pH‐Dependent Nitrotyrosine Formation in Ribonuclease A is Enhanced in the Presence of Polyethylene Glycol (PEG)

Protein nitration can occur as a result of peroxynitrite‐mediated oxidative stress. Excess production of peroxynitrite (PN) within the cellular medium can cause oxidative damage to biomolecules. The in vitro nitration of Ribonuclease A (RNase A) results in nitrotyrosine (NT) formation with a strong dependence on the pH of the medium. In order to mimic the cellular environment in this study, PN‐mediated RNase A nitration has been carried out in a crowded medium. The degree of nitration is higher at pH 7.4 (physiological pH) compared to pH 6.0 (tumor cell pH). The extent of nitration increases significantly when PN is added to RNase A in the presence of crowding agents PEG 400 and PEG 6000. PEG has been found to stabilize PN over a prolonged period, thereby increasing the degree of nitration. NT formation in RNase A also results in a significant loss in enzymatic activity.     

{110}晶面取向Ag3PO4多面体的水热制备及可见光催化活性

采用简易水热法在聚乙二醇-6000 (PEG-6000)辅助下合成了Ag₃PO₄多面体.系统考察了水热反应温度、时间及PEG-6000用量对产物形貌和结构的影响.通过X射线衍射(XRD),扫描电子显微镜(SEM),紫外-可见漫反射光谱(UV-Vis DRS)和荧光(PL)光谱等测试手段对光催化剂进行了表征.结果表明,适宜的水热温度及PEG-6000用量是制备具有{110}活性晶面取向Ag₃PO₄多面体的必要条件,该多面体通过纳米颗粒的Ostwald熟化效应生长而成.可见光催化降解罗丹明B (RhB)的实验表明,该Ag₃PO₄多面体活性明显优于其它水热条件下所制备的非{110}取向晶面样品和离子交换法所得纳米颗粒,其降解反应速率常数(k)为离子交换法所得Ag₃PO₄纳米颗粒的8.3倍.总有机碳含量(TOC)及循环实验证明,该Ag₃PO₄多面体可以有效地矿化RhB并保持较好的循环稳定性.活性自由基捕获实验表明,空穴(h⁺)和羟基自由基(·OH)是光催化氧化的主要活性物种.结合活性物种的氧化还原电位以及Ag₃PO₄的能带结构分析,提出了催化反应界面光生电子-空穴(e^--h⁺)对的分离及转移机制.     

锂离子液体作为聚乙二醇添加剂的摩擦学性能研究

利用2-恶唑烷酮(OZO)、尿素、三乙二醇二甲醚(G3)和四乙二醇二甲醚(G4)与四氟硼酸锂(LiBF4)、六氟磷酸锂(LiPF6)、三氟甲烷磺酸锂(LiSO3CF3)和双(三氟甲烷磺酰)亚胺锂(LiTFSI)的配位作用,在聚乙二醇(PEG)中合成了一系列锂离子液体润滑油添加剂,如[Li(OZO)]BF4、[Li(OZO)] PF6、[Li(OZO)]SO3CF3和[Li(OZO)] TFSI等,并对其物理化学性质和摩擦学性能进行了研究.结果显示:这类离子液体在PEG中具有较好的溶解性,作为PEG的添加剂,显示出优于传统离子液体(1-丁基-3-甲基咪唑双三氟甲烷磺酰亚胺盐)的减磨抗磨性能;阳离子对这一系列离子液体添加剂的摩擦学性能影响不明显,以TFSI-为阴离子的离子液体表现出最好的减摩性能.     

PEG-6000对Mn-Zn铁氧体纳米粉体烧结特性的影响

利用化学共沉淀回流法制备Mn-Zn铁氧体纳米粉体的过程中,加入适量PEG-6000,试图通过在纳米颗粒表面形成一保护层以起到抑制其团聚的目的.研究结果表明,PEG-6000的加入不仅减小了纳米粒子的尺寸,还有效缓解了它们的团聚.将这些纳米Mn-Zn铁氧体粉体进行成型烧结,材料的起始磁导率随烧结温度的升高呈抛物线规律变化,并于1200 ℃达到最大值.而且添加PEG-6000的样品起始磁导率比未添加的提高了约20;.导致这一变化的原因应归咎于纳米粉体稳定性的改善以及烧结后材料内部组织均匀度的提高和晶粒尺寸的减小.     

晶硅片切割用水基切割液摩擦学性能的研究

重点研究了晶硅片切割用水基切割液中润滑剂的摩擦性能影响因素.选用低分子量的聚乙二醇(PEG)作为润滑剂,研究了不同分子量PEG作为润滑剂的摩擦学性能.在使用PEG300作为水基切割液润滑剂的情况下,相比纯水可减小硅片表面的粗糙度达86.51;;磨损体积可以减少50;,磨损表面磨屑变少.     

Size- and Surface- Dual Engineered Small Polyplexes for Efficiently Targeting Delivery of siRNA

Though siRNA-based therapy has achieved great progress, efficient siRNA delivery remains a challenge. Here, we synthesized a copolymer PAsp(-N=C-PEG)-PCys-PAsp(DETA) consisting of a poly(aspartate) block grafted with comb-like PEG side chains via a pH-sensitive imine bond (PAsp(-N=C-PEG) block), a poly(l-cysteine) block with a thiol group (PCys block), and a cationic poly(aspartate) block grafted with diethylenetriamine (PAsp(DETA) block). The cationic polymers efficiently complexed siRNA into polyplexes, showing a sandwich-like structure with a PAsp(-N=C-PEG) out-layer, a crosslinked PCys interlayer, and a complexing core of siRNA and PAsp(DETA). Low pH-triggered breakage of pH-sensitive imine bonds caused PEG shedding. The disulfide bond-crosslinking and pH-triggered PEG shedding synergistically decreased the polyplexes’ size from 75 nm to 26 nm. To neutralize excessive positive charges and introduce the targeting ligand, the polyplexes without a PEG layer were coated with an anionic copolymer modified with the targeting ligand lauric acid. The resulting polyplexes exhibited high transfection efficiency and lysosomal escape capacity. This study provides a promising strategy to engineer the size and surface of polyplexes, allowing long blood circulation and targeted delivery of siRNA.     

Influence of poly(ethylene glycol) on the partition of a charged spin probe

The influence of poly(ethylene glycol) on the partition of a charged long chain spin probe between membranes and an external phase is studied. The partition coefficient is derived from the ESR spectra. Membranes of different properties are used (egg lecithin liposomes, erythrocytes) to differentiate between the influence of the external phase and the specific properties of the membrane.The partition coefficient is decreased in an exponential manner on increasing the PEG concentration, which indicates a lowering of the thermodynamic stability of the membranes. The determination of the change in the difference of the chemical potential is dependent on the PEG concentration.The membrane destabilization induced by PEG is caused in an indirect manner by a change of the chemical potential difference as result of the changed water structure and the osmotic pressure, surface tension and hydration of the membrane. This destabilization could be connected with the high fusogenic activity of PEG.     

Chromatography of glycols. Regularities in the retention of C3−C6 branched glycols in gas-solid and gas-liquid chromatography

Summary Linear correlation between the major physico-chemical properties of glycols and their relative retention volumes measured by gas-solid (GSC) and gas-liquid (GLC) chromatography is shown. The coefficients of the linear regression equations describing the relationship between the relative retention volumes and the physico-chemical parameters (boiling point, density, etc.) are given. The values of the change in the free energy for the stationary phases studied are given as well as the increments of this change per −CH₂- and CH₃-group. The main factors determining the retention of branched glycols on Polysorb, Tween and poly(ethylene glycol) are shown to be the distance between the hydroxyl groups in their molecules, the presence of alkyl substituents and the type and the number of these substituents.     

On the ionic conductivity of polymer electrolytes in terms of hole fraction

A theoretical model to interpret the conductivity of ions through polymer electrolytes is established in terms of the temperature and pressure‐dependent hole fraction computed from Simha‐Somcynsky hole theory. The model successfully linearizes the logarithm of PPG and PEG conductivity data with NaCF₃SO₃ in a 20:1 ratio for a broad range of temperature and pressure. The conductivity parameter and transmission coefficient with an additive hole fraction constant are discussed and compared for both species. The derivative of the logarithm of conductivity with respect to the hole fraction decreases inversely with the hole fraction and saturates at about 0.08 and 0.12 hole fractions for PPG and PEG, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2249–2254, 2008     

Thermogelling behaviors of poly(caprolactone‐b‐ethylene glycol‐b‐caprolactone) triblock copolymer in the presence of hyaluronic acid

In this article, we studied the effect of hyaluronic acid (HA) on thermogelation of poly(caprolactone‐b‐ethylene glycol‐b‐caprolactone) (PCL‐PEG‐PCL) aqueous solution designed as an injectable system for prevention of postsurgical tissue adhesion. The PCL‐PEG‐PCL triblock copolymers were simply synthesized by ring‐opening polymerization of ε‐caprolactone (CL) in the presence of PEG as a polymeric initiator. The synthesized copolymers were confirmed by proton nuclear magnetic resonance (¹H‐NMR) spectroscopy. Possible interactions between HA and PCL‐PEG‐PCL triblock copolymers in the blend were evaluated by Fourier‐transform infrared spectroscopy (FTIR). The effect of HA on the micellization of PCL‐PEG‐PCL aqueous solution was investigated by dye solubilization method and electrophoretic lighting scattering (ELS) spectrophotometer. Also, the thermogelling behaviors of the PCL‐PEG‐PCL triblock copolymers in the presence of HA and their mechanism were investigated by test tube inverting method, ¹³C‐NMR, ¹H‐NMR, Advanced Rheometic Expansion System (ARES), and differential scanning calorimetry (DSC). The PCL‐PEG‐PCL/HA blend aqueous solutions undergo the sol‐gel‐sol transition in response to an increase in temperature (10–60 °C) and the gelation of the PCL‐PEG‐PCL was rather accelerated by HA. Presumably, this accelerated gelation seems to arise from the attractive interactions between them and the effect of chain confinement in the micelle corona region. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3629–3637, 2008