Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Crack path instabilities in DCDC experiments in the low speed regime

We studied the low speed fracture regime (10⁻⁴-10⁻⁹ m s⁻¹) in different glassy materials (soda-lime glass, glass ceramics) with variable but controlled length scale of heterogeneity. The chosen mechanical system enabled us to work in pure mode I (tensile) and at a fixed load on double cleavage drilled compression specimen. The internal residual stresses of studied samples were carefully relaxed by appropriate thermal treatment. By means of optical and atomic force microscopy techniques fracture surfaces have been examined. We have shown for the first time that the crack front line underwent an out-of-plane oscillating behavior as a result of a reproducible sequence of instabilities. The wavelength of such a phenomenon is in the micrometer range and its amplitude in the nanometer range. These features were observed for different glassy materials providing that a typical length scale characterizing internal heterogeneities was lower than a threshold limit estimated to few nanometers. This effect is the first clear experimental evidence of crack path instabilities in the low speed regime in a uniaxial loading experiment. This phenomenon has been interpreted by referring to the stability criterion for a straight crack propagation as presented by Adda-Bedia et al. [Phys. Rev. Lett. 76 (1996) 1497].     

$M$-半群的直觉$(S,T)$-模糊$M$-子半群的性质

K.T.Atanassov在1986年首先引入直觉模糊集的概念,本文利用s-范数和t-范数,引入M-半群的直觉(S,T)-模糊M-子半群的概念,刻画其性质和特征,我们再进一步给出了直觉(S,T)-直积的概念,并由此探讨了一些有意义的相关结论。     

五羟色胺分子选择性电极研究

本应用自己合成的联萘２０－冠－６作为活性载体，进行了五羟色胺分子选择性电极研究。电极在１０＾－＾５－１０＾－＾２ｍｏｌ／Ｌ浓度范围内对五羟色胺具有稳定的线性响应，平均斜率为６３ｍＶ／ＰＣ，检测下限为２．７×１０＾－＾６ｍｏｌ／Ｌ。     

Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

New Spiro Compounds from Cyclophosphazenes and Cyclodi[phosphadiazanes] Chlorocyclophosphazenes (Cl₂P = N)₃ and (Cl₂p = N)₄ react with dihydrazidophosphoric acid derivatives in THF in the presence of triethylamine to give the spirocyclic compounds Cl₄N₃P₃(NHN(CH₃))₂P(S)OC₆H₅, Cl₆N₄P₄(NHNH)₂P(S)OC₆H₅. Constitutions have been confirmed by MS, NMR, IR and elemental analysis.     

停流—荧光动力学分析法测定痕量钛的研究

利用自行组装的停流-荧光动力学分析仪,采用停流法汇合流体动力注入技术,研究了钛与3.5-二溴水杨基荧光酮的荧光增强动力学反应性质,讨论了流速、进样时间对方法灵敏度和精密度的影响,提出了一个快速、简便、精确测定钛的分析方法,并用于稀土样品及合成样品中痕量钛的测定.方法检测限为8×10~(-3)ppm,大多数元素的干扰均可用动力学方法消除.     

On bimeasurings II

We answer some questions posed in [L. Grunenfelder, M. Mastnak, On bimeasurings, J. Pure Appl. Algebra 204 (2006) 258-269] concerning the universal bimeasuring bialgebra via a construction of suitable subcoalgebras of the universal measuring coalgebra.     

Motivic Serre invariants of curves

In this article, we generalize the theory of motivic integration on formal schemes topologically of finite type and the notion of motivic Serre invariant, to a relative point of view. We compute the relative motivic Serre invariant for curves defined over the field of fractions of a complete discrete valuation ring R of equicharacteristic zero. One aim of this study is to understand the behavior of motivic Serre invariants under ramified extension of the ring R. Thanks to our constructions, we obtain, in particular, an expression for the generating power series, whose coefficients are the motivic Serre invariant associated to a curve, computed on a tower of ramified extensions of R. We give an interpretation of this series in terms of the motivic zeta function of Denef and Loeser.     

Mechanism of the reaction of neutral and anionic N-nucleophiles with α-halocarbonyl compounds

N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly accepted. Bridged TS are formed by both the substitution mechanism S _N 2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates of N-acylalkylation, as was demonstrated by localization of the corresponding TS. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007.