同步辐射软X射线近边吸收谱方法研究长期施肥对黑土有机碳官能团的影响

以定位20年的黑土肥料试验为平台,利用同步辐射软X射线近边吸收谱(C-1s NEXAFS)方法,研究了长期施用化肥以及化肥配施玉米秸秆对土壤有机碳官能团的影响。结果表明：与不施肥的空白处理(CK)相比,单施化肥(N,NPK)后土壤的芳香C和羧基C含量增加,脂族C和羰基C含量下降,脂族C/芳香C比值降低;与单施化肥处理相比,化肥配施玉米秸秆后芳香C含量下降而脂族C含量增加,脂族C/芳香C比值增加,并随玉米秸秆用量增加表现的更为明显;无论配施玉米秸秆与否,NPK肥混施处理的芳香C、脂族C以及脂族C/芳香C比值均高于单施N肥处理。上述结果说明,单施化肥比不施肥使土壤有机碳官能团中芳香类化合物的相对比例增加,而脂肪烃类化合物的相对比例下降;化肥配施玉米秸秆则比单施化肥增加了脂肪烃类化合物的相对比例,配施高量比低量玉米秸秆的增加趋势更为明显,同时NPK肥混施比单施N肥有利于提高脂肪烃类化合物的相对比例。C-1s NEXAFS方法能够原位表征长期定位施肥条件下土壤有机碳官能团组成的变化。     

硝基芴酮与脂肪胺相互作用的ESR研究

本文用ESR方法研究了五种硝基芴酮与九种脂肪胺间的相互作用。讨论了芴酮衍生物的电子亲合势、脂肪胺的电离势及其空间位阻对相互作用的影响。     

Synthesis of organic phenothiazine-based molecular glasses and effect of racemic/homochiral aliphatic chain on near-infrared photorefractive property

Organic near-infrared photorefractive molecular glasses with a phenothiazine moiety are designed and synthesized through the introduction of linear, racemic/homochiral asymmetrically branched aliphatic chains into photorefractive chromophore as an auxiliary group. The compounds are characterized with ¹H-NMR, IR, FAB-MS, UV–vis, TG, DSC, etc. The effect of different aliphatic chains on the absorption and thermal properties is investigated in detail. The molar absorption coefficiency at the absorption maximum wavelength showed that the homochiral asymmetrically branched aliphatic chain has a strong hypochromic effect in the dilute solution when it is introduced into photorefractive chromophore. The DSC measurement indicated that the introduction of asymmetrically branched aliphatic chain is the key issue to design organic molecular glasses whether it is racemic or homochiral. The effect of racemic/homochiral asymmetrically branched aliphatic groups on photorefractive property is investigated carefully with poly(N-vinylcarbazole) (PVK) as a photoconductor and with (2,4,7-trinitro-9-fluorenylidene) malononitrile (TNFM) as a photosensitizer. The results suggested that the racemic group is more beneficial to the improvement of photorefractive performance than the homochiral when the homochiral cannot induce rigid photorefractive chromophore to be much more ordered.     

脂肪族醚类化合物核磁共振碳谱模拟

利用原子电性作用矢量(atomic electronegativity interaction vector, AEIV)对脂肪族醚类化合物中碳原子局部化学微环境进行表征, 并结合γ-效应参数与其核磁共振碳谱(¹³C NMR)建立定量构谱相关(QSSR)模型,建模计算值和留一法(leave-one-out, LOO)交互校验(cross-validation, CV)预测值的复相关系数(R)分别为0.995 7和0.994 2. 进一步使用外部样本对所得模型稳定性能进行检验,其外部校验相关系数(Q_ext)为0.996 3,结果表明： AEIV、γ-效应参数与¹³C NMR谱化学位移显著相关.     

光促进下脂肪酸甲酯的合成及质谱(MS)分析

本文报道了光促进下脂肪酸甲酯合成的新方法,并对１９种甲酯化产物的质谱（ＭＳ）图进行了分析。通过对这些甲酯ＭＳ图的分析,对含两种γ－Ｈ脂肪酸甲酯的Ｍｃｌａｆｆｅｒｔｙ重排进入了深入的探讨,并对同一类型甲酯随碳链增长时重排的规律进行了讨论。     

Fe(Ⅲ)对脂肪酸13C NMR信号的影响

研究了Fe (Ⅲ)对脂肪酸¹³C NMR信号的影响.结果表明,Fe (Ⅲ)对脂肪酸¹³C NMR信号的影响的机理是电子自旋弛豫对核自旋弛豫的影响;产生这种影响的必要条件是Fe (Ⅲ)与脂肪酸之间的缔合.该影响沿化学键传递并随距离的增加而迅速衰减.破坏Fe (Ⅲ)与脂肪酸之间的缔合,可使这种影响消失.利用该现象可帮助某些化合物¹³C NMR信号的归属,并可对某些分子在溶液中的状态进行研究.     

西北地区侏罗纪煤显微组分结构的Micro-FTIR研究

我国西北地区侏罗纪煤资源丰富,揭示该地区煤显微组分的微观化学结构特征是对其进行合理高效利用的必要前提。采用透射式显微傅里叶红外光谱技术(Micro-FTIR)对西北地区侏罗纪煤中主要显微组分——镜质体、丝质体、半丝质体的分子结构特征进行了分析。结果表明,相对于丝质体,镜质体和半丝质体的脂肪氢相对含量较高,而芳香氢、CO相对含量较低,半丝质体的脂肪氢相对含量高于丝质体的这一分子结构特点是导致西北地区侏罗纪煤虽富含惰质组却具有较高反应性的一个重要原因;相对于强还原型煤,弱还原型煤镜质体、半丝质体和丝质体皆具有较低的脂肪氢相对含量及较高的CO相对含量,成煤过程中不同强度的氧化作用是造成煤具有不同还原类型的原因之一。     

Micro-FTIR study on structure of macerals from Jurassic coals in Northwestern China

Jurassic coal in Northwest China is rich in resources and it is a necessary premise to reveal the chemical structure characteristics of the coal macerals in this region before the coal is put into reasonable and efficient use. Micro-FTIR technique was used to investigate the chemical composition and structures of vitrinite semifusinite and fusinite from Jurassic coal in Northwestern China. The results show that vitrinite and semifusinite have more aliphatic hydrogen, but fusinite has more aromatic hydrogen and C=O structure. The aliphatic hydrogen in semifusinite is higher than that in fusinite and it is this structure characteristic of semifusinite that led to the richer inertinite but higher reactivity of the Northwestern China coal. Not only vitrinite but also semifusinite and fusinite with weaker reducibility have less aliphatic hydrogen and more C=O structures than those with stronger reducibility. The different intensity of oxidation in the process of coalification is one of the causes that led to different type of reducibility.     

吉林桦甸油页岩及热解产物的红外光谱分析

热化学转化是油页岩综合利用的关键技术.用石英管反应器在500℃下热解吉林桦甸三个矿区(大城子四层、公合四层、公朗头十一层)的油页岩,分别得到其热解半焦和页岩油,并在600和700℃热解大城子四层油页岩,以考察热解产物与热解温度的关系.用红外光谱考察了原料及热解产物.结果表明,页岩油与油页岩有机质所含官能团相似,主要都以...     

脂肪醇对槲皮素-环糊精包合物包合作用的研究

采用荧光光谱法研究了 β 环糊精及其衍生物与槲皮素的包合作用 ,测定了包合物的形成常数 ,并用等摩尔连续变化法确定了包合物形成的计量比 ,探讨了有机小分子醇对包合过程的影响。结果表明 :槲皮素 环糊精包合物包合能力强弱顺序为 :HP β CD >M β CD >β CD ,脂肪醇对槲皮素 环糊精包合物包合作用的影响与其所含碳数及体积有关     

二苯甲酮与烃的光化夺氢反应中产生的活泼自由基的ESR研究

本文用具立体阻碍的自旋捕捉剂2,4,6-三-特丁基亚硝基苯(TBN)与ESR相结合的方法,研究了十种烷烃及四种芳烃与二苯甲酮光化夺氢反应中产生的活泼自由基。结果表明,R₃R₂R₁Ċ和TBN形成烷氧苯胺自由基加合物。R-ĊH-R'与TBN形成烷氧苯胺自由基加合物和氮氧自由基加合物。TBN可用于区分有、无空间位阻的烷烃,芳烃自由基。自旋加合物的ESR波谱可表明自由基中未偶电子所在碳原子附近的有效质子数目。     

A Combined FTIR and Textural Study of the Oxidation of a Bituminous Coal

A FTIR study to detect the chemical modifications involved during the oxidation of a Spanish coal from the Central Asturian Basin (Spain) has been carried out. The coal was oxidized at 473 K for periods of 3, 7, 14 and 42 days, and at 543 K for 1, 2, 3, 4 and 14 days. Results show that at each temperature there was an increase in oxygenated functions (carboxyls, esters, anhydrides, ethers) and a gradual decrease in aliphatic and aromatic structure. There are remarcable differences at the two temperatures. Intermediate states of oxidation, less condensated structures and an appreciable proportion of the aliphatic C-H groups are predominant in coal samples oxidized at 473 K. When oxidation is carried out at 543 K, more oxidized forms, a more marked process of decarboxylation and more condensated structures appear, also aliphatic groups disappears almost totally. Chemical analysis and textural properties of each oxidized coal sample have been carried out, and a correlation between chemical changes detected by FTIR and textural properties has been attempted.     

Introduction of amino groups on the surface of thin photo definable epoxy resin layers via chemical modification

The introduction of amine groups on the surface of dielectric resins improves the adhesion with electrochemically deposited metals. In this work, etched epoxy resin surfaces are modified with aliphatic amines via a two step wet chemical reaction approach. First, cyanuric chloride is introduced on the surface. Next, the remaining reactive sites of cyanuric chloride are used to couple an aliphatic polyamine. Both reaction steps are optimized by variation of reaction parameters such as concentration, chemicals, temperature and time. A detailed surface characterization after each reaction step is provided using following techniques: ATR-IR, SEM-EDS, XPS and AFM.     

Contribution a l'etude des mecanismes de relaxation dielectrique des amines primaires dans le domaine ultra-hertzien

The authors have studied the mechanism of dielectric relaxation of primary amines from the point of view of the following characteristics : relaxation time distribution, activation energy, resultant behaviour of autocorrelation function of the orientational polarisation, spectral density of energy as a function of temperature and chain length of the aliphatic type molecules.The analysis of the relaxation mechanism is made on the basis of semi-empirical macroscopic model of Davidson-Cole. The relaxation mechanism can be analysed as a function of the combined effects of intermolecular and intramolecular relations which are related to the dipolar behaviour of amine group as well as the effect of hydrocarbonic aliphatic chain.     

脂肪醇甲酸酯类酞菁铜配合物的合成、表征及荧光性能

报道了四甲酰氯酞菁铜的合成及其与反应得到正丁醇、正戊醇、正己醇、正辛醇、正十二醇5个含脂肪链取代基的酞菁铜衍生物.分别用红外光谱、紫外-可见光谱、元素分析、核磁共振氢谱等方法对这些衍生物进行了结构和取代度的表征,并研究了该系列酞菁铜衍生物在有机溶剂中的溶解性及荧光性能与浓度、取代基的关系.研究结果表明在一般有机溶剂中这些酞菁铜衍生物的溶解性显著提高,荧光强度不随浓度的变化而线性变化、长链要高于短链取代酞菁铜衍生物的荧光强度.     

Ultrasonic acceleration of iodination of unactivated aliphatic hydrocarbons

Iodination of unactivated aliphatic hydrocarbons with iodoform (CHI3) and solid NaOH were greatly accelerated under ultrasonic irradiation. The mechanism of the sonochemical acceleration was studied.     

脂肪酮和脂肪酰卤羰基17O-NMR化学位移的研究

提出计算脂肪酮和脂肪酰卤羰基¹⁷O-NMR化学位移的公式：δ_cal=δ_0n+C×Δα，通过线性回归法确定了22种取代基参数.经回归检验表明该公式计算结果置信度为99.5%，与实验值的偏差Δδ在10.0以内的羰基¹⁷O-NMR化学位移计算值在90%左右.     

Dehydration reaction of hydroxenin monoacetate in carbon tetrachloride and an aliphatic alcohol under ultrasound irradiation

A new method for the preparation of an E/Z mixture of vitamin A acetate from hydroxenin monoacetate is described. This two-step reaction was studied by changing the reaction parameters (reaction temperature, ultrasound power, and reaction time) and the alcohol used. This approach consists of the dehydration reaction of hydroxenin monoacetate under ultrasound irradiation in CCl4 and an aliphatic alcohol under an inert atmosphere. The formation of small amounts of HCl from CCl4 and an aliphatic alcohol under ultrasound irradiation is followed by the dehydration reaction of hydroxenin monoacetate. An E/Z mixture of vitamin A acetate was obtained resulting in the desired pentaenes. Some ethers derivatives were also formed as by-products, isolated and characterized. Study of the reaction mechanism is also reported here.     

Optical and Physical Properties of Carbodiimides

Electronic (ultraviolet and visible), infrared, far infrared, and Raman spectra are listed for selected aliphatic and aromatic carbodiimides. Analysis of the spectral bands associated with the aliphatic substances are presented. Also included are the results of physical property measurements (dipole moment, vapor pressure, density, and surface tension) associated with several of the alkyl carbodiimides. In addition, a relationship is presented that correlates the v(C-C) modes of the alkyl carbodiimides, alkyl chlorides, alkyl isocyanates, alkyl isothiocyanates, and alkanes. This expression has the form v(C-C) = A(R)^m, where A and m are constant terms and R represents a variable that is based upon mass ratios.     

Effects of alkyl side chains on properties of aliphatic amino acids probed using quantum chemical calculations

Effects of alkyl side chains (R‐) on the electronic structural properties of aliphatic amino acids are investigated using quantum mechanical approaches. The carbon (C 1s) binding energy spectra of the aliphatic amino acids are derived from the C 1s spectrum of glycine (the parent spectrum) by the addition of spectral peaks, depending on the alkyl side chains, appearing in the lower energy region IP < 290 eV (where IP is the ionization potential). The two glycyl parent spectral peaks of the amide 291.0 eV [C₍₂₎] and carboxylic 293.5 eV [C₍₁₎] C atoms are shifted in the aliphatic amino acids owing to perturbations depending on the size and structure of the alkyl chains. The pattern of the N 1s and O 1s spectra in glycine is retained in the spectra of the other amino acids with small shifts to lower energy, again depending on the alkyl side chain. The Hirshfeld charge analyses confirm the observations. The alkyl effects on the valence binding energy spectra of the amino acids are concentrated in the middle valence energy region of 12–16 eV, and hence this energy region of 12–16 eV is considered as the `fingerprint' of the alkyl side chains. Selected valence orbitals, either inside or outside of the alkyl fingerprint region, are presented using both density distributions and orbital momentum distributions, in order to understand the chemical bonding of the amino acids. It is also observed that the HOMO–LUMO energy gaps of the aliphatic amino acids are reduced with the growth of the alkyl side chain.