双子(Gemini)表面活性剂合成及研究进展

综述了阳离子型、阴离子型、非离子型和两性离子型四类双子表面活性剂的合成及研究进展,指出未来双子表面活性剂研究的主要方向为获得更高的表面活性、降低合成和使用成本、不同类型的表面活性剂协同强化、提高安全环保性和拓宽应用领域等。     

Rational Design of Polymeric Hybrid Micelles with Highly Tunable Properties to Co‐Deliver MicroRNA‐34a and Vismodegib for Melanoma Therapy

A polymeric hybrid micelle (PHM) system with highly tunable properties is reported to co‐deliver small molecule and nucleic acid drugs for cancer therapy; this system is structurally simple and easy‐to‐fabricate. The PHM consists of two amphiphilic diblock copolymers, polycaprolactone‐polyethylenimine (PCL‐PEI) and polycaprolactone‐polyethyleneglycol (PCL‐PEG). PHMs are rationally designed with different physicochemical properties by simply adjusting the ratio of the two diblock copolymers and the near neutral PHM‐2 containing a low ratio of PCL‐PEI achieves the optimal balance between high tumor distribution and subsequent cellular uptake after intravenous injection. Encapsulating Hedgehog (Hh) pathway inhibitor vismodegib (VIS) and microRNA‐34a (miR‐34a) into PHM‐2 generates the VIS/PHM‐2/34a co‐delivery system. VIS/PHM‐2/34a shows synergistic anticancer efficacy in murine B16F10‐CD44⁺ cells, a highly metastatic tumor model of melanoma. VIS/PHM‐2/34a synergistically attenuates the expression of CD44, a vital receptor indicating the metastasis of melanoma. Intriguingly, inhibiting Hh pathway by VIS is accompanied by downregulation of CD44 expression, revealing that Hh signaling might be an upstream regulator of CD44 expression in melanoma. Thus, co‐delivery of miR‐34a and VIS demonstrates great potential in cancer therapy, and PHM offers a structurally simple and highly tunable platform for the co‐delivery of small molecule and nucleic acid drugs in tumor combination therapy.     

甘二酯对油脂中抗氧化剂活性的影响

研究sn-1,3-棕榈酸甘二酯对纯净菜籽油氧化稳定性的影响,以期探明其作用机理,为油脂加工和储存提供科学的依据。通过柱层析的方法制备仅含甘三酯成分的纯净菜籽油,测定DAG在菜籽油中形成反相胶束的临界浓度,并在反相胶束体系中,研究DAG及与天然抗氧化剂γ-生育酚及合成抗氧化剂(TBHQ、BHA、BHT)联合作用对纯净菜籽油氧化稳定性的影响。结果表明:DAG在菜籽油中的临界胶束浓度为0.5%;在反相胶束体系中,DAG的添加促进了纯净菜籽油的氧化,DAG对不同种类的抗氧化剂活性的影响存在差异,DAG增强了弱极性抗氧化剂γ-生育酚、BHT的活性,但是减弱了极性较强的抗氧化剂TBHQ、BHA的活性。     

Impact of Phosphoethanolamine Reverse Micelles on Lipid Oxidation in Bulk Oils

Phospholipids are important minor components in edible oil that play a role in lipid oxidation. Surface active phospholipids have an intermediate hydrophilic–lipophilic balance value, which allows them to form association colloids such as reverse micelles in bulk oil. These association colloids can influence lipid oxidation since they create lipid–water interfaces where prooxidants and antioxidants can interact with triacylglycerols. In this study, we examined the formation of reverse micelles in a stripped oil system by dioleoyl phosphoethanolamine (DOPE) and the effect of these physical structures on lipid oxidation kinetics. The critical micelle concentration (CMC) of DOPE was approximately 200 µmol/kg oil at 45 °C. Oxidation kinetics studies showed that DOPE was prooxidative when it was above its CMC (400 and 1,000 µM), reducing the lag phase from 14 days (control) to 8 days. The addition of combinations of DOPE and dioleoyl phosphocholine (DOPC) resulted in formation of mixed micelles with a CMC of 80 µmol/kg oil at 45 °C. These mixed micelles were also prooxidative when concentrations (100 and 500 µM) were above the CMC, decreasing the lag phase from 14 to 8 days. These findings provide a better understanding of the role of phospholipids in lipid oxidation of edible oil and could contribute to better antioxidant solutions.     

Association Colloids Formed by Multiple Surface Active Minor Components and Their Effect on Lipid Oxidation in Bulk Oil

Association colloids formed by surface active minor components play an important role in the oxidative stability of bulk oils. To imitate the formation of nanostructures in refined oils, multiple surface active minor components including phospholipids, free fatty acids, diacylglycerols and sterols were added to stripped corn oil. The critical micelle concentration (CMC) of the mixed components was determined. The impact of mixed minor components at below and above their CMC on oxidative stability of bulk oil and on antioxidant activity of α-tocopherol and Trolox was investigated. The CMC of the mixed surface active components in bulk oil was 20 µmol/kg oil in the presence of 383 ± 2 ppm of water. 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) played an important role on the formation of association colloids since it was the most important component in forming the association colloids as confirmed by CMC and fluorescence probe studies. The association colloids formed by the mixed components showed prooxidative activity in bulk oil as determined by monitoring the formation of lipid hydroperoxide and hexanal. The activity of α-tocopherol or Trolox was not changed by mixed components association colloids. These results suggest that association colloids both physically and chemically impacted the oxidative stability and activity of antioxidants in bulk oil.     

不同方法测定两种表面活性剂的临界胶束浓度

采用电导法及表面张力法分别测定了十二烷基硫酸钠(阴离子表面活性剂)和十二烷基三甲基氯化铵(阳离子表面活性剂)的临界胶束浓度,两种实验方法测得十二烷基硫酸钠的临界胶束浓度约为7.0×10-3mol·dm-3,十二烷基三甲基氯化铵的临界胶束浓度约为1.60×10-2mol·dm-3,两种方法所得结果一致。     

Effects of pH and Surfactant Precipitation on Surface Tension and CMC Determination of Aqueous Sodium n-Alkyl Carboxylate Solutions

Aqueous solutions of sodium tetradecanoate (S14C) and sodium dodecanoate (S12C) were used to evaluate complicated precipitation phenomena and to monitor the effects of bulk pH adjustments on surface tension and critical micelle concentrations (CMC) determination from surface tension plots. Limited solubilities of pure sodium n-alkyl carboxylates in solution near the CMC have been reported previously many times. In this study, precipitation encountered with solutions prepared from vender-supplied S12C was eliminated through additional purification. As sodium alkyl carboxylates discussed in the literature are commonly used as received from the manufacture without additional purification, the wide range of reported CMC values as well as precipitation near the CMC for S12C are also likely due to impurities. However, complete solubility for S14C solution concentrations near the reported CMC values was not obtained through additional purification of purchased material. Hence, some CMC values reported in the literature for S14C should be reconsidered, as discontinuities in the slope of surface tension versus concentration plots are likely caused by the formation of a precipitate not micelle aggregation. In addition and in agreement with other studies, solution pH adjustments revealed a minimum surface tension for maximum solubility near the pK _a value for S14C.     

β-环糊精对曲拉通X-114紫外光谱抗干扰性能的影响

辛基苯基聚氧乙烯醚（曲拉通X-114）和脂肪醇聚氧乙烯醚（AEO-9）之间的相互作用能对水溶液中曲拉通X-114的紫外光谱产生明显影响。实验结果表明,在200～350nm范围内,曲拉通X-114的最大吸收波长为223nm,AEO-9的紫外吸光度接近于0;在水溶液中,AEO-9能减弱曲拉通X-114的紫外吸光度,降幅达3.4%;AEO-9还能显著降低曲拉通X-114的表观临界胶束浓度（cmc）,当AEO-9的浓度从0增加到0.050mmol/L 和0.100mmol/L时,曲拉通X-114的表观cmc从0.219mmol/L分别降至0.207mmol/L和0.202mmol/L。实验结果进一步表明,β-环糊精（β-CD）能有效降低AEO-9对曲拉通X-114的紫外吸光度及表观cmc的影响,在曲拉通 X-114和AEO-9复配水溶液中,按物质的量比1∶1加入β-CD,复配水溶液中曲拉通X-114的回收率从95.8%～103.3%变化至99.0%～100.1%,表明了β-CD能明显降低AEO-9对曲拉通X-114的干扰作用。红外光谱表征结果（FTIR）、核磁共振氢谱表征（¹H NMR）及热重差热分析表征结果（TG-DSC）表明,曲拉通X-114进入β-CD 分子空腔并形成包结物,是阻断曲拉通X-114分子形成混合胶束以及消除AEO对曲拉通X-114的干扰的主要原因。     

作为药物载体的聚氨酯纳米胶束的研究进展

聚氨酯材料具有生物相容性好、合成简单且分子结构可设计性强等优点,不可降解的聚氨酯材料在生物医学领域已经得到应用。目前可生物降解聚氨酯纳米胶束用作药物载体的研究受到广泛关注。本综述主要从生物相容性、刺激响应性、靶向作用、细胞摄取能力强的聚氨酯纳米胶束这几个方面,介绍了作为药物载体的可生物降解聚氨酯纳米胶束的研究进展。