Synthesis, Characterization and Photophysical Properties of Metallopolyynes and Metallodiynes of Platinum(II) with Dibenzothiophene Derivatives

Soluble, thermally stable, and easily processable platinum(II) polyyne polymers of the form trans-[–Pt(PBu₃)₂C≡CRC≡C–]_n (R = 2,8-disubstituted dibenzothiophene, 2,8-disubstituted and 3,7-disubstituted dibenzothiophene-S,S-dioxide units) have been prepared in good yields by CuI-catalyzed polymerization involving the dehydrohalogenating coupling of trans-[PtCl₂(PBu₃)₂] and HC≡CRC≡CH. We report their optical absorption and photoluminescence spectra and compare the results with the monomeric model complexes trans-[Pt(Ph)(PEt₃)₂C≡CRC≡CPt(Ph)(PEt₃)₂]. The different electronic properties and linkage geometry of the central R group lead to new organometallic materials with distinct photophysical traits. The polymer with more conjugated 3,7-disubstituted dibenzothiophene-S,S-dioxide mainly displays fluorescence band, while its isomer with less conjugated 2,8-disubstituted spacer effectively enhances the intersystem crossing rate and strong phosphorescence emission can be detected even at room temperature.     

Ordering of block copolymer/nanoparticle composite thin films

The ordering behavior of polymer nanocomposites composed of gold nanoparticles confined in the polystyrene (PS) domains of PS based block copolymers was investigated. The results reveal that the self‐assembly of nanoparticles in the PS domains improved the ordering of microdomains. This is attributed to the presence of nanoparticles that reduced the degree of segregation of the system, causing slow phase separation. This facilitates the packing of the cylindrical microdomains, leading to a well‐ordered structure of the composite. When particles were incorporated into the major domains of cylindrically ordered block copolymer, the connectivity of the domains allowed particles to move to the top of the film to gain additional entropy of the system. In contrast, when particles were organized in parallel cylinders in the block copolymer, they were confined in the cylinders which prevented them from diffusing in the depth direction. The aggregation of nanoparticles was amplified when the composite was annealed in air. We believe that the results from this study will enable more understanding of the effects of nanoparticles on the ordering of block copolymer/nanoparticle composite thin films and will provide a tool in the fabrication of composite thin films. Copyright © 2012 Society of Chemical Industry     

The dispersion of magnetic nanorods in poly(2‐vinylpyridine)

The dispersion of magnetic nanorods in poly(2‐vinylpyridine) (PVP) as a function of rod length, particle loading and molecular weight of PVP was investigated. The nanorods were organized into small spherical clusters at low particle loading. Further increasing the particle concentration caused an increase in the size of the aggregates. Additionally, the internal structure of the nanorods developed into a raft‐like structure, forming rectangular clusters. The incorporation of longer nanorods in the PVP amplified the magnetic interaction energy, which created conditions to induce extensive aggregation. The entanglement of the polymer also played an important role in the arrangement of the nanorods. This behavior could be categorized into two regimes, M_PVP > M_e and M_PVP < M_e, where M_PVP and M_e are the number‐average molecular weight and entanglement molecular weight of PVP, respectively: for M_PVP > M_e, PVP formed entanglements that prevented nanorods from extensive aggregation; for M_PVP < M_e, PVP could not form entanglements, and nanorods could move freely in the PVP, and thus significant rod aggregation occurred. Simple calculations to assess the contribution of the magnetic interaction, the van der Waals interaction and the free energy of mixing of the system to the arrangement of magnetic nanorods in the homopolymer are discussed. © 2013 Society of Chemical Industry     

A Preliminary Investigation of the ISG Glass Vapor Hydration

During the geological disposal of high-level waste, the nuclear glass is expected to be first hydrated in water vapor prior to liquid alteration. In the present work, we investigated the vapor hydration of the International simple glass (ISG) at 175°C and different relative humidities (60%, 80% and 98%). The glass hydration was investigated by nuclear reaction analysis (NRA) and Fourier transform infra-red spectroscopy. The chemical and mineralogical compositions of the alteration products were studied using scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDS) and μ-Raman spectroscopy, respectively. The NRA results gave water diffusion coefficients of 2.31–7.34 × 10⁻²¹ m²/s_, in good agreement with the literature data on borosilicate glasses altered in aqueous media. The glass hydration increased with relative humidity percentage and the SEM-EDS analysis showed a slight enrichment in Si and loss of Na in the hydrated glass layer compared with the pristine glass. The hydration rate of the ISG glass was little higher than that of the French SON68 glass hydrated using water vapor. The corrosion products were analcime, tobermorite, and calcite, which were typical of the SON68 glass hydrated in similar conditions.     

Engineering a pharmacologically superior form of leptin for the treatment of obesity

Leptin plays a central role in the homeostasis of body weight through its regulatory effects on appetite and energy expenditure, yet in trials as a therapeutic agent for the treatment of obesity in humans it has been disappointing. The poor clinical efficacy of leptin results from its short circulating half-life, low potency and poor solubility, necessitating large and frequent doses to obtain even modest clinical benefit. Engineered Fc-leptin immunofusins, consisting of the Fc fragment of an immunoglobulin gamma chain followed by leptin, exhibit improved pharmacological properties with very consistent and potent biological activities. Furthermore, in extending the circulating half-life of the protein in vivo from a few minutes for leptin to many hours for Fc-leptin, these proteins have the potential to reduce drastically the dosage and frequency of administration required to obtain clinical benefit. The results of this study show that the engineered leptin immunofusins described here have significantly enhanced pharmacological properties in comparison with the recombinant leptin that was used in clinical trials. As such, they could represent an important step towards a therapeutically superior form of leptin if the disappointing performance of leptin in early clinical trials was due to its poor pharmacological properties rather than any conceptual weakness in the strategy of using leptin for the treatment of obesity and its related disorders.     

CD26 Induces Colorectal Cancer Angiogenesis and Metastasis through CAV1/MMP1 Signaling

CD26 has been reported as a marker for colorectal cancer stem cells endowed with tumor-initiating properties and capable of colorectal cancer (CRC) metastasis. In this study, we investigated the functional effect of CD26 on CRC angiogenesis and metastasis, and the potential underlying mechanism. The functional effects of CD26 overexpression or repression were determined by a wound healing experiment, and cell migration and invasion assays in vitro and in mouse models. Differentially expressed genes regulated by CD26 were identified by genome-wide mRNA expression array and validated by quantitative PCR. CD26 functionally regulated CRC cell migration and invasion in vitro and angiogenesis and metastasis in vivo. Genome-wide mRNA expression array and qPCR showed that MMP1 was up-regulated in CD26+ subpopulation, and a subsequent experiment demonstrated the regulatory effect of CD26 on MMP1 in CRC cell lines with CD26 repression or overexpression. Furthermore, overexpression of CAV1 abrogated the CD26-regulated MMP1 induction in CRC cell lines. This study demonstrated the functional roles of CD26 in inducing CRC migration, invasion, angiogenesis and metastasis and identified the potential involvement of MMP1 and CAV1 in such process. CD26 is an attractive therapeutic target for combating tumor progression to improve the prognosis of CRC patients.     

Synthesis,Characterization and Catalytic Activities of Palladium(II) Nitroaryl Complexes

Two palladium(II) nitroaryl complexes trans-[bromo(p-nitrophenyl)bis(triphenylphosphine)palladium(II)] 1 and trans-[bromo(2,4-dinitrophenyl)bis(triphenylphosphine)palladium(II)] 2 have been synthesized. The complexes were characterized by FTIR and NMR (¹H, ¹³C and ³¹P) spectroscopy and elemental analysis. The molecular structure of complex 2, as confirmed by X-ray crystallography, reveals that the Pd atom and its neighboring groups (two PPh₃, Br and phenylene group) lie in a slightly distorted square plane. In the UV–Vis spectra of the complexes 1 and 2, the palladium to aryl charge transfer bands were observed. The emission peaks from the singlet excited states (S₁ → S₀) were observed in the photoluminescence spectra of the complexes. The thermal stability of the complexes has been studied by thermal gravimetric analysis (TGA). TGA data showed that both complexes are thermally stable up to 200 °C, and complex 1 is more stable than 2. The catalytic efficiency of the new palladium(II) complexes was studied as demonstrated using the Sonogashira coupling reactions with good yields. The experimental results suggest that the Sonogashira coupling reactions can be performed at moderate temperature (50 °C) using these new palladium(II) complexes as catalysts.     

Influence of the microstructure of gums on the mechanical properties of silicone high consistency rubbers

This paper is devoted to the characterization and processing of high molar mass vinyl‐bearing polysiloxanes in high consistency silicone rubber (HCR) formulations. The molar masses of five different polydimethylsiloxane gums, bearing vinyl groups at the ends and along their chains, were evaluated by size exclusion chromatography and rheometry. ²⁹Si and ¹H NMR spectroscopy allowed the precise determination of the vinyl content and of the distribution in the different polymers. Typical HCRs formulated from these gums were heat‐cured to process silicone rubber materials that were then tested mechanically. The macromolecular properties were correlated to the final material network structure. The amount of reactive vinyl moieties, rather than their distribution along or at the end of chains, is a key parameter to tailor the material mechanical properties. © 2016 Society of Chemical Industry     

两层浆砌块模型房屋动力特性试验研究

本文介绍两层免浆砌块房屋模型动力特性试验情况及测试数据分析结果。为模型地震反应试验并判定结构减震性能提供试验依据。