Controlled synthesis and chemical modification of unsaturated aliphatic (Co)polyesters based on 6,7‐dihydro‐2(3H)‐oxepinone

A pure unsaturated cyclic ester, 6,7‐dihydro‐2(3H)‐oxepinone (DHO2), was prepared by a new synthetic route. The copolymerization of DHO2 with ?‐caprolactone (?CL) was initiated by aluminum isopropoxide [Al(OⁱPr)₃] at 0 °C as an easy way to produce unsaturated aliphatic polyesters with nonconjugated C?C double bonds in a controlled manner. The chain growth was living, as certified by the agreement between the experimental molecular weight at total monomer conversion and the value predicted from the initial monomer/initiator molar ratio. The polydispersity was reasonably low (weight‐average molecular weight/number‐average molecular weight ≤ 1.2). The homopolymerization of DHO2 was, however, not controlled because of fast intramolecular transesterification. Copolymers of DHO2 and ?CL were quantitatively oxidized with the formation of epoxides containing chains. The extent of the epoxidation allowed the thermal properties and thermal stability of the copolyesters to be modulated. The epoxidized copolyesters were successfully converted into thioaminated chains, which were then quaternized into polycations. No degradation occurred during the chemical modification. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2286–2297, 2002     

香草醛异烟酰腙与钴、镍、铜、锌和镉配合物的合成和性质研究

本文合成了香草醛异烟酰腙(H₂L^Ⅰ)和邻香草醛异烟酰腙(H₂L^Ⅱ)与钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)和镉(Ⅱ)的九个新配合物:M(HL^Ⅰ)₂·nH₂O[M(Ⅱ)=Co、Ni、Cu、Zn和Cd,n=0,2]和M(HL^Ⅱ)₂·nH₂O[M(Ⅱ)=Co、Ni、Cu和Zn,n=0-3]。采用     

锗(Ⅳ)与邻苯二酚和含氮配体混配配合物的合成与表征

首次合成了四种锗(Ⅳ)与邻苯二酚和α-氨基酸的混配配合物［Ge(C₆H₄O₂)₂·2AA］,(AA=α-甘氨酸(gly)、α-苏氨酸(thre)、α-缬氨酸(val)、α-白氨酸(leu)；两种锗(Ⅳ)与邻苯二酚和杂环二胺类的混配配合物［Ge(C₆H₄O₂)₂·(DA)］，(DA=2,2′-联吡啶(bipy)、1，10-邻菲咯啉(phen)。用元素分析、摩尔电导、红外和紫外光谱、核磁及热分析等方法研究了配合物的组成和性质，表明配合物有两种结构类型，一类是反式八面体，另一类为顺式畸变八面体。     

COT-H在金属Ru表面上沉积的光电子能谱分析

采用紫外光电子能谱（UPS），分析了不对称四苯基四苯乙炔基环辛四烯（COT H）有机发光材料与金属之间的界面电子结构，研究了在金属/COT H界面上的逸出功变化.UPS谱中位于费米能级以下5.6、7.9和10.2 eV处的三个谱峰分别来自于COT H材料中苯环的πCC、σCC和σCH轨道.位于3.8 eV处的谱峰反映了八个苯环聚合后具有π轨道特性的C－C键.从UPS谱图中可以看到， COT H材料的最高占有态（HOS：highest occupied state）位于费米能级以下1.8 eV处.COT H材料的逸出功只有3.2 eV，比清洁Ru表面的逸出功小1.0 eV.角分辨紫外光电子能谱（ARUPS）的结果表明,组成COT H分子应该近似平行于衬底表面.     

Direct, facile aldehyde and ketone alpha-selenenylation reactions promoted by L-prolinamide and pyrrolidine sulfonamide organocatalysts

[reaction: see text] A new catalytic method for direct alpha-selenenylation reactions of aldehydes and ketones has been developed. The results of exploratory studies have demonstrated that L-prolinamide is an effective catalyst for alpha-selenenylation reactions of aldehydes, whereas pyrrolidine trifluoromethanesulfonamide efficiently promotes reactions of ketones. Under optimized reaction conditions, using N-(phenylseleno)phthalimide as the selenenylation reagent in CH2Cl2 in the presence of L-prolinamide (2 mol %) or pyrrolidine trifluoromethanesulfonamide (10 mol %), a variety of aldehydes and ketones undergo this process to generate alpha-selenenylation products in high yields. Mechanistic insight into the L-proline and L-prolinamide catalyzed alpha-selenenylation reactions of aldehydes with N-(phenylseleno)phthalimide has come from theoretical studies employing ab initio methods and density functional theory. The results reveal that (1) the rate-limiting step of the process involves attack of the enamine intermediate at selenium in N-(phenylseleno)phthalimide and (2) the energy of the transition state for the reaction catalyzed by prolinamide is lower than that promoted by proline. This result is consistent with experimental observations. The role of hydrogen bond interactions in stabilizing the transition states for this process is also discussed.     

Study of inclusive production of π± and protons in\bar p p interactions at 32 GeV/c

Results are presented on the inclusive production of π^± mesons and protons in \(\bar p\) p interactions at an incident antiproton momentum of 32 GeV/c in the MIRABELLE bubble chamber, based on a sample of 55,000 inelastic events. The spectra of π⁺(π^?) andp( \(\bar p\) ) are separated in the whole kinematically admitted region of phase space by a statistical method. The semi-inclusive and inclusive cross sections and the main average characteristics of π andp production are calculated. The invariant differential cross sections are studied as functions of the Fevnman scaling variablex, the rapidity and the transverse momentum. Thex distribution of π^± mesons in the proton fragmentation region does not show any significant contribution from quark exchange or annihilation processes. A possible contribution of hard quark scattering on mesons or baryons is observed for large transverse momenta.     

Characterization of Semtex by supercritical fluid extraction and off-line GC-ECD and GC-MS

Researchers using electron capture for the detection of explosive vapors currently claim the ability to detect the presence of RDX in Semtex – a plastic explosive comprising hexahydro-1,3,5-trinitro-1,3,5-triazane (RDX) in a matrix of styrene-butadiene copolymer and hydrocarbon oil. The vapor pressure of RDX at room temperature is 0.006 ppb, and therefore well below the detection limit of electron capture detection (ECD). The positive response generated by ECD is, consequently, not from the presence of RDX, but from some other component. This paper describes the extraction and identification of several compounds in Semtex, along with the determination of which is responsible for the positive response of an ECD-based detector. From the results of supercritical fluid extraction and off-line gas chromatography combined with electron capture and mass spectrometric detection, it has been concluded that ethylene glycol dinitrate is the component responsible for the positive ECD response. This conclusion is based on the requirements necessary for ECD detection, i.e. electronegativity, and a sufficient vapor pressure. The other compounds present were eliminated as possible choices because they either can not be detected by an ECD or do not have sufficient vapor pressure under ambient conditions.     

Dynamic electrophoresis of a sphere in a spherical cavity: arbitrary surface potential

The boundary effect on the dynamic electrophoretic behavior of a charged entity is examined by considering a sphere in a spherical cavity. The present study extends previous analysis to the case of an arbitrary level of electrical potential where the effect of double-layer distortion can be significant. The governing equations are solved numerically based on a pseudo-spectral method, which is found to be sufficient in solving the corresponding electrophoresis problem when a static electric field is applied. The result of numerical simulation reveals that as the size of a cavity decreases, both the magnitude of the mobility and the inertial force acting on a particle decrease accordingly. Also, while the distortion of the ionic cloud should not be ignored, in general, when the surface potential of a particle is high, its influence on the magnitude and on the phase angle of the mobility is alleviated by the presence of the cavity.     

Investigation of the crystallization process in 2 nm CdSe quantum dots

Investigation of the growth of CdSe nanocrystals ( approximately 160 atoms) to the uniquely stable size of 2 nm allows the monitoring of the crystallization process in semiconductor quantum dots. By using a combination of optical techniques, high-resolution transmission electron microscopy (HRTEM), and powder X-ray diffractometry (XRD), new phenomena were explored during the CdSe nanocrystal growth process, which involved significant morphological reconstruction and crystallization of the initially formed amorphous nanoparticles. During the crystallization, the absorption onset of the CdSe quantum dots blue shifted toward higher energies at 3 eV (414 nm), while the photoluminescence red shifted to lower energies. Furthermore, an apparent increasing Stokes shift was observed during the formation of small CdSe nanoparticles. On the other hand, the photoluminescence excitation spectra showed constant features over the reaction time. Additionally, results from HRTEM and XRD studies show that the CdSe nanoparticles were amorphous at early reaction stages and became better crystallized after longer reaction times, while the particle size remained the same during the crystallization process. These observations demonstrate the important role of the surface on the optical properties of small CdSe quantum dots and facilitated the spectroscopic monitoring of the crystallization process in quantum dots.     

Determination of oleanolic acid and ursolic acid in cornel by cyclodextrin-modified micellar electrokinetic chromatography

A cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) method was established for the determination of oleanolic acid and ursolic acid in cornel. The two components were separated in the running buffer of 40 mmol/L sodium borate containing 5% methanol, 25 mmol/L SDS and 15 mmol/L hydroxypropyl-beta-cyclodextrin (HP-beta-CD). The applied voltage was 24 kV. The wavelength of detection was 200 nm. The temperature was kept at 25 C. Cinnamic acid was used as the internal standard. The analytical performance of the method was tested with respect to linearity, precision and recovery. The calibration curves were linear in the range of 10.15-243.6 microg/mL, r=0.9993 (oleanolic acid) and 10.07-241.7 microg/mL, r=0.9994 (ursolic acid); the intra-day precision (RSD) was less than 3.7% (oleanolic acid) and 4.1% (ursolic acid); the inter-day precision (RSD) was less than 4.2% (oleanolic acid) and 4.9% (ursolic acid). The limits of detection were 1.6 microg/mL for both components. The method proved to be sensitive, rapid, accurate and suitable for the determination of oleanolic acid and ursolic acid in cornel.