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.     

CRYSTALLIZATION AND MECHANICAL PROPERTIES OF POLYPROPYLENE FILLED WITH SiO2 NANOPARTICLES

Oleic acid （OA）-modified SiO2 （OA-m-SiO2） nanoparticles were prepared using surface modification method. Infrared spectroscopy （IR） was used to investigate the structure of the OA-m-SiO2 nanoparticles, and the result showed that OA attached onto the surface of SiO2 nanoparticles through esterification. Effect of OA concentration on the dispersion stability of OA-m-SiO2 in heptane was also studied, and the result indicated that OA-m-SiO2 nanoparticles were dispersed in heptane more stably than the unmodified ones. OA-m-SiO2 nanoparticles can also be dispersed in polypropylene （PP） matrix in nano-scale. The effect of OA-m-SiO2 on crystallization of PP was studied by means of DSC. It was found that the introduction of OA-m-SiO2 resulted in significant increase in the crystallization temperature, crystallization degree and crystallization rate of PP, and OA-m-SiO2 could effectively induce the formation of β-crystal PP. Effect of OA-m-SiO2 content on mechanical properties of PP/OA-m-SiO2 nanocomposites was also studied. The results show that OA-m-SiO2 can significantly improve the mechanical properties of PP.     

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.     

(μ3-S)FeCo2(CO)7(dppfe)的合成和晶体结构

通过简单取代反应,合成了一个新的混金属簇合物(μ3-S)FeCo2(CO)7(dppfe) (2) (dppfe=Ph2PC5H4FeC5H4PPh2).利用IR,1H NMR,MS 和 X-ray单晶衍射的方法对簇合物2进行了结构表征.簇合物2的晶体属于三斜晶系,空间群为Pī.晶胞参数: a=1.132 4(15) nm, b=1.3670(17) nm, c=1.5769(2) nm,α=114.646(2)°,β=100.340(2)°,γ=100.113(3)°, V=2.0953(5) nm3.     

人类钙营养状况,缺钙后果及其对策

人类缺钙是世界性普遍存在的问题，中国人由于膳食结构缺陷及传统饮食习惯而使食物中钙的吸收受到影响，因而缺钙尤其普遍。     

Peptide late-stage C(sp3)–H arylation by native asparagine assistance without exogenous directing groups

There is a strong demand for novel native peptide motifs for post-synthetic modifications of peptides without pre-installation and subsequent removal of directing groups. Herein, we report an efficient method for peptide late-stage C(sp³)–H arylations assisted by the unmodified side chain of asparagine (Asn) without any exogenous directing group. Thereby, site-selective arylations of C(sp³)–H bonds at the N-terminus of di-, tri-, and tetrapeptides have been achieved. Likewise, we have constructed a key building block for accessing agouti-related protein (AGRP) active loop analogues in a concise manner.

An efficient method for peptide late-stage C(sp³)-H arylations assisted by unmodified side chain of asparagine (Asn) without any exogenous directing group has been reported.