Injection, Transport, Absorption and Phosphorescence Properties of a Series of Blue-Emitting Ir(III) Emitters in OLEDs: a DFT and Time-Dependent DFT Study

Quantum-chemistry methods were explored to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of blue-emitting Ir(III) complexes {[(F-2-ppy)(2)Ir(pta -X/pyN4)], where F-2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = phenyl(1); p-tolyl (2); 2,6-difluororophenyl (3); -CF3 (4), and pyN4 = pyridine-1,2,4-tetrazolate (5)}, which are used as emitters in organic light-emitting diodes (OLEDs). The mobility of hole and electron were studied computationally based on the Marcus theory. Calculations of Ionization potentials (IPs) and electron affinities (EAs) were used to evaluate the injection abilities of holes and electrons into these complexes.

Negative differential resistance and multilevel memory effects in organic devices

Negative differential resistance ( NDR) and multilevel memory effects were obtained in organic devices consisting of an anthracene derivative, 9,10-bis-{ 9,9-di-[ 4-(phenyl-p-tolyl-amino)-phenyl]-9H-fluoren-2-yl}-anthracene ( DAFA), sandwiched between Ag and ITO electrodes. The application of a negative bias voltage leads to negative differential resistance in current-voltage characteristics and different negative voltages produce different conductance currents, resulting in the multilevel memory capability of the devices. The NDR property has been attributed to charge trapping at the DAFA/Ag interface. This opens up a wide range of application possibilities of such organic-based NDR devices in memory and logic circuits.

Synthesis and chemical properties of [Z]-1-[2-(triaryl stannyl)vinyl]cyclooctanol

The compounds of [Z]-1-[2-(triphenyl stannyl) vinyl] cyclooctanol (1) and [Z]-1-[2-(tri-p-tolyl stannyl) vinyl] cyclooctanol (2) were synthesized by the reactions of triphenyltin hydride and tri-p-tolyltin hydride with 1-ethynyl cyclooctanol. The crystal structure of compound 1 was determined. The reactions of compound 1 and 2 with IC1, Br-2, I-2 formed nine organotin halides. The organotin oxide or hydroxide were prepared by the reactions of [Z]-1-[2-(phenyl dibromo stannyl) vinyl] cyclooctanol (6) and [Z]-1-[2-(diphenyl monobromo stannyl) vinyl] cyclooctanol (5) with KOH. Three complexes were obtained by the reactions of [Z]-1-[2-(phenyl diiodide stannyl) vinyl] cyclooctanol (8) with three ligands (2,2'-bipyridyl,5-nitro-1,10-phenanthroline,8-Hydroxyquinoline). The sixteen new compounds synthesized in this paper were characterized by means of elemental analysis, IR, H-1 NMR. The reaction mechanism of triphenyltin hydride and tri-p-tolyltin hydride with 1-ethynyl cyclooctanol were also proposed.

两种海藻提取物的化学成分和生物活性的研究及其应用

本论文的研究工作由两部分组成，第一部分研究了海带（Laminaria japonica）水提取物中的活性物质，并研究了提取物对蔬菜促生长的影响及其作用机制。第二部分对三列凹顶藻(Laurencia tristicha)乙醇提取物的乙酸乙酯相进行了活性筛选和化学成分研究，并对其中分离得到的单体化合物进行了生物活性筛选。 第一部分主要以中国人工养殖的海带为原料，使用与海藻多糖生产相结合的提取技术并浓缩其中的有效成分。对浓缩提取物进行了蔬菜的农田效果实验，并对作物抗旱性能的增加、作物硝酸盐积累的减少、作物品质的改善、以及作物抵抗病毒病的能力等影响进行了作用机制方面的研究。海藻浓缩提取物进行的农田效果实验表明：作物抗旱型相对含水量RWC值在92%~94%之间；病毒病的防治效果最高可达到91%；作物的品质有明显的改善，最重要的是首次发现海藻提取物有降低蔬菜中硝酸盐的含量（硝酸盐的含量是与有机蔬菜区别的重要指标之一）的作用。该部分研究工作的创新性主要体现在：（1）首次在国内外提出和采用与海藻多糖生产相结合的提取技术。该技术的应用不但减少了提取成本，使工业化生产成为可能,更重要的是使我国的海藻工业生产可能实现高值化和开辟综合利用的新途径。（2）首次发现海藻中的小分子海藻多糖具有和细胞激动素、甜菜碱、植物生长素等活性物质同样的生物活性。 第二部分的研究是在查阅了大量的近20年来国内外有关红藻凹顶藻中化学成分研究的相关文献的基础上，对凹顶藻中的次生代谢产物进行了综述。该论文主要是通过对红藻三列凹顶藻的95%乙醇提取物的乙酸乙酯相进行化学成分分析和生物活性筛选以期能够发现具有药用前景的活性先导化合物。 为了寻找具有生物活性的化合物，我们对采自我国南海硇洲岛海域的红藻三列凹顶藻的95%乙醇提取物的乙酸乙酯相进行了活性筛选。采用MTT法对其在KB细胞株、Bel-7402细胞株、PC-3M细胞株、MCF-7细胞株、Ketr-3细胞株模型上进行了细胞毒活性测试；采用酶模型对其进行了Na+,K+-ATPase的抑制活性测试；采用MTT法对其在犬主动脉血管模型上进行了血管平滑肌细胞增殖抑制活性测试；结果表明，三列凹顶藻的95%乙醇提取物的乙酸乙酯相对Na+,K+-ATPase和犬血管平滑肌细胞增殖具有一定的抑制活性。 利用正相和反相色谱、Sephadex LH-20色谱以及反相HPLC等手段进行分离纯化，从我国南海海域的红藻三列凹顶藻中分离得到33种化学成分，通过波谱学方法（IR、MS、NMR）以及X-ray单晶衍射试验对其化学结构进行了确证，其中化合物L1~L8为新结构化合物，化合物L5为具有新骨架的全新结构化合物，化合物L9~L13为新天然产物，化合物L18和L22系首次从海洋生物中获得，所有化合物均为首次从该属海藻中得到。新化合物L1~L8均为倍半萜类化合物，命名分别为：(1R,3R)-(-)-3-(3-hydroxy-4-methylphenyl)- 1,3-dimethyl–2-methylidene cyclopentanol (L1), (1R,3R)-(-)-3-(4-methylphenyl)-1,3-dimethyl-2-methylidenecyclopentanol (L2)， (1R, 3R)-(-)-3-(2-hydroxy-4-methylphenyl)-1,3-dimethyl–2–methylidenecyclopentanol (L3)，(+)-(1S,2R)–2-(3–hydroxy–4–methylphenyl)-1,2-[3.1.0]bicy-clohexane (L4)，()-(1S,2R) -5-hydroxy–6–methyl-spiro-dihydrobenzofuran-2(3H),2-{1-methyl-[3.1.0]bicyclohexane} (L5), (+)-6-methyl-2-(p-tolyl)hept-4-en-2,6-diol (L6)，(3R,3aS,8bS)-(-)-2,3,3a,8b–tetrahydro–7-bromo – 3 a– hydroxymethyl - 3, 6, 8b - trimethyl-1H- cyclopenta[b] benzofuran (L7 )，(3R, 3aS, 8bS) - (-) - 2,3,3a,8b–tetrahydro–3 a–hydroxymethyl-3,6,8b -trimethyl -1H – cyclopenta [b] benzofuran (L8)。25个已知结构化合物确定为：(+)-(1R,2R)-4-bromo-1,5, 9–trimethyl–12– methylidene–8–oxa-tricyclo[7.2.1.02]dodeca-2,4,6-triene (L9)，(3S,3aR,8bS)-(-)-2,3,3a, 8b– tetra -hydro–7-bromo–3–hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopenta[b]benzofu- ran (L10 )，(3R, 3aR, 8bS) - (-) - 2, 3, 3a, 8b – tetrahydro – 7 - bromo – 3 – hydroxy - 3,3a,6,8b - tetramethyl - 1H - cyclopenta [b] benzofuran (L11 )，(3S,3aR,8bS) - (-) - 2, 3, 3a, 8b – tetrahydro –3–hydroxy -3, 3a, 6, 8b - tetramethyl-1H-cyclopenta[b]benzofuran (L12 )， ( 3aR, 8bS) - (-) - 3a,8b –dihydro–7 - bromo – 3, 3a, 6, 8b - tetramethyl - 1H - cyclopenta[b]benzofuran (L13 )，aplysinol (L14 ) ，aplysin (L15)，laurebiphenyl (L16)，johnstonol (L17)，gossonorol (L18)，7,10-epoxy-ar- bisabol-11-ol (L19)，10-epi-7,10-epoxyarbisabol-11-ol (L20) 3β-hydroxy- 5α, 6α-epoxy- β- ionone (L21 )，3β-hydroxy-5β,6β-epoxy-β-ionone (L22 )，胆甾醇 (L23 )，胆甾-5-烯-3β,7α二醇胆甾-5-烯-3β,7α二醇 (L24)，β-谷甾醇 (L25)，叶绿醇 (L26 )，玉米黄素 (L27 )，对羟基苯甲醛 (L28 )，3-吲哚甲醛 (L29 )，1-O-十六烷酰基-3-O-β-D-吡喃半乳糖基-丙三醇(L30 )，1-O-十八烷酰基-3-O-β-D-吡喃半乳糖基-丙三醇 (L31 )，丙三醇-1-软脂酸单酯 (L32 )，正十六碳酸 (L33 )。 采用MTT法对其中23个单体化合物在Bel-7402细胞株、BGC-823细胞株、A549细胞株、A2780细胞株、HCT-8细胞株和HELL细胞株模型上进行了细胞毒活性测试；采用MTT法对其中13个单体化合物在犬主动脉血管模型上进行了血管平滑肌细胞增殖抑制活性测试；结果表明，部分单体化合物显示出一定的生物活性。

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Influence of Local Magnetic Fields on P-Doped Si Floating Zone Melting Crystal Growth in Microgravity

A two-dimensional axisymmetric numerical model is presented to study the influence of local magnetic fields on P-doped Si floating zone melting crystal growth in microgravity. The model is developed based on the finite difference method in a boundary-fitted curvilinear coordinate system. Extensive numerical simulations are carried out, and parameters studied include the curved growth interface shape and the magnetic field configurations. Computed results show that the local magnetic field is more effective in reducing the impurity concentration nonuniformity at the growth interface in comparison with the longitudinal magnetic field. Moreover, the curved growth interface causes more serious impurity concentration nonuniformity at the growth interface than the case with a planar growth interface.

Kinetics and Force Dependence of P-selectin/PSGL-1 Interactions Measured by AFM

Leukocytes roll along the endothelium of postcapillary venules in response to inflammatory and thrombotic processes. The rolling under hydrodynamic shear forces is a first step in directing leukocytes out of the blood stream into sites of inflammation and is mediated by the selectins, a family of extended, modular, and calcium-dependent lectin receptors. The interactions between P-, E-or L-selectins and their count.

An Analytical Solution for Three-Dimensional Diffraction of Plane P-Waves by a Hemispherical Alluvial Valley with Saturated Soil Deposits

An analytical solution for the three-dimensional scattering and diffraction of plane P-waves by a hemispherical alluvial valley with saturated soil deposits is developed by employing Fourier-Bessel series expansion technique. Unlike previous studies, in which the saturated soil deposits were simulated with the single-phase elastic theory, in this paper, they are simulated with Biot's dynamic theory for saturated porous media, and the half space is assumed as a single-phase elastic medium. The effects of the dimensionless frequency, the incidence angle of P-wave and the porosity of soil deposits on the surface displacement magnifications of the hemispherical alluvial valley are investigated. Numerical results show that the existence of a saturated hemispherical alluvial valley has much influence on the surface displacement magnifications. It is more reasonable to simulate soil deposits with Biot's dynamic theory when evaluating the displacement responses of a hemispherical alluvial valley with an incidence of P-waves.

应用光阱技术测量P-selectin/PSGL-1键解离的断裂力

选择素(selectin)与配体相互作用在诸如炎症反应、肿瘤转移等生物学过程中具有重要作用;作用力影响受体-配体键解离.本文发展了基于光阱技术的新实验方法,用于考察P-选择素(P-selectin)与P-选择素糖蛋白配体-1(P-selectin Glycoprotein Ligand 1, PSGL-1)相互作用的解离过程.采用黏滞力法对光阱刚度系数进行标定,并通过分子在玻璃小球表面的功能化表征,研究力作用下P-selectin/PSGL-1键的解离,得到了在较低加载率(<25 pN/s)下键解离的断裂力分布,发现键的最可几断裂力随加载率而增加.实验结果在较低加载率下补充和验证了已有的结论.

Quantifying the Effects of Contact Duration, Loading Rate, and Approach Velocity on P-Selectin-PSGL-1 Interactions Using AFM

Kinetics and its regulation by extrinsic physical factors govern selectin-ligand interactions that mediate tethering and rolling of circulating cells on the vessel wall under hemodynamic forces. While the force regulation of off-rate for dissociation of selectin-ligand bonds has been extensively studied, much less is known about how transport impacts the on-rate for association of these bonds and their stability. We used atomic force microscopy (AFM) to quantify how the contact duration, loading rate, and approach velocity affected kinetic rates and strength of bonds of P-selectin interacting with P-selectin glycoprotein ligand I (PSGL-1). We found a saturable relationship between the contact time and the rupture force, a biphasic relationship between the adhesion probability and the retraction velocity, a piece-wise linear relationship between the rupture force and the logarithm of the loading rate, and a threshold relationship between the approach velocity and the rupture force. These results provide new insights into how physical factors regulate receptor-ligand interactions.

Distinct Element Analysis on Propagation Characteristics of P-Wave in Rock Pillar with Finite length

以节理岩体等效刚度的概念为基础,讨论了离散元刚性块体模型中节理刚度的选取问题。采用面-面接触模型模拟了纵波在一维岩体中的传播,给出了纵波波形；研究了阻尼比、软弱夹层以及节理间是否可拉对波传播规律的影响。

The Heterogeneous Growth of P(3MeTh)--An Ellipsometric Study

Successive thicker P(3MeTh) layers are analysed by ex situ conventional and imaging ellipsometry. Thin films display a smooth surface, are compact and homogeneous while for a growth charge above 20 mC cm(-2) the polymer structure modifies to a still uniform but less dense layer. A two-layer model is used and a mathematical procedure is developed to obtain, simultaneously, from the experimental ellipsometric parameters, Delta and Psi, the thickness and the complex refractive index of P(3MeTh) films grown up to 80 mC cm(-2). Thicker polymer layers are disordered and present a high degree of surface roughness. 

The application of B-P constitutive equations in finite element analysis of high velocity impact

We present in this paper the application of B-P constitutive equations in finite element analysis of high velocity impact. The impact process carries out in so quick time that the heat-conducting can be neglected and meanwhile, the functions of temperature in equations need to be replaced by functions of plastic work. The material constants in the revised equations can be determined by comparison of the one-dimensional calculations with the experiments of Hopkinson bar. It can be seen from the comparison of the calculation with the experiment of a tungsten alloy projectile impacting a three-layer plate that the B-P constitutive equations in that the functions of temperature were replaced by the functions of plastic work can be used to analysis of high velocity impact.

Forced extension of P-selectin construct using steered molecular dynamics

P-selectin, a 70-nm-long cellular adhesive molecule, possesses elastic and extensible properties when neutrophils roll over the activated endotheliam of blood vessel in inflammatory reaction. Transient formation and dissociation of P-selectin/ligand bond on applied force of blood flow induces the extension of P-selectin and relevant ligands. Steered molecular dynamics simulations were performed to stretch a single P-selectin construct consisting of a lectin (Lec) domain and an epithelial growth factor (EGF)-like domain, where P-selectin construct was forced to extend in water with pulling velocities of 0.005-0.05 nm/ps and with constant forces of 1000-2500 pN respectively. Resulting force-extension profiles exhibited a dual-peak pattern on various velocities, while both plateaus and shoulders appeared in the extension-time profiles on various forces. The force or extension profiles along stretching pathways were correlated to the conformational changes, suggesting that the structural collapses of P-selectin Lec/EGF domains were mainly attributed to the burst of hydrogen bonds within the major beta sheet of EGF domain and the disruptions of two hydrophobic cores of Lee domain. This work furthers the understanding of forced dissociation of P-selectin/ligand bond.

Low Spring Constant Regulates P-Selectin-Psgl-1 Bond Rupture

Forced dissociation of selectin-ligand bonds is crucial to such biological processes as leukocyte recruitment, thrombosis formation, and tumor metastasis. Although the bond rupture has been well known at high loading rate r(f) (>= 10(2) pN/s), defined as the product of spring constant k and retract velocity v, how the low r(f) (< 10(2) pN/s) or the low k regulates the bond dissociation remains unclear. Here an optical trap assay was used to quantify the bond rupture at r(f) <= 20 pN/s with low k (similar to 10(-3)-10(-2) pN/nm) when P-selectin and P-selectin glycoprotein ligand 1 (PSGL-1) were respectively coupled onto two glass microbeads. Our data indicated that the bond rupture force f retained the similar values when r(f) increased up to 20 pN/s. It was also found that f varied with different combinations of k and v even at the same r(f). The most probable force, f