The transition from direct to delayed ionisation of C 60

The timescale for the coupling of electronic and vibrational excitation in isolated fullerenes is determined by recording positive ion time-of-flight mass spectra on excitation with ultrashort laser pulses at 790 nm of the same fluence but different pulse durations. The coupling leads to the onset of a delayed ionisation “tail” on the parent fullerene ion peak. This occurs for a pulse duration of 500-1000 fs, depending on laser fluence. Received 20 October 2000     

Infrared spectral study of molecular vibrations in amorphous, nanocrystalline and AlO(OH) · αH2O bulk crystals

Amorphous, nanocrystalline, and bulk AlO(OH) · xH₂O crystals have six fundamental modes (FM) of vibration in a nonlinear AlO(OH) molecular structure. Most of them appear in groups of four IR and Raman bands. Their positions and relative intensities differ significantly in three specimens. The nanocrystals (monoclinic structure with z=8 molecules per unit cell) have four OH stretching bands at values enhanced by up to 360 cm⁻¹ at 3120, 3450, 3560 cm⁻¹ in comparison to those in bulk crystals or amorphous specimens. The first two bands are broad, bandwidth Δν_1/2200 to 350 cm⁻¹, while the other two are sharp, Δν_1/290 cm⁻¹. The sharp bands shift to 3525 and 3595 cm⁻¹ after heating the sample at 100°C. They no longer appear after heating at 300 or 500°C for 2 h (the specimen decomposes to Al₂O₃), leaving behind only two bands at 3100 and 3400 cm⁻¹. A Δν_1/2 value of 500 cm⁻¹ appears in the 3400 cm⁻¹ in a delocalized distribution of H atoms. Two bands also occur at 3098 and 3300 cm⁻¹ in bulk crystals (orthorhombic structure with z=4) or at 2990 and 3515 cm⁻¹ in an amorphous sample. More than one bands appear in a FM vibration in occurrence of sample in more than one conformers. The amorphous sample has approximately the same conformer structure as the bulk crystals. An amorphous surface structure exists in nanocrystals with a group of three bands at 1420, 1510 and 1635 cm⁻¹ in an interconnected network structure. It encapsulates the nanocrystals in an amorphous shell. Its volume fraction, 33% estimated from the integrated intensity in three bands, determines 2.2 nm thickness in the shell in spherical shape of nanocrystals in 35 nm diameter.     

Complex-scaling treatment for high-lying doubly excited resonances for screened Coulomb helium atom

This work presents an investigation on the doubly excited ¹S ^e autoionizing states of screened helium atom lying below the n = 4 threshold of the He⁺ ion. The potential generated in this system is represented by a Yukawa type potential. We have employed complex-coordinate rotation method, as it is a powerful scheme to study high lying resonances. Hylleraas type wave function is used to consider the correlation effect between all the charged particles. Our resonance parameters for the resonances lying below the He⁺ (n = 2) threshold agree well with those of the existing calculations by using the stabilization method. Resonances associated with higher thresholds are new calculations. All the present results are well converged with basis length N = 444.     

MYC基因在人类HL－60和CEM癌细胞系中原位表达的研究

以细胞分子原位杂交方法对两种不同类型的人类白血细胞系ＨＬ－６０和ＣＥＭ，以及正常人白细胞中Ｃ－ｍｙｃ基因的表达进行了比较研究．结果证明：ＨＬ－６０细胞中Ｃ－ｍｙｃ基因有异常高水平的表达，而在ＣＥＭ细胞和正常人白血球与淋巴细胞中则没有明显的Ｃ－ｍｙｃ转录产物．Ｓｏｕｔｈｅｒｎ分析表明，ＨＬ－６０细胞基因组中Ｃ－ｍｙｃ基因有显著的扩增现象；而ＣＥＭ细胞基因组中的Ｃ－ｍｙｃ基因的拷贝数与正常人血细胞的接近，属正常水平表达。再次证明了ＨＬ－６０细胞系Ｃ－ｍｙｃ基因的异常高水平表达，与该基因的大量扩增紧密相关．还对两种癌细胞系的癌变机理和细胞原位杂交在基因表达研究中的应用进行了讨论．     

负载型磷钨酸催化剂的制备及催化合成ＥＴＢＥ的性能研究

采用水热法合成纯硅介孔分子筛Si-MCM-41, 并用浸渍法将磷钨酸(PWA)负载到介孔分子筛Si-MCM-41上, 制得了磷钨酸负载量不同的催化剂x%PWA/MCM-41. 利用XRD, FT-IR, Py-IR, BET, TEM对载体和催化剂进行分析. 结果表明, 负载后的PWA颗粒粒径明显减小, 粒径约为10个纳米, PWA在载体表面实现了均匀分布, 通过叔丁醇和乙醇在高压反应釜内生成乙基叔丁基醚的反应测试催化剂的催化性能. 结果表明, 负载型催化剂和纯PWA相比, 前者使叔丁醇(TBA)的转化率、ETBE的选择性有很大提高, 当磷钨酸负载量为30%时TBA的转化率最大. 最优的催化剂制备及反应条件是: 载体550 ℃煅烧脱模, PWA负载量为30%, 催化剂煅烧温度为300 ℃, 醚化反应温度为120 ℃, 乙醇与叔丁醇的摩尔比为2∶ 1, 催化剂的用量为1.4 g.     

光谱法研究羟基葫芦[6]脲与对氨基苯磺酸的分子识别作用

光谱法研究羟基葫芦[6]脲与对氨基苯磺酸的分子识别作用;紫外光谱法;荧光光谱法;分子识别;包结作用;羟基葫芦[6]脲;对氨基苯磺酸     

高氯酸二水邻菲咯啉合铜配合物的合成和晶体结构

Crystal structure of the title compound， Cu(phen)(H₂O)₂·ClO₄(phen=1，10-phenanthroline)， was deter-mined by X-ray crystallography. It crystallizes in the monoclinic system， space group C2/c with lattice parameters a=1.49071(4)nm， b=1.38594(4)nm， c=0.70292(1)nm， β=108.509(1)° and Z=4; The Cu(Ⅰ) ion is chelated by a phen ligand and two aqua ligands in cis arrangement and assumes a C2 symmetric square-planar geometry with the CuN₂O₂ core. Eight Cu(phen)(H₂O)₂·ClO₄ molecules are interconnected by strong hydrogen bonds between coordinated water molecules and uncoordinated perchlorate anions to form a molecular scale cavities along c axis. The bond distances of Cu-N and Cu-O are 0.2003(4)nm and 0.1973(3)nm， respectively. CCDC： 197600.     

偏氟乙烯/三氟氯乙烯交替共聚物在TATB表面吸附的分子动力学模拟

采用COMPASS力场和NVT正则系综的动力学模拟方法, 搭建了聚合度分别为10, 50和100的偏氟乙烯(VDF)/三氟氯乙烯(CTFE)交替共聚物, 对交替共聚物在1,3,5-三氨基-2,4,6-三硝基苯(TATB)的(0,0,1)晶面上的吸附和结构进行了分子动力学(MD)模拟. 结果表明, 在300～320 K温区, 聚合度为100的VDF/CTFE交替共聚物链对TATB晶体有理想的表面活性和吸附能力, 以train型构象平铺于TATB表面. 通过对聚合度为10的交替共聚物的多链体系在TATB表面吸附的MD模拟, 表明了VDF/CTFE交替共聚物具有非凝聚吸附的高表面活性特征. 对搭建的乙酸乙酯溶剂化的聚合度为50的VDF/CTFE交替共聚物在TATB晶体表面吸附的模拟, 实验证明了溶剂小分子能够降低共聚物链的吸附能力, 且链以tail型构象吸附于TATB表面.     

PW_(11)/SBA-15介孔杂化材料的直接合成与表征

采用三嵌段共聚物EO20PO70EO20(P123)为模板剂,正硅酸乙酯(TEOS)和缺位Keggin型多金属氧酸盐Na7PW11O39(PW11)为无机前驱体,由共缩合法一步合成了PW11/SBA-15介孔杂化材料.通过红外(IR)光谱、紫外-可见漫反射光谱(UV-Vis/DRS)、X射线衍射(XRD)、低温N2吸附、透射电子显微镜(TEM)等手段对杂化材料和合成过程进行了表征.结果表明:杂化材料中不仅多金属氧酸盐的Keggin单元保留完整,且共价键联于介孔孔道内部,而且样品基本具有规整有序的六方介孔结构.TEOS预水解时间的长短对有序结构的构筑有明显影响,随预水解时间延长,样品的介观有序性增加.这是因为多金属氧酸盐对模板剂P123有盐析作用,其作用大小与多金属氧酸盐前驱物的溶解度有关.     

溴化 N-烷基取代咪唑中离子热合成硅磷酸铝分子筛

 以溴化N-烷基取代咪唑离子液体为反应介质,采用离子热法合成了AEL型硅磷酸铝分子筛,并考察了不同离子液体和反应物中正硅酸四乙酯的添加量对分子筛结构的影响. 结果表明,以1-乙基-3-甲基溴化咪唑为反应介质,并引入正硅酸四乙酯时,产物为含有未知结构晶体的AEL型硅磷酸铝分子筛,而且随着正硅酸四乙酯添加量的增大,未知结构晶体增多. 以1-己基-3-甲基溴化咪唑为反应介质时,产物为高结晶度的上述未知结构晶体.