超高压微射流均质中花生球蛋白的机械力化学效应研究

以花生球蛋白为原料,研究超高压微射流均质对花生球蛋白作用的机械力化学效应,通过电镜扫描(SEM)、SDS-PAGE、荧光光谱(FLU)和差热式扫描(DSC)对超高压微射流均质后花生球蛋白的微观形貌、亚基组成、表面疏水性和热稳定性进行分析。结果表明：在超高压微射流的机械力作用下,花生球蛋白的亚基和分子量几乎不受影响;花生球蛋白的颗粒和热稳定性随着处理压力的增大而减小,分别在80 MPa和120 MPa时达到最小;表面疏水性随着处理压力的增大而增强,在160 MPa时达到最大。超高压微射流均质过程的机械力化学效应可使花生球蛋白的微观形貌和三维结构改变,热稳定性降低。     

兼具有强阴离子性与疏水缔合性的丙烯酰胺三元共聚物

在微乳液介质中实施了丙烯酰胺 (AM)、苯乙烯 (St)、2 丙烯酰胺基 2 甲基丙磺酸钠 (NaAMPS)的共聚合 ,制备了既含有强阴离子性基团 (—SO3Na)又含有疏水基团 (St)的丙烯酰胺三元共聚物AM NaAMPS St;通过红外光谱法、紫外分光光度法及元素分析法对共聚物的结构及组成进行了表征 ;稀释外推粘度法测定了共聚物的特性粘数 ;测定了共聚物纯水溶液及盐水溶液的表观粘度 ;荧光探针法考察了三元共聚物的疏水缔合性以及离子基团对疏水缔合性的影响规律 .实验结果表明 ,在聚丙烯酰胺 (PAM )分子主链上同时引入强阴离子性基团与疏水基团后 ,阴离子的电粘效应与疏水基团的疏水缔合作用相互协同 ,会使共聚物水溶液的黏度显著提高 ;盐溶液对疏水缔合作用的增强效应与强阴离子基团对盐的较大容忍度相互结合 ,会使共聚物水溶液的抗盐性能明显得以提高 ;大分子链上的强阴离子基团磺酸根的存在 ,在一定程度上会削弱疏水基团之间的疏水缔合作用 ,即对疏水基团的疏水缔合行为会产生一定的负性影响 .     

二茂铁接枝聚丙烯酰胺水溶液的流变行为研究

采用“Post-Modification”技术在二甲基亚砜中直接对聚丙烯酰胺进行烷基化反应,接枝二茂铁官能团(Fc),制备出一种具有氧化还原性质的二茂铁改性聚丙烯酰胺(PAM-Fc).通过红外光谱(FTIR)、核磁氢谱(1H-NMR)、热失重(TGA)、电化学、动态流变测试等方法对PAM-Fc的化学结构、电化学活性和流变特性进行了表征.研究结果表明,PAM-Fc具有氧化还原性,相比PAM呈现更好的热稳定性,这主要源于Fc基团稳定了PAM分子链的自由基.Fc基团在水溶液中的疏水缔合作用会导致体系黏度显著增大.通过添加NaCl、β-环糊精或H2O2等可以对PAM-Fc水溶液的黏度进行有效调控.其中,NaCl可以屏蔽PAM-Fc分子链上的电荷,β-环糊精能够包合Fc基团,H2O2则可将疏水的还原态Fc基团氧化成亲水的氧化态Fc,从而实现PAM-Fc水溶液流变行为的调节.     

叔丁醇-水混合溶剂的混合状态对牛血清白蛋白构象的影响

应用动态光散射法测定了叔丁醇(TBA)-水混合溶剂中牛血清白蛋白(BSA)流体动力学半径, 并通过分析BSA的荧光光谱和紫外-可见光吸收光谱, 研究BSA在TBA-水混合溶剂中的构象变化. 同时, 通过分析TBA-水二元体系和BSA-TBA-水三元体系静态散射光的变化, 探讨TBA-水溶剂体系的混合状态及其对BSA在水溶液中构象变化的影响. 结果表明, TBA-水溶剂体系的混合状态与BSA的构象变化密切相关, 低浓度的混合溶剂中, 水分子在TBA周围形成疏水水化结构, 与蛋白质疏水基团的选择性结合, 破坏了蛋白质的稳定结构, 但是, 少量TBA的加入削弱了蛋白质疏水基团间的疏水相互作用, 有利于蛋白质形成更紧密的构象; 高浓度的混合溶剂中, TBA分子相互聚集形成胶束, 削弱了对蛋白质的变性作用.     

铕(Ⅲ)对伴清蛋白溶液构象的影响

用TNS疏水探针研究了脱铁伴清蛋白(apoOTf)和不同形式的铕伴清蛋白(EuN-OTf,Eu2-OTf)的表面疏水暴露程度,依次为apoOTfEuN-OTfEu2-OTf,表明Eu3+与脱铁伴清蛋白N端结合引起蛋白构象变化大,与C端结合引起蛋白构象变化小.此外,由盐酸胍对3种蛋白变性实验,发现Eu3+与脱铁伴清蛋白的结合稳定了蛋白的结构,稳定性依次为apoOTfEuN-OTfEu2-OTf.离子强度效应也充分表明3种蛋白内部疏水基团相互作用依apoOTfEuN-OTfEu2-OTf顺序增大,稳定性也依次增大.本研究对进一步探讨Eu3+的生物效应提供理论依据.     

力诱导化学变化在聚合物材料中的应用

随着聚合物材料化学的飞速发展,设计并实现具有力学响应的聚合物材料变得十分重要。其中,力敏基团的设计合成是力响应材料设计的重点。根据在力的诱导下所发生变化的力敏基团种类的不同,本文主要从共价键和非共价相互作用的变化两个方面进行综述。对共价键变化的讨论将主要集中在作用于力敏基团的力源上,即超声、拉力、压力等;对非共价相互作用的变化将对不同的作用分别进行介绍,包括氢键、π-π相互作用等。通过对力化学机理的深入研究和更多力敏基团的设计,科研工作者期待开发更多元、更实际、多功能的材料,相信力化学的发展会带给聚合物材料新的生命。     

原位法常压干燥制备疏水SiO2气凝胶及其热稳定性

在正硅酸乙酯(TEOS)酸碱两步催化的溶胶-凝胶过程中, 加入干燥控制化学添加剂(DCCA)N,N-二甲基甲酰胺(DMF)和三甲基氯硅烷(TMCS)的混合溶液, 进行原位疏水改性处理, 并结合常压干燥工艺制备了高比表面积的疏水SiO2气凝胶. 利用N2物理吸附, 全自动X射线衍射仪(XRD), 傅立叶变换红外光谱仪(FTIR), 扫描电子显微镜(SEM)等对样品的形貌结构进行了表征. 实验结果表明, 原位疏水改性比非原位疏水改性制备的SiO2气凝胶具有更大的比表面积, 可达979 m2·g-1, 气凝胶表面存在憎水性基团—CH3, 有良好的疏水性. 500 ℃热处理后, 气凝胶因失去大量的—CH3基团, 由憎水性转为亲水性; 800 ℃高温热处理后, 疏水SiO2气凝胶仍处于非晶态, 具有良好的热稳定性能.     

脲醛树脂微胶囊的改性

为了提高脲醛树脂微胶囊的稳定性,选择化学结构不同的聚乙烯醇、苯酚、三聚氰胺对脲醛树脂进行了改性.通过优化反应条件,得到了具有良好耐热、耐水性的脲醛树脂微胶囊.采用光学显微镜观测了微胶囊的形貌;用FT-IR表征了微胶囊的化学结构;用TGA分析了微胶囊的热性能.研究结果表明:3种改性后的微胶囊的热稳定性均有所提高,其中苯酚改性的微胶囊热稳定性最好;聚乙烯醇改性微胶囊的疏水性下降,苯酚和三聚氰胺改性的微胶囊的疏水性都有所增强.     

基于动态建构化学的自愈合水凝胶及其在生物医学领域的应用展望

自愈合水凝胶与传统水凝胶相比,经受力破坏后仍可恢复其结构和功能,具有自我修复损伤的特点,是近年来备受关注的一种智能软材料.动态建构化学概念的引入,极大地促进了多响应性动态自愈合水凝胶的发展.本文综述了近年来基于动态建构化学合成自愈合水凝胶的方法,包括多重氢键作用、疏水相互作用、亚胺键、酰腙键等,并分析探讨了影响凝胶自愈合性能的因素及其在生物医学领域的潜在应用,还对其未来的发展进行了展望.     

聚乙烯醇对碳纳米管负载氧化铁影响的研究

采用液相化学沉积法制备了碳纳米管负载的Fe2O3. TEM观察发现， 添加聚乙烯醇作为表面活性剂可以实现碳纳米管对Fe2O3的有效负载， 未添加聚乙烯醇两者出现物相分离. 聚乙烯醇均匀吸附在碳纳米管表面, 增强碳纳米管在水溶液中的分散, 其疏水基团与碳纳米管以范德华力结合, 其亲水基团与Fe2O3·nH2O结合, 对碳纳米管有效负载Fe2O3起到了桥梁作用. 在样品煅烧过程中, 聚乙烯醇熔融后均匀地包裹在碳纳米管表面上, 进一步阻止了两者在煅烧过程中的物相分离.     

Thermal analysis of mechanoactivated mixtures of tunisia phosphorite and ammonium sulfate

The thermal behavior of Tunisia phosphorite and ammonium sulfate mixtures are examined by non-isothermal thermogravimetry in air atmosphere. It has been shown that the thermal stability of mixtures have different behavior after mechano-chemical treatment due to phase changes in the mixtures. New solid phases are confirmed by the stages and rate of mass changes and also by the heat effects observed. New phases are also confirmed by using X-ray diffraction method. Based on the data obtained by the mechanism of chemical transformations is proposed. The kinetics of mechano-activated mixtures decomposition is significantly influenced by the time of treatment and proceeds in few stages. Stage I is attributed to the effect of partially ammonia releasing, when the next stages are associated with the decomposition of apatite structures. Because of the interfacial interactions during mechano-chemical treatment insoluble phosphorous forms from apatite structures are transformed to the soluble forms suitable for plants nutrition. The results have shown that the soluble form can be controlled by the initial components ratio and conditions of treatment on the way to obtain slow releasing nutrition products. This revised version was published online in July 2006 with corrections to the Cover Date.     

Optimization of microfluidization for the homogeneous distribution of cellulose nanocrystals (CNCs) in biopolymeric matrix

Microfluidization, which is a high-pressure homogenization technique, was used to develop highly dispersed cellulose nanocrystal (CNC) reinforced chitosan based nanocomposite films. A three factor central composite design with five levels was designed to systematically optimize the microfluidization process. The three factors were the CNC content, the microfluidization pressure and the number of microfluidization cycles. Response surface methodology was used to obtain relationship between the mechanical properties of the nanocomposite films and the factors. Polynomial equations were generated based on the regression analysis of the factors and the predicted properties of the nanocomposite films were in good agreement with the experimental results. Microfluidization effectively reduced the CNC–chitosan aggregates and improved the mechanical properties of the nanocomposite films. Microscopic analysis of the microfluidized nanocomposite films revealed a 10–15 times reduction in the size of the aggregates compared to the non-microfluidized CNC/chitosan films and an increase in the root mean square surface roughness (Rq).     

Mechano-chemical Activation of Dolomite

Mechano-chemical activation is a widely used method for increasing the reaction activity of solids and, consequently, to accelerate solid phase reactions and to reduce the temperature of the subsequent thermal decomposition. Thermal decomposition of triboactivated calcium carbonate is a subject of different studies while dolomite decomposition has limited data. The present work represents a study of thermal stability and phase transitions of mechano-chemical activated dolomite under different conditions, namely using various amounts and kind of milling balls and the duration of activation. Temperatures of decomposition of MgCO₃ and CaCO₃ are specified. The study includes the determination of the thermal stability and the rate of thermal decomposition of activated dolomite. This revised version was published online in July 2006 with corrections to the Cover Date.     

叶绿素锌钠盐的制备及其稳定性

以鲜菠菜叶为原料,经过皂化、酸化、锌代及成盐等过程,得到叶绿素锌钠盐;测定了其紫外可见吸收光谱;利用相对光强度探讨了叶绿素锌钠盐的光稳定性和热稳定性,以及几种食品添加剂和常见金属离子对叶绿素锌钠盐稳定性的影响.结果表明,叶绿素锌钠盐的耐光性较差,在一定温度下具有较好的耐热性.几种常见食品添加剂对叶绿素锌钠盐的稳定性影响不大;银离子对叶绿素锌钠盐的稳定性影响较大.     

Influence of triboactivation conditions on the synthesis in natural phosphate-ammonium sulphate system

Summary No data is available in the literature about the effects of mechano-chemical activation on the processes of chemical interaction in the Tunisia phosphorite-ammonium sulphate mixture. The purpose of this paper is to study the chemical and thermal reactions in mixtures of Tunisia phosphorite and ammonium sulphate in a mass ratio of 1:1, triboactivated in a planetary mill using different mill balls for a period of 10 h. Using chemical, thermal, X-ray powder diffraction and infrared spectroscopy to analyse the activation products, and analysing the changes occurring during the TG-DTA-DTG measurements, allowed to determine the chemical transformations in the system and to assess the degree of transformation of non-soluble forms of phosphorus from the natural phosphate into soluble. Data from the studies have registered the changes in the solids resulting form preliminary mechano-chemical activation of samples. The additional endo- and exothermic effects resulting from thermal decomposition in the temperature range of up to 1373 K are proof of the changes during the TG-DTA-DTG studies and of new interactions occurring in the system. The results from the thermal and spectroscopic methods show that triboactivation using different mill balls and modes of operation produce new compounds in the form of ortho-, pyro- and tripolyphosphates, soluble in the soil solution. The data obtained are part of the complex studies on the way to optimize the composition and conditions of triboactivation and subsequent thermal treatment aimed to produce high-efficiency slow-acting fertilizer products.     

The effect of thermal processing on PVC—II. The effect of lubricants and stabilizers

The effects of lubricants and a tin maleate stabilizer on the mechanochemical and thermal degradation of PVC during processing have been studied at 170° and 210°. The protective mechanism of the two types of additive were found to be complementary in that the lubricants reduced the severity of the mechano-chemical process whereas the tin maleate stabilizer reduced the rate of hydrogen chloride elimination during the second stage by reacting with allylic chlorine, with conjugated unsaturation and with hydrogen chloride.     

The effect of thermal processing on PVC—I. Chemical and physical changes in unstabilized PVC

Unstabilized PVC processed at 170 and 210°C was found to undergo immediate mechano-chemically induced thermal oxidation with the formation of unsaturation and peroxides. The peroxides were partially in the form of cross-links between polymer molecules at this stage and were manifested in the form of solvent insoluble gel. Conjugated double bonds and colour formation both increased linearly with time. The evidence suggests that the initial mechano-chemical process sensitizes the polymer to subsequent thermal degradation.     

新型芳香重氮盐的光与热稳定性研究

合成了几种芳香重氮盐感光材料,发现1的最大吸收峰位于343 nm,与355 nm激光器的光谱能很好地重叠.2和3的吸收光谱分别红移至453 nm和 433 nm,在可见光范围内与高压汞灯有很大的光谱重叠.2具有比3更好的热稳定性及快速的光分解速度.     

Mechanisms of antioxidant action: Mechanochemical addition of thiol antioxidants to ABS

It is shown that thiol-containing antioxidants and stabilisers can be chemically reacted with ABS in high yields and in substantial concentrations under conditions of high temperature and high shear during processing. The resulting antioxidant concentrates are shown to be very effective thermal and photo-oxidative stabilisers for ABS when used as masterbatch additives for unstabilised ABS. Synergistic combinations of a bound antioxidant (BHBM (I(a))) and a bound uv stabiliser (EBHPT (II)) confer a high level of uv stability on ABS when incorporated into ABS. All the antioxidants show a high resistance to removal from the polymer by solvent extraction. The effect of the mechano-chemical process on the efficiency of adduct formation and on the effectiveness of the stabilisers so formed is discussed.