病毒样颗粒自组装与解组装的动力学研究

豇豆褪绿斑驳病毒(cowpea chlorotic mottle virus,CCMV)的衣壳蛋白可自组装形成空心病毒样颗粒(virus-like particles,VLPs),并应用于构筑纳米容器或纳米反应器.为了探究其自组装与解组装的动力学机制和时间尺度,利用荧光光谱结合动态激光光散射研究了CCMV衣壳蛋白在无模板分子诱导时的自组装与解组装的动力学过程,获得其动力学方程,并明确了自组装与解组装的时间尺度在分钟级别.CCMV衣壳蛋白在pH=4.70~5.31条件下5 min内完成自组装,pH越低自组装速度越快.自组装过程可分为两个阶段:第一阶段遵循二级反应动力学,生成二聚体蛋白的寡聚体;第二阶段满足成核生长动力学模型,寡聚体进一步组装形成VLPs前体,最终形成完整的C CMV VLPs.在pH=7.60~8.62条件下解组装的时间尺度介于5~10 min之间,pH越高解组装速度越快.解组装过程中CCMV VLPs首先膨胀形成松散的组装结构,随后整体解散,满足二级反应动力学.对病毒衣壳蛋白自组装过程的深入了解有助于人们在时空间尺度精准调控其纳米容器和纳米反应器的构筑及功能.

嵌段聚合物PGMA-b-PDEAEMA_x的合成及其CO_2诱导解组装行为

以甲基丙烯酸二乙基氨基乙酯为疏水段,聚甲基丙烯酸甘油酯为亲水段,采用可逆加成-断裂转移聚合合成了具有不同嵌段比例的甲基丙烯酸甘油酯-b-甲基丙烯酸二乙氨基乙酯二嵌段聚合物(PGMA-b-PDEAEMAx),其结构经1H NMR和GPC表征。聚合物通过自组装形成球形胶束、线性胶束聚集体和囊泡结构;向聚合物溶液中通入CO2后,其自组装解体。

小分子级联自组装/解组装策略在精准癌症诊疗中的应用

“智能”识别及靶向癌细胞是精确诊断与高效治疗的关键。目前的策略中,使用小分子共价前体探针(或药物)存在机体代谢速度快及对其他器官毒副作用大的局限;使用纳米探针(或载药)体系则存在分子量不明确、生物穿透性低和易被网状内皮系统捕获等问题。肿瘤“原位自组装”策略兼具了小分子和纳米体系的优点,利用小分子作为前体可提高药物分子在肿瘤组织的生物穿透性,而自组装形成的纳米结构则提供了更好的生物利用度、更高的代谢稳定性和更长的滞留时间。在此基础上,研究者们通过设计多个肿瘤特异性生物分子顺次激活分子前体,进一步开发了小分子顺次级联自组装/解组装策略,以实现肿瘤组织的精准定位和肿瘤细胞的高选择性。在癌症的诊疗应用中,该策略可有效提高诊断信号的灵敏度,时空追踪癌细胞内的系列动态生物过程,同时实现药物的有效富集,并降低对正常细胞的副作用。该文概述了当前增强型级联自组装、级联自组装/解组装策略的研究进展,为癌症诊疗提供了新见解。

超两亲分子:可控组装与解组装

与基于共价键的两亲性分子相对照,超两亲分子系指基于非共价键构筑的两亲分子.基于超分子体系的分子工程学的思想,本文总结了超两亲分子的各种类型,包括小分子型、聚合物型和响应性超两亲分子等,以及组装超两亲分子的各种推动力,如主客体相互作用、基于电荷转移作用和不同分子间的协同作用等.研究表明,超两亲分子的研究既可丰富传统的胶体界面化学,又为高级结构的可控组装提供了新的构筑基元,并为制备功能超分子材料开拓了新的途径.

鲨鱼肝铁蛋白亚基解离与组装机理的研究

小批量制备质谱纯鲨鱼肝铁蛋白(Liver Ferritin of Sphyrna zygaena,SZLF)。在弱酸介质(pH1.0)中,天然电泳结果显示,SZLF蛋白质亚基20 min后开始解离。选用透射电子显微镜跟踪SZLF亚基解离与重组装全过程和蛋白壳与铁核尺寸变化,发现SZLF在亚基酸解离过程中,随着pH值的降低,铁核和蛋白壳的尺寸呈现相同的变化趋势,这种变化趋势可能与铁核内层铁的释放和蛋白壳的解离与去折叠有关。SZLF蛋白壳的重组装过程则是一个快速过程,并且是由松散熔球态向紧密态转变的过程。SZLF由单类型亚基组成,而马脾铁蛋白(Horse Spleen Ferritin,HSF)由H和L两种亚基类型组成。在基质pH3.0条件和激光辅助下,混合HSF和SZLF仍然可释放各自的亚基且形成准亚基离子,供基质辅助激光解析电离飞行时间质谱分析,说明此时SZLF的亚基间相互作用强度减弱但并没有去折叠。TEM技术在铁蛋白解离和重组装过程中的应用,为进一步研究铁蛋白纳米包装的过程和机理提供新颖的、可行的和更加直观的研究手段。

化学生物学中识别与组装的若干问题

化学与生物学的交叉与融合产生了新学科———化学生物学,开拓了化学和生物学研究的新领域,使人类得以从分子水平来阐释生命过程,揭示生命的奥秘。分子识别和组装是体系的构筑与功能集成的基础,也是自然界生物进行信息存贮、复制和传递的基础。以此来研究构筑具有特定生物学功能的超分子体系,对揭示生命现象和过程具有重要意义。本文结合我们的研究工作从(1)谷胱甘肽过氧化物酶(GPX)模拟与底物识别;(2)医用再生材料与活性支架;(3)类病毒颗粒的组装与解组装3个方面讨论了化学生物学中的识别与组装的意义。

Identification of origin of insulating polymer maneuvered photoredox catalysis

Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.

Interzeolite transformation from FAU to CHA and MFI zeolites monitored by UV Raman spectroscopy

As a powerful and sensitive tool for the characterization of zeolite building units,UV Raman spectroscopy has been used to monitor interzeolite transformation from FAU to CHA and MFI zeolites.The results show that the behavior of double 6-membered rings(D6Rs)in the FAU zeolite framework plays an important role during the formation of the target product in the interzeolite transformation.For the transformation of FAU to CHA,because both zeolites contain the same D6R units,direct transformation occurs,in which the D6Rs were largely unchanged.In contrast,for the transformation of FAU to MFI,the D6Rs can be divided into two single 6-membered rings(S6Rs),which further assembled into the MFI structure.In this crystallization,5-membered rings(5Rs)are only observed in the MFI framework formation,suggesting that the basic building units in the transformation of FAU to MFI are S6Rs rather than 5Rs.These insights will be helpful for further understanding of the interzeolite transformation.

Microwave-assisted ionothermal synthesis of hierarchical microcube-like BiOBr with enhanced photocatalytic activity

Bismuth oxybromide（BiOBr） with a hierarchical microcube morphology was successfully synthesized via microwave-assisted ionothermal self-assembly method. The as-obtained BiOBr was composed of regular multi-layered nanosheets, which were formed by selective adsorption of ionic liquids on the Br-terminated surface, followed by the formation of hydrogen bond-co-π-π stacking.The synthesized BiOBr exhibited high activity, excellent stability, and superior mineralization ability in the photocatalytic degradation of organic dyes under visible light owing to its enhanced light absorbance and narrow bandgap. Furthermore, photo-generated electrons were determined to be the main active species by comparison with different trapping agents used in the photocatalytic reactions.

Effect of Extractive-Dissolving Treatment on the Characteristics of Laminated Wood Assembled from Oily Keruing Wood

Utilization of oily keruing wood for laminated wood product has not been optimal yet because of the appearance of extractive substance as oil on wood surface and hence disturbing the bonding process. A study has been conducted by manufacturing laminated wood from oily keruing wood （Dipterocarpus hasseltii） after extracting its oil by boiling the wood in the mixture of water and ethanol solution in several proportions. The assessment on the treated wood and the resulting laminated wood covered some characteristics i.e., wettability, static bending, bonding strength, ethanol-water solution can improve wetting properties significantly and delamination. The results show that boiling treatment in The extractive does not affect mechanical characteristics of the laminated wood. Increasing of water proportion in ethanol-water solution causes the decreasing of the bonding strength and increasing delamination value of the laminated wood. The result also shows that oily keruing wood after the treatment can be used as material for laminated wood.

Assembly and disassembly of mammalian chromosome pellicle

By means of indirect double immunofluorescent staining, the coordination of PI antigen and perichromonucleolin (PCN), the constituent of nuclear periphery and nucleolus respectively, in the assembly and disassembly of chromosome pellicle during mitosis was studied. It was found that in 3T3 cells, during mitosis PI antigen began to coat the condensing chromosome .surface earlier.than PCN did. However, both of them completed their coating on chromosome at approximately the same stage of mitosis, prometaphase metaphase. The dissociation of PI antigen from chromosome pellicle to participate the formation of nuclear periphery took, place also ahead of that of PCN. At early telophase PI antigen had been extensively involved in the formation of nuclear periphery, while PCN remained in association with the surface of decondensing chromosomes. At late telophase, when PI antigen was localized in an fairly well formed nuclear periphery, PCN was in a stage of forming prenucleolar bodies.

In situ Investigation on Layer-by-Layer Deposition of Polyelectrolytes by Quartz Crystal Microbalance

The effect of salt concentration on layer-by-layer deposition of poly（sodium 4-styrene sulfonate） （PSSS）/poly（vinylbenzyl trimethylammonium chloride） （PVTC） was investigated by use of quartz crystal microbalance with dissipation （QCM-D）. The changes in frequency and dissipation demonstrate that the addition of NaC1 leads the thickness of PSSS/PVTC multilayer to increase. The deposition of PSSS/PVTC is dominated by surface charge overcompensation level at lower salt concentrations. However, it is mainly determined by the interpenetration of polyelectrolytes at a higher salt concentration, as reflected in the oscillation of dissipation change.

Controlled Release of the Indomethacin Microencapsulation Based on Layer-by-layer Assembly by Polyelectrolyte Multilayers

Indomethacin has been encapsulated with polyelectrolyte multilayers for controlled release. Gelatin and alginate were alternatively deposited on indomethacin microcrystals. The released amount of indomethacin from coated microcrystals in pH6. 8 phosphate buffer solution （PBS） was measured with a UV spectrophometer. The polyelectrolyte multilayer capsule thickness was proved to control the release rate. The effects of osmotic pressure existed during the release process of indomethacin from microcapsules coated by （gelatin/alginate） 4.

Photocatalytic degradation of formaldehyde using mesoporous TiO_2 prepared by evaporation-induced self-assembly

The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission electron microscopy(HR-TEM) and N2 adsorption desorption and adsorption are used to study the effects of the synthesized process condition on the microstructure of the as-synthesized mesoporous Ti O2. The photocatalytic performances of as-synthesized samples are evaluated by the degradation of the formaldehyde under ultraviolet light irradiations. The results demonstrate that the as-synthesized mesoporous Ti O2 are anatase with the uniform size about 20-40 nm. The sample is prepared using cetyltrimethyl ammonium bromide(CTAB) as the template with average pore size distribution of 8.12 nm, specific surface area of 68.47 m2/g and pore volume of 0.213 m L/g. The samples show decomposition of formaldehyde 95.8% under ultraviolet light irradiations for 90 min. These results provide a basic experimental process for preparation mesoporous Ti O2, which will posses a broad prospect in terms of the applications in improving indoor air quality.

精准宏观超分子组装

宏观超分子组装是近年来超分子科学的新兴研究方向,其本质是表面修饰有大量超分子官能团的宏观构筑基元的界面组装.由于组装过程中存在较多热力学亚稳态,导致最终产生大量非精准组装体,整体结构有序度低,制约了其在高性能超分子材料方面的应用,因此,如何实现精准宏观超分子组装,构建有序超分子结构,成为了制约宏观超分子组装发展的瓶颈问题之一.本专论从宏观超分子组装的概念与组装机制出发,根据宏观超分子组装过程的特点,分析阐述了组装体中存在不同界面匹配度的热力学亚稳态的问题;继而,从能量面的角度展开分析,总结和归纳了提高组装结构有序度的精准组装策略,包括:(1)利用组装体热力学稳定性差异,设计各向异性构筑基元诱导目标组装结构的形成,发展自纠错策略提高组装界面匹配度;(2)引入宏观构筑基元的组装动力学设计,使构筑基元发生自驱动运动并通过界面长程力取向,使组装界面达到高度匹配,实现近热力学平衡态的精准组装,直接获得精准结构.进而,结合精准宏观超分子组装制备的有序结构,我们展望了其在构建组织工程支架方面的应用前景.

Tunable Self-assembled Weak Polyelectrolyte Brushes

The authors have investigated the pH and ionic strength response of self-assembled layers formed by adsorption of amphiphilic weak polyelectrolytes. Using the SFA （Surface Forces Apparatus） the authors measured force-distance profiles of poly （isoprene）-poly （acrylic acid） block copolymers adsorbed on mica. Also by Atomic Force Microscopy the authors captured single polyelectrolyte molecule adsorbed on a surface. The effect of salt concentration （Cs） and pH upon the height of the brush layers was explored mainly by measuring the forces between two adsorbed polyelectrolyte brushes. At pH = 4 our results are in good agreement with the scaling prediction L0 ∝Cs-1/3 Changing the pH from 4 to 10 causes a remarkable swelling of the polymer layer, but only a weak dependence on salt concentration was detected at the higher pH. This can be attributed to the degree of dissociation, which depends on the local pH value. At low pH the polyelectrolyte chains have a low charge density, while on increasing the pH the degree of dissociation rises, and the increased charge density is followed by swelling of the adsorbed layer. The local concentration of ions in the brush is now greater than that of pH = 4 and approximately equivalent to 0.3 M. So the swelling is only weakly dependent on salt concentration in the range 0.01-1.0 M. The results demonstrate the tunable nature of such self-assembled polyelectroiyte brushes whose height and range of interactions, can be systematically controlled by adjusting the pH and ionic strength of the medium.

Photoelectrode for water splitting: Materials,fabrication and characterization

Photoelectorchemical（PEC） water splitting is an attractive approach for producing sustainable and environment-friendly hydrogen. An efficient PEC process is rooted in appropriate semiconductor materials, which should possess small bandgap to ensure wide light harvest, facile charge separation to allow the generated photocharges migrating to the reactive sites and highly catalytic capability to fully utilize the separated photocharges. Proper electrode fabrication method is of equal importance for promoting charge transfer and accelerating surface reactions in the electrodes. Moreover,powerful characterization method can shed light on the complex PEC process and provide deep understanding of the rate-determining step for us to improve the PEC systems further. Targeting on high solar conversion efficiency, here we provide a review on the development of PEC water splitting in the aspect of materials exploring, fabrication method and characterization. It is expected to provide some fundamental insight of PEC and inspire the design of more effective PEC systems.

Symmetry-breaking assembled porous calcite microspheres and their multiple dental applications

Biomedical applications of porous calcium car- bonate （CaCO3） microspheres have been mainly restricted by their aqueous instability and low remineralization rate. To overcome these obstacles, a novel symmetry-breaking assembled porous calcite microsphere （PCMS） was con- structed in an ethanol/water mixed system using a two-step vapor-diffusion/aging crystallization strategy. In contrast to the conventional additive-induced crystallization method, the present strategy was performed under mild conditions and was free from any foreign additives, thus avoiding the potential contamination of the final product. Meanwhile, the prepared PCMSs were characterized by their highly uniform spherical morphology and large open pores, which are fa- vorable for large protein delivery. An antimicrobial study of immunoglobulin Y （IgY）-loaded PCMSs revealed excellent antimicrobial activity against Streptococcus mutans. More importantly, they showed surprisingly rapid transformation to bone minerals in physiological medium. Evaluation of the in vitro efficacy of PCMSs in dentinal tubule occlusion demonstrated their powerful potential to serve as a catalyst in the repair of dental hard tissue. Therefore, the developed PCMSs show great promise as multifunctional biomaterials for dental treatment applications.