红外光谱和逐步判别分析法应用于油菜籽的研究

用傅里叶变换红外光谱(FTIR)和逐步判别分析法对油菜籽的品种和产地进行鉴别研究。测试了来自5个产地17个油菜籽品种188份油菜籽皮样品的红外光谱,按产地和品种选择训练样本,每个品种选择5份为训练样本,剩下的作为测试样本,选择1 800～950 cm-1范围的光谱信息,在SPSS20.0的判别分析模块中采用逐步法,Fisher线性判别准则,分别建立油菜籽品种和产地的鉴别模型来判别样品的品种和产地;比较了逐步判别分析中五种筛选建模信息的算法所建立的模型对实验样品品种和产地的鉴别效果。基于油菜籽皮红外光谱信息的品种判别分析,五种筛选变量的算法所建立的模型都能较好的识别油菜籽的品种,“Wilks’ Lambda”法所建模型的识别效果最好,判别正确率为97.9%。基于油菜籽皮红外光谱信息的产地判别分析,五种筛选变量的算法所建立的产地判别模型也都能较好的识别油菜籽的产地,“Unexplained variance”法所建模型的识别效果最好,判别正确率为98.4%。研究结果表明,基于油菜籽皮中红外光谱信息的品种和产地判别分析,有望成为油菜籽品种和产地鉴别的方法。     

Enzyme mechanisms: interplay of theory and experiment

An overview is given on experimental and theoretical methods applied to the study of enzyme mechanisms. While experiments provide more or less precise data on realistic systems, the obtained information often overlap and a mixture of observations has to be resolved in order to appropriately understand enzymatic processes at the molecular level. On the other hand, computations to be done on adequate models reflecting all important properties of the system, may not provide results that are accurate enough to be compared with experiments. It is stressed that in a computational study the level of sophistication of the model and the method applied to it should be about the same in order to obtain sound results. A case study, the catalytic mechanism of serine proteases, is discussed in detail calling attention to the problems where the interplay between computations and experimental studies was necessary to understand mechanistic details. It is computational chemistry that lead to the discovery of the crucial role of the protein electrostatic field in the acceleration of the enzyme reaction as well as protonation state of the side chains of the active site. We stress that computational studies are especially important in the right interpretation of experimental observations and should replace speculations based on textbook chemistry.     

不同部位人体气味的分析研究

运用SPME-GC/MS法对同一个体腋窝部、手部和足部的人体气味样品进行了采样分析,通过比较3个部位人体气味样品色谱图中共有成分相对峰面积比和非共有成分,结合使用相似度法对3个部位的人体气味进行了比较分析,三者具有较高的相似度,但仍存在一些细微的差别。     

Theoretical Study on the Hetero-Diels-Alder Reactions between 3-Pyridinedithioesters and 1-Phenylsulfanylbutadiene

The mechanism, catalytic effect and solvent effect of the hetero-Diels-Alder reac- tions between 3-pyridinedithioesters and 1-phenylsulfanylbutadiene have been studied theoretically using density functional theory (DFT) at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C bond and the opposite results are found in other reactions. The BF3 catalyst may lower the activation barriers by changing the energies of LUMO for 3-pyridine- dithioester. THF solvent has trivial influence on the potential energy surface of these reactions. With the BF3-catalyzed reactions, regioselectivity and stereoselectivity observed experimentally were predicted correctly by calculations and these results originate probably from C-H···F interaction in two transition states.     

Density Functional Theory Study on the Adsorption of Dioxygen on Small Pt-Pd Clusters

1 INTRODUCTION The bimetallic nanoclusters are of standing inte- rest since they can exhibit catalytic, electronic and optical properties distinct from those of corre- sponding pure nanoclusters[1～4]. Palladium and pla- tinum, well known for their catalytic properties, are often used as the catalyst in different fuel cells[5～8]. Several experimental results illustrate that for the oxygen reduction reaction (ORR), which is one of the primary reactions taking place in many fuel cells and…     

识宋学与辨新局：钱穆《中国近三百年学术史》论学旨趣解析

钱穆《中国近三百年学术史》“识宋学”以“识近代”的论学逻辑,对应的是“理学反动说”背后隐然预流的以“科学”返看“宋学”的主流认识。“识宋学”首在驳周敦颐“宋学”开山说,以此澄清“宋学”精神,去玄注实。其次破“道统”说,重流变,以集合内外的阳明“心学”为宋明理学的自身进化结果。在此脉络下,最终以上通于阳明《拔本塞源论》的黄宗羲晚年定论,体现“内圣外王,有体有用,举凡政治教育,道德才能,莫不一以贯之”的学术大境界,又能突破“理学”束缚,开出学术的新格局。寄托了钱穆的学术理想。     

Purple subphthalocyanine-phthalocyanine dyad: Synthesis,photophysicochemical properties and DFT study

A new phthalocyanine-subphthalocyanine heterodyad ( 5 ) was prepared by Pd(0)-catalyzed Sonogashira coupling reaction between an asymmetrical phthalocyanine ( 3 ) bearing monoiodo and multiple triazolide moieties on its backbone and a subphthalocyanine ( 4 ) bearing axially propargyl group. The structure of this heterodyad ( 5 ) was subsequently confirmed by the conventional spectroscopic techniques. The photophysical and photochemical properties including; fluorescence and singlet oxygen generation of ( 5 ) along with its building chromophores ( 3 ) and ( 4 ) were also investigated. Interestingly, a purple colored solution was observed by this novel dyad which was significantly different from those colors (green or blue) obtained by phthalocyanine-subphthalocyanine conjugates. Based on steady state absorption spectroscopic data and transient absorption results, the synthesized dyad 5 was free of aggregation and there is good energy transfer occurs between Pc and subPc moieties. This result was confirmed using density functional theory (DFT) and time-dependent DFT (TDDFT) analyses: B3LYP exchange-correlation functional and the 6–31 + G(d) basis set.     

化学原理课程小班教学方法的研究与实践

In this paper, the contents and methods of small-class teaching of chemical principles were introduced in detail, including the allocation of teaching time, the allocation of lecturing and self-study contents, organizing seminar and literature reading, as well as the cultivation of students' innovation ability. The reform of teaching content and teaching method in the process of implementing were introduced.     

Mechanistic modeling of the reaction kinetics of phenyl glycidyl ether (PGE) + aniline using heat flow and heat capacity profiles from modulated temperature DSC

Modulated temperature DSC (MTDSC) has been performed on phenyl glycidyl ether (PGE) + aniline in order to obtain the non-reversing heat flow and heat capacity profiles simultaneously in a wide range of cure temperatures and mixture compositions. The epoxy (PGE) conversion as determined from the former signal corresponds to the one obtained from separate high performance liquid chromatography (HPLC), while the latter signal contains information on the individual reaction steps. Optimized kinetic parameters using a mechanistic approach, including both reactive and non-reactive complexes can successfully simulate MTDSC measurements for isothermal reaction temperatures ranging from 50 to 120 °C and for non-isothermal experiments with mixture compositions corresponding to concentrations of aniline in a range from 1.68 to 6.53 mol kg⁻¹. Concentration profiles for three mixture compositions as obtained from HPLC are also well predicted. The activation energies for the primary amine and secondary amine-epoxy reaction catalyzed by hydroxyl groups are 50 and 52 kJ mol⁻¹, respectively, while the initiation of the reaction corresponds to the primary amine-epoxy reaction catalyzed by primary amine groups with an activation energy of 72 kJ mol⁻¹. A negative substitution effect can be calculated at 0.18 from the ratio of secondary amine to primary amine-epoxy reaction rate constants.     

湛江市鲜瘦猪肉营养价值的比较研究

首次报道湛江市鲜瘦猪肉的水分含量、干重及无机金属元素含量。与全国代表值比较实验测得水分含量高４．７１％，干重均值低４．７１％，两者经统计学处理均呈现极显著性差异，人体重要的无机金属营养元素Ｚｎ、Ｃｕ、Ｆｅ、Ｃａ、Ｍｇ、Ｎａ、Ｋ均呈现极显著性的降低，上述结果提示，湛江市现市售鲜瘦猪肉的营养价值已显著下降。