Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

NMR Study of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam. II. Investigation of the propagation center

The nature of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam initiated by octanoylium hexachlcroantimonate, SbCl₅, and Ph₃CAsF₆ in perdeuterated tetrachloroethane or its mixture with o-dichlorobenzene was studied using ¹H, ¹³C, ¹⁹F, ³¹P, ⁷⁵As, and ¹²¹Sb nuclear magnetic resonance (NMR) of model oligomers and the products of their end-capping with triphenylphosphine. In all cases, the nature of the propagation center has been found to be of an acylium ion pair with an SbCl₆^? or AsF₆^? counterion coordinated with the nearest benzoylamide group and cosolvated by the solvent. © 1994 John Wiley & Sons, Inc.     

1-甲基环氧乙烷-1-丙炔醚的结构测定及其核磁图谱

以¹H-NMR谱和¹³C双自旋回波的APT脉冲序列测定文献中尚未曾发表的化合物HC≡C-CH₂-O-C^CH₃-_O-CH₂文中计算了峰强度与脉冲间隔时间的关系,讨论了各谱线的相位并区分出-CH₃、-CH₂、-CH和季碳。     

Microbial Baeyer-Villiger Oxidation of Ketones by Cyclohexanone and Cyclopentanone Monooxygenase – A Computational Rational for Biocatalyst Performance

Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids.     

原伊鲁烷型倍半萜醇芳香酸酯的碳谱研究

作者自人工发酵得到的蜜环菌Armillaria mellea (Vahl.ex Fr.) Quel.菌丝体中分离出十七个原伊鲁烷型倍半萜醇芳香酸翻,在研究这些化合物的化学结构中,对其全去偶碳谱,偏共振谱或INEPT谱,C-H COSY谱和远程C-H COSY谱进行比较仔细地分析,指定了每个化合物各碳的归属,讨论了其碳谱的特征,并指出¹³C NMR谱是对新的该类型化合物结构测定的有效方法.     

Sodium anion photodetachment up to the 4s threshold. AK-matrixL 2 basis calculation

Summary AK-matrix method implemented with anL ² basis has been utilized to investigate the¹ P ⁰ continuum of the sodium anion below the 4s threshold. The results include the ground-state electron binding energy, the static dipole polarizability, the partial and total photodetachment cross-sections and the asymmetry parameter β. The authors of this paper have agreed to not receive the proofs for correction.     

13C NMR spectra of azolopyridines and their quaternary salts

¹³ C NMR spectra of some azole series have been investigated: 2-pyridylbenzimidazoles, 2-pyridylimidazo [4,5-b]-pyridines, 2-pyridylimidazo[4,5-c]-pyridines, analogous oxazole compounds, as well as their mono- and bisquaternary salts. Some problems, related to the structure of these compounds in solution, have been discussed.V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Moscow 117975. Torino University, Italy. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 866–872, April, 1992.