X-射线荧光光谱法测定白云石中主次量组分

采用粉末压片x-射线荧光光谱法测定白云石中氧化镁、氧化钙、二氧化硅、三氧化二铝、三氧化二铁和二氧化钛含量。采用校正曲线和基体校准一体的回归方程进行谱线重叠干扰校正和基体效应校正。将白云石样品进行磨细处理,在压片机上制成样片,直接在X-射线荧光光谱仪上按照选定的分析条件,以标准样品做工作曲线,利用工作曲线测定样品含量。通过与国家标准化学法以及熔片法对照,分析结果与标准值、熔片法结果吻合,主含量元素测定结果相对误差不超过10％,同一样品12次测定结果相对标准偏差不超过10％。该方法简便、快速、准确、重现性好。     

预应变对中子辐照高纯铝拉伸性能的影响

金属材料的中子辐照硬化和脆化一直都是核能安全领域十分关注的重要问题之一. 为了进一步认识预应变对中子辐照金属材料塑性形变和最终断裂特性的影响规律, 及其微观机理, 本文研究了10%拉伸预应变高纯铝的拉伸应力-应变曲线、失稳应力和失稳应变等随辐照剂量的变化规律. 结果表明, 辐照剂量越高, 预应变高纯铝内部孔洞的尺寸和数密度越高, 导致屈服强度和极限拉伸强度越高, 均匀延伸率和失稳应变越小, 表现出典型的辐照硬化和脆化效应, 但失稳应力与辐照剂量几乎无关. 相同辐照剂量条件下, 预应变引入的高密度位错能够显著降低辐照孔洞的尺寸和数密度, 加之辐照退火效应的综合影响, 导致预应变能够降低高纯铝屈服强度的增长率和失稳应变的下降率, 从而表现出一定的抑制辐照硬化和脆化的能力, 预应变还能够提高高纯铝的失稳应力, 但整体而言预应变并不能提高高纯铝的延性. 最后, 基于J-C本构模型的中子辐照退火态金属材料的脆化模型能够直接应用于预应变金属材料, 且模型预测结果与实验结果吻合较好.      

Hydrothermal syntheses, crystal structures, and characteristics of a series of Cd-btx coordination polymers (btx = 1,4-Bis(triazol-1-ylmethyl)benzene)

Four novel cadmium-btx (btx = 1,4-bis(triazol-1-ylmethyl)benzene) coordination polymers [Cd(btx)(2)(NO(3))(2)](n)(1), [Cd(btx)(2)Cl(2)](n)(2), [Cd(btx)(SO(4))(H(2)O)(2)](n)(3), and [Cd(btx)(S(2)O(7))(H(2)O)](n)(4) have been prepared by hydrothermal reaction (140 or 180 degrees C) and characterized. Both 1 and 2 have two-dimensional rhombohedral grid structures, 3 possesses a two-dimensional rectangular grid structure, and 4 displays a three-dimensional framework, which is formed by btx bridging parallel layers. To the author's best knowledge, polymer 4 is the first Cd(II) polymer in which the Cd(II) ion is eight-coordinated in a hexagonal bipyrimidal geometry. In addition, we studied the effects of temperature on the hydrothermal reaction system of btx and CdSO(4) and found that different products can be obtained at different temperatures. Furthermore, polymer 3 possesses a very strong third-order NLO absorptive effect with an alpha(2) value of 1.15 x 10(-)(9) m W(-1). Polymers 2-4 display strong fluorescent emissions in the solid state at room temperature. The DTA and TGA results of the four polymers are in agreement with the crystal structures.     

硅烷化处理的纳米ZSM-5的结构表征及催化性能

采用多次浸渍法和化学反应沉积法对纳米HZSM-5分子筛外表面进行了硅烷化处理,考察了改性后纳米ZSM-5对甲苯歧化的催化活性.采用改进的Hammett指示剂法和吡啶吸附红外光谱研究了催化剂的酸性位,采用X射线衍射和29Si MASNMR对催化剂的结构进行了表征.研究结果表明,硅烷化处理降低了纳米ZSM-5酸性位的浓度,从而降低了纳米ZSM-5的催化活性.硅烷化处理还减少了纳米ZSM-5中Si的Q4物种,降低了纳米ZSM-5的相对结晶度,同时硅烷化处理产生了脱铝作用.骨架铝含量的减少导致催化剂的酸性位减少,催化活性降低.     

DNA-Intercalative Platinum Anticancer Complexes Photoactivated by Visible Light

Photoactivatable agents offer the prospect of highly selective cancer therapy with low side effects and novel mechanisms of action that can combat current drug resistance. 1,8-Naphthalimides with their extended π system can behave as light-harvesting groups, fluorescent probes and DNA intercalators. We conjugated N-(carboxymethyl)-1,8-naphthalimide (gly-R-Nap) with an R substituent on the naphthyl group to photoactive diazido Pt^IV complexes to form t,t,t-[Pt(py)₂(N₃)₂(OH)(gly-R-Nap)], R=H ( 1 ), 3-NO₂ ( 2 ) or 4-NMe₂ ( 3 ). They show enhanced photo-oxidation, cellular accumulation and promising photo-cytotoxicity in human A2780 ovarian, A549 lung and PC3 prostate cancer cells with visible light activation, and low dark cytotoxicity. Complexes 1 and 2 exhibit pre-intercalation into DNA, resulting in enhanced photo-induced DNA crosslinking. Complex 3 has a red-shifted absorption band at 450 nm, allowing photoactivation and photo-cytotoxicity with green light.     

Compound-Specific Isotope Analysis of Amino Acid Labeling with Stable Isotope Nitrogen (15N) in Higher Plants

Individual free amino acid δ¹⁵N values in plant tissue reflect the metabolic pathways involved in their biosynthesis and catabolism and could thus aid understanding of environmental stress and anthropogenic effects on plant metabolism. In this study, compound-specific nitrogen isotope analysis of amino acid by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) was carried out to determine individual free amino acid δ¹⁵N values. High correlations were observed between the δ¹⁵N values obtained by GC-C-IRMS and elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) determinations, and the mean precision measured was better than 1 ‰. Cation-exchange chromatography was employed to purify the sample, and the difference between prior to and following passage through the resin was within 1 ‰. The amino acid δ¹⁵N values of plant leave samples following incubation in ¹⁵N-nitrate at different time points were determined. A typical foliar free amino acid ¹⁵N-enrichment pattern was found, and glutamine was the most rapidly labeled amino acid; other amino acids derived from the GS-GOGAT cycle were also enriched. The pyruvate family amino acids were labeled less quickly followed by the aromatic amino acids. This study highlighted that amino acid metabolism pathways had a major effect on the δ¹⁵N values. With the known amino acid metabolism pathways and δ¹⁵N values determined by the presented method, the influence of various external factors on the metabolic cycling of amino acid can be understood well.

     

氢化物发生-原子荧光光谱法分析钢铁中痕量锑

建立氢化物发生-原子荧光光谱法分析钢铁中痕量锑的新方法.试验了钢铁中常见元素Cu、V、Cr、Mn、Mo、Si、W、Ni和Ti等对锑元素测定的影响.考察了原子化器高度、载气流速、屏蔽气流速、载流酸和硼氢化钾浓度等因素对测定的影响,优化了测定条件.结果表明,在选定的实验条件下,碘化钾-抗坏血酸混合溶液不仅能作为Sb5+的预还原剂,并且还能有效掩蔽Fe、Cu、V、Cr、Mn、Mo、Si、W和Ti的干扰,而共存元素Ni的干扰需要EDTA-硫脲进行联合掩蔽.方法的线性范围为0～120 ng/mL(相关系数r=0.9990),检出限为0.24 ng/mL,测定结果的相对标准偏差为5.1 %(n=10).用该法对国家标准钢样进行分析,测定结果与标准值相符合.     

A series of metal-organic polymers assembled from MCl2 (M = Zn, Cd, Co, Cu): structures, third-order nonlinear optical and fluorescent properties

In this paper four metal-organic polymers {[Zn(fcz)Cl2].CH3OH}n 1, {[Cd(fcz)2Cl2].CH3OH.2H2O}n 2, {[Co(fcz)2Cl2].2CH3OH}n 3 and {[Cu(fcz)2Cl2].2CH3OH}n 4 (fcz = fluconazole: alpha-(2,4-difluorophenyl)-alpha-(1H-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole-l-ethanol) were synthesized and characterized by X-ray single crystal diffraction. Polymer consists of 1-D infinite chains arranged along the b-axis. All of polymers 2-4 exhibit a 2-D rhombohedral grid structure. We study the third-order nonlinear optical properties of fcz and polymers 1-4 in DMF solution by using 8 ns laser pulses at 532 nm, and find that 1 and 4 exhibit different NLO properties from fcz and both 2 and 3 show similar NLO properties to fcz. 1 possesses strong NLO refractive effects and large NLO absorptive behaviors. 2, 3 and fcz exhibit strong refractive effects, but their NLO absorptive behaviors are weaker than that of 1. The NLO effects of 4 are very weak. The study of optical limiting (OL) effects by using 40 ps laser pulses at 532 nm shows that fcz and polymer 3 possess a strong OL effect. The optical limiting threshold values of 0.15 J cm(-2) for fcz and 0.16 J cm(-2) for are comparable to those of many heterothiometallate clusters. Polymers 1, 2 and 4 show a weak OL effect. The fluorescent spectra in DMF solution (concentration: 1 x 10(-4) mol dm(-3)) show that polymers 1-4 exhibit different luminescence properties from fcz. The maximum wavelength of polymers 1-3 are blue shifted gradually by 2-12 nm while polymer 4 exhibits a fluorescent self-quenching phenomenon. These results demonstrate that metal ions play an important part in the NLO and fluorescent properties of coordination polymers.     

一种求解非线性整数规划问题的填充函数算法(英文)

在本文中,对于求解非线性整数规划的问题,提出了一个新的填充函数和相应的算法,该函数只有一个参数,具有较好的可操作性.数值试验显示,该算法是有效和可靠的.