Thermal and optical properties of highly fluorinated copolymers of methacrylates

Copolymers of pentafluorophenylhexafluoroisopropyl methacrylate (FPPMA) with trifluoroethyl methacrylate (TFEMA) were prepared in THF solution and in bulk using azobisisobutyronitrile as a free radical initiator. The monomer reactivity ratios of TFEMA (M₁) and FPPMA (M₂) were calculated as r₁ = 0.55 and r₂ = 0.07. The refractive indices of poly(TFEMA) and poly(FPPMA) are very similar as 1.435 and 1.430, respectively, at 532 nm, and the copolymer films were transparent. The glass transition temperatures (T_g) of the copolymers were in the range of 80–90°C and showed a negative deviation from the Gordon–Taylor equation. The thermal decomposition temperature (T_d) was increased with the content of FPPMA in copolymers. Low water absorption for 1:1 FPPMA/TFEMA copolymer was detected. Copolymers of FPPMA with hexafluoroisopropyl methacrylate (HFPMA) were also prepared. The monomer reactivity ratios of HFPMA (M₁) and FPPMA (M₂) were calculated as r₁ = 0.43 and r₂ = 0.10. The T_gs of the copolymers were in the range of 88–95°C and showed also a negative deviation from the Gordon–Taylor equation. T_g and T_d of the copolymers were increased with the content of FPPMA. The refractive index of poly(HFPMA) (1.384 at 532 nm) is much lower than that of FPPMA homopolymer, but copolymer films obtained were clear and transparent. Copyright © 2013 John Wiley & Sons, Ltd.     

DSC分析及原位FT-IR法对聚合物接枝碳纳米管/环氧树脂固化体系的固化反应的研究

合成了一种扩链脲修饰的多壁碳纳米管(MWCNT-PEG-TU),差示扫描量热分析(DSC)结果表明,MWCNT-PEG-TU可明显提高E-51环氧树脂/双氰双胺(DICY)固化体系的固化反应活性。利用原位傅里叶变换红外光谱(in situ FT-IR)法研究了MWCNT-PEG-TU/E-51环氧树脂/DICY固化体系的等温固化动力学,该固化体系在不同温度下的dα/dt与α的关系曲线较好地符合Kamal自催化反应模型。     

IPET:测定独个生物大分子三维空间结构的实验方法

蛋白质的动态特性和结构活性对于蛋白质功能的调控具有根本意义。传统的结构确定方法(包括X射线和电子显微镜单颗粒分析技术等)往往需要成千上万不同蛋白质分子的平均信号,因此难以确定蛋白质分子的动态结构。而电子显微断层成像技术是一种对独个生物个体结构从不同的观测角度照相、并计算来恢复该个体的三维结构密度图的方法。传统的冷冻电子断层成像重构方法采用整个大尺寸电镜图像进行重构计算,通常用来研究细菌、细胞切片等大尺寸生物个体在较低分辨率下的结构;由于分辨率的限制,不足以获得小尺寸的蛋白质分子的结构细节。最近,任罡研究小组提出一种独个生物颗粒的电子显微断层成像方法(individual-particle electron tomography,IPET)。该方法通过减小图像尺寸(直至所选区域只包含单个蛋白质分子)的策略,运用提出的FETR(focused electron tomography reconstruction)算法来提高独个大分子重构的分辨率。此方法不需要初始模型和大量分子的平均信号,同时能够容忍一定的测角误差。本文综述了IPET/FETR方法在确定独个分子结构过程中的具体步骤以及如何应用该方法来研究蛋白动态特性和结构变化特征。期望通过该综述和国内同行交流,分享最新的前沿研究,为赶超世界科技前沿的建设添砖加瓦。     

Optimization of microwave‐assisted extraction for anthocyanins,polyphenols, and antioxidants from raspberry (Rubus Coreanus Miq.) using response surface methodology

Anthocyanins (Acys), polyphenols, and antioxidants were extracted from raspberry (Rubus Coreanus Miq.) using a highly efficient microwave‐assisted extraction technique. Different solvents, including methanol, ethanol, and acetone, were tested. The colors of the extracts varied from light yellow to purple red or dark red. SEM and other nutrient analyses verified that ethanol was the most favorable medium for the microwave‐assisted extraction of raspberry due to its high output and low toxicity. Effects of process parameters, including microwave power, irradiation time, and solvent concentration, were investigated through response surface methodology. Canonical analysis estimated that the highest total Acys content, total polyphenols content, and antioxidant activity of raspberry were 17.93 mg cyanidin‐3‐O‐glucoside equivalents per gram dry weight, 38.57 mg gallic acid equivalents per gram dry weight, and 81.24%, respectively. The polyphenol compositions of raspberry extract were identified by HPLC with diode array detection, and nine kinds of polyphenols were identified and quantified, revealing that chlorogenic acid, syringic acid, and rutin are the major polyphenols contained in raspberry fruits. Compared with other fruits and vegetables, raspberry contains higher Acy and polyphenol contents with stronger antioxidant activity, suggesting that raspberry fruits are a good source of natural food colorants and antioxidants.     

Ligand‐Functionalization of BPEI‐Coated YVO4:Bi3+,Eu3+ Nanophosphors for Tumor‐Cell‐Targeted Imaging Applications

In this study, surface‐functionalized, branched polyethylenimine (BPEI)‐modified YVO₄:Bi³⁺,Eu³⁺ nanocrystals (NCs) were successfully synthesized by a simple, rapid, solvent‐free hydrothermal method. The BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs with high crystallinity show broad‐band excitation in the λ=250 to 400 nm near‐ultraviolet (NUV) region and exhibit a sharp‐line emission band centered at λ=619 nm under excitation at λ=350 nm. The surface amino groups contributed by the capping agent, BPEI, not only improve the dispersibility and water/buffer stability of the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs, but also provide a capability for specifically targeted biomolecule conjugation. Folic acid (FA) and epidermal growth factor (EGF) were further attached to the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs and exhibited effective positioning of fluorescent NCs toward the targeted folate receptor overexpressed in HeLa cells or EGFR overexpressed in A431 cells with low cytotoxicity. These results demonstrate that the ligand‐functionalized, BPEI‐coated YVO₄:Bi³⁺, Eu³⁺ NCs show great potential as a new‐generation biological luminescent bioprobe for bioimaging applications. Moreover, the unique luminescence properties of BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs show potential to combine with a UVA photosensitizing drug to produce both detective and therapeutic effects for human skin cancer therapy.     

Collagen and collagen mimetic peptide conjugates in polymer science

Collagen, the most abundant protein in animal kingdom, has attracted scientists in supramolecular chemistry, biomedical and materials science. This review describes the recent developments and progress of collagen mimetic peptide based materials. Research on collagen mimetic peptides was initially developed by biochemists to elucidate the structure and stability of collagen, followed by biologists and polymer chemists to produce nanostructured fibrous scaffolds with collagen mimetic peptides as the building blocks. Modern synthesis methods have been developed and particular ligation chemistries basing on activated ester, click chemistry, carbodiimide chemistry or other ligation chemistries provide versatile methods to prepare collagen–polymer conjugates. These conjugates with collagen mimetic peptides as the building blocks show exciting stimuli responsive or spontaneously assembly behavior. The corresponding synthetic techniques of well-defined collagen architectures and assembly behaviors are discussed in detail in the present review.     

Vitrifolin A: A Norlabdane Diterpenoid from the Fruits of Vitex trifolia Linn. var. simplicifolia Cham

A new norlabdane diterpenoid, named vitrifolin A, was isolated from the fruits of Vitex trifolia Linn. var. simplicifolia Cham. Its structure was elucidated by mean of spectroscopic methods, including HRESIMS, IR, 1D and 2D NMR. The inhibitory effect of vitrifolin A on nitric oxide production in lipopolysaccarideactivated mouse macrophages was also evaluated.     

Non-enzymatic hydrogen peroxide sensor based on a gold electrode modified with granular cuprous oxide nanowires

Granular nanowires with a diameter of about 60 nm were fabricated from cuprous oxide (Cu₂O) by an electrochemical method using anodic aluminium oxide as the template. A non-enzymatic sensor for hydrogen peroxide (H₂O₂) was then developed on the basis of a gold electrode modified with Cu₂O nanowires and Nafion. The resulting sensor enables the determination of H₂O₂ with a sensitivity of 745 μA?mM^?1?cm^?2, over a wide linear range (0.25 μM to 5.0 mM), and with a low detection limit (0.12 μM). The results demonstrate that the use of such granular nanowires provides a promising tool for the design of non-enzymatic chemical sensors.