Persulphate initiated polymerisation of methacrylamide—I: Kinetics and molecular weight dependences

A kinetic study of the aqueous persulphate initiated polymerisation of methacrylamide has shown that the rate of polymerisation is represented by the equation $\text{R}{}_{\mathrm{p}}\text{= k [}\text{M}\text{] [}\text{I}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ where the overall rate constant, $\text{k = 1.3 × 10}{}^9\text{exp}\text{(?18,400/}\text{RT}\text{) 1}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{mol}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}\text{s}{}^{\mathrm{?1}}$. Chain transfer with monomer, where C_M = 5.4 × 10^?3 at 60°, is shown to be the dominant transfer step. Comparison with kinetic studies of the analogous acrylamide polymerisation shed doubt on the ‘cage effect’ interpretation of complex orders with respect to monomer. An alternative explanation is proposed.     

Crystallographic studies and structural systematics of the C2c alkali metal metavanadates

Four compounds in the system (Li, Na)VO₃ were synthesized and their structures refined in the space group $\text{C2}\text{c}$. Site population analysis showed that their compositions are (Na_0.5Li_0.5)VO₃, (Na_0.62Li_0.38)VO₃, (Na_0.71Li_0.29)VO₃ and (Na_0.84Li_0.16)VO₃. All have the structure of LiVO₃ and α-NaVO₃ which are related to the $\text{C2}\text{c}$ silicate pyroxenes. Structural data of eight compounds in the system (K, Na, Li)VO₃ were compiled, and correlations were established by multiple regression analyses between the effective ionic radii r_M1 and r_M2 of the alkali metal ions and various structural parameters. The size of the M2 site and the relative displacement of the (VO₃)_∞ chains are found to depend primarily on r_M2 only. The size of the M1 site and the amount of chain rotation are affected by both r_M1 and r_M2. Changes in lattice parameters are related to the chain movements. The anomalous chain configuration of LiVO₃ is also discussed.     

Tetrapyrrole derivatives substituted with ferrocenylethynyl moieties. synthesis and electrochemical studies

Up to eight redox-active ferrocenyl units have been incorporated, through the unsaturated ethynyl linkers, on the periphery of a series of cyclic tetrapyrrole derivatives including zinc(II) phthalocyanine and 2,3-naphthalocyanine, and nickel(II) meso-diphenylporphyrin. The synthesis of the former two macrocycles 4 and 7 involves the Sonogashira coupling reaction of ferrocenylethyne with 4,5-dichlorophthalonitrile (1) or 6,7-dibromonaphthalonitrile (5), respectively, followed by a base-promoted cyclization. The meso-bis(ferrocenylethynyl)porphyrin 11 has been prepared from the dibromo analogue 10 also by a palladium-catalyzed coupling reaction. These novel macrocyclic compounds have been spectroscopically and electrochemically characterized. As revealed by cyclic voltammetry, the ferrocenyl moieties appear to be electrochemically independent in these complexes and there is no significant electronic coupling among the iron(II) centers.     

反应原料组成对单分散苯乙烯微球粒径及其分布的影响

采用分散聚合工艺制备微米级单分散聚苯乙烯微球，并对分散聚合反应的内部影响因素(分散稳定剂、助稳定剂、单体、引发剂)进行了研究．结果表明，随着分散稳定剂和助稳定剂用量的增加，聚苯乙烯微球的粒径减小；随着单体和引发剂用量的增加，聚苯乙烯微球的粒径增大．分散稳定剂和单体用量是影响聚苯乙烯微球粒径分布的两个主要内部因素．     

Syntheses and spectroscopic properties of energy transfer systems based on squaraines

The purpose of this project was to prepare fluorescent dyes that could absorb energy at relatively short wavelengths, and fluoresce in the near-IR region. To achieve this, copper- and palladium-mediated C-N couplings were used to prepare the ‘cassettes’, i.e the carbazole derivative 3b and the carbazole-, phenothiazine-, and phenoazine-squaraines 4b-d. These compounds have carbazole, phenothiazine, and phenoazine donor-components that absorb around about 300-320 nm, and squaraine acceptor-parts that fluoresce in the range 650-700 nm. The efficiencies of energy transfer from the donor to the acceptor, and the overall quantum yields of the cassettes were determined.     

Selection rules for Raman scattering from eigenmodes of spherical nanoparticles

The elastic vibrations of spherical nanoparticles have been widely studied by Raman scattering. However, there exist more than one set of selection rules for Raman scattering from these vibrations. For instance, Kanehisa has stated that only torsional modes with angular momentum l = 2 are Raman-active, while Tanaka et al. proposed that spheroidal modes of even l and torsional modes of odd l are Raman-active. These contradict selection rules of Duval which states that only spheroidal modes of l = 0 or 2 are Raman-active. Our present calculations based on a macroscopic model show that all torsional modes have vanishing intensity in the Raman spectrum.     

Ion-pair formation observed in a pulsed-field ionization photoelectron spectroscopic study of HF

The pulsed-field ionization (PFI) photoelectron (PE) spectrum of HF has been recorded at the chemical dynamics beamline of the advanced light source over the photon energy range 15.9-16.5 eV using a time-of-flight selection scheme at a resolution of 0.6 meV. Rotationally-resolved structure in the HF+(X 2 pi 3/2, 1/2, v+ = 0, 1) band systems are assigned. The spectral appearance of these systems agrees with a previous VUV laser PFI-PE study. Importantly, extensive rotationally-resolved structure between these two vibrational band systems is also observed. This is attributed to ion-pair formation via Rydberg states converging on the v+ = 1 vibrational levels of the HF+(X 2 pi 3/2, 1/2) spin-orbit states. These Rydberg states are assigned to the 1 sigma+ part of the nd-complexes (sigma, pi, and delta). Ion-pair formation is observed in this study by the detection of F- ions. Some partially rotationally-resolved structure in a previously published threshold photoelectron spectrum is similarly attributed to ion-pair formation (F- detection) through a combination of the v+ = 17 level of the (A 2 sigma+) 3s sigma Rydberg state and the (X 2 pi 3/2, 1/2, v+ = 1) 7d Rydberg states. On the basis of the present study, an accurate experimental value for the dissociation energy of the ground state of HF has been obtained, D0(HF) = 5.8650(5) eV.     

Preparation and chiral recognition of a novel chiral stationary phase for high-performance liquid chromatography, based on mono(6A-N-allylamino-6A-deoxy)-perfunctionalized beta-cyclodextrin and covalently bonded silica gel

A novel chiral stationary phase (CSP) was prepared by immobilizing mono(6A-N-allylamino-6A-deoxy)-perphenylcarbamoylated beta-cyclodextrin onto the surface of silica gel via hydrosilylation. The chromatographic properties of this column were tested with a wide range of structurally diverse racemic compounds and drugs under reverse phases. Separation mechanisms involved are also discussed.     

Gas chromatographic-mass spectrometric analysis of acids and phenols in distilled alcohol beverages. Application of anion-exchange disk extraction combined with in-vial elution and silylation

A GC-MS protocol for profiling spirits, based on 19 acids and phenolic compounds, has been proposed and evaluated. The method combined a simple preconcentration procedure based on solid-phase (anion-exchange) disk extraction, and in-vial elution and silylation of the analytes. The derivatized extract was directly injected into the GC-MS system. These analytes were: C6, C8, C10, C12 acids, pyruvic acid, 2-furoic acid, succinic acid, fumaric acid, glutaric acid, lactic acid, glycolic acid, malic acid, tartaric acid, citric acid, vanillin, syringaldehyde, coniferaldehyde, vanillic acid and gallic acid. The profiles of six different spirits were found reproducible from day-to-day with <20% RSD for measurements of most of the analytes at different concentrations. Recoveries of individual analytes appear to be affected by the level of tannins in the spirits, and they varied from sample to sample. The method of standard addition was used to quantify age-related analytes. Good linearity of response with correlation coefficients in the range of 0.992-0.999 was obtained. The results of the study indicate that for spirits of the same brand but of different ages, the amounts of these analytes appear to increase with the ageing period.     

Bis[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(perchlorato‐κO)copper(II) bis­[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(methanol‐κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square‐planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen‐bonding network.