Synthesis and biological evaluation of guanidine-type iminosugars

The preparation of carbohydrate mimics in which the endocyclic oxygen has been replaced by a guanidine-type nitrogen atom is reported. The synthetic strategy involves the furanose --> piperidine rearrangement of 5-deoxy-5-guanidino-L-idose precursors. The reaction proceeds through elimination of water to give 3-oxopiperidines, which were isolated as the corresponding hydrates. Biological evaluation of the new glycomimetics evidenced a strong influence of the nature of the substituents at the nitrogen atoms on the glycosidase inhibitory properties.     

Self-assembling porphyrin-modified peptides

[structure: see text] We report the synthesis and characterization of a novel supramolecular assembly that features long-range electronic coupling between porphyrins covalently attached to a designed peptide scaffold. The resulting construct self-assembles to form extended organized aggregates in which the porphyrins engage in exciton coupling.     

Self-assembling bipyridinium multilayers

The identification of strategies to assemble nanostructured films with engineered properties on solid supports can lead to the development of innovative functional materials. In particular, the self-assembly of electroactive multilayers from simple molecular building blocks on metallic electrodes can offer the opportunity to regulate the exchange of electrons between the underlying substrate and solution species. In this context, we designed an experimental protocol to prepare electroactive films from bipyridinium bisthiols. Specifically, we found that a compound incorporating two bipyridinium dications at its core and terminal thiol groups self-assembles into remarkably stable multilayers on polycrystalline gold. The surface coverage of the resulting films can be regulated by adjusting the exposure time of the gold substrate to the bipyridinium solution. Control experiments with appropriate model compounds demonstrate that both bipyridinium dications as well as both thiol groups must be present in the molecular skeleton to encourage multilayer growth. The resulting films transport electrons efficiently from the electrode surface to the film/solution interface. Indeed, they mediate the reduction of Ru(NH(3))(6)(3+) in the electrolyte solution but prevent the back oxidation of the resulting Ru(NH(3))(6)(2+). Furthermore, these polycationic bipyridinium films capture electrostatically Fe(CN)(6)(4-) tetraanions, which can also be exploited to transport electrons across the interfacial assembly. In fact, electrons can travel through the bipyridnium(2+/1+) couples to redox probes in solution and then back to the electrode through the Fe(CN)(6)(4/3-) couples. Thus, our original approach to self-assembling multilayers can produce stable electroactive films with unique electron transport properties, which can be regulated with a careful choice of the anionic components.     

Effect of amidoalkyl group as spacer on aggregation properties of guanidine-type surfactants

Dodecanoyl amidoalkylguanidine hydrochlorides (C(12)A(m)G, m = 2, 3, 4, 6) are cationic surfactants that have an amidoalkyl group (A(m)) as spacer between the cationic guanidine and hydrophobic groups in the molecule. The effect of the A(m) group on the aggregation properties of the surfactants was evaluated through measurements of their critical micelle concentration (cmc) value, Krafft point, phase behavior, area occupied by one molecule at the air/water interface, and micellar aggregation number. Dodecylguanidine hydrochloride (C(12)A(0)G) with no A(m) group is a unique cationic surfactant because it exhibits a strong tendency for self-assembly when compared with common ionic surfactants, due to the hydrogen bonding between its guanidine groups in addition to the hydrophobic interaction between its alkyl chains [M. Miyake, K. Yamada, N. Oyama, Langmuir 24 (2008) 8527-8532]. In contrast, C(12)A(m)G showed a decreasing tendency for self-assembly with increasing alkyl chain length, m, of the A(m) group up to m = 3, above which the tendency increased. Such changes in aggregation tendency of the surfactants were suggested to arise from an increased bulkiness of the hydrophilic part caused by the A(m) group, resulting in a decrease in the hydrogen bonding between the guanidine groups and an increase in micellization through the cooperative hydrophobic interaction between the hydrophilic groups. From the balance of these effects, the area of the hydrophilic part of C(12)A(4)G was the largest and the hydrogen bonding between the guanidine groups in C(12)A(4)G was weakened. It is suggested in guanidine-type surfactant that A(4) gave a similar aggregation tendency to traditional ionic surfactants and a weak effect for skin.     

模板法组装微米级微球

运用毛细微模塑(MIMIC)技术, 排列得到了线状和折叠状微球串, 并对MIMIC驱动微球自组装的机理进行了初步研究; 借助微液滴做模板, 排列得到含有不同数目的微球环或准环. 加热到微球的软化温度以上, 使紧密挨着的微球相互粘接, 然后溶解掉底膜, 获得了自由的刚性微球串. 期望改变微球的联结方式, 以获得自由的柔性微球串, 如果把单个微球看作高分子的“链节单元”, 微球串就近似地看作高分子链的简单直接“模型”, 有望用来模拟高分子凝聚态基本物理问题.     

Self-assembling a molecular pegboard

This paper describes the design, construction, and application of a self-assembled, chemically addressable DNA nanogrid composed of DNA tiles of nanometer dimensions. This self-assembled structure permits precise placement of molecules at predetermined locations on a "molecular pegboard". We used the indexed DNA nanogrids to identify single molecules of DNA that hybridize at particular locations.     

Self-assembling ensembles of silicomolybdic acid-diamines

Modification of the surface of the conductive glass [conductive layer is indium-tin oxide (ITO)] by diamines (1,8-diaminooctane and piperazine) and organic polycations [poly(diallyldimethylammonium chloride) and poly(allylamine) hydrochloride] followed by the formation of electroactive composites with silicomolybdic acid H₄SiMo₁₂O₄₀ was carried out. The two-layer ITO/cationic/anionic coatings were shown to differ by the shape of cyclic voltammograms depending on the cationic component.     

Self-assembling metal–organic coordinated fractal crystals

<正>Fractals are essentially characterized by their self-similarity at different scales and non-integer Hausdorff dimensions[1],while crystals always show certain symmetries and discrete diffraction diagrams[2].Thus,a fractal crystal by definition must be identical at all scales with a compatible symmetry with crystals.Although fractals,e.g.snowflakes,trees,coastlines and blood-vascular systems,     

胶原大分子自组装研究进展

胶原是人类最主要的结构蛋白,在体内通过自组装形成具有D带的纤维结构,构成人体的各种组织。胶原蛋白具有优异的生物相容性、生物可降解性、无毒性、低免疫性等特点,在材料科学、生物医学、组织工程、生物传感器等领域得到了越来越多的研究和应用。近年来,人们发现,通过合理调控外界环境,胶原蛋白在体外能自组装形成有序的超分子聚集结构,胶原蛋白在体外的自组装行为引起了研究者的广泛关注,逐渐成为研究的热点。本文概括了胶原的自组装机理、外界环境条件对胶原自组装的影响以及胶原自组装基复合材料等方面的工作。     

Self-assembling phenylpropyl ether dendronized helical polyphenylacetylenes

The first example of a self-assembling phenylpropyl ether based dendronized polymer has been reported and its preferred helical handedness has been determined. Dendronized polymer poly(10) and its nondendritic analogue poly(8) are high-cis-content polyphenylacetylenes (PPAs) prepared by using [Rh(nbd)Cl]2/NEt3 (nbd: 2,5-norbornadiene). Both polymers possess a stereocenter in their side chain, which selects a preferred helical handedness. Based on negative exciton chirality observed in the CD spectra of poly(10), we have designated this molecule as a right-handed helical polymer, which persists over a wide temperature range. Poly(10) self-organizes into both Phiioh and Phih lattices in bulk. The Phiioh-to-Phih transition is associated with thermoreversible cis-cisoidal to cis-transoidal isomerization of the helical PPA, accompanied by a dramatic decrease in the column diameter and a decrease in the pi-stacking correlation length along the column. A model for the right-handed helical dendronized PPA has been proposed wherein dendrons from adjacent column strata interdigitate to effectively fill space.     

Self-assembling peptide scaffolds for regenerative medicine

Biomaterials made from self-assembling, short peptides and peptide derivatives have great potential to generate powerful new therapies in regenerative medicine. The high signaling capacity and therapeutic efficacy of peptidic scaffolds has been established in several animal models, and the development of more complex, hierarchical structures based on peptide materials is underway. This highlight discusses several classes of self-assembling peptide-based materials, including peptide amphiphiles, Fmoc-peptides, self-complementary ionic peptides, hairpin peptides, and others. The self-assembly designs, bioactive signalling strategies, and cell signalling capabilities of these bioactive materials are reported. The future challenges of the field are also discussed, including short-term goals such as integration with biopolymers and traditional implants, and long term goals, such as immune system programming, subcellular targeting, and the development of highly integrated scaffold systems.     

Self-assembling bilayers of palladiumthiolates in organic media

Alkylthiolates of palladium forming a homologous series (butyl to octadecyl) have been prepared and characterized using X-ray diffraction and STM. The thiolates adopt an unusual bilayered lamellar structure, whose thickness is governed by the length of the alkyl chain. These mesophases melt in the temperature range, 60° to 100°C, with the melting point increasing linearly with the thiol chain length. There is evidence to suggest that the alkyl chains are orientationally disordered especially prior to melting.     

氧化锌纳米线自组装定向生长动力学研究

研究了以极性高分子(如聚丙烯酰胺)长分子链作为自组装网络, 利用高分子软模板控制ZnO纳米点成核和ZnO纳米线定向生长, 从而使ZnO纳米线在半导体硅衬底上自组装生长的过程; 采用差示扫描量热法(DSC)测试了高分子络合-烧结法制备ZnO纳米线的结晶曲线, 对其结晶动力学进行了研究, 推导出结晶动力学方程为: 1－X_t＝exp(－7.475×10^－2t^1.9); 并利用热重(TG)测试结果, 通过热分解反应, 导出了反应动力学方程: dα/dT＝(3.76×10²³/Φ)e^－21340.8/T(1－α) ^2.8, 从而得到了化学反应速度随时间、浓度和温度变化的关系, 并用结果解释了实验现象.     

自组装型紫杉醇键合物前药的合成与性能

以p-氨基苯乙酸(APA)和六亚甲基二异氰酸酯(HDI)为连接基团,将短链聚乙二醇单甲醚(mPEG)键合到紫杉醇(PTX)上,获得双亲型PTX前药mPEG-APA-PTX和mPEG-HDI-PTX.考察了这两种前药在自主装、体外药物释放动力学、体外细胞毒性和体内血浆清除速率等方面的表现.结果表明:两前药均能在水中自组装形成稳定的纳米颗粒,载药量高达28％;mPEG-HDI-PTX纳米颗粒在水溶液中非常稳定,细胞毒性很弱,在血液系统中清除很快,而mPEG-APA-PTX纳米颗粒在pH=7.4的环境下可缓慢释放出原药PTX,细胞毒性与临床用紫杉醇针剂Tax-ol(R)相当,体内循环时间较Taxol(R)明显延长;mPEG-APA-PTX是一种可自组装、载药量高、体内循环时间长的新型纳米前药.     

单分子层自组装技术应用于硝酸铵防吸湿的探讨

表面活性剂;单分子层自组装技术应用于硝酸铵防吸湿的探讨     

Synthesis and Self-assembling of Coumarin-based Low-molecular Weight Organogelators

Four coumarin derivatives(4a―4d) with different alkoxy chains were synthesized. It was found that compound 4d showed a better gelation ability than the other compounds, for example, it could self-assemble into organogels in various organic fluids via ultrasound treatment or heating-cooling process, whereas compound 4c could only gel in a few mixed solvents and compounds 4a, 4b could not form organogel. The results from fluorescent and FT-IR spectra indicate that π-π interaction had an effect on the formatio...     

Self-assembling DNA dendrimers: a numerical study

DNA is increasingly used as a specific linker to template nanostructured materials. We present a molecular dynamics simulation study of a simple DNA-dendrimer model designed to capture the basic characteristics of the biological interactions, where selectivity and strong cooperativity play an important role. Exploring a large set of densities and temperatures, we follow the progressive formation of a percolating large-scale network whose connectivity can be described by random percolation theory. We identify the relative regions of network formation and kinetic arrest versus phase separation and show that the location of the two-phase region can be interpreted in the same framework as reduced valency models. This correspondence provides guidelines for designing stable, equilibrium self-assembled low-density networks. Finally, we demonstrate a relation between bonding and dynamics, by showing that the temperature dependence of the diffusion constant is controlled by the number of fully unbonded dendrimers.     

Self-assembling two-dimensional nanophotonic arrays for reflectivity-based sensing

We propose a nanoplasmonic platform that can be used for sensing trace levels of heavy metals in solutions via simple optical reflectivity measurements. The considered example is a lead sensor, which relies on the lead-mediated assembly of glutathione-functionalized gold nanoparticles (NPs) at a self-healing water/DCE liquid | liquid interface (LLI). Capillary forces tend to trap each NP at the LLI while the negatively charged ligands prevent the NPs settling too close to each other. In the presence of lead, due to chelation between the lead ion and glutathione ligand, the NPs assemble into a dense quasi-2D interfacial array. Such a dense assembly of plasmonic NPs can generate a remarkable broad-band reflectance signal, which is absent when NPs are adsorbed at the interface far apart from each other. The condensing effect of the LLI and the plasmonic coupling effect among the NP array gives rise to a dramatic enhancement of the reflectivity signals. Importantly, we show that our theory of the optical reflectivity from such an array of NPs works in perfect harmony with the physics and chemistry of the system with the key parameter being the interparticle distance at the interface. As a lead sensor, the system is fast, stable, and can achieve detection limits down to 14 ppb. Future alternative recognizing ligands can be used to build sister platforms for detecting other heavy metals.

We propose a nanoplasmonic platform that can be used for sensing trace levels of heavy metals in solutions via simple optical reflectivity measurements at the liquid–liquid interface.