Synthesis and structure characterization of ladder-like polymethylsilsesquioxane (PMSQ) by isolation of stereoisomer

The stereo cyclic siloxane compounds having tetra hydroxyl and tetra methyl group were synthesized by hydrolysis of tetrahydrido tetramethyl cyclosiloxane consisting of four stereoisomers. Among the stereo cyclic isomers, cis-trans-cis tetrahydroxyl tetramethyl cyclosiloxane (2) was separated by recrystallization and was used as a monomer species for preparation of ladder-like polymethylsilsesquioxane (PMSQ). The isolated isomer was directly polymerized in THF with potassium carbonate (K₂CO₃) by systematic ring condensation. The hydrolyzed stereoisomers were characterized by ¹H and ²⁹Si NMR, and HPLC. The structure of the synthesized PMSQs were characterized by size exclusion chromatography (SEC), MALDI-TOF mass, ²⁹Si NMR, and small angle X-ray scattering (SAXS).     

Spin-adapted density matrix renormalization group algorithms for quantum chemistry

We extend the spin-adapted density matrix renormalization group (DMRG) algorithm of McCulloch and Gulacsi [Europhys. Lett. 57, 852 (2002)] to quantum chemical Hamiltonians. This involves using a quasi-density matrix, to ensure that the renormalized DMRG states are eigenfunctions of S?(2), and the Wigner-Eckart theorem, to reduce overall storage and computational costs. We argue that the spin-adapted DMRG algorithm is most advantageous for low spin states. Consequently, we also implement a singlet-embedding strategy due to Tatsuaki [Phys. Rev. E 61, 3199 (2000)] where we target high spin states as a component of a larger fictitious singlet system. Finally, we present an efficient algorithm to calculate one- and two-body reduced density matrices from the spin-adapted wavefunctions. We evaluate our developments with benchmark calculations on transition metal system active space models. These include the Fe(2)S(2), [Fe(2)S(2)(SCH(3))(4)](2-), and Cr(2) systems. In the case of Fe(2)S(2), the spin-ladder spacing is on the microHartree scale, and here we show that we can target such very closely spaced states. In [Fe(2)S(2)(SCH(3))(4)](2-), we calculate particle and spin correlation functions, to examine the role of sulfur bridging orbitals in the electronic structure. In Cr(2) we demonstrate that spin-adaptation with the Wigner-Eckart theorem and using singlet embedding can yield up to an order of magnitude increase in computational efficiency. Overall, these calculations demonstrate the potential of using spin-adaptation to extend the range of DMRG calculations in complex transition metal problems.     

Measurement and analysis of forces in bubble and droplet systems using AFM

The use of atomic force microscopy to measure and understand the interactions between deformable colloids - particularly bubbles and drops - has grown to prominence over the last decade. Insight into surface and structural forces, hydrodynamic drainage and coalescence events has been obtained, aiding in the understanding of emulsions, foams and other soft matter systems. This article provides information on experimental techniques and considerations unique to performing such measurements. The theoretical modelling frameworks which have proven crucial to quantitative analysis are presented briefly, along with a summary of the most significant results from drop and bubble AFM measurements. The advantages and limitations of such measurements are noted in the context of other experimental force measurement techniques.     

Proteomic analysis reveals platelet factor 4 and beta-thromboglobulin as prognostic markers in severe acute respiratory syndrome

Previously, we reported that proteomic fingerprints were present in sera of patients with severe acute respiratory syndrome (SARS), and could separate patients into subgroups with different prognoses. In the present study, we examined the prognostic values of the SARS-associated proteomic features by biostatistical analysis, and deciphered the identities of those with prognostic values. Data of 20 SARS-associated serum proteomic features and ten serological variables from 38 SARS adult patients before treatment were subjected to multivariate logistic regression. Proteomic features of m/z 6634, m/z 7769, m/z 8635, and m/z 8865 were identified as independent prognostic markers. After purification by cation-exchange chromatography and gel electrophoresis, proteomic features of m/z 7769 and m/z 8865 were found to be platelet factor 4 (PF4) and beta-thromboglobulin (beta-TG) by tandem mass spectrometry, respectively. The associations of decreased serum PF4 and increased serum beta-TG levels with poor prognosis were confirmed by Western blot. Previous studies suggest that PF4 and beta-TG are involved in the pathogenesis of acute respiratory distress syndrome (ARDS) in a negative and positive way, respectively. Our results suggest that PF4 and beta-TG may also play similar roles in the development of ARDS in SARS patients.     

Direct synthesis of aqueous quantum dots through 4,4'-bipyridine-based twin ligand strategy

We report a new class of derivatized 4,4'-bipyridinium ligands for use in synthesizing highly fluorescent, extremely stable, water-soluble CdSe and CdTe quantum dots (QDs) for bioconjugation. We employed an evaporation-condensation technique, also known as solvated metal atom dispersion (SMAD), followed by a digestive ripening procedure. This method has been used to synthesize both metal nanoparticles and semiconductors in the gram scale with several stabilizing ligands in various solvents. The SMAD technique comprised evaporation condensation and stabilization of CdSe or CdTe in tetrahydrofuran. The as-prepared product was then digestively ripened in both water and dimethyl formamide, leading to narrowing of the particle size distributions. The ligands were synthesized by nucleophilic substitution (S(N)2) reactions using 4,4'-bipyridine as a nucleophile. Confocal microscopy images revealed the orange color of the nanocrystalline QDs with diameters of ~5 nm. The size has been confirmed by using transmission electron microscopy. As a part of our strategy, 85% of the 4,4'-bipyridinium salt was synthesized as propionic acid derivative and used to both stabilize the QDs in water and label basic amino acids and different biomarkers utilizing the carboxylic acid functional group. Fifteen percent of the 4,4'-bipyridinium salt was synthesized as N-propyl maleimide and used as a second ligand to label any protein containing the amino acid cysteine by means of a 1,4-Michael addition.     

On parameter estimation of threshold autoregressive models

This paper studies the threshold estimation of a TAR model when the underlying threshold parameter is a random variable. It is shown that the Bayesian estimator is consistent and its limit distribution is expressed in terms of a limit likelihood ratio. Furthermore, convergence of moments of the estimators is also established. The limit distribution can be computed via explicit simulations from which testing and inference for the threshold parameter can be conducted. The obtained results are illustrated with numerical simulations.     

Facing the change and meeting the challenge: mathematics curriculum of Tongwen Guan in China in the second half of the nineteenth century

It is commonly recognized that the second wave of transmission of Western science and mathematics into China took place in the second half of the nineteenth century, thereby starting a process of modernization which has become synonymous with ??westernization?? of the country. In this context mathematics education in China also went through a process of modernization. During this period of great change reformers faced serious challenge and went through a ??mental struggle??. This paper discusses this challenge and mental struggle by taking a close look at the controversy over the establishment of Tianwen Suanxue Guan (School of Astronomy and Mathematics) in Tongwen Guan (School of Combined Learning), one of the schools of Western learning at the time. The attempt to integrate Western mathematics with Chinese traditional mathematics is also discussed through the study of some questions sampled from examinations and students?? homework assignments of this school.     

综合核方法求解辐射输运问题的求积组选取

简要介绍求解辐射输运方程的综合核方法,分析计算误差和收敛性,提出新的求积组和误差修正方法,提高综合核方法的计算精度.通过对基准问题的计算比对表明,采用提出的求积组并通过误差修正,综合核方法在低阶时的结果具有较高的计算精度.     

食品中化学添加剂的功能与风险控制*

食品中的化学添加剂是指由化学方法合成的一类食品添加剂。本文探讨了食品中化学添加剂产生和发展的原因,指出化学合成的食品添加剂是天然物质群的一种补充与完善,概述了化学合成食品添加剂的一般性质和功能,介绍了食品添加剂联合专家委员会(JECFA)、美国、欧盟和中国对食品添加剂进入市场前的安全性评价程序和方法,以及美国、欧盟和中国在化学添加剂投入使用后实施监督管理的机构、法律依据、质量标准等,总结了影响食品中化学添加剂安全风险控制的主要因素,最后在此基础上,提出如何从政府、企业、科研三方面完善风险控制体系和有效保障食品安全的建议。     

Momentum and heat transport in a finite-length cylinder wake

This paper reports an experimental study of turbulent momentum and heat transport in the wake of a wall-mounted finite-length square cylinder, with its length-to-width ratio L/d = 3–7. The cylinder was slightly heated so that heat produced could be considered as a passive scalar. A moveable three-wire probe (a combination of an X-wire and a cold wire) was used to measure velocity and temperature fluctuations at a Reynolds number of 7,300 based on d and the free-stream velocity. Measurements were performed at 10 and 20d downstream of the cylinder at various spanwise locations. Results indicate that L/d has a pronounced effect on Reynolds stresses, temperature variance and heat fluxes. The downwash flow from the free end of the cylinder acts to suppress spanwise vortices and, along with the upwash flow from the cylinder base, makes the finite-length cylinder wake highly three-dimensional. Reynolds stresses, especially the lateral normal stress, are significantly reduced as a result of suppressed spanwise vortices at a small L/d. The downwash flow acts to separate the two rows of spanwise vortices further apart from the wake centerline, resulting in a twin-peak distribution in temperature variance. While the downwash flow entrains high-speed fluid into the wake, responsible for a small deficit in the time-averaged streamwise velocity near the free end, it does not alter appreciably the distribution of time-averaged temperature. It has been found that the downwash flow gives rise to a counter-gradient transport of momentum about the central region of the wake near the free end of the cylinder, though such a counter-gradient transport does not occur for heat transport.