Targeted Polypeptide–Microtubule Aggregation with Cucurbit[8]uril for Enhanced Cell Apoptosis

Tunable protein assemblies not only hold a dominant position in vital biological events but are also a significant theme in supramolecular chemistry. Herein, we demonstrated that the intertubular aggregation of microtubules (MTs) could be efficiently regulated by a synergistic polypeptide–tubulin interaction and host–guest complexation. The benzylimidazolium‐modified antimitotic peptide (BP) could recognize the MTs and concurrently form stable inclusion complexes with avirulent cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) in different binding stoichiometries. The self‐assembling morphology of MTs was converted from fibrous to nanoparticulate aggregates via extensive BP?CB[8] cross‐linkage, leading to significant cell apoptosis and tumor ablation in vivo. The targeted (BP?CB[8])@MT ternary assembly provides a facile supramolecular method to enhance the protein–protein interactions, which may be developed as a therapy for degenerative diseases, such as cancer.     

紫杉醇微悬臂梁免疫传感器方法的研究

以巯基化的紫杉醇单抗修饰微梁镀金表面,制备了高灵敏的紫杉醇微悬臂梁免疫传感器.利用酶联免疫吸附测定方法对巯基化前后紫杉醇单抗的活性变化,以及巯基化单抗在微梁上的修饰进行检测与验证.采用紫杉醇微悬臂梁免疫传感器对不同浓度的紫杉醇溶液进行检测.结果表明:虽然巯基化后紫杉醇单抗的活性降低了18.6%,但巯基化紫杉醇单抗可以修...     

卟啉化合物的聚集作用

从静电作用、μ-氧配位、边基配位、π－π键合等结合方式概述了卟啉化合物的聚集作用。     

Synthesis and biological evaluation of (-)-dictyostatin and stereoisomers

Total syntheses of (−)-dictyostatin, 6,16-bis-epi-dictyostatin, 6,14,19-tris-epi-dictyostatin, and a number of other isomers and analogs are reported. Three main fragments—top, middle, and bottom—were first assembled and then joined by olefination or anionic addition reactions. After appending the two dienes at either end of the molecule, macrolactonization and deprotection completed the syntheses. The work proves both the relative and absolute configurations of (−)-dictyostatin. The compounds were evaluated by cell-based measurements of increased microtubule mass and antiproliferative activity, and in vitro tubulin polymerization assays as well as competitive assays with paclitaxel for its binding site on microtubules. These assays showed dictyostatin to be the most potent of the agents and further showed that the structural alterations caused from 20- to >1000-fold decreases in activity.     

Aggregation Behaviour of Some Reactive Dyes

The absorption spectra of aqueous solutions of monochlorotriazine reactive dyes, C.I. Reactive Red 9 and Reactive Orange 13 were measured in the presence of 5, 10, 25 and 50% (v/v) of ethanol, pyridine and dioxane-water mixtures and in varied concentrations of KCl, NaCl and LiCl. The varying position, intensity and shape of absorption bands are interpreted in terms of aggregation and disaggregation of dyes in solutions. The aggregation behaviour of the reactive dyes in solutions and in the presence of additives is related to their apparent deviations from Beer's law and aggregation numbers (N). The aggregation constant (K.) of the monomer/dimer equilibrium is calculated. Dyes in ethanol-water mixtures record a larger aggregation number and aggregation constant than in the presence of pyridine. Dioxane is classified as anon-polar solvent and hence has a more disaggregating influence. The value of the aggregation number and constant are increased with increasing salt conentration and the order of degree of aggregation is KCl > NaCl > LiCl related to the order of ionic radii of K⁺, Na⁺ and Li⁺ ions.     

烷基壳聚糖纳米微球的制备及其紫杉醇负载研究

在碱性条件下通过卤代烃的N-烷基取代反应制备得到烷基壳聚糖衍生物。X射线光电子能谱计算结果表明烷基取代反应主要发生在壳聚糖的氨基上。动态光散射研究表明，该衍生物在水中可自动形成粒径在10—200nm范围的纳米微粒，负载紫杉醇后微球的粒径增大，在磷酸缓冲液（pH=7．4）中体外释放研究表明，随着烷基链长的增加，紫杉醇在磷酸缓冲液中达到平衡时的浓度降低。     

Electrochemical Studies of Paclitaxel Interaction with Tubulin

Paclitaxel can stabilize microtubules and induce microtubule assembly, so people areinterested in the interaction of paclitaxel with tubulin. This interaction has been studiedby fluorometry'. but the electrochemical method has not been adopted to study it so far.Pig-brain tubulin was purified by temperature-depen4ent assemly(disassemblyprocedure=, protein concentrations were estimated by Bradford method and its purity wasdetermined by SDS-polyacrylamide gel electrophoresis (295 % purity). A …     

壳聚糖的表面活性和聚集

壳聚糖是甲壳素的脱乙基产物 ,作为唯一的阳离子型聚电解质天然多糖 ,具有许多独特的性质 ,在生物、医学、食品、水处理等许多领域有广泛的应用或呈现出诱人的应用前景 [1～ 4].然而 ,从表面化学的角度 ,壳聚糖是否具有表面活性、在水溶液中是否聚集尚是一个有争议的问题 [5、 6].本研究结果表明壳聚糖具有表面活性 ,在水溶液中单个分子就能聚集 ,临界聚集浓度 cac≈ 0,对非极性有机物芘具有明显的增溶作用 .属于结构特殊的阳离子型高分子表面活性 剂 .1实验部分 1.1试剂 　　壳聚糖：以虾壳为原料 ,用稀碱处理除去蛋白质 ,再用稀酸处理除去…     

紫杉醇衍生物的三维定量构效关系研究

利用比较分子力场分析(CoMFA)方法对98个紫杉醇衍生物的三维定量构效关系(3D-QSAR)进行了分析,发现影响其活性的立体能与静电能之比为61.6/38.4.进一步分析表明,C-13侧链基团的改变对其活性影响较大,尤其是2'-OH对保持活性是至关重要的;而母环其它位置取代基的改变对活性影响较小.该模型交叉验证r_cv²=0.714,非交叉验证r₂=0.901;以此模型对验证组10个化合物活性进行预测,r_pred²=0.812,表明模型具有很好的预测能力,对紫杉醇的改性或新类似物的合成具有指导意义.     

西部松小蠹集合信息素(±)-exo-Brevicomins的合成

以丙炔醇为起始原料,经烷基化、炔键移位、氧化、环化等反应合成了西部松小蠢集合信息素。     

Aggregation behaviors of amine-oxide gemini surfactants

The micellar aggregation of a series of gemini surfactants [N, N’-dimethyl-N, N’-bis(2-alkylamideethyl)-ethylenediamine oxide (alkyl?=?C₁₁H₂₃, C₁₃H₂₇, C₁₅H₃₁)] in aqueous media has been investigated. The results show that there is an excellent agreement among the critical micelle concentration (CMC) values obtained by surface tension and steady-state fluorescence methods. Because of the occurrence of self-coiling or the formation of pre-micellization, the CMC values, the I₁/I₃ values, and the micelle aggregation numbers (N_agg) at CMC (N_m) increase with the hydrophobic alkyl chain length increasing. Besides, vesicles are observed above the CMC for all these surfactants.     

高分子的折叠与聚集

总结了作者有关高分子折叠和聚集方面的工作。最初,作者研究了聚（N-异丙基丙烯酰胺）（PNIPAM）均聚物的折叠或叫做“线团-塌缩球的转变”,然后研究了含有疏水和亲水基团的PNIPAM共聚物的折叠。作者研究了疏水作用和亲水作用对折叠的影响,发现了融化球,有序线团等折叠过程中的中间态。另一方面,作者研究了两亲性高分子在水中的聚集与稳定。作者的结果表明,如果高分子链所形成的稳定聚集体为核-壳结构,则每个亲水基团所占有的面积为一个常数。如聚集体不是核-壳结构,即部分亲水基团分布在聚集体内部,则上述关系不再成立。随亲水基团含量的增加,聚集体将由球状变为超枝化结构。     

尿液中纳米微晶的团聚促进泌尿系结石的形成

采用纳米粒度仪和透射电子显微镜(TEM)比较研究了尿石症患者与健康对照者尿液中纳米微晶的尺寸、粒度分布、聚集状态、自相关函数和ξ电位随放置时间的变化. 患者尿样放置3 h后, 其尿微晶平均粒径(D_a)由506 nm增至958 nm, 粒度分布范围变宽, 自相关时间由1.84 s延长到3.93 s, ξ电位由-1.34 mV降低至-3.89 mV; 而健康对照者尿微晶的D_a仅由330 nm增加至416 nm, 自相关时间由1.44 s延长至2.10 s, ξ电位由-8.35 mV降低至-8.90 mV. 此结果表明, 尿石症患者和健康对照者尿液中的纳米微晶不但在尺寸、粒度分布、聚集、自相关函数和ξ电位等方面存在明显的差异, 而且患者尿微晶的稳定性比对照者的差; 随着时间的延长, 患者尿液中的纳米微晶会逐渐团聚, 而对照者尿微晶的团聚要轻微得多. 从两类尿液中尿大分子和小分子抑制剂的浓度、尿微晶表面形成双电层的稳定性等方面进行了分析, 结果表明, 尿微晶的聚集是泌尿系结石生长的关键因素.     

双烃链表面活性剂的聚集行为及其应用

介绍了双烃链表面活性剂的基本性质、分类及其在纳米材料和生命科学等领域的某些应用, 并以二(2-乙基己基)琥珀酸酯磺酸钠(AOT)和二(2-乙基己基)磷酸钠(NaDEHP)为例, 介绍了二者的相行为, 反胶束的形成、性质等的差异, 并结合自己的工作探讨了二者与大分子的相互作用.     

Aggregation behavior of poly(N-isopropylacrylamide) microspheres

Electrophoretic mobility and aggregation in suspensions of three types of microspheres (Ms 1, Ms 2 and Ms 3) are studied at different pH, ionic strengths and temperatures of the medium. Here Ms 1 is a core particle composed of poly(N-isopropylacrylamide-co-styrene). Ms 2 is a core-shell microsphere consisting of Ms 1 as the particle core covered with a surface layer of poly(N-isopropylacrylamide) hydrogel. Ms 3 is also a core-shell microsphere composed of MS-1 covered with a surface layer of poly(N-isopropylacrylamide-co-acrylic acid) hydrogel. The charge density zN and the softness parameter 1/λ of the microspheres were obtained from the electrophoretic mobility data on the basis of an electrokinetic theory of soft particles. It is shown that when zN is large, suspensions of microspheres are always stable, showing no aggregation. When zN is small, the suspensions are stable for large 1/λ but show strong aggregation for small 1/λ.     

Inclusion Complex of Paclitaxel in Hydroxypropyl-β-cyclodextrin

Introduction Paclitaxel （as Taxol） is a kind of diterpenoid natural product extracted from Chinese yew. It has been reported to have high anti-tumor effects, such as the activity against oophorama, mammary cancer, encephaloma, cervical carcinoma, and non- small-cell lung carcinoma. One of the major problems of paclitaxel applied to therapy is its extremely low solubility in water. In addition, paclitaxel is administered as a slow infusion in a vehicle consisting of Cremophor EL （ polyoxyethylated castor oil ）. However, Cremophor has been observed to cause severe, occasionally fatal hypersensitivity reactions in animals and humans. Therefore, paclitaxel therapy includes a prophylactic regimen of antihistamines and corticosteroids , along with a prolonged infusion time to reduce the severity and incidence of hypersensitivity reactions. Because of the reasons mentioned above, currently its preparation needs to be improved further.     

Aggregation Behaviors of Novel Amphiphilic Dendrimers at Solid-Liquid Interface

Generation 1 poly(amidoamine) dendrimer is modified with different alkyl tails. A series of novel quaternary ammonium with dendrimeric framework has been obtained, which is abbreviated as QPAMC_m (m represents the carbon number of the alkyl tail). The modified dendrimers were deposited onto the mica substrate from the solution and the aggregation properties including the morphology and the dynamic process of the adsorption were studied by atomic force microscope (AFM), x-ray photoelectron spectroscopy (XPS), and contact angle measurement. Results show that the bulk concentration and the length of hydrophobic tails significantly affect the aggregate morphology at mica-aqueous interface. With the increasing of the bulk concentration and the adsorption time the sphere aggregates transform to semi-continuous film, which is very different from conventional surfactants and linear polymers. The interaction between the hydrophobic tails might be stronger and the alkyl chains may tilt or wind when the end tail is long enough. The contact angle measurement indicates that the hydrophobicity of the solid surface adsorbed with the dendrimers vary regularly. The contact angles rise with the increasing periphery alkyl chains length of the dendrimers.     

Aggregation of Mordant Black 11 in aqueous solution

Summary Spectrophotometry was employed to study the aggregation of Mordant Black 11 (MB-11) in aqueous solution. The aggregation number and constant were determined using the maximum slope method. The aggregation characteristics obtained by this method were then compared with other methods. In addition, the spectral change as a result of dimerization of MB-11 was interpreted in terms of the usual cluster model of water exerting hydrophobic interaction around the dye ions.

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Aggregation von Mordant-Schwarz 11 in wäßriger Lösung

Zusammenfassung Mittels Spektrophotometrie wurde das Aggregationsverhalten von Mordant-Schwarz 11 (MB-11) in wäßriger Lösung untersucht. Die Aggregationszahl und-konstante wurde nach der Maximalanstiegsmethode bestimmt. Die Aggregationscharakteristika wurden mit Ergebnissen aus anderen Methoden verglichen, und die spektroskopischen Veränderungen als Resultat der Dimerisierung von MB-11 wurden im Rahmen des Cluster-Modells und der hydrophoben Wechselwirkung am Farbstoff-Ion diskutiert.

     

水溶性聚电解质—表面活性剂复合物的聚集行为

聚电解质在溶液中与相反电荷的表面活性剂通过解电作用与疏水作用可形成聚电解质－表面活性剂复合物，依据反应条件生成的复事物可以是水溶性也可以是非水溶性的。水溶性的聚电解质－表面活性剂复合物由于有许多工业应用，因此近几十上来水溶性聚电解质－表面活性剂复合物的形成和结构已爱到人们的广泛重视。本文对水溶性聚电解质－表面活性剂复合物的聚集过程、聚集结构作了简要概述，此外对荧光光谱在这一领域的应用进行了重点介绍     

Aggregation kinetics of polymer colloids in reaction limited regime: experiments and simulations

The kinetics of reaction-limited cluster aggregation of fluorinated polymer colloids in a broad range of particle volume fractions has been investigated experimentally by measuring independently the Fuchs stability ratio W and the time evolution of both the average radius of gyration and the average hydrodynamic radius of the aggregates mass distribution. The W value is determined from the aggregation rate at the very initial stage of the aggregation, where the presence of triplets is negligible. The time evolutions of and are then simulated using the cluster mass distribution calculated from the population balance equations with various aggregation kernels proposed in the literature. It is found that, when the measured W value is used, the only kernels that can correctly simulate the experimental results are the product kernel and the one derived by Odriozola et al. (Europhys. Lett. 53 (2001) 797), with some proper tuning of the exponent in the kernel. For the particle volume fraction phi<1%, the obtained value for the exponent is 0.4 and independent of phi, while it tends to decrease for larger phi values, most likely indicating a significant effect of multi-body interactions on the aggregation kinetics.