Aggregate States and Energetic Disorder in Highly Ordered Nanostructures of para‐Sexiphenyl Grown by Hot Wall Epitaxy

We report on photoluminescence (PL) and thermally stimulated luminescence (TSL) in highly ordered nanostructures of para‐sexiphenyl (PSP) grown by hot wall epitaxy (HWE). A low‐energy broad band is observed in the PL spectra that can be attributed to the emission from molecular aggregates. While the intrinsic exciton emission in steady‐state PL dominates at low temperatures, the emission from aggregates increases with elevating temperature and its magnitude depends sensitively on film preparation conditions. Time‐resolved PL measurements showed that the aggregate emission decays with a life‐time of ≈ 4 ns, which is approximately an order of magnitude larger than the lifetime of singlet excitons. TSL data suggests the presence of an energetically disordered distribution of localized states for charge carriers in PSP films, which results from an intrinsic disorder in this material. A low‐temperature TSL peak with the maximum at around 30 K evidences for a weak energy disorder in PSP films, and has been interpreted in terms of a hopping model of TSL in disordered organic materials.     

Application of ultrasonic waves in activation of microcrystalline cellulose

In this work, microcrystalline cellulose (MCC) was activated with ultrasonic waves. The influences of ultrasonic treatment on the changes of supramolecular structures and morphology structure were studied by WAXS and SEM. The accessibility of the MCC was characterized by water retention value (WRV) and specific surficial area. The influence of ultrasonic treatment on the reactivity of MCC was investigated through the reaction of MCC being oxidized into 2,3‐diadehyde cellulose (DAC) by periodate sodium. The mechanism of the reactivity change of ultrasonically treated MCC was examined. The results showed that the degree of crystallinity of MCC decreased and the degree of polymerization showed little change after treatment with ultrasonic waves. The morphologial variation of the treated MCC was significant when compared with the untreated MCC, which contribute to the improvement of accessibility. The aldehyde content of DAC prepared from ultrasonically treated MCC was improved from 64.19 to 85.00%, indicating that the regioselective oxidation reactivity of MCC was significantly improved. The aldehyde content was found to first increase with time of ultrasonic treatment to a point, and then decrease as time progressed. In addition, the aldehyde content was found to increase with an increase in ultrasonic power. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Measurement of metal nanolayers optical parameters using surface plasmon resonance method

The results of experimental definition of optical parameters of silver nanolayers by the method of surface plasmon resonance (SPR) are described. The goniometric installation for measurement of angular dependences of reflection of light by layered nanosructures at the attenuated internal reflection (angular spectrum of reflection) is designed. Calculation of optical parameters of nanolayers is executed taking into account the form of a curve of tin angular spectrum of reflection. The text was submitted by the authors in English.     

Dehydropeptide Supramolecular Hydrogels and Nanostructures as Potential Peptidomimetic Biomedical Materials

Supramolecular peptide hydrogels are gaining increased attention, owing to their potential in a variety of biomedical applications. Their physical properties are similar to those of the extracellular matrix (ECM), which is key to their applications in the cell culture of specialized cells, tissue engineering, skin regeneration, and wound healing. The structure of these hydrogels usually consists of a di- or tripeptide capped on the N-terminus with a hydrophobic aromatic group, such as Fmoc or naphthalene. Although these peptide conjugates can offer advantages over other types of gelators such as cross-linked polymers, they usually possess the limitation of being particularly sensitive to proteolysis by endogenous proteases. One of the strategies reported that can overcome this barrier is to use a peptidomimetic strategy, in which natural amino acids are switched for non-proteinogenic analogues, such as D-amino acids, β-amino acids, or dehydroamino acids. Such peptides usually possess much greater resistance to enzymatic hydrolysis. Peptides containing dehydroamino acids, i.e., dehydropeptides, are particularly interesting, as the presence of the double bond also introduces a conformational restraint to the peptide backbone, resulting in (often predictable) changes to the secondary structure of the peptide. This review focuses on peptide hydrogels and related nanostructures, where α,β-didehydro-α-amino acids have been successfully incorporated into the structure of peptide hydrogelators, and the resulting properties are discussed in terms of their potential biomedical applications. Where appropriate, their properties are compared with those of the corresponding peptide hydrogelator composed of canonical amino acids. In a wider context, we consider the presence of dehydroamino acids in natural compounds and medicinally important compounds as well as their limitations, and we consider some of the synthetic strategies for obtaining dehydropeptides. Finally, we consider the future direction for this research area.     

Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly(?-caprolactone)-block-polydimethylsiloxane-block-poly(?-caprolactone) triblock copolymer

Poly(?-caprolactone)-block-polydimethylsiloxane-block-poly(?-caprolactone) triblock copolymer (PCL-b-PDMS-b-PCL) was synthesized via the ring-opening polymerization of ?-caprolactone with dihydroxypropyl-terminated PDMS (HTPDMS) as the initiator. The triblock block copolymer was characterized by means of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). The triblock copolymer was incorporated to prepare nanostructured thermosetting blends. The morphology of the epoxy thermosets containing PCL-b-PDMS-b-PCL were investigated by means of atomic force microscopy (AFM), transmission electronic microscopy (TEM) and small-angle X-ray scattering (SAXS). The thermomechanical properties of the nanostructured blends were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The formation of the nanostructures in the thermosetting composites was judged to follow the self-assembly mechanism in terms of the difference in miscibility of PDMS and PCL subchains with epoxy resin after and before curing reaction.     

β-环糊精-氧化石墨烯超分子杂化体的构筑及应用进展

β-环糊精是由7个D-吡喃葡萄糖单元通过α-1,4-糖苷键键连成环的超分子主体分子，“内疏水、外亲水”的独特结构赋予了其优异的分子识别能力；氧化石墨烯类材料凭借其优良特性成为近几年的研究热点。由β-环糊精和氧化石墨烯构筑的超分子杂化体在兼具二者特有性能的基础上又有新功能的引入。本文综述了β-环糊精-氧化石墨烯超分子杂化体的构筑方式，按二者间的连接方式，分别为共价键和非共价键两种连接方式，其中通过共价键连接是目前最主要的构筑方式；此外对β-环糊精-氧化石墨烯超分子杂化体的特征和表征进行了简述。同时对β-环糊精-氧化石墨烯超分子杂化体在水污染处理、电化学检测、药物控释和催化等领域的应用进展进行了综述。最后对该超分子杂化体在构筑和应用上的发展趋势进行了展望。     

季戊四醇的超分子化学

介绍季戊四醇的超分子化学,包括超分子网状结构、螺环冠醚、非常规液晶、富勒烯衍生物、固相光催化反应、Janus树枝状分子等等。     

pH sensitive supramolecular vesicles from cyclodextrin graft copolymer and benzimidazole ended block copolymer as dual drug carriers

Supramolecular assemblies from chitosan-graft-β-cyclodextrin (CS-g-CD) and benzimidazole ended poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL-BM) were formed based on the inclusion complexation between β-cyclodextrin and benzimidazole. The supra-amphiphiles self-assembled into complex vesicles with PCL/β-CD as the hydrophobic membrane, hydrophilic PEG and CS as the corona. The hydrophobic membrane and aqueous lumen of vesicles exhibited efficient entrapment both for hydrophobic curcumin (CUR) and hydrophilic doxorubicin (DOX). The drug loading of vesicles was more than 20.2% and 38.4% for CUR and DOX, respectively. Decreasing pH to acidic condition or increasing temperature, more controllable and rapid release of two drugs was observed. Cytotoxicity assays revealed that dual drug-loaded vesicles retained high cell proliferation inhibition efficiency than free drugs.GRAPHICAL ABSTRACT