most mesogens are randomly oriented at low pressure. As the pressure gets higher, the adsorption and orientability increase depending on the type of confinement and spacer number. As a result, clear submolecular partitioning and smectic A like structure have been identified.     

Structure of Cyclic Aryl Thiosester Dimer Based on o—Phthaloyl Dichloride and Bis（4—mercaptophenyl）Sulfide

A Cyclic aryl thioester dimer was prepared by the reaction of o-phthaloyl dichloride and bis(4-mercaptophenyl)sulfide in good yield under pseudo-high dilution conditions via interfacial polycondensation.The structure of the cyclic dimer was confirmed by a conmbination of MALDI-TOF-Ms,FTIR,gel permeation chromatography and NMR analyses.The X-ray diffraction study of the single crystal of cyclic thioester dimer obtained form two sotutions reveals no severe internal strain on the cyclic structure.     

uvrB-dependent, recF-independent post-replication (or replication) repair in Escherichia coli

In UV-damaged cells, a large fraction of pyrimidine dimers may remain unexcised and may be tolerated by a uvrB recA lexA-dependent non-excisional mode of repair (M. Sedliaková, J. Brozmanová, F. Ma ek and K. Kleibl, Biophys. J., 36 (1981) 429-441). We show here that a similar repair pathway operates in the Escherichia coli recF 143 single mutant but not in the recF uvrB double mutant. This indicates that the putative repair pathway is recF independent.     

钾双原子分子23ΠG-x3∑+u跃迁扩散带增益特性研究

报道了用单光子激发产生Ｋ2 23Πｇ-ｘ3∑+ｕ跃迁扩散带的实验结果，讨论了此扩散带发射增益特性随温度和缓冲气体压力等条件的变化规律。实验测得了1.2％ cm-1的增益系数。     

The aΔg→XΣg magnetic dipole transition of S2

Emission spectra of the 0-0 band of the a¹Δ_g→X³Σ⁻_g magnetic dipole transition of S₂ have been observed in the near-infrared spectral region near 4400 cm⁻¹. The S₂ molecules were generated in a fast-flow system by passing S_x or S₂Cl₂ vapor in Ar carrier gas through a microwave discharge and were excited by electronic-to-electronic energy transfer from metastable singlet oxygen O₂(a¹Δ_g). Medium-resolution spectra of the b¹Σ⁺_g→X³Σ⁻_g and a¹Δ_g→X³Σ⁻_g transitions of S₂ were measured with a Fourier-transform spectrometer. By comparing the bandshape of the 0-0 band of the a→X system with a computer simulation calculated with literature data of the rotational constants of the X and a states, the origin of the 0-0 band was determined to be ν₀=4394.25±0.2 cm⁻¹.     

599.2 nm diffuse band radiation generated by two-photon exciting molecular and atomic potassium

Diffuse band radiation around 599. 2 nm in K_2 was generated by the two photon pumping potassium dimers or by the two-photon resonant pumping atomic potassium with following atoms-molecules collision energy transfer. The pumping wavelengths are in a wide range of 697-745 nm. The relevant mechanisms were discussed.     

双卟啉金属铑配合物的合成

本文报道二种新的配体：双四苯基卟啉基对苯二甲亚胺（Ｉ），双［（５，１０，１５－三甲苯基）－２０－苯基）卟啉基］对苯二甲亚胺（Ⅱ），并合成了相应的单金属铑配合物Ⅲ．Ⅳ，进行了元素分析，电子光谱，红外光谱．质子核磁共振及光助还原水放氢实验．     

Binding of singlet oxygen with a stacked guanine dimer

Geometry optimization calculations were performed using the B3LYP/6‐31+G* method on the complexes of ¹O₂ and ³O₂ molecules with a stacked dimer of planar guanine, varying the distance (D) between the planes of the guanine molecules. In this process, geometries of the guanine molecules were held fixed, D was fixed at different values, while the bond lengths of ¹O₂ and ³O₂ as well as their orientations with respect to the guanine molecules were optimized for each value of D. The complexes in their most stable geometries were solvated in water using the integral equation formalism of the polarized continuum model of the self‐consistent reaction field theory. In gas phase, the most stable complex between ¹O₂ and the guanine dimer (2G.¹O₂) is formed when D is about 6 Å, while the most stable complex between ³O₂ and the guanine dimer (2G.³O₂) is formed when D is about 3.75 Å. In the minimum total energy geometry of 2G.¹O₂, ¹O₂ is located between the guanine molecules, above the imidazole ring of one of them. However, in the minimum total energy geometry of 2G.³O₂, ³O₂ is located outside the stack of guanine molecules, near the amino group of one of them. The solvation calculations showed that in aqueous media, ¹O₂ would bind with the stacked guanine dimer more strongly than in gas phase, while ³O₂ would not bind with the same. The mode of binding of ¹O₂ with the stacked guanine dimer is such that it seems that ¹O₂ would replace one basepair in DNA, as happens in the intercalative mode of binding of drugs and other molecules, and it can lead to the formation of 8‐oxoguanine that has a mutagenic nature. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005