A method and program for mass quantum chemical calculations of protein—ligand docking complexes

A new fast computational method for mass calculations of docking complexes by the AM1/PM3 semiempirical methods is proposed. The computation time is shortened by at least an order of magnitude compared to alternative schemes of quantum chemical calculations. The root-mean-square deviation of the AM1 calculated energies of formation of complexes from the results obtained by conventional diagonalization procedure is at most 0.4 kcal mol⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 418–420, February, 2008.     

Synthesis and simple separation of β-pyrrole sulfonated porphycenes

New water-soluble porphycenes having sulfonic acid groups at the β-pyrrolic positions were synthesized and characterized by UV-vis, NMR, IR, and mass spectroscopy as well as elemental analyses. The series of mono- to tri-sulfonato derivatives were simply separated by the extraction method.     

双（十二烷基亚磺酰）乙烷溶剂萃取钯及其机理的研究

本文研究用双（十二烷基亚磺酰）乙烷萃取钯的性能，在ＫＩ存在下从７ｍｏｌ／Ｌ盐酸介质中用含有ＢＤＳＥ的氯仿能定量萃取钯，有机的钯可被硫脲或氨溶液反萃继之用ＴＭＫ－ＴｒｉｔｏｎＸ－１００光度法测定，研究了萃取的最佳条件及干扰情况，斜率法测得萃合物组成为Ｐｄ：Ｉ：ＢＤＳＥ＝１：２：１，红外光谱证实萃合物中ＢＤＳＥ的二个亚砜以硫原子与钯配位，萃合物为异位体络合物，提出了选择性萃取分离钯的新方法。     

Synthesis of poly-yne polymers containing transition metals,disilane, disiloxane and phosphine groups in the main chain

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-²-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane.     

Determination of the rate of rapid lipid transfer induced by poly(ethylene glycol) using the SLM Fourier transform phase and modulation spectrofluorometer

Rate constants were determined for the transfer of the fluorescent lipid probe 1-palmitoyl-2-[[2-[4-(6-phenyl-trans-1,3,5-hexatrienyl)phenyl]ethyl] oxy]carbonyl]-3-sn-phosphatidylcholine (DPHpPC) between large, unilamellar extrusion vesicles composed either of dipalmitoyl phosphatidylcholine (DPPC) or of DPPC mixed with a small amount (0.5 mol%) of lyso phosphatidylcholine (Lyso PC). Transfer of the lipid probe in the presence of varying concentrations of poly(ethylene glycol) (PEG) was monitored using the SLM 48000-MHF Multi-Harmonic Fourier Transform phase and modulation spectrofluorometer to collect multifrequency phase and modulation fluorescence data sets on a subsecond time scale. The unique ability of this instrument to yield accurate fluorescence lifetime data on this time scale allowed transfer to be detected in terms of a time-dependent change in the fluorescent lifetime distribution associated with the lipid-like DPHpPC probe. This probe demonstrates two short fluoresence decay times (ca. 1.1–1.4 and 4.3–4.8 ns) in a probe-rich environment but a single long lifetime (ca. 7 ns) in a probe-poor environment. A simple two-state model for initial lipid transfer was used to analyze the multifrequency data sets collected over a 4-s time frame to obtain the time rate of change of the concentrations of donor and acceptor probe populations following rapid mixing of vesicles with PEG. The ability to measure fluorescence lifetimes on this time scale has allowed us to show that the of rate of lipid transfer increased dramatically at 35% PEG in both fusing and nonfusing vesicle systems. These results are interpreted in terms of a distinct interbilayer structure associated with intimate bilayer contact induced by high and potentially fusogenic concentrations of PEG.     

苯对N,N-二甲基甲酰胺化合物1H NMR的影响研究

本文研究了N,N-二甲基甲酰胺(DMF)在四氯化碳和苯混合溶剂中的¹H NMR。观察到N,N-二甲基甲酰胺(DMF)分子中两个甲基和混合溶剂中苯的共振吸收峰的化学位移随苯的摩尔分数增加而逐渐移向高场,而且两个甲基共振吸收峰向高场移动的程度不同,α甲基较β甲基为甚。DMF分子中两个甲基和混合溶剂中苯的化学位移可以用线性方程表示(δ=A+Bx),这里x是混合溶剂中苯的摩尔分数。相关系数R接近于-1。     

HPMBP与N_（503）协同萃取钯（Ⅱ）的研究

研究了ＨＰＭＢＰ与Ｎ５０３的氯仿溶液从硝酸介质中协萃钯（Ⅱ）的性能．用斜率法和等摩尔系列法确定萃合物组成为（ＣＨ３ＣＯＮＨＲ２）Ｐｄ（ＰＭＢＰ）３；求得该协萃反应的平衡常数及协萃配合物的生成常数分别为：ｌｇｋ１２＝１．５４，ｌｇβ１２＝２．３９．考察了温度对协萃平衡的影响，测定了协萃反应的热力学函数．     

Ethylene polymerization by chromium complexes with phosphorous‐bridged bisphenoxy ligand

Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl₃(THF)₃, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl₃(THF)₃ in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)^?1 h^?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (M_w = 128,700, M_w/M_n = 1.8) was obtained using a 6 ‐TIBA/B(C₆F₅)₃ system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007     

Synthesis and properties of triethylammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinane

The reaction of bis(hydroxymethyl)phenylphosphine with isobutyl diphenylborate in the presence of triethylamine leads to the formation of triethylammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinane (1). The reaction of compound 1 with electrophilic reagents (O, S, Se, CH₂O, RHal) leads to quaternization of the phosphorus atom, giving the corresponding phosphine oxides, sulfides, and selenides and P,B-containing betaines. In the reactions of compound 1 with amines aminomethylphosphines of the diazaphosphorinane and diazadiphosphacyclooctane series are formed. Ammonium 1,3,2,5-dioxaborataphosphorinanes dissociate in solutions and enter into ion exchange with phosphonium iodides, leading to phosphonium 1,3,2,5-dioxaborataphosphorinanes. The latter, in the case of the aminomethylphosphonium cation, undergo intramolecular rearrangement with the formation of P,B-containing betaines and aminomethylphosphines.Deceased.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1398–1405, June, 1992.     

泡沫分离,带溶剂萃取和沉淀法提取庆大霉素

研究了用文题法从水相中分离砂大霉素的各种操作因素对分离过程的影响。在最适条件下，种方法对庆大霉素配制液的收率分别为７２％，８８％，８７％，无机盐能使沉淀收率提高。将上述３法用于发酵液时，泡沫法和萃取法的收率均有显著降低，而沉淀法依然能达到很高的收率，ψ＝捍沉淀率约为１００％．