PHOTODYNAMIC EFFECTS ON CELLS IN VITRO EXPOSED TO HEMATOPORPHYRIN DERIVATIVE and LIGHT

Abstract Several effects of hematoporphyrin derivative (HpD) and light on NHIK 3025 cells in vitro were studied. The treatment resulted in a partly repairable reduction of the rate of thymidine incorporation into DNA, a division delay, a reduced rate of protein synthesis, a reduced rate of active cellular uptake of α-aminoisobutyrate, a reduction in the colony-forming ability and an increased permeability of the cell membrane to chromate. Thymidine incorporation was by far the most sensitive parameter studied. However, comparison of the photodynamic effects after 1 and 18 h incubation with HpD prior to irradiation indicated that neither the reduced rate of DNA synthesis nor any of the other observed effects was the main primary cause of cell inactivation under all conditions. Several of the effects, such as increased permeability of the cell membrane to chromate, reduction in the rate of protein synthesis and reduction in the rate of repair of the damage to the mechanism of DNA synthesis, were clearly of secondary nature. When seen in relation to cellular survival, membrane damage was more important after short incubation times with HpD than after long incubation times.     

CeO2对CO选择性氧化催化剂氧传递速率的影响及模型模拟

采用共沉淀法和浸渍法制备了5%CuO/Al2O3催化剂,用脉冲H2滴定法研究助剂CeO2对CO选择性氧化催化剂反应过程中氧的传递速率的影响,并建立数学模型进行了模拟计算,得出助剂CeO2对CuO/Al2O3催化剂氧传递速率的影响规律。     

聚合物负载的钯-咪唑催化烯烃加氢

A polymer-supported palladium-imidazole catalyst was used to catalyze the hydrogenation of various olefins under mild conditions. The rate of hydrogenation was studied. The effects of factors such as substrate concentration,catalyst concentration,partial pressure of hydrogen and temperature on initial rate of reaction of selected olefins were investigated. A mechanism for the reaction was proposed from the rate equation. The effects of the solvent and structure of the olefin on the rate of hydrogenation were investigated. The catalyst showed good reusability without any leaching of metal from the support. The homologous analog of the polymer-supported catalyst could not be used as catalyst for the hydrogenation of olefins in methanol because there was precipitation of the metal during reaction.     

A chemometric study of active parameters and their interaction effects in a nebulized sheath-liquid electrospray interface for capillary electrophoresis-mass spectrometry

A chemometrics approach has been used for evaluating the effect of four experimental parameters when coupling capillary electrophoresis (CE) to electrospray ionization-mass spectrometry (ESI-MS). Electrospray voltage, sheath-liquid flow rate, nebulizing gas flow rate, and spray needle position in respect to the MS orifice were varied according to a full factorial design. In addition to main effects, two interaction effects could be identified as significant when measuring the peak intensity of the analytes, from a sample mixture containing peptides and pharmaceuticals. The first interaction effects, between the nebulizing gas flow rate and the sheath-liquid flow rate, and the second interaction effect, between the nebulizing gas flow rate and the spray position, could further explain the impact that these variables have on the spray performance. The number of theoretical plates and the baseline noise were also measured. The sheath-liquid flow was found to significantly affect the separation efficiency, while the noise level mainly was controlled by the nebulizing gas flow. The same factorial design was also used for a CE capillary with lower internal diameter (ID) and the effects of the same variables were compared on those capillaries using equal injection volume for both capillaries. Similar trends were obtained in both capillaries but capillary ID was shown to be a significant variable when evaluating both capillaries in a single model. It was found that a capillary with 25 microm ID provided improved CE-MS performance over than corresponding 50 microm ID capillary. Enhanced sensitivity was obtained using the narrow-bore capillary, and at lower sheath-liquid flow rate the 25 microm ID capillary also gave rise to more efficient peaks.     

质子化双氧/硫杂卟啉内氢原子迁移反应的理论研究

在确定各反应体系反应物、产物稳定构象的基础上, 采用B3LYP/6-31G**方法在Gaussian 03程序下, 对质子化的双氧/硫杂卟啉的内氢迁移(IHAT)反应进行研究, 寻找并优化相应的过渡态, 比较其迁移反应速率的差异. 计算结果表明, 质子化双氧/硫杂卟啉的构象稳定性仍然是由芳香性、空间位阻、静电作用共同决定的. 质子化后的双取代体系的内氢迁移反应速率大小差异显著, 内环取代对IHAT反应速率的影响主要来源于电子效应, 而非构象变化; 且双取代对体系IHAT反应速率的影响要远大于单取代.     

TEP-DMAc混合溶剂对PVDF膜性能的影响

利用非溶剂相转化法(NIPS)制备聚偏氟乙烯(PVDF)膜,考察了聚乙二醇(PEG200)与N,N-二甲基乙酰胺(DMAc)的质量比对膜分相速率和膜性能的影响,讨论了以磷酸三乙酯(TEP)和DMAc的混合液作溶剂对PVDF膜凝胶速率、膜结构和膜通量的影响。结果表明:PEG200的加入减弱了溶剂对聚合物的溶解能力,但铸膜液的分相行为由延迟分相转变为瞬时分相,膜通量提高。随着混合溶剂中TEP含量的增大,铸膜液的黏度增大,分相速率减慢;在高质量比m(TEP)/m(DMAc)时,膜表面的孔增多,指状孔膜结构逐渐消失,整个膜截面呈海绵状,膜通量变大,力学性能提高。     

Structural, mechanistic, and computational analysis of the effects of anomeric fluorines on anomeric fluoride departure in 5-fluoroxylosyl fluorides

The effects of fluorine substitution at the C-5 center of pyranosyl fluorides on the reactivity at the C-1 anomeric center was probed by studying a series of 5-fluoroxylosyl fluoride derivatives. X-ray structures of their per-O-acetates detailed the effects on the ground-state structures. First-order rate constants for spontaneous hydrolysis, in conjunction with computational studies, revealed that changes in the stereochemistry of the 5-fluorine had minimal effects on the solvolysis rate constants and that the observed rate reductions were broadly similar to those caused by additional fluorine substitution at C-1 but significantly less than those due to substitution at C-2. Differences in the trapping behavior of 5- versus 2-fluoro-substituted glycosyl fluorides with α- and β-glycosidases arise more from differences in steric effects and hydrogen-bonding interactions than from intrinsic reactivity differences.     

Hot tensile fracture characteristics and constitutive modelling of polyether-ether-ketone (PEEK)

The effects of strain rate and deformation temperature on the deformation behaviors of polyether-ether-ketone (PEEK) were studied by uniaxial tensile tests with the temperature range of 23–150 °C and strain rate of 0.01–1 s⁻¹. The effects of deformation temperature and strain rate on the hot tensile deformation behavior and fracture characteristics were investigated by scanning electron microscope (SEM) and discussed in detail. SEM experimental results suggest that fracture morphology is not strain rate sensitive but temperature sensitive. Based on the tensile results, the Johnson-Cook and modified Johnson-Cook constitutive models were established for PEEK. Furthermore, a comparative study has been made on the accuracy and effectiveness of the developed models to predict the flow stress. The results show that the original Johnson-Cook model reflects the deformation behavior more accurately throughout the entire test temperature and strain rate range under uniaxial tensile conditions.     

醋酸奥曲肽治疗肝硬化失代偿期上消化道出血的临床效果观察

目的醋酸奥曲肽治疗肝硬化失代偿期上消化道出血的临床效果。方法按照随机数字表法将60例肝硬化失代偿期上消化道出血患者均分为实验组和对照组,分别采取单纯垂体后叶素和醋酸奥曲肽+垂体后叶素治疗,比较两组患者治疗效果。结果实验组患者治疗总有效率明显高于对照组,差异具有显著性(P0.05);两组患者不良反应总发生率对比,差异无统计学意义(P0.05)。结论醋酸奥曲肽+垂体后叶素治疗能够有效缩短肝硬化失代偿期上消化道出血止血时间,提高治疗效果,不良反应发生率低,临床应用价值较高。     

超声波提取-气相色谱法测定油田区土壤中21种酚类化合物

采用超声波提取—气相色谱法测定油田区土壤中21种酚类化合物,主要研究了提取时间及净化条件等对测定结果的影响.对比了加压流体萃取与超声波提取方式对回收率的影响,结果表明:超声波提取法回收率优于加压流体萃取法,其中2,4-二硝基酚和4-硝基酚两种化合物比加压流体萃取法回收率提高了30%.以10.0 g土壤样品计,酚类化合物的检出限为0.01～0.05 mg/kg,样品加标回收率为81.5%～110%,精密度为2.6%～11%.经有证标准物质验证,相对误差为2.6%～14%.试验结果表明,超声波提取法适合于油田区土壤中21种酚类化合物的测定.     

The effects of sample size and heating rate on the kinetics of the thermal decomposition of CaCO3

Isothermal and dynamic methods were used to study the rate of weight loss of CaCO₃. Sample sizes were controlled in the range of 1–32 mg. The contracting area rate law proved universally applicable. A pronounced dependence of the activation enthalpy, pre-exponential term, and rate constant upon sample weight and heating rate was observed. This dependence is discussed primarily in terms of the effects of self-cooling and sample geometry. The concept of a unique activation energy is questioned.     

Effect of diffusion in solid acid catalyzed inulin hydrolysis

Hydrolysis of inulin was investigated employing various solid acids as hydrolytic catalysts. The catalytic performances of several ion exchange resins were compared. The effects of the particle size and porosity on the hydrolysis reaction were found to be significant, indicating that the intraparticle diffusion of reactants controls the reaction rate. Theoretical models were developed, therefore, to analyze the effects of intraparticle diffusion occurring in a sequential reaction. The results were found to be consistent with experimental observations regarding the adverse effects of pore diffusion and the reaction pattern.     

淀粉基高吸水性树脂吸水性能的测定条件评价

研究了测定条件对淀粉基高吸水性树脂吸水性能的影响,分别考察了测定方法、树脂粒径、初始加水量、水介质pH、温度及溶液中盐的质量分数对树脂吸水倍率和吸水速率的影响.结果表明,采用100目网筛过滤法测定树脂的吸水性能结果较准确;当吸水介质与干树脂的质量比为2 400∶1,pH为7时,可以使树脂达到最大饱和吸水倍率;在树脂粒径96～180μm范围内,随着树脂粒径的减小、水介质温度的升高及盐浓度的降低,树脂的吸水倍率和吸水速率增大.     

索尔维型催化剂的丙烯聚合动力学的研究

用封闭和开放体系测定了索尔维(Solvay)型催化剂-AlEt_2Cl体系丙烯聚合时温度对聚合速度的影响,测定了反应级数和速度常数,采用下式: E=2.303R log(K_2/K_1)[(T_1·T_2)/(T_2-T_1)] E=2.303R log(V_2/V_1)[(T_1·T_2)/(T_2-T_1)]分别求得了活化能。     

A NEW TYPE LOW SHEAR RATE VISCOMETER FOR HIGH MOLECULAR WEIGHT POLYMER

In this paper, the effects of shear rate on the intrinsic viscosity measurement of partiallyHydrolysed Polyacrylamide (HPAM) in salt solution were studied with homemade multi-bulb viscometer and low shear rate rheometer. The critical shear rate of HPAM in saltsolution for high molecular weight HPAM was determined. A low shear rate capillaryviscometer was designed in which the [η] approached to value at zero shear rate can beobtained for HPAM-salt system. The effect of molecular weight on shear rate dependenceof viscosity was also studied.     

UV-光固化光纤涂料的研制

本文采用环氧丙烯酸酯与聚氨酯丙烯酸酯共混聚合的方法制备出新型的UV-光固化光纤涂料,其主要性能较好.研究了基体组成、引发剂、稀释剂以及固化工艺对UV-固化光纤涂料的光固化速度的影响.通过实验发现,环氧丙烯酸酯与聚氨酯丙烯酸酯的配比为 4:6～6:4、稀释剂的含量不大于20%时固化速度较快、性能较好,同时固化时灯距与固化膜厚度对固化速度的影响较大.     

表面活性剂对HDEHP萃取动力学的影响

用上升液滴法测定二(2-乙基己基)磷酸(HDEHP)从硫酸盐介质中萃取Co^2^+的速率。研究体系中加入不同表面活性剂所引起萃取速率的不同改变: 三辛基氧化膦(TOPO)因与HDEHP形成可萃取的Co^2^+活性分子缔合物, 降低了萃取过程活化能而使反应加速; 十二烷基磺酸钠(SDS)和十六烷基三甲基溴化铵(CTMAB)因占据发生萃取反应的界面区, 减小了HDEHP与Co^2^+反应的机会而使反应减速; SDS还因其在界面形成较强的负电场(层), 造成Co^2^+的附加势能而使萃取速率有更大幅度的降低。     

The role of proton donors in SmI2-mediated ketone reduction: new mechanistic insights

The effects of proton donors (alcohols and water) on the rate of reduction of acetophenone by SmI2 have been examined utilizing stopped-flow spectrophotometric studies. The rate orders with respect to proton source and the kinetic isotope effects were determined as well. The reaction was first-order in phenol, 2,2,2-trifluoroethanol, methanol, and ethanol and zero-order in 2-propanol and 2-methyl-2-propanol when 25 equiv of proton source were used in the reduction. Methanol, ethanol, 2,2,2-trifluoroethanol, and phenol also showed a direct correlation between the pKa of the alcohol and the rate of reduction. Under the same conditions, water had a fractional rate order of 1.4. Further studies showed that water has a rate order of 1 at lower concentrations (<8 equiv) and a rate order of 2 at higher concentrations (>80 equiv). These results clearly indicate that the nature of the proton donor and its concentration affects the rates of reduction. Water has a high affinity for SmI2 (compared to that of the alcohols), and the onset of coordination at relatively low concentrations channels the reaction through a mechanistically distinct pathway.     

粒度对纳米氧化镍与硫酸氢钠水溶液反应动力学的影响

以纳米氧化镍与硫酸氢钠水溶液为反应体系,研究了不同粒度反应物反应的动力学参数,并讨论了粒度对动力学参数的影响.结果表明,反应物粒度对该反应的速率常数、指前因子和表观活化能均有显著的影响;随着反应物粒径的减小,速率常数增大,指前因子和表观活化能减小,且指前因子的对数和表观活化能分别与反应物粒径的倒数呈线性关系.