Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

Complexation of Ni (II) and Zn(II) ions by 3-(1-naphthyI)-2-mercaptopropenoic acid

The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H₂NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm^–3 in NaClO₄ as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP) ₂ ^2– , Zn(NMP) and Zn(NMP) ₂ ^2– , refined by the MINIGLASS program, are reported.     

Formation of Bi-Sb, Bi-Sn, and Bi-Sb-Sn Nanoclusters in Silica Xerogel Matrices from Mixed-Metal Oxide Precursors

Homogeneous mixed-metal oxides of the general formula (Bi/E/Si)O _x , where E represents a dopant element (E=Sb, Sn, or Sb/Sn), can be prepared using typical sol-gel processing techniques. Reduction of the in-situ Bi(III) and E ions by hydrogen affords nanocomposites of Bi-Sb, Bi-Sn, or Bi-Sb-Sn widely dispersed throughout the silica xerogel matrix. The materials prepared have high Bi-E metal loading of 52–60 wt. % containing Bi-E alloy nanoclusters of 12–15 nm average diameter. These results demonstrate a convenient method for the production of practical quantities of nanostructured bismuth alloy ceramic composites at high metal content.     

煤中有机硫形态结构和热解过程硫变迁特性的研究

利用热解 质谱并结合固定床热解反应装置，对煤中有机硫的形态主其对加氢热解过程 变迁特性的影响，进行了较系统的研究。结果表明，煤中有机硫的形态结构在褐煤中主要以脂肪族、芳香族硫化物为主，而在 煤中则主要以各种不同芳构化程度的噻吩结构为主，初步表明煤中有机硫形态结构随煤变质程度的变迁呈较强的连续递变性。煤热解过程中硫在呼产物中的变迁和分布与煤中有机硫的形态结构特点密切相关。较高芳构化噻吩结构不完全的氧     

Pure Organic Phase Phenol Biosensor Based on Tyrosinase Entrapped in a Vapor Deposited Titania Sol‐Gel Membrane

A novel amperometric biosensor was constructed for the determination of phenols in pure organic phase. This biosensor was fabricated by immobilizing tyrosinase in a titania sol‐gel membrane which was obtained with a vapor deposition method. This method was facile and avoided the calcination step needed in conventional titania sol‐gel process. The titania sol‐gel membrane could effectively retain the essential water layer around the enzyme molecule needed for maintaining its activity in organic phase. The experimental parameters such as solvent and operating potential were optimized. At ?100 mV this biosensor showed a good amperometric response to phenols in pure chloroform without any mediator and rehydration of the enzyme. For catechol determination the sensor exhibited a fast response of less than 5 seconds. The sensitivity of different phenols was as follows: catechol > phenol > p‐cresol. Additionally, the apparent Michaelis‐Menten constants of the encapsulated tyrosinase to catechol, phenol and p‐cresol were found to be 0.15±0.003, 0.17±0.008 and 0.21±0.004 mM, respectively. The biosensor had also good reproducibility and stability. This work provided a promising platform for the construction of pure organic phase biosensors and the determination of substrates with poor water solubility.     

Brownian confinement and pinning in a Poissonian potential. II

Summary We continue our study ofd-dimensional Brownian motion in a soft repulsive Poissonian potential over a long time interval [0,t]. We prove here a pinning effect: for typical configuratons, with probability tending to 1 ast tends to , the particle gets trapped close to locations of near minima of certain variational problems. These locations lie at distances growing almost linearly witht from the origin, and the particle gets pinned within distance smaller than any positive power oft of one such location. In dimension 1, we can push further our estimates and show that in a suitable sense, the particle gets trapped with high probability, within time t and within distance (logt)²⁺ from a suitable location at distance of ordert/(logt)³ from the origin.This article was processed by the author using the LATEX style filepljour1m from Springer-Verlag     

Processes of flats induced by higher dimensional processes III

Stationary processes of k-flats in ^d can be thought of as point processes on the Grassmannian _k ^d of k-dimensional subspaces of ^d . If such a process is sampled by a (d–k+ j)-dimensional space F, it induces a process of j-flats in F. In this work we will investigate the possibility of determining the original k-process from knowledge of the intensity measures of the induced j-processes. We will see that this is impossible precisely when 1<k<d–1 and j=0,...,2[r/2]–1, where r is the rank of the manifold _k ^d . We will show how the problem is equivalent to the study of the kernel of various integral transforms, these will then be investigated using harmonic analysis on Grassmannian manifolds.The research of the first and third authors was supported in part by NSF grants DMS-9207019 and DMS-9304284. The research of the second author was supported in part by NFR contract number R-RA 4873-306 and the Swedish Academy of Sciences.     

A note on “small representations of finite distributive lattices as congruence lattices”

G. Grätzer, H. Lakser, and E. T. Schmidt proved that every distributive lattice with n join-irreducible elements can be represented as the congruence lattice of a small lattice L, that is, a lattice L with O(n ² ) elements. G. Grätzer, I. Rival, and N. Zaguia proved that, for any <2, O(n ² ) can not be improved to O(n ). In this note we show that the theorem about small representation can be improved further to get a more delicate result.     

Determination of heavy metal concentration in feed and permeate streams of polymer enhanced ultrafiltration process

Polymer enhanced ultrafiltration (PEUF) is a newly developed method for the removal of heavy metals from aqueous solutions. This method was applied for the removal of mercury and cadmium with the presence of polyethyleneimine (PEI) as a water soluble polymer. After ultrafiltration experiments for metal–polymer mixtures, two separate streams, namely, retentate and permeate, former of which contains mainly metal–polymer complex and free polymer molecules while latter of which mainly contains free metal ions, were obtained. At the end of PEUF experiments, performance of operation was determined by concentration analyses which was achieved by atomic absorption spectroscopy (AAS) applied in a different way for permeate and retentate streams considering the effect of presence of polymer. For mercury analysis, cold vapor AAS was applied. It was observed that the presence of PEI did not affect the atomic absorption signal when 10% HCl was added to the sample solutions. For calcium and cadmium, flame AAS was used. It was observed that change in PEI concentration results in change in measured concentration of calcium and cadmium. Therefore, two new approaches were developed for accurate measurement of concentrations of calcium and cadmium. It was also observed that presence of other metals did not affect the accuracy of the measurement of a particular metal in the concentration range studied.     

On spectral properties ofq-oscillator operators

The property of self-adjointness of the operatorQ =a ₊ +a _- in three types ofq-oscillator algebras is considered. Spectral measures and generalized eigenfunctions ofQ are found in the cases when this operator is bounded. Generalized eigenvectors are expressed in terms ofq-Hermite polynomials. If the operatorQ is unbounded, then its closure is not self-adjoint. However, in this case, admits self-adjoint extensions. Deficiency subspaces are one-dimensional. These subspaces are explicitly found.