大基组在价键计算中的处理

编写了普适性的多键表自洽场程序，该程序能对单电子轨道展开系数和键表系数同时优化，其中单电子轨道的展开空间可任意定义，实际计算建议采用“杂化”轨道形式，即每个单电子轨道只对一个原子的基函数展开。对Ｈ２、Ｌｉ２及ＨＬｉ采用不同基组进行计算，结果表明用３个键表自洽计算所得能量与ＭＰ２结果相近，且我们的计算对键的共价性和离子性分析非常直观。     

Immobilization of Glucose Oxidase on Cellulose／Cellulose Acetate Membrane and its Detection by Scanning Electrochemical Microscope （SECM）

Cellulose/cellulose acetate membranes were prepared and functionalized by introducingamino group on it, and then immobilized the glucose oxidase (Gox) on the functionalizd membrane.SECM was applied for the detection of enzyme activity immobilized on the membrane.Immobilized biomolecules on such membranes was combined with analysis apparatus and can beused in bioassays.     

氮化锇配合物离子[OsN(mnt)2]-的电子结构和光谱性质的理论研究

理论研究了离子型配合物[OsN(mnt)2]-[mnt=S2C2(CN)2)]的电子结构和光谱性质, 考察不同配体三价N、二硫氰烯S2C2(CN)2和金属Os的相互作用对光化学性质的影响. 分别在B3LYP/LANL2DZ和CIS/LANL2DZ水平上优化了配合物的基态和激发态结构. 与基态(1A1)相比, 激发态(3A2)的Os≡N 的键长缩短了0.0066 nm, 这与计算得到的频率增大一致, 使用TD-DFT方法计算得到了配合物的吸收和发射光谱. 计算得到的位于300 nm(f=0.1497)和262 nm(f=0.2890)的强吸收都来自1A1→1B1跃迁, 分别指认为SC→Os≡N+CN 和N+SC→Os≡N+CN的电子跃迁. 最低能量的吸收位于446 nm(f=0.0206) 处, 来自1A1→1B2的电子跃迁, 指认为N→Os和 N+SC→CN. 计算得到配合物在气态的磷光发射位于678 nm(A3A2→X1A1)处, 而在丙酮溶液中则蓝移到了625 nm处, 跃迁属性不变, 都是N→Os和S→Os的跃迁.     

New Rare Earth（Ⅲ） Complexes with H2tmtaa

A series of Ln(tmtaa)(Htmtaa)·CH_2Cl_2(Ln=Sm,Tb,Er and Yb)complexes were prepared and characterized byinfrared spectra,mass spectra and molecular electronic spectroscopy as well as DSC measurement.A sandwichstructure containing all the eight nitrogen atoms of tmtaa and Htmtaa was proposed for these complexes.X-rayphotoelectron spectra(XPS)of these complexes revealed that four nitrogen atoms of both tmtaa and Htmtaa werechemically equivalent to each other,respectively.The acidic hydrogen of Htmtaa did not bind specifically to any ni-trogen atom of Htmtaa,but was shared by all the four nitrogen atoms.The magnetic properties of these complexeswere found to be in good agreement with their theoretical values.     

纳米TiO2的光生电荷迁移特性研究

利用场诱导光电压谱(简称FISPS)和瞬态光伏(简称TPV)技术研究了TiO₂的光生电荷的产生和传输机制.发现光生电荷在体块TiO₂上的迁移机制不同于在纳米TiO₂上的迁移机制，也不同于在结界面空间电荷区的迁移机制. 400 ℃处理的TiO₂颗粒表面具有大量的表面态，光生电荷被表面态捕获-释放机制控制着光伏行为的过程是慢过程. 800 ℃处理的TiO₂已经形成了完整的能带结构，光伏响应除了表现带-带跃迁外,还有一个在带边的自由激子带，光生电荷被表面自建场驱动进行传递的过程是快过程. 600 ℃处理的TiO₂混晶由锐钛矿型和金红石型两种构型组成，在两相之间存在着较低势垒的结界面．它的光伏响应受控于两种机制 ：光生电荷在两相间结界面空间电荷区的传输和在表面自建场驱动下的传输.当激发光强较小时，界面空间电荷区的光生电子由于积累的浓度较小而不能隧穿过结界面，这种场助隧穿只有在外场作用下才能发生.     

提升教学魅力,打造一门好课——《材料表面与界面》教学改革探索

《材料表面与界面》为高分子材料与工程专业复合材料方向的限选课。本课程对于学生奠定学科基础、培养学生对复合材料方向的兴趣具有重要的先导作用。笔者以"提升教学魅力,打造一门好课"为改革目标,充分贯彻了"教学内容是教学魅力的根本,教学方法与教学手段是将教学内容高效转化为教学魅力的催化剂"这一指导思想,从教学内容与教学方式两方面进行改革。从教学反馈看,这些改革措施能够改善教学效果,提高学生学习效率,得到了学生的认可。     

聚四氟乙烯纤维辐照接枝制备弱酸性离子交换剂及其对Cu~(2+)的吸附

以聚四氟乙烯纤维为基体通过6 0 Co辐射引发与丙烯酸接枝制备弱酸性阳离子交换纤维 .产物功能基含量为 3 0 6mmol g,在pH =5时该纤维达到对Cu2 + 的最大动态吸附量为 10 7 4 8mg g.使用不同浓度HCl对饱和吸附铜的接枝纤维进行洗脱 ,证实该纤维对铜离子具有优异的解吸性能     

Synthesis of Thiourea Derivatives on Soluble Polymeric Support

A modified poly(ethylene glycol) (PEG) has been developed as the soluble polymeric supports for liquid phase synthesis of novel thiourea derivatives.In each step of the sequence,the PEG-bound products were precipitated in cold Et2O and the unreacted materials and by-products were removed by simple filtration.The progress of reaction,purity of the isolation and the structure of the PEG-bound products were easily monitored by TLC,IR and ^1H NMR spectra.Representative thiourea derivatives were obtained in moderate yields with excellent purity from this modified PEG-bound product by the cleavage with 50% TFA/H2O.     

Growth and Characterization of Crystal Nd_(0.06)Y_(0.94)Sr_6Sc(BO_3)_6

<正>The crystal of Nd0.06Y0.94Sr6Sc(BO3)6 with the dimensions up to 35 mm × 28 mm × 13 mm was grown by a top-seeded solution growth method from Li6B4O9 flux. The grown crystal was characterized by X-ray powder diffraction. The optical absorption of the crystal shows that it has a strong absorption band at 8070 A, and the absorption coefficient is 2.17cm-1 with a FWHM of 41 A, which can match with the wavelength of the diode-laser (LD) and is suitable for the LD pumping. Based on the Judd-Ofelt theory, the three parameters of line oscillator strength Ω(λ) (λ = 2, 4 and 6) of the Nd3+ion in the crystal were calculated as follows: Ω2= 1.194 × 10-20, Ω4= 4.186 × 10-20 and Ω6 = 3.351 × 10-20cm2, which are relatively larger. The results indicate that the crystal Nd0.06Y0.94Sr6Sc(BO3)6 may be a kind of high-efficient laser material for diode-pumped.     

LLDPE/纳米SiO_2复合材料的力学性能和光学性能研究

采用熔融共混方法制备了LLDPE 纳米SiO2 复合材料 ,并对该体系的力学性能和光学性能进行了系统研究 .结果表明 ,随着纳米SiO2 的加入 ,复合材料的弹性模量显著提高 ,冲击强度与拉伸强度呈峰形变化 ,且均在SiO2 含量为 3phr左右达到最大值 .加入少量的纳米SiO2 后 ,复合材料薄膜对长波红外线 (7～ 1 1 μm)的吸收能力较LLDPE膜有了显著提高 ,透光率略有下降但雾度提高 ,透光质量得到改善 .同时表明 ,纳米SiO2 的表面处理方法对膜的光学性能有显著影响