pH非敏感型自交联共轭亚油酸囊泡的构建和表征

以共轭亚油酸(Conjugated linoleic acid, CLA)为构造pH非敏感型脂肪酸囊泡(Fatty acid vesicle, FAV)的分子砌块, 通过碱异构化法从亚油酸半合成CLA, 然后采用pH刺激响应自组装法获得CLA的不饱和脂肪酸囊泡(Ufasome), 采用紫外辐照诱导方式对CLA-ufasome实施囊泡内化学绑定, 获得一种新的pH非敏感型FAV. 通过酸碱滴定和表面张力实验确定CLA-ufasome形成的适宜pH范围和浓度, 利用透射电子显微镜(TEM)表征了自交联CLA的FAV的形貌, 并通过动态光散射(DLS)法测定了自交联CLA的FAV的稳定性. 结果表明, 以CLA为分子砌块, 当浓度为3 mmol/L时在pH=8.6条件下构建CLA-ufasome, 紫外辐照2.5 h后得到粒径为10~20 nm, 壁厚为2.0 nm的自交联CLA的FAV, 并具有pH非敏感的特性. 以抗癌药物五氟尿嘧啶为目标包覆药物, 体外释放实验结果表明, 自交联CLA的FAV对五氟尿嘧啶具有良好的缓释效果.     

自交联共轭亚油酸囊泡基荧光纳米点的构筑及其荧光特性

提出了一种生物质碳源借助自组装和自交联手段“构筑”碳基荧光纳米点(FNDs)的新策略,不同于经历裂解、脱水、缩聚和碳化等复杂且不可控反应的“合成”途径。本文以共轭亚油酸(CLA)为碳源,利用其表面活性和聚合活性制得呈蓝绿光发射的自交联共轭亚油酸囊泡基荧光纳米点(SCU-FNDs),粒径易控(平均粒径为17 nm)且具有良好水分散性,FNDs产率高达73.9%。该法简便温和、绿色经济、有利于大规模制备。荧光实验结果显示SCU-FNDs的荧光强度随囊泡表面羧酸基团减少而减弱,随自交联度增大而增大; 同时其荧光强度具有良好的温度线性响应性,升/降温过程均符合I/I₀ = -0.00977T+ 1.229 (T = 25-85 ℃, R² = 0.99)。这些荧光特性皆可以用SCU-FNDs的自组装和自交联结构特性予以解释。     

高内相/自乳液聚合的共轭亚油酸低聚体的囊泡化及稳定性

采用自乳化法制备了高内相共轭亚油酸(CLA)的水包油(O/W)乳液, 并通过热引发乳液聚合反应得到共轭亚油酸低聚体(oligo-CLA); 将oligo-CLA用于自组装脂肪酸囊泡(FAV). 透射电子显微镜和动态激光光散射表征结果均表明, 在pH=8.6~13范围内得到了囊泡粒径为10~30 nm的FAV, 此结果对提高FAV的pH适应性具有理论意义. 自乳液聚合实验结果表明, 该高内相自乳化/热引发低聚反应策略可以使浓度高达75.3%(质量分数)的CLA完成无外加表面活性剂乳液聚合, 并使共轭双键总自交联率达到33%且控制oligo-CLA的平均聚合度约为6, 对规模化生产oligo-CLA及构筑FAV具有实用价值. 与CLA相比, oligo-CLA具有更好的低温溶解性, 由其自组装的FAV具有更好的环境适应性, 如耐酸性和抗钙皂能力, 而且显示出较好的钙响应囊泡体积膨胀率; 以极少量非离子表面活性剂Span 40或AEO₂辅助oligo-CLA形成的杂化囊泡具有更宽的pH适应性. 因此, 所制备的FAV在药物释放体系、 日用化学产品、 家用洗涤剂和个人护理产品中具有更广阔的应用前景.     

聚联乙炔囊泡负载的Bola型两亲分子识别三聚氰胺过程中Chaotrope促进型显色机制及热力学

用聚联乙炔囊泡为载体,将bola型两亲分子1,12-二乳清酸十二胺盐(DDO)对三聚氰胺的分子识别作用用肉眼可见的颜色变化显示出来.通过比较不同碳链长度的聚联乙炔囊泡对分子识别过程的反映,发现二十三烷基-2.4-二炔酸(TCDA)囊泡的显色灵敏度较高.研究表明,TCDA肉眼可见的颜色变化来自于DDO与三聚氰胺多重氢键的形成以及溶液环境中水结构的变化.为了更好地理解显色机理,用差示扫描量热(DSC)仪详细研究了分子识别过程中聚联乙炔囊泡的相变行为及热力学参数.结果表明:TCDA囊泡和带有识别分子的DDO/TCDA囊泡在三聚氰胺存在下,相变温度Tm均向高温方向移动,并且,随三聚氰胺浓度的增加,Tm值逐渐增大直至囊泡瓦解;但是Tm值的变化没有与囊泡变色必然关联,仅仅DDO/TCDA囊泡具有变色现象,而且,只有当三聚氰胺的浓度超过分子识别氢键形成所需理论量时,肉眼才能可见明显的由蓝到红的颜色变化.为了理解溶液中过量的三聚氰胺对囊泡变色的作用,选用蔗糖和尿素作为典型的水结构促进剂和水结构破坏剂(chaotrope),详细研究了它们对聚联乙炔囊泡反映分子识别过程中相变温度的影响及显色规律.结果表明,过量的三聚氰胺在溶液中起到类似尿素水结构破坏剂的作用.这种作用和分子识别过程中多重氢键的形成对聚联乙炔囊泡的变色缺一不可.本研究首次揭示了由水结构破坏剂参与的聚联乙炔囊泡变色机理,有助于理解共轭聚合物热相变过程中的Hofmeister效应.     

单十二烷基磷酸酯辅助共轭亚油酸的囊泡化研究

以共轭亚油酸(CLA)为模型脂肪酸,与安全、温和的阴离子表面活性剂单十二烷基磷酸酯(MLP)进行复配,动态激光光散射和透射电镜表征结果表明,CLA在中性至弱酸性环境中仍然能够囊泡化.通过pH滴定曲线研究了CLA和MLP 2种分子的荷电物种随pH值的变化规律,据此分析各物种间的相互作用,并推断经MLP辅助CLA能够在中性至弱酸性环境中囊泡化的动因是CLA-MLP间的氢键或离子-偶极作用.     

共轭亚油酸与海藻酸钠囊泡化自组装纳米容器及其药物缓释性能

脂肪酸囊泡(FAV)是一类重要的纳米容器,然而其形成pH范围较窄且偏碱性环境,限制了其应用。 本文将共轭亚油酸(CLA)与海藻酸钠(SA)在近中性环境下共同自组装囊泡化纳米容器并提高其膜稳定性。动态激光光散射(DLS)和透射电子显微镜(TEM)结果表明,当SA质量分数为25%~50%时复合体系可在近中性条件下自组装形成50~250 nm尺寸的囊泡化纳米容器,且pH=7.4时随着质量分数增加囊泡化纳米容器直径增大。 根据SA和CLA在中性环境的物种存在形式推测,二者通过氢键作用驱动形成囊泡化纳米容器。 体外模拟释放实验表明,囊泡化纳米容器具有较高包覆率和较优缓释效果,有望应用于药物传输领域。     

基于自交联杂萘联苯聚芳醚阴离子交换膜制备及其物理化学性质

以氯甲基杂环聚醚酮(CMPPEK)为原料,加入三乙胺进行铵化,并分别加入二乙烯三胺(DETA)和二乙胺(DEA),生成的仲胺基(或叔胺基)与邻近分子链氯甲基团进行自交联.经过制膜和离子交换反应,制备了DETA自交联杂萘联苯聚芳醚阴离子交换膜(DETA-QPPEK-OH)和DEA自交联杂萘联苯聚芳醚阴离子交换膜(DEA-QPPEK-OH).采用傅里叶变换红外(FTIR)光谱对制备自交联膜的化学结构进行表征.研究了DETA-QPPEK-OH和DEA-QPPEK-OH膜的理化性质,结果表明前者具有较低吸水率和更低溶胀度.通过研究DETAQPPEK-OH和DEA-QPPEK-OH膜的离子传导率随温度的变化规律,结果表明在80°C时其离子传导率分别达到0.060和0.028 S cm-1,表明本文制备的自交联膜具有较高离子传导率.此外还通过热重分析(TGA)对两类自交联膜的热稳定性进行了研究.     

聚共轭亚油酸基网状纳米金的制备及表面增强拉曼散射和催化性能

以天然不饱和脂肪酸共轭亚油酸(CLA)为绿色单体, 通过简单的分子自组装和可控自交联反应制备聚共轭亚油酸(PCLA)聚集体. 透射电子显微镜(TEM)结果显示, PCLA聚集体的形貌呈现独特网状结构, 其联结单元为来自于CLA胶束的膨大颗粒. 采用氯金酸在极性聚合物表面原位还原, 2 d后在网状PCLA基底上制备得到以CLA胶束为核(20 nm)的网状纳米金结构, 而且网状PCLA的原位还原作用与模板作用相结合是获得PCLA基网状纳米金的充分必要条件. 与普通球形胶态金纳米颗粒[(5±1) nm]相比, PCLA基网状纳米金对苯硫酚具有更好的表面增强拉曼散射(SERS)效应, 对对硝基苯酚具有更好的催化还原效果.     

新型含苯硼酸和喹啉的囊泡荧光多糖传感器的制备

利用合成的含有识别基团苯硼酸和荧光读出基团喹啉的新型双亲化合物对硼酸苯甲基-8-十六烷氧基溴化喹啉(BHQB)在水中自组织成囊泡,囊泡的相变温度为52.4℃;当向囊泡体系加糖时,BHQB囊泡中的喹啉生色基在508nm的荧光峰强度急剧减弱,425nm处荧光逐渐增强.荧光强度变化可能归于所形成的硼酸酯改变了双亲化合物中硼原子的杂化轨道形式,进一步引起了整个分子内部的电子云排布所致.BHQB囊泡与糖的相互作用而导致体系荧光强度变化,并且这种变化的幅度与加入糖的种类和量均有关.因此体系有可能应用于检测生物物质如糖的化学传感器.     

检测维生素C的囊泡荧光传感器的制备

利用合成的含有识别基团苯硼酸和荧光读出基团萘的新型双亲化合物(DNMPBA)在THF/水选择性溶剂中自组织成囊泡,囊泡的相变温度为56.8℃;当向囊泡体系加维生素C时,DNMPBA囊泡中的萘生色基在345nm的荧光峰强度急剧减弱.荧光强度减弱归于所形成的硼酸酯增强了DNMPBA双亲化合物中一个氧原子孤对电子对萘生色基的淬灭作用.DNMPBA囊泡与维生素C的相互作用而导致体系荧光强度变化,使该体系有可能应用于检测生物物质如维生素C的化学传感器.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。