反应挤出法合成S/B多嵌段共聚物的研究

在阴离子引发体系下 ,以双螺杆挤出机为反应器 ,采用丁二烯、苯乙烯混和单体加料方式 ,本体法一步合成了S B多嵌段共聚物 .考察了螺杆转速、进料速率以及不同丁苯配比对反应挤出合成PS及S B嵌段共聚物聚合转化率的影响 .用1 H NMR、IR、DMA、TEM等方法对S B嵌段共聚物进行了表征 ,结果表明共聚物由多个微小的丁二烯嵌段和少量无规段组成 .当丁二烯含量少至 15 %左右时 ,其嵌段可回缩成球状 ,粒径大约在 30～ 5 0nm .该材料的韧性随着共聚物中丁二烯含量的增加而逐渐提高 ,特别是断裂延伸率的提高尤为显著     

The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

Photoelectron spectra of vinyl- and 1-alkynylgermanes and stannanes

Primary vinylic and acetylenic germanes and stannanes, synthesized by a chemoselective reduction of the corresponding trichloro derivatives, were investigated by ab initio quantum chemical methods and photoelectron spectroscopy. In particular, the PE spectra display very well-resolved bands which show the increasing destabilizing effect of 14 group heteroatom α-substitution of double or triple carbon–carbon bonds.     

Comparison of Different Sorbents for Solid-Phase Extraction of Phenoxyalkanoic Acid Herbicides

An HPLC procedure for determination of phenoxyalkanoic acid herbicides in water samples is proposed. The analytical column Phenomenex C18(2) Luna 5 µm and UV detection at 225 nm were applied. Baseline resolution was achieved in isocratic mode with a mobile phase consisting of acetonitrile/acetic acid (40/60, v/v), adjusted to pH 2.5. SPE sorbents – C₁₈ BondElut, phenyl-silica, LiChrolut SAX and polymeric sorbents – were compared for isolation and preconcentration of 6 phenoxyalkanoic acid herbicides. Higher (above 95%) and more reproducible recoveries were obtained with polymeric and phenyl-silica sorbents using pure methanol for elution. The method was tested for river water samples with the limit of detection in the range of 2–3 µg L⁻¹ (for 50 mL sample) and a reproducibility of 5% RSD.     

Thermal stability of products prepared by the combination of cyclodextrins and zeolites

Derivatographic and calorimetric measurements were used to study the thermal properties of combined inclusion compounds of zeolite-cyclodextrin type and of zeolite-cyclodextrin-pharmaceutical type. There were differences in the characteristic decomposition temperature intervals and in the modes of cyclodextrin and pharmaceutical liberation from the products. Calorimetric measurements revealed that the process in the newly-formed complex host is connected with a glass transition. The products are intended for use in veterinary medicine.     

Oxathiaphospholane approach to the synthesis of oligodeoxyribonucleotides containing stereodefined internucleotide phosphoroselenoate function

5'-O-DMT-deoxyribonucleoside-3'-O-(2-selena-4,4-pentamethylene-1,3,2-oxathiaphospholane) monomers, derivatives of dA, dC, dG, and T, can be resolved into pure P-diastereomers by silica gel column chromatography. They have been used for DBU-promoted, either solution- or solid-phase synthesis of P-stereodefined phosphoroselenoate analogues of oligodeoxyribonucleotides. Fast- and slow-eluting monomers are precursors of phosphoroselenoate internucleotide linkage of R(P) and S(P) absolute configuration, respectively. [reaction: see text]     

Polycondensed nitrogen heterocycles. Part 17. Isoxazolo[4,3-d]pyrazolo[3,4-f][1,2,3]triazepine. A new ring system

The title compounds were prepared by nitration of compounds 2 , reduction of the dinitro derivatives 4 and diazotization of the diamino derivatives 6 followed by an intramolecular coupling reaction. Compound 4a showed good activity against Salmonella cholerasuis and Clostridium perfringens bacteria.     

Characterisation of Sugar Cane Combustion Particles in the Araraquara Region, Southeast Brazil

Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the respirable size range makes the study of this fraction important in view of possible health and climatic effects. The annual burning of sugar cane plantations causes emission of huge amounts of pyrogenic particles. Aerosol samples were collected in Araraquara city, São Paulo state, Brazil, during the harvest season for fine and coarse particles and bulk; they were analysed by electron-probe microanalysis, including facilities for low-Z element determination (low-Z EPMA) and by energy-dispersive X-ray fluorescence (EDXRF), in order to investigate the elemental composition of individual particles and bulk samples, respectively. Numerical analysis of the EPMA results by hierarchical clustering shows high contributions of carbonaceous particles that can be distinguished mainly in two different types: biogenic and carbon-rich. Additionally, two significant contributions of aluminosilicate particles were identified: as rather pure aluminosilicates or mixed with carbonaceous species. The EDXRF results are compatible with those of aerosol particles in Amazon, which is nowadays one of the main sources of biogenic particles in the world.     

Polarization and polarizability in extended one-dimensional organic materials

The modern theory of polarization in extended insulators is applied to one-dimensional models for conjugated polymers and charge transfer salts. Closed expressions for the dependence of the polarization on the site and bond energy alternations are presented for uncorrelated models, and results from exact real-space diagonalization are obtained for correlated models. Changes in polarization induced by lattice phonons or molecular vibrations are directly related to the intensity of infrared bands in the far and mid-IR, respectively. We model intensities by introducing linear electron-vibration coupling and show that coupling to delocalized electrons generates a combination band consisting of a lattice phonon and a molecular vibration. The displaced dipole operator is defined on a real-space basis allowing for the finite field calculation of linear polarizability in finite size systems with periodic boundary conditions. Size-consistency arguments are used to demonstrate that the resulting polarizability becomes exact in the thermodynamic limit, and numerical calculations demonstrate that this approach leads to reliable results that converge rapidly to the thermodynamic limit.     

Threshold detection using indicator-displacement assays: an application in the analysis of malate in Pinot Noir grapes

The mathematics for modeling indicator-displacement assay isotherms is presented and contrasted to the classical host-guest binding isotherm. It is shown that the signal response can be tuned to occur closer to 1 equiv of guest relative to a standard binding algorithm. This delay in response leads to a better triggering protocol for threshold detection schemes. The determination of malate in Pinot Noir must was calculated using this new mathematical model, which demonstrates how a color change can be tuned to occur near a desired concentration of analyte.