肾上皮细胞损伤使草酸钙晶体黏附增强的分子机制

研究了非洲绿猴肾上皮细胞(Vero)在损伤前后与一水合草酸钙(COM)和二水合草酸钙(COD)晶体的黏附作用及其引起的细胞反应,探讨了肾结石形成机理.COM和COD晶体与损伤细胞的黏附加重了细胞的过氧化损伤程度,导致损伤细胞的活力进一步降低,乳酸脱氢酶(LDH)释放量和活性氧(ROS)进一步增加,坏死细胞数量进一步增多,细胞体积缩小,并出现凋亡小体.COM晶体对细胞的损伤能力显著大于COD晶体.扫描电子显微镜(SEM)观测结果表明,损伤组Vero与COM微晶的黏附作用显著强于对照组,且能促进COM微晶的聚集.共聚焦显微镜观测结果表明,Vero损伤后,其表面表达的晶体黏附分子透明质酸(HA)显著增加,HA分子是促进微晶黏附的重要原因.细胞表面草酸钙的黏附量和晶体聚集程度与细胞的损伤程度成正相关.本文结果从分子和细胞水平上提示,细胞损伤是导致草酸钙肾结石形成的重要因素.     

缺陷LB膜诱导草酸钙晶体环图形形成

利用存在缺陷的LB膜来模拟受损伤的肾上皮细胞膜, 研究了膜缺陷的微结构及其影响一水草酸钙(COM)晶体成核、生长、沉积图形和黏附的分子机制. 二棕榈酰磷脂酰胆碱(DPPC)LB膜经草酸钾处理后可形成圆形缺陷, 并诱导COM微晶排列成环状图形, 相比之下, 没有经草酸钾处理的LB膜只诱导零散的六边形COM晶体生成. 随着生长时间增加, 环内单个COM晶体的尺寸明显增加, 空心的环状晶体图形倾向于转变为实心的圆形图形, 且小尺寸(5~20 mm)的圆形晶体图案数量增加. 本结果有助于在分子和超分子的水平上进一步了解肾上皮细胞膜损伤后诱导肾结石形成的分子机制.     

HKC细胞损伤对草酸钙晶体成核和聚集的促进作用

采用H2O2对人肾小管上皮细胞(HKC)进行损伤. HKC损伤后,其活力降低,并表达骨桥蛋白(OPN). 损伤细胞促进草酸钙晶体的成核、聚集,并促进一水草酸钙(COM)晶体的形成,但对晶体生长的促进作用不明显. 本文结果提示,HKC细胞损伤后增加了肾结石形成的危险性.     

LB膜中的缺陷畴区及其诱导形成环形草酸钙图形

利用存在缺陷的LB膜来模拟受损伤的肾上皮细胞膜诱导肾结石矿物草酸钙(CaOxa)晶体生长. 经2.5 mmol·L-1的草酸钾溶液对二棕榈酰磷脂酰胆碱(DPPC)的LB膜进行处理后, 可强化LB膜中液态扩张相(LE)和液态凝聚相(LC)之间的结构差异, 原子力显微镜(AFM)证实了圈状缺陷的存在. 以LB膜的圈状缺陷为模板, 诱导了一水草酸钙(COM)晶体环状图案. 相比之下, 未经草酸钾处理的LB膜只诱导生成零散的六边形COM晶体.     

缺陷LB膜诱导草酸钙晶体的生长

肾结石形成与肾上皮细胞膜损伤密切相关, 但细胞膜损伤后的微结构及其与肾结石微晶粘附的分子机制仍不清楚. 本文采用经草酸钾处理后存在缺陷的二棕榈酰磷酯酰胆碱(DPPC)的LB膜为模型, 采用原子力显微镜(AFM)、荧光显微镜和扫描电子显微镜(SEM)研究了模型膜的缺陷畴区及其对一水草酸钙(COM)晶体生长的促进作用. LB膜内圆形的缺陷畴区可以诱导圆形COM晶体图形生成, 圆形晶体图形的直径从3 mm到150 mm不等. 在圆形区域内, 单个COM晶体的尺寸大都在1～3 μm, 以针状、四边形或不规则的形状存在; 而在同等条件下正常LB膜诱导的COM晶体没有圆形聚集现象, 单个COM晶体在LE/LC相边界生长, 其尺寸显著增加至5～10 mm. 不同性质LB膜促进COM成核和生长的强弱依次为: 经草酸钾处理的LB膜缺陷畴区>>正常LB膜的LC/LE边界＞正常LB膜非边界区域>>无膜诱导. 从缺陷LB膜的活性位点及其对COM晶体成核的促进作用等方面讨论了上述实验结果.     

修复前后Vero细胞调控草酸钙晶体生长的差异

采用扫描电子显微镜(SEM)和流式细胞仪等多种方法研究了降解大豆多糖(SPS)对损伤的非洲绿猴肾上皮细胞(Vero)的修复作用;研究了修复前后Vero调控草酸钙(CaOxa)晶体形成的差异。经H2O2氧化损伤的Vero在被SPS修复后,其细胞活力、细胞外SOD活性及细胞内线粒体膜电位均增加,细胞形态逐渐恢复到接近正常细胞。在诱导草酸钙(CaOxa)晶体生长过程中,修复细胞可以减少棱角尖锐的一水草酸钙(COM)晶体生成,诱导更多的二水草酸钙(COD)晶体。三种状态Vero诱导的晶体尺寸从小到大顺序为:正常细胞<修复细胞<损伤细胞。本文结果表明,降解大豆多糖可以修复受损伤的Vero细胞,降低肾结石形成的危险性,提示SPS有可能是一种潜在的绿色防石药物。     

不同羧基含量广金钱草多糖对草酸钙晶体生长、聚集及细胞表面黏附的抑制作用

为了探讨羧基化前后广金钱草多糖(DSPs)对草酸钙(CaC₂O₄)晶体成核、生长和聚集的调控作用,采用FTIR、粉末X射线衍射、扫描电镜、ζ电位和热重分析(TGA)等方法,对具有不同羧基(—COOH)含量(质量分数)的 DSPs调控形成的 CaC₂O₄晶体进行表征,比较了各DSPs对纳米一水合草酸钙(nano-COM)损伤后HK-2细胞(人肾近端曲小管上皮细胞)表面的黏附分子的表达差异和nano-COM在细胞表面的黏附差异。结果表明,DSPs均可抑制COM晶体生长,并诱导二水合草酸钙(COD)晶体形成,同时增加CaC₂O₄晶体表面的ζ电位绝对值,抑制晶体间的聚集。随着多糖中—COOH含量从1.17%增加至7.45%、12.2%和17.7%,相应的多糖 DSP0、DSP1、DSP2 和 DSP3 对 CaC₂O₄晶体生长的调控能力依次增强。TGA 表明晶体中吸附有多糖,在 0.2 g·L^-1DSPs存在下,掺入晶体中的DSP0、DSP1、DSP2和DSP3的质量分数分别为1.54%、2.94%、7.96%和8.12%。细胞实验表明,DSPs可显著降低 HK-2 细胞表面黏附分子 CD44 和 Annexin A2 的表达,并减少 nano-COM 在细胞表面的黏附量。DSPs 能够抑制CaC₂O₄晶体成核、聚集、生长及其在肾上皮细胞表面的黏附,这些均有利于抑制CaC₂O₄肾结石的形成,其中羧基化程度最高的DSP3的能效最佳。     

草酸钾诱导的LB膜缺陷及对草酸钙堆积图形的影响

采用扫描电子显微镜(SEM)和原子力显微镜(AFM)研究了经不同浓度草酸钾(K2C2O4)处理后二棕榈酰磷酯酰胆碱(DPPC)的缺陷LB膜及其对一水草酸钙(COM)成核和生长的影响. K2C2O4的处理可进一步破坏LB膜中圆形畴区内的分子列阵, 尤其是使处在液态扩张相(LE)/液态凝集相(LC)边界的分子列阵无序程度增加, 从而促进了COM晶体在此处的成核和生长, 最终诱导圆形堆积的COM晶体图形出现. 随着损伤LB膜的K2C2O4浓度c(K2C2O4)从0.3 mmol/L增加到5.0 mmol/L, 其对LB膜畴区有序结构的破坏作用逐渐增强, 圈状堆积的晶体图形数量增多. 当c(K2C2O4)为0.3 mmol/L时, 主要诱导实心的圆形堆积的COM晶体图形, 而当c(K2C2O4)增加至5.0 mmol/L时, 生成圈状COM晶体图形, 且图形的半径减小. 这一研究结果将有助于从分子和超分子水平上了解肾小管上皮细胞膜损伤后的微结构变化及其与肾结石形成的关系.     

HKC细胞损伤前后对草酸钙晶体吞噬能力的差异

采用人类肾脏近端小管上皮细胞系(HKC)建立氧化性损伤模型,研究损伤前后HKC调控草酸钙(CaOxa)结晶的差异。采用CCK-8法检测HKC的细胞活性;利用激光共聚焦显微镜观察HKC损伤后表达的晶体粘附分子骨桥蛋白(OPN);采用倒置显微镜观察HKC的形态变化;采用扫描电子显微镜(SEM)观察HKC微结构及其诱导的晶体;采用X射线衍射分析(XRD)表征晶体的组分。在CaOxa过饱和溶液中,正常HKC主要诱导形成二水草酸钙(COD)晶体,而损伤HKC则同时诱导了COD和一水草酸钙(COM)晶体。正常HKC对COD晶体有较强的吞噬能力,而损伤HKC的这种能力较弱;HKC损伤后表达OPN,促进CaOxa晶体的成核和聚集,从而增加了肾结石形成的危险性。     

动态硼酸酯键管控邻苯二酚基团与功能黏附性高分子设计

“黏附”是一种普遍存在的多尺度相互作用,其实质是界面处化学键、氢键或范德华力等的形成.近年来,在贻贝仿生的基础上将黏性因子邻苯二酚基团嵌入到动态硼酸酯聚合物中,成为了功能黏附性高分子的重要发展方向.本专论从分子黏附、微/纳表面黏附和宏观表面黏附3个尺度,介绍硼酸酯键管控邻苯二酚基团在高分子材料功能化方面的研究进展.分子黏附,主要讨论硼酸酯聚合物中邻苯二酚基团与分子或离子相互作用规律及其对材料形貌和刺激响应性能的调控;微/纳表面黏附,论述硼酸酯聚合物体系超分子驱动力和组装机制,介绍其在微/纳材料功能化改性方面的研究进展;宏观表面黏附,讨论硼酸酯键管控邻苯二酚基团与黏附性能调控的关联规律,介绍硼酸酯聚合物功能黏附材料在宏观组装、攀爬机器人领域的应用.最后,从新型硼酸酯聚合物设计、动态键精准管控和器件化应用的角度,对该领域未来前景和发展趋势做出了展望.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。