Preparation and Characterization of New Optically Active Poly(amide-imide)s from N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine and Aromatic Diamines

Five new optically active aromatic poly(amide-imide)s (PAIs) 5a–e were prepared from a direct polycondensation reaction of a new diacid of N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic)-bis-L-isoleucine 3 with various aromatic diamines 4a–e in a medium consisting of triphenyl phosphite (TPP), calcium chloride (CaCl₂), pyridine (Py) and N-methyl-2-pyrrolidone (NMP). The polycondensation reaction produced a series of novel poly(amid-imide)s 5a–e in quantitative yields with inherent viscosities of 0.39–0.51 dL/g. The resulting polymers were fully characterized by means of ¹H-NMR, FT-IR spectroscopy, elemental analyses, inherent viscosity, solubility test, specific rotation and thermal properties of them were investigated using TGA/DTG and differential scanning calorimeter (DSC). The diacid 4 was synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6- tetracarboxylic dianhydride 1 with L-isoleucine 2 in acetic acid solution.     

Ultra high performance liquid chromatography-quadrupole-time of flight analysis for the identification and the determination of resveratrol and its metabolites in mouse plasma

Resveratrol is a polyphenol that has numerous interesting biological properties, but, per os, it is quickly metabolized. Some of its metabolites are more concentrated than resveratrol, may have greater biological activities, and may act as a kind of store for resveratrol. Thus, to understand the biological impact of resveratrol on a physiological system, it is crucial to simultaneously analyze resveratrol and its metabolites in plasma. This study presents an analytical method based on UHPLC-Q-TOF mass spectrometry for the quantification of resveratrol and of its most common hydrophilic metabolites. The use of ¹³C- and D-labeled standards specific to each molecule led to a linear calibration curve on a larger concentration range than described previously. The use of high resolution mass spectrometry in the full scan mode enabled simultaneous identification and quantification of some hydrophilic metabolites not previously described in mice. In addition, UHPLC separation, allowing run times lower than 10 min, can be used in studies that requiring analysis of many samples.     

Modelling phenolic and technological maturities of grapes by means of the multivariate relation between organoleptic and physicochemical properties

The ripeness of grapes at the harvest time is one of the most important parameters for obtaining high quality red wines. Traditionally the decision of harvesting is to be taken only after analysing sugar concentration, titratable acidity and pH of the grape juice (technological maturity). However, these parameters only provide information about the pulp ripeness and overlook the real degree of skins and seeds maturities (phenolic maturity). Both maturities, technological and phenolic, are not simultaneously reached, on the contrary they tend to separate depending on several factors: grape variety, cultivar, adverse weather conditions, soil, water availability and cultural practices. Besides, this divergence is increasing as a consequence of the climate change (larger quantities of CO₂, less rain, and higher temperatures).     

Combined use of three forms of chiroptical spectroscopies in the study of the absolute configuration and conformational properties of 3-phenylcyclopentanone, 3-phenylcyclohexanone,and 3-phenylcycloheptanone

Three forms of chiroptical spectroscopies, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD) have been employed to study the configuration and conformational properties of the three molecules: (S)-3-phenylcyclopentanone, (S)-3-phenylcyclohexanone, and (S)-3-phenylcycloheptanone (including (S)-3-phenylcyclopentanone-2,2,5,5-d₄ and (S)-3-phenylcyclohexanone-2,2,6,6-d₄). ECD and VCD spectra in the mid-IR for the three molecular systems are marginally dependent on fine conformational details, as interpreted in terms of standard DFT computational methods, with common spectroscopic features to the three systems clearly identified. Accounting for vibronic coupling mechanisms reproduces the structuring of ECD n→π^∗ band. The ORD curves are quite similar for the three types of molecules, but their interpretation highlights a crucial role played by conformations of the cycloalkanone ring in the case of (S)-3-phenylcycloheptanone. The same conclusions are reached by considering the VCD spectra in the CH-stretching region.     

内部激励源二自由度结构扬声器振动特性分析

有别于多数基于简单振子结构的扬声器,针对一类内部激励源二自由度(IE2DOF)结构的扬声器,用类比线路图法建立集总参数模型,计算分析了这种结构的频率响应,同时计算了其固有共振频率和固有反共振频率。使用叠加法分析内部激励源对频响的影响。最后实际测量和理论计算吻合,进一步支持了理论模型,揭示了IE2DOF结构扬声器的振动特性。     

A quick,easy, cheap,effective, rugged,and safe sample pretreatment and liquid chromatography with tandem mass spectrometry method for the simultaneous quantification of 33 mycotoxins in Lentinula edodes

Lentinula edodes, one of the most cultivated edible fungi in the world, are usually neglected for mycotoxins contamination due to the initial thinking of its resistance to mycotoxingenic molds. In the present study, a sensitive and reliable liquid chromatography with tandem mass spectrometry method was developed for the simultaneous quantification of 33 mycotoxins in L. edodes. Targeted mycotoxins were extracted using a quick, easy, cheap, effective, rugged, and safe procedure without any further clean‐up step, and analyzed by liquid chromatography with tandem mass spectrometry on an Agilent Poroshell 120 EC‐C₁₈ column (100 × 3 mm, 2.7 μm) with a linear gradient elution program using water containing 5 mM ammonium acetate and methanol as the mobile phase. After validation by determining linearity (R² > 0.99), sensitivity (LOQ ≤ 20 ng/kg), recovery (73.6–117.9%), and precision (0.8–19.5%), the established method has been successfully applied to reveal the contamination states of various mycotoxins in L. edodes. Among the 30 tested samples, 22 were contaminated by various mycotoxins with the concentration levels ranging from 3.3–28 850.7 μg/kg, predicting that the edible fungus could be infected by the mycotoxins‐producing fungi. To the best of our knowledge, this is the first report about real mycotoxins contamination in L. edodes.     

Injectable,Interconnected, High‐Porosity Macroporous Biocompatible Gelatin Scaffolds Made by Surfactant‐Free Emulsion Templating

High‐porosity interconnected, thermoresponsive macroporous hydrogels are prepared from oil‐in‐water high internal phase emulsions (HIPEs) stabilized by gelatin‐graft‐poly(N‐isopropylacrylamide). PolyHIPEs are obtained by gelling HIPEs utilizing the thermoresponsiveness of the copolymer components. PolyHIPEs properties can be controlled by varying the aqueous phase composition, internal phase volume ratio, and gelation temperature. PolyHIPEs respond to temperature changes experienced during cell seeding, allowing fibroblasts to spread, proliferate, and penetrate into the scaffold. Encapsulated cells survive ejection of cell‐laden hydrogels through a hypodermic needle. This system provides a new strategy for the fabrication of safe injectable biocompatible tissue engineering scaffolds.

     

过渡态理论在化学体系中的2个应用实例*

在大学本科一二年级的物理化学教学中,化学动力学章节的学习涉及到对不同时间尺度的认识。本文利用过渡态理论得到的速率常数表达公式,以乙烷分子碳/碳单键旋转和水分子氢键交换的动力学过程为例,对这2个应用实例的动力学过程所发生的时间尺度做出估算。这些时间尺度的估算对于学生理解不同动力学过程的物理图像至关重要,同时也有助于加强学生对重要公式的理解并能够将这些公式在化学体系中灵活运用。     

Slow turning reveals enormous quadrupolar interactions (STREAQI)

We introduce a new solid-state NMR method, which uses very slow sample rotation to visualize NMR spectra whose width exceeds feasible spectrometer bandwidths. It is based on the idea that if we reorient a tensor by a known angle about a known axis, the shifts in the NMR frequencies observed across the spectral width allow us to reconstruct the entire tensor. Called STREAQI (Slow Turning Reveals Enormous Anisotropic Quadrupolar Interactions), this method allows us to probe NMR nuclei that are intractable to current methods. To prove the concept and demonstrate its promise we have implemented the method for several 79Br containing samples with quadrupolar coupling constants in the range of 10-50 MHz.