The effect of the trifluoropropyl group in polysiloxane stationary phases used for capillary gas chromatography

Four poly(methyl 3,3,3-trifluoropropyl siloxanes) with trifluoro-propyl group content (group substitution) between 8 and 35 percent have been synthesized and characterized as stationary phases for gas chromatography in borosilicate glass capillary columns. Results are compared with those from two commercial stationary phases–a polydimethylsiloxane and a poly(methyl 3,3,3-trifluoropropyl siloxane) with a fifty percent trifluoropropyl group content (group substitution). Retention index values, McReynolds constants, polarity (as defined by McReynolds) and retention polarity (as defined by Takács) increase regularly with the trifluoropropyl group content of the stationary phase. The temperature coefficient of the retention indices of the McReynolds probes, and that of the polarities, have been determined at temperatures between 60 and 180 °C. Specific retention volumes do not follow the linear dependence on trifluoropropyl group content observed for retention indices or polarities. Substances with electron-donor groups show maximum retention for a trifluoropropyl group content of ca 30%, whereas the retention of hydrocarbons, halogenated compounds, and alcohols decreases as the degree of trifluoropropyl group substitution increases from 0 to 50%. It is felt that a polysiloxane with a trifluoropropyl group content of ca 30 to 35% would be the best choice for the separation of ketones, nitro compounds or amines.     

Oxidation resistant germanium nanowires: bulk synthesis, long chain alkanethiol functionalization, and Langmuir-Blodgett assembly

A simple method is developed to synthesize gram quantities of uniform Ge nanowires (GeNWs) by chemical vapor deposition on preformed, monodispersed seed particles loaded onto a high surface area silica support. Various chemical functionalization schemes are investigated to passivate the GeNW surfaces using alkanethiols and alkyl Grignard reactions. The stability of functionalization against oxidation of germanium for various alkyl chain lengths is elucidated by X-ray photoelectron spectroscopy. Among all schemes tested, long chain alkanethiols (> or = C12) are found to impart the most stable GeNW passivation against oxidation upon extended exposure to ambient air. Further, the chemically functionalized oxidation-resistant nanowires are soluble in organic solvents and can be readily assembled into close-packed Langmuir-Blodgett films potentially useful for future high performance electronic devices.     

Microfluidic three-dimensional biomimetic tumor model for studying breast cancer cell migration and invasion in the presence of interstitial flow

Cell migration and invasion are critical steps in cancer metastasis, which are the major cause of death in cancer patients. Tumor-associated macrophages(TAMs) and interstitial flow(IF) are two important biochemical and biomechanical cues in tumor microenvironment, play essential roles in tumor progression. However, their combined effects on tumor cell migration and invasion as well as molecular mechanism remains largely unknown. In this work, we developed a microfluidic-based 3 D breast cancer model by co-culturing tumor aggregates, macrophages, monocytes and endothelial cells within 3 D extracellular matrix in the presence of IF to study tumor cell migration and invasion. On the established platform, we can precisely control the parameters related to tumor microenvironment and observe cellular responses and interactions in real-time. When co-culture of U937 with human umbilical vein endothelial cells(HUVECs) or MDA-MB-231 cells and tri-culture of U937 with HUVECs and MDA-MB-231 cells, we found that mesenchymal-like MDA-MB-231 aggregates activated the monocytes to TAM-like phenotype macrophages. MDA-MB-231 cells and IF simultaneously enhanced the macrophages activation by the stimulation of colony-stimulating factor 1(CSF-1). The activated macrophages and IF further promoted vascular sprouting via vascular endothelial growth factor(VEGFα) signal and tumor cell invasion. This is the first attempt to study the interaction between macrophages and breast cancer cells under IF condition. Taken together, our results provide a new insight to reveal the important physiological and pathological processes of macrophages-tumor communication. Moreover, our established platform with a more mimetic 3 D breast cancer model has the potential for drug screening with more accurate results.     

ATMP(氨基三甲叉膦酸)及其顺磁性Co(Ⅱ)配合物的核磁共振研究

本文用¹H、³¹P和¹³C核磁共振谱研究了ATMP(氨基三甲叉膦酸,以简式H₆L表示)及其顺磁性Co(Ⅱ)配合物。测定了不同C_co/C_ATMP摩尔比在不同pH值下的各向同性位移。定性地讨论顺磁性Co(Ⅱ)配合物在不同pH条件下的组成、电荷和空间构型变化对化学位移的影响。运用快速交换反应中化学位移与配合物浓度的关系,确定不同pH下的条件稳定常数。     

直接硼氢化物燃料电池

直接硼氢化物燃料电池是一种新型的燃料电池,具有理论比能量高,产物清洁无污染,燃料易于储存和运输等特点,可广泛应用于小型便携式电子产品和移动电源,近年来受到越来越多研究者的关注。本文在介绍了直接硼氢化物燃料电池工作原理的基础上讨论了阳极催化剂、阴极催化剂的研究进展,并探讨了电解液和温度等条件对电池性能的影响,简要分析了发展直接硼氢化物燃料电池面临的主要问题。     

有机铋化学近十年的研究进展

铋及其化合物具有相对价廉、低毒性、低放射性等特点,已应用于医药、催化、化妆品和电子技术等领域。本文回顾了近10多年来有机铋化学的研究状况,主要从以下4个方面进行综述：（1）新型有机铋化合物的合成途径与结构特征;（2）有机铋化合物作为交联偶合、氧化、芳基化和其它反应的试剂;（3）作为催化剂;（4）作为生物医药用于溃疡、肿瘤和放射治疗等。文中着重于从分子水平关联新型有机铋化合物的结构与其化学和生物活性之间关系。此外,还介绍了有机铋化学研究领域的不足和今后的发展趋势。     

非晶态固体的结构可以决定性能吗?

晶态固体的力学性能与塑性变形主要由结构缺陷,比如位错的运动决定.而在非晶态固体中结构如何决定性能,仍然是固体力学、材料学和凝聚态物理学共同关心但尚未解决的核心问题之一.传统材料学研究的经典范式为"结构决定性能".遵循这一信条,已经有大量的实验表征与理论、模拟研究,尝试将非晶态固体的某种结构特征与性能建立一一对应关系.但是,科学界对于非晶固体结构-性能关系成立与否,以及背后隐藏的规律知之甚少.本文针对非晶态固体的变形机制以及其微结构特征,基于分子动力学模拟,定量评估短程简单结构与中长程复杂结构在决定非晶态固体动力学性能方面的效用.通过海量抽样每种具体玻璃结构的激活能(标识激发难易程度),尝试将结构参数与激活能建立定量关系,从而揭示出非晶态固体结构-性能关系的隐藏主控因素为结构的空间关联,受限比几何结构本身更关键.只有某种结构在空间上呈现亚纳米级的空间关联长度,这种完备结构才有可能有效地决定非晶态固体的力学性能,而短程简单结构则无效.进一步,给出了评价非晶态固体结构预测性能有效性的普适定量方法,为建立广义无序物质的结构-性能关系提供了筛选准则.     

A Novel Ternary Composite of Polyurethane/Polyaniline/Nanosilica with Antistatic Property and Excellent Mechanical Strength: Preparation and Mechanism

Chinese Journal of Polymer Science - Antistatic and strength properties are of vital importance for polyurethane rubber used in moving parts of many industrial instruments. Herein, polyurethane was...     

Metal-Free Phosphination and Continued Functionalization of Pyridine: A Theoretical Study

This study investigates the mechanism of metal-free pyridine phosphination with P(OEt)₃, PPh₃, and PAr₂CF₃ using density functional theory calculations. The results show that the reaction mechanism and rate-determining step vary depending on the phosphine and additive used. For example, phosphination of pyridine with P(OEt)₃ occurs in five stages, and ethyl abstraction is the rate-determining step. Meanwhile, 2-Ph-pyridine phosphination with PPh₃ is a four-step reaction with proton abstraction as the rate-limiting step. Energy decomposition analysis of the transition states reveals that steric hindrance in the phosphine molecule plays a key role in the site-selective formation of the phosphonium salt. The mechanism of 2-Ph-pyridine phosphination with PAr₂CF₃ is similar to that with PPh₃, and analyses of the effects of substituents show that electron-withdrawing groups decreased the nucleophilicity of the phosphine, whereas aryl electron-donating groups increased it. Finally, TfO⁻ plays an important role in the C–H fluoroalkylation of pyridine, as it brings weak interactions.     

Simultaneous treatment with sorafenib and glucose restriction inhibits hepatocellular carcinoma in vitro and in vivo by impairing SIAH1-mediated mitophagy

Transarterial chemoembolization (TACE) is the first-line treatment for unresectable intermediate-stage hepatocellular carcinoma (HCC). It is of high clinical significance to explore the synergistic effect of TACE with antiangiogenic inhibitors and the molecular mechanisms involved. This study determined that glucose, but not other analyzed nutrients, offered significant protection against cell death induced by sorafenib, as indicated by glucose deprivation sensitizing cells to sorafenib-induced cell death. Next, this synergistic effect was found to be specific to sorafenib, not to lenvatinib or the chemotherapeutic drugs cisplatin and doxorubicin. Mechanistically, sorafenib-induced mitophagy, as indicated by PINK1 accumulation, increased the phospho-poly-ubiquitination modification, accelerated mitochondrial membrane protein and mitochondrial DNA degradation, and increased the amount of mitochondrion-localized mKeima-Red engulfed by lysosomes. Among several E3 ubiquitin ligases tested, SIAH1 was found to be essential for inducing mitophagy; that is, SIAH1 silencing markedly repressed mitophagy and sensitized cells to sorafenib-induced death. Notably, the combined treatment of glucose restriction and sorafenib abolished ATP generation and mitophagy, which led to a high cell death rate. Oligomycin and antimycin, inhibitors of electron transport chain complexes, mimicked the synergistic effect of sorafenib with glucose restriction to promote cell death mediated via mitophagy inhibition. Finally, inhibition of the glucose transporter by canagliflozin (a clinically available drug used for type-II diabetes) effectively synergized with sorafenib to induce HCC cell death in vitro and to inhibit xenograft tumor growth in vivo. This study demonstrates that simultaneous treatment with sorafenib and glucose restriction is an effective approach to treat HCC, suggesting a promising combination strategy such as transarterial sorafenib-embolization (TASE) for the treatment of unresectable HCC.Subject terms: Liver cancer, Mitophagy, Apoptosis