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).     

A decomposition result for a class of polling models

Boxma and Groenendijk have shown that the workload in polling models decomposes into two independent variables. This paper demonstrates a different type of decomposition that has an explicit multi-dimensional form. This decomposition does not apply to all polling models, but does, for example, apply to models with constant switch-over times and either exhaustive or gated service disciplines. For such models, we show that the population of customers present in the system (represented by a vector indicating the number of customers at each queue) at key time points breaks into two independent subpopulations: (1) the population of customers present in the related model with zero switch-over times; (2) another population, which is particularly easy to analyze. This result has a number of theoretical and applied implications.     

Importance of the choice of assumptions and models in the estimation of analytical quality specifications

The validity of any model depends on its ability to imagine the situation or problem to which it is applied. Further, the assumptions made in relation to the model are determining for the actual outcome. Within the field of clinical biochemistry a lot of models for analytical quality specifications, based on a variety of concepts and ’clinical settings’, have been proposed. A hierarchical structure for application of these approaches and models has been agreed on at several occasions in 1999. In this hierarchy, the highest rank is given to evaluation of analytical quality specifications based on ’clinical settings’/’clinical outcome’ models, followed by specifications based on biological variation and on ’clinicians opinions’. This contribution, deals with the problems of combining random and systematic errors and the implications of application of different models to a variety of clinical settings. Received: 1 June, 2002 Accepted: 17 July 2002 Presented at the European Conference on Quality in the Spotlight in Medical Laboratories, 7–9 October 2001, Antwerp, Belgium     

Probing the surface polarity of native celluloses using genuine solvatochromic dyes

The surface polarity of native celluloses has been investigated by the following solvatochromic dyes: dicyano-bis (1,10)-phenanthroline iron (II) Fe(phen)2 (CN)2 (1), bis(4-N,N-dimethylamino)-benzophenone (2), and cou-marine 153 (3). Linear Solvation Energy (LSE) relationships and the UV/Vis data have been used to characterize the surface polarity of different native cellulose batches in terms of the empirical Kamlet–Taft polarity parameters (hydrogen bond acidity), (hydrogen bond basicity), and * (dipolarity/polarizability). , , *and calculated Reichardt's E T (30) values are reported for various native and regenerated cellulose samples with different degrees of crystallinity. The degree of crystallinity of the cellulose samples has been determined by X-ray. The microcrystalline environment of cellulose can be exactly parameterized in terms of the , and *values. It shows a fairly strong acidity and a low dipolarity/polarizability. For the amorphous sections smaller and larger * values are observed. The correspondence of the empirical polarity parameters determined has been discussed in relation to results from pyrene fluorescence and zetapotential measurements.     

Aryl-bis(triorganylphosphine)nickel phenoxides

Compounds of general formulatrans-ArNi(PR₃)₂OAr' (R = Et, cyclohexyl; Ar = 2-MeC₆H₄, 2-FC₆H₄; Ar' = 4-FC₆H₄, 4-NO₂C₆H₄) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR₃)₂Cl with TlBF₄. Syntheses of 4-fluorophenoxide complexes, ArNi(PR₃)₂OC₆H₄F-4, additionally give some quantities oftrans-[ArNi(PR₃)₂OC₆H₄F-4][HOC₆H₄F-4] adducts. Exchange reactions MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4 + XC₆H₄OH 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄X + 4-FC₆H₄OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK _eq and pK _a of XC₆H₄OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995.     

Microenvironmental differences amongst micelles of various shapes and structures

Micelles of different amphiphiles adopt different shapes and internal packing arrangements in water, depending on their chemical structures and the conditions of the medium. Two microenvironmental features, namely the polarity and the microviscosity that the aggregate offers to a solubilized molecule, have been monitored using extrinsic fluorescence probes. While the differences between micelles of spherical and rod-like shapes are not always distinct, stacked micelles and peptide micelles offer distinctly lower polarity and higher microviscosity to solubilizates than the others.     

丁二烯－甲基丙烯酸甲酯嵌段共聚物的阴离子聚合及表征

讨论了用阴离子方法进行了二烯与甲基丙烯酸甲酯共聚合的过程，并用ＧＰＣ、ＦＴＩＲ、ＮＭＲ和动态粘弹谱对共聚物进行了表征．证明所得聚合物为具有较高分子量、窄分布的二嵌段共聚物．     

Electrophilic addition of lead tetraacetate to 2-carene in an acidic medium

Oxidation of 2-carene by lead tetraacetate in acetic acid afforded p-menth-1(10),2-dien-7-ol, 2-acetyl-6,6-dimethylbicyclo[3.1.0]hexane, p-menth-2-ene-1,7-diol, p-menth-1-ene-3,7-diol, and 2-(m-tolyl)propanol-2.Deceased.A. M. Butlerov Scientific Research Chemical Institute, V. I. Ul'yanov-Lenin Kazan' State University, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 147–150, January, 1992.