含萘酰亚胺荧光聚合物的合成及对Pd2+识别研究

以4-溴-1,8-萘二甲酸酐为原料,经亚胺化、酯化等反应,设计合成了一种新的乙烯基荧光功能单体N-甲基丙烯酰氧乙基-4-溴-1,8-萘酰亚胺(NPMA),并用此单体与N-异丙基丙烯酰胺(NIPAAm)通过自由基聚合制备了荧光共聚物PⅠ、PⅡ和PⅢ.采用1H NMR(核磁共振氢谱)、UV-vis(紫外-可见)光谱和荧光光谱对共聚物的结构及性能进行了表征,结果表明聚合物对金属pd2+具有高灵敏度的选择性识别作用.     

含金刚烷结构胺类固化剂的制备与性能

以1,3-二溴金刚烷为原料,合成了一种环氧树脂固化剂1,3-二[4-(4-氨基苯氧基)苯基]金刚烷(BAPPA),并采用傅里叶变换红外光谱、核磁共振波谱等对其结构进行了表征,用差示扫描量热分析研究了环氧树脂(E51)/BAPPA体系的固化反应动力学,根据Kissinger方程计算出体系的反应活化能为43.57kJ/mol。对E51/BAPPA固化物的耐湿热性能、动态热机械性能、力学性能、介电性能的表征结果表明,环氧树脂固化物的拉伸强度为98MPa,玻璃化转变温度(Tg)为176.3℃,Td5高达406℃,吸水率、介电常数比相同条件下E51/DDM固化物分别降低了34.9%和15.7%。     

钛氧酞菁的合成工艺研究

以钛酸四丁酯和1,3-二亚氨基异吲哚啉为原料,高收率地合成了钛氧酞菁(TiOPc).分别考察了原料处理方法、反应介质、反应物配比、酞酸四丁酯投料温度及反应时间对产物收率的影响,适宜的合成条件是粗品1,3-二亚氨基异吲哚啉经过w(NaOH)=0.5%的碱性溶液处理,以蒸馏干燥过的邻二氯苯为溶剂,投料比n(1,3-二亚氨基异吲哚啉):n(钛酸四丁酯)=3:1,回流反应3h,收率达到91.26%.     

Gemini表面活性剂的合成及在乳化炸药中的应用

以N,N-二甲基十二烷基叔胺和1,3-二溴丙烷为原料,无水乙醇为溶剂合成阳离子型Gemini表面活性剂.反应产物以混合溶剂乙酸乙脂-乙醇重结晶纯化后,用红外光谱及核磁共振进行结构表征,并将其作为晶形改变剂及助乳剂应用于乳胶基质中,使乳化炸药具有小而分布均匀的W/O粒子和较强的稳定性及良好的爆炸性能.     

1，3-双（叠氮乙酰氧基）-2-乙基-2-硝基丙烷的合成与性能

以2-乙基-2-硝基-1,3-丙二醇为原料,经酯化、叠氮化两步反应,合成出了1,3-二(叠氮乙酰氧基)-2-乙基-2-硝基丙烷(ENPEA),总收率为83%。利用红外光谱、核磁共振、元素分析对ENPEA的结构进行了表征。探讨了叠氮化反应的影响因素,确定其最佳反应条件为:n(Na N3)n(ENPE)为2.21.0,混合溶剂中水占总体积的13%~20%,反应时间2 h;性能测试得到ENPEA的玻璃化转变温度为-43.4℃,热分解峰温为252.4℃,密度为1.34 g/cm3,特性落高为120.2 cm(落锤2 kg),爆炸概率为4%(摆角66°)。     

新型耐高温高闪点导热油—1,3-二辛基1,1,3,3-四苯基二硅氧烷的合成

通过二苯基二氯硅烷与辛基格氏试剂进行选择性反应,然后经过水解以及分子间脱水两步反应生成1,3-二辛基1,1,3,3-四苯基二硅氧烷(OPDS)。并利用NMR、MS、IR对其结构进行了表征。采用国家标准对介质油的耐热和耐燃性能进行测试,结果表明,所合成的OPDS沸点580℃,闪点280℃,燃点300℃,显示出高于常见介质油的耐热和耐燃性能,在耐高温导热油应用领域具有显著的应用价值。     

一种新型含硅脂环族四酸的合成研究

以1,3二甲基-1,3-二苯基二硅氧烷与降冰片烯单酐为反应物,通过酯化、硅氢加成和酸化3个步骤合成了一种新型含硅脂环族四酸,并对其进行了结构表征和溶解性研究.红外光谱(FTIR)与核磁共振(1 H NMR和13C-NMR)证实了目标产物含硅脂环族四酸被成功合成,且该四酸在常规有机溶剂中具有良好的溶解性.同时,研究表明:这是一条可以在一定程度上提高某些高位阻反应物之间硅氢加成反应活性的合成路线.     

双缩合螺吡喃的合成与光谱性能

利用过量Fischer碱与3,5-二溴水杨醛反应合成了4-(2-亚甲基-1,3,3-三甲基吲哚啉-2′-基)-6,8-二溴-1,3′,3′-三甲基-螺[3,4-二氢-2H-1-苯并吡喃-2,2′-吲哚啉],经元素分析、红外光谱、核磁共振氢谱和熔点确认了其化学结构.利用紫外-可见光谱和荧光光谱对目标化合物的吸收光谱和光致发光光谱进行了研究,探索了目标产物的光致变色 性能.结果表明,该化合物较相应单缩合螺吡喃多了1个吲哚单元且熔点提高了50℃,其紫外-可见吸收光谱中开环体在 555nm处有最大吸收波长,荧光光谱中在433nm处可观察到荧光.     

一种基于D-π-A型芴衍生物的合成、核磁共振谱及光谱性能研究

合成了一种具有D-π-A结构特征的新型芴衍生物:2-(2,4-二氟苯基)-7-(4-甲氧基苯基)-9,9-二辛基芴(1)。通过元素分析、红外光谱(IR)以及全面的一维核磁共振氢谱(1 H NMR)、碳谱(13 C{1 H}NMR)、氟谱(19F{1 H}NMR)对其结构进行了全面表征。通过优化反应物的投料顺序,得到较为合理的合成方法。详细分析了核磁共振谱谱线特征。利用紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明,在CH2Cl2溶液中,化合物1在300~330nm波段有吸收峰,归属于π-π*跃迁;其光学带隙Eg为3.39eV,发射峰值位于383nm,并且具有强烈的深蓝色荧光发射(激发波长为310nm),在CH2Cl2溶液中量子效率达到0.70。此外,化合物1的吸收和发射光谱具有溶剂极性依耐性。     

1,1,4,4-四苯基-1,3-丁二烯衍生物的合成

以苯乙酮和溴代苯为原料,通过格氏反应先制得1,1-二苯基乙醇(1),收率为91.3%;(1)经脱水和氯甲基化得到1,1-二苯基-3-氯丙烯(2),收率为92.9%;(2)再与二苯甲酮衍生物经格氏反应制得了1,1,4,4-四苯基-1,3-丁二烯衍生物(3a)和(3b),收率高于54.0%,并对各步合成的工艺条件进行了研究.HPLC测得(3a)和(3b)质量分数均高于99.0%.通过紫外光谱、红外光谱、质谱、1H NMR和元素分析对产物的组成和结构进行了鉴定.     

NMR approach to the quantification of nonstatistical 13C distribution in natural products: vanillin

Quantitative (13)C NMR conditions have been established that permit the precise determination of site-specific (13)C/(12)C ratios at low or natural abundance. Spectral acquisition parameters have been optimized in order to obtain minimum intensity distortions over the spectral width and in relation to the major sources of inaccuracy: the relaxation times, the decoupling pulse and power, and nuclear Overhauser effects. A major reduction in experimental time resulting from a study of the relaxation times and variance analysis has been achieved. The influence of (1)H decoupling conditions on peak areas was shown to be critical in that different relative peak areas are obtained according to the decoupling power. The efficiency with which the quantitative (13)C NMR method can determine site-specific (13)C/(12)C ratios in natural products has been tested for 12 independent samples of vanillin from different sources. Discriminatory analysis performed in the space defined by the site-specific carbon isotope ratios allows natural vanillin and that from different synthetic origins to be unambiguously distinguished.     

Determination of site-specific carbon isotope ratios at natural abundance by carbon-13 nuclear magnetic resonance spectroscopy.

Site-specific natural isotope fractionation of hydrogen studied by deuterium NMR (SNIF-NMR) spectroscopy is a powerful source of information on hydrogen pathways occurring in biosyntheses in natural conditions. The potential of the carbon counterpart of this method has been investigated and compared. Three typical molecular species, ethanol, acetic acid, and vanillin, have been considered. Taking into account the requirements of quantitative 13C NMR, appropriate experimental procedures have been defined and the repeatability and reproducibility of the isotope ratio determinations have been checked in different conditions. It is shown that the carbon version of the SNIF-NMR method is capable of detecting small differences in the carbon-13 content of the ethyl fragment of ethanols from different botanical or synthetic origins. These results are in agreement with mass spectrometry determinations of the overall carbon isotope ratios. Deviations with respect to a statistical distribution of 13C have been detected in the case of acetic acid and vanillin. However, since the method is very sensitive to several kinds of systematic error, only a relative significance can be attached at present to the internal parameters directly accessible. Isotope dilution experiments have also been carried out in order to check the consistency of the results. In the present state of experimental accuracy, the 13C NMR method is of more limited potential than 2H SNIF-NMR spectroscopy. However it may provide complementary information. Moreover it is particularly efficient for detecting and quantifying adulterations that aim to mimic the overall carbon-13 content of a natural compound by adding a selectivity enriched species to a less expensive substrate from a different origin.     

Accurate quantitative 13C NMR spectroscopy: repeatability over time of site-specific 13C isotope ratio determination

The stability over time (repeatability) for the determination of site-specific 13C/12C ratios at natural abundance by quantitative 13C NMR spectroscopy has been tested on three probes: enriched bilabeled [1,2-13C2]ethanol; ethanol at natural abundance; and vanillin at natural abundance. It is shown in all three cases that the standard deviation for a series of measurements taken every 2-3 months over periods between 9 and 13 months is equal to or smaller than the standard deviation calculated from 5-10 replicate measurements made on a single sample. The precision which can be achieved using the present analytical 13C NMR protocol is higher than the prerequisite value of 1-2 per thousand for the determination of site-specific 13C/12C ratios at natural abundance (13C-SNIF-NMR). Hence, this technique permits the discrimination of very small variations in 13C/12C ratios between carbon positions, as found in biogenic natural products. This observed stability over time in 13C NMR spectroscopy indicates that further improvements in precision will depend primarily on improved signal-to-noise ratio.     

Highly Dispersed Copper Nanoparticles Supported on Activated Carbon as an Efficient Catalyst for Selective Reduction of Vanillin

Highly dispersed copper nanoparticles (Cu NPs) supported on activated carbon (AC) are effectively synthesized by one‐pot carbothermal method at temperature range of 400–700 °C. The X‐ray diffraction, transmission electron microscopy, X‐ray photoelectron spectroscopy, and Brunauer–Emmett–Teller analysis reveal that Cu NPs with diameters of 20–30 nm are evenly anchored in carbon matrix. The 15 wt%‐Cu/AC‐600 catalyst (derived at 600 °C) exhibits best bifunctional catalysis of aqueous‐phase hydrodeoxygenation (HDO) and organic‐phase transfer‐hydrogenation reaction (THR) to selectively transform vanillin to 2‐methoxy‐4‐methylphenol (MMP). In HDO of vanillin, the as‐prepared catalyst achieves a 99.9% vanillin conversion and 93.2% MMP selectivity under 120 °C, 2.0 MPa H₂ within 5 h. Meanwhile, near‐quantitative vanillin conversion and 99.1% MMP selectivity are also obtained under 180 °C within 5 h in THR of vanillin by using 2‐propanol as hydrogen donor. The transforming pathways of vanillin are also proposed: vanillin is transformed into MMP via intermediate of 4‐hydroxymethyl‐2‐methoxyphenol in HDO case and by direct hydrogenolysis of vanillin in THR course. More importantly, the activity and the selectivity do not change after 5 cycles, indicating the catalyst has excellent stability. The Cu‐based catalyst is relatively cheap and preparation method is facile, green, and easy scale‐up, thus achieving a low‐cost transformation of biomass to bio‐oils and chemicals.     

Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses

Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.     

Light Stability of Vanillin Solutions in Ethanol

Ethanolic solutions of vanillin, used as food flavouring are readily decomposed by the action of sunlight to 6,6'-dihydroxy-5,5'-dimethoxy-1,1'-biphenyl-3,3'-dicarbaldehyde (dehydrodi-vanillin). The decomposition is accompanied by the formation of a yellow colour and a slightly bitter taste. The U.S. Pharm-acopoeia (1975) spectroscopie assay of vanillin would be in-appropriate for samples contaminated with dehydrodivanillin, since the absorption maxima of vanillin are at 279 and 311 nm whereas the maxima for dehydrodivanillin are 279, 310nm with a shoulder at 337 nm.     

Release of Thymol,Cinnamaldehyde and Vanillin from Soy Protein Isolate Films into Olive Oil

This study investigates the release of thymol, cinnamaldehyde and vanillin from soy protein isolate (SPI) films into olive oil. The SPI‐based films were casted with thymol, cinnamaldehyde and vanillin to obtain antimicrobial packaging films. The release of thymol, cinnamaldehyde and vanillin from the SPI films into olive oil at temperatures of 5°C, 20°C, 40°C and 60°C was determined by high‐performance liquid chromatography. The partition coefficients of thymol, cinnamaldehyde and vanillin between the SPI film and the olive oil were obtained. They decreased linearly with the increase of temperature. The diffusion coefficients of thymol, cinnamaldehyde and vanillin were determined by fitting the mathematical model to the experimental data. The Arrhennius equation could adequately describe the relationship between the temperature and the diffusion coefficients of thymol, cinnamaldehyde and vanillin, respectively. The activation energies for the release of thymol, cinnamaldehyde and vanillin were obtained, and they were respectively 55.92, 57.34 and 18.32 kJ mol^?1. Copyright © 2011 John Wiley & Sons, Ltd.     

升温加速法研究内衬纸中乙基香兰素在盒包内的迁移分布

目的 探明内衬纸上的加香物质在盒包内的迁移分布规律。方法 将乙基香兰素涂布到内衬纸中并制成小盒，通过升温加速法模拟室温下长期贮存的情形，跟踪检测乙基香兰素迁移到盒包内不同材料中的含量。结果 得出结论如下:乙基香兰素主要被商标纸和框架纸吸附(53.5%～56.4%)，少量被滤嘴吸附(8.3%～9.2%)，然后是被卷烟纸吸附(5.3%～7.2%)，烟丝中吸附的含量最低(3.7%～4.4%);乙基香兰素在滤嘴中的分布比较稳定，维持在8.3%～12.1%，但在其他盒包材料中的分布比值随贮存时间增加逐渐降低，脱附进入环境中;内衬纸中添加的乙基香兰素的初始含量，对在盒包内其他材料中的分布比无显著影响(商标纸和框架纸除外)。结语 本文提供了一种研究内衬纸上的加香物质在盒包内的迁移分布的方法，可预测及分析内衬纸的加香效果，为加香盒包卷烟的设计开发提供思路。     

Preparation of gold nanoparticles modified with tetrathiafulvalene via direct sulfur bridge

A new tetrathiafulvalene-modified gold colloid was prepared. The modification or coordination of 2-[4,5-ethylenedisulfanyl-1,3-dithiol-2-ylidene]-1,3-dithiole-4-thiolate to the surface of gold nanoparticles was characterized by UV-Vis and Raman spectra, and cyclic voltammograms. The most valuable point of the modified gold nanoparticles is their redox activities. The cyclic voltammogram of the tetrathiafulvalene-modified gold colloid on a Pt electrode showed two pair of redox peaks, at E1/2 = +0.67 V and at +0.87 V (vs. a saturated calomel electrode, in MeCN-0.1 M Bu4NClO4), corresponding to TTF/TTF*+ and TTF*+/TTF2+, respectively. A gold electrode modified with a self-assembled monolayer of the tetrathiafulvalene was also prepared and its cyclic voltammogram behaviors were in accordance with those of the nano-Au system. The E1/2 data are higher than those of the neutral mother precursor and the separation of E1/2(1) to E1/2(2) becomes very narrow. The data of E1/2 also revealed that electrochemical behavior of the no-spacer system (TTF-S-Au) are different from that of a spacer system (TTF-S-(CH2)n-Au).     

1，3－戊二烯阳离子聚合物链结构

采用以三氟甲基磺酸铝（（ＣＦ３ＳＯ３）３Ａｌ）为引发剂，二氯甲烷为溶剂的阳离子聚合方法制备了聚（１，３－戊二烯）。用ＩＲ、１ＨＮＭＲ和１３ＣＮＭＲ对聚合物结构进行了表征，并基于聚合物１ＨＮＭＲ谱对聚合物链结构进行了定量计算，聚合物环状和线型链结构分别占５４％和４６％，而线型链中的５种结构单元：反－１，４、顺－１，４、反－１，２、顺－１，２和３，４结构分别为２３％、１０％、１０％、１％和２％。