含钆温度敏感高分子核磁共振成像(MRI)造影剂的制备及研究

合成了一种新型可聚合型含钆单体,在温敏单体N-异丙基丙烯酰胺存在下,采用无皂乳液聚合法一步制备了含钆温度敏感的高分子微球.透射电子显微镜测试表明微球呈单分散性;动态光散射测试表明高分子微球的平均水合粒径约260 nm,呈现很窄的粒径分布;当温度从25℃升到45℃时,其粒径减小约60 nm,表明含钆高分子微球具有较好的温度敏感性.体外MRI测试表明,所得高分子微球的体外弛豫率为8.01(mmol/L)-1S-1(3 T),能有效的增强MRI信号,具有优良的MRI造影功能.上述结果表明,所得微球作为一种多功能MRI造影剂,在生物医学领域极具应用前景.     

The formulation of a self-consistent constricted variational density functional theory for the description of excited states

We outline here a self-consistent approach to the calculation of transition energies within density functional theory. The method is based on constricted variational theory (CV-DFT). It constitutes in the first place an improvement over a previous scheme [T. Ziegler, M. Seth, M. Krykunov, J. Autschbach, F. Wang, Chem. Phys. 130 (2009) 154102] in that it includes terms in the variational parameters to any desired order n including n = ∞. For n = 2, CV(n)-DFT is similar to TD-DFT. Adiabatic TD-DFT becomes identical to CV(2)-DFT after the Tamm-Dancoff approximation is applied to both theories. We have termed the new scheme CV(n)-DFT. In the second place, the scheme can be implemented self-consistently, SCF-CV(n)-DFT. The procedure outlined here could also be used to formulate a SCF-CV(n) Hartree-Fock theory. The approach is further kindred to the ΔSCF-DFT procedures predating TD-DFT and we describe how adiabatic TD-DFT and ΔSCF-DFT are related through different approximations to SCF-CV(n)-DFT.     

Determination of leakage from antibody adsorbent: composition analysis and pH effect

To study the leakage at different solution pH values, IgG Sepharose 6FF®, a commercially available immunoadsorbent, was used as a model. The leaked substance consists of three parts: (1) ligands and its fragments; (2) ligands plus matrix fragments in which ligands are chemically attached to the adsorbent matrix; and (3) matrix fragments. Buffer solution pH values had a great effect on both the kinetics and the amount of ligand leakage. Cross‐linking of the adsorbent matrix could reduce both matrix leakage and antibody leakage at pH 3.0, but its effect was limited at pH 11.0 for ligand leakage. Copyright © 2013 John Wiley & Sons, Ltd.     

Projection‐based variational multiscale method for incompressible Navier–Stokes equations in time‐dependent domains

A variational multiscale method for computations of incompressible Navier–Stokes equations in time‐dependent domains is presented. The proposed scheme is a three‐scale variational multiscale method with a projection‐based scale separation that uses an additional tensor valued space for the large scales. The resolved large and small scales are computed in a coupled way with the effects of unresolved scales confined to the resolved small scales. In particular, the Smagorinsky eddy viscosity model is used to model the effects of unresolved scales. The deforming domain is handled by the arbitrary Lagrangian–Eulerian approach and by using an elastic mesh update technique with a mesh‐dependent stiffness. Further, the choice of orthogonal finite element basis function for the resolved large scale leads to a computationally efficient scheme. Simulations of flow around a static beam attached to a square base, around an oscillating beam and around a plunging aerofoil are presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Band gap dependence with temperature of semiconductors from solar cells electrical parameters

Using experimental measurements of the open-circuit voltage and the short-circuit current density at different temperatures, for a solar cell, we investigate numerically the band gap evolution with temperature for the semiconductor constituting the concerned device. The application of the approach in the case of silicon semiconductor gives satisfying results compared to previous works.     

Optical spectroscopy to study confined and semi-closed explosions of homogeneous and composite charges

Confined and semi-closed explosions of new class of energetic composites as well as TNT and RDX charges were investigated using optical spectroscopy. These composites are considered as thermobarics when used in layered charges or enhanced blast explosives when pressed. Two methods to estimate fireball temperature histories of both homogeneous and metallized explosives from the spectroscopic data are also presented, compared and analyzed. Fireball temperature results of the charges detonated in a small explosion chamber under air and argon atmospheres, and detonated in a semi-closed bunker are presented and compared with theoretical ones calculated by a thermochemical code. Important conclusions about the fireball temperatures and the physical and chemical phenomena occurring after the detonation of homogeneous explosives and composite formulations are deduced.     

On Bifurcations of Equilibria of Intrinsically Curved, Electrically Charged, Rod-like Structures that Model DNA Molecules in Solution

DNA molecules in the familiar Watson–Crick double helical B form can be treated as though they have rod-like structures obtained by stacking dominoes one on top of another with each rotated by approximately one-tenth of a full turn with respect to its immediate predecessor in the stack. These “dominoes” are called base pairs. A recently developed theory of sequence-dependent DNA elasticity (Coleman, Olson, & Swigon, J. Chem. Phys. 118:7127–7140, 2003) takes into account the observation that the step from one base pair to the next can be one of several distinct types, each having its own mechanical properties that depend on the nucleotide composition of the step. In the present paper, which is based on that theory, emphasis is placed on the fact that, as each base in a base pair is attached to the sugar-phosphate backbone chain of one of the two DNA strands that have come together to form the Watson–Crick structure, and each phosphate group in a backbone chain bears one electronic charge, two such charges are associated with each base pair, which implies that each base pair is subject to not only the elastic forces and moments exerted on it by its neighboring base pairs but also to long range electrostatic forces that, because they are only partially screened out by positively charged counter ions, can render the molecule’s equilibrium configurations sensitive to changes in the concentration c of salt in the medium. When these electrostatic forces are taken into account, the equations of mechanical equilibrium for a DNA molecule with N + 1 base pairs are a system of μN non-linear equations, where μ, the number of kinematical variables describing the relative displacement and orientation of adjacent pairs is in general 6; it reduces to 3 when base-pair steps are assumed to be inextensible and non-shearable. As a consequence of the long-range electrostatic interactions of base pairs, the μN × μN Jacobian matrix of the equations of equilibrium is full. An efficient numerically stable computational scheme is here presented for solving those equations and determining the mechanical stability of the calculated equilibrium configurations. That scheme is employed to compute and analyze bifurcation diagrams in which c is the bifurcation parameter and to show that, for an intrinsically curved molecule, small changes in c can have a strong effect on stable equilibrium configurations. Cases are presented in which several stable configurations occur at a single value of c.      

Forming of AA5182-O and AA5754-O at elevated temperatures using coupled thermo-mechanical finite element models

A temperature-dependent anisotropic material model was developed for two aluminum alloys AA5182-O and AA5754-O and their anisotropy parameters were established. A coupled thermo-mechanical finite element analysis of the forming process was then performed for the temperature range 25–260 °C (77–500 °F) at different strain rates. In the developed model, the anisotropy coefficients for Barlat’s YLD2000-2d anisotropic yield function [Barlat, F., Brem, J.C., Yoon, J.W., Chung, K., Dick, R.E., Lege, D.J., Pourboghrat, F., Choi, S.H., Chu, E., 2003. Plane stress yield function for aluminum alloy sheets – Part 1: Theory. Int. J. Plasticity 19, 1297–1319] in the plane-stress condition and the parameters for the isotropic strain hardening were established as a function of temperature. The temperature-dependent anisotropic yield function was then implemented into the commercial FEM code LS-DYNA as a user material subroutine (UMAT) using the cutting-plane algorithm for the integration of a general class of elastoplastic constitutive models [Abedrabbo, N., Pourboghrat, F., Carsley, J., 2006b. Forming of aluminum alloys at elevated temperatures – Part 2: Numerical modeling and experimental verification. Int. J. Plasticity 22 (2), 342–737]. The temperature-dependent material model was used to simulate the coupled thermo-mechanical finite element analysis of the stamping of an aluminum sheet using a hemispherical punch under the pure stretch boundary condition (no material draw-in was allowed). Simulation results were compared with experimental data at several elevated temperatures to evaluate the accuracy of the UMAT’s ability to predict both forming behavior and failure locations. Two failure criteria were used in the analysis; the M–K strain based forming limit diagrams (ε-FLD), and the stress based forming limit diagrams (σ-FLD). Both models were developed using Barlat’s YLD2000-2d anisotropic model for the two materials at several elevated temperatures. Also, as a design tool, the Genetic Algorithm optimization program HEEDS was linked with the developed thermo-mechanical models and used to numerically predict the “optimum” set of temperatures that would generate the maximum formability for the two materials in the pure stretch experiments. It was found that a higher temperature is not needed to form the part, but rather the punch should be maintained at the lowest temperature possible for maximum formability.     

Flow structure and wall layer control in a lower half heated upper half cooled enclosure with superimposed temperature deviations

This paper presents an investigation on the effects of superimposed temperature deviations as a control technique for the flows and mixing in lower half heated upper half cooled enclosures. Results show that the strength of the wall layer depends on the difference between the wall surface temperature and the fluid core temperature. The location of the head-on collision between a pair of upward/downward wall layers, which controls the mixing and fluid exchange between the two halves, is determined by the wall layer flow momentum strengths. Elevating/reducing the wall temperature by a superimposed temperature deviation is an effective control for the flow and mixing in such enclosures. Heat transfer analysis shows that the superimposed temperature deviations have minor effects on the total heat flow rate from the lower walls. Thus, this technique can be applied onto reactor vessels without modifying the reactor vessel configuration.