Synthesis of crosslinked nanostructured saccharidic vinyl copolymers and their functionalization

Saccharidic monomers and a macromonomer were synthesized and copolymerized in the presence of divinylbenzene (DVB) as crosslinker in conditions of separation of phases to give hydrophilic nanostructured sugar-based vinyl copolymers. Appropriate model molecules such as N-benzyl-d-gluconamide for the saccharidic copolymers and 4-(4-chlorobutoxy)benzaldehyde and (E)-4-(4-chloro-2-butenyloxy)benzaldehyde for electrophilic reagents prefiguring possible copper amine oxidase inhibitors allowed identification of conditions for useful monofunctionalizations mainly at the position 2 of the saccharidic units. The examined samples of the nanostructured copolymers from one of the monomers proved to be stable enough to tolerate the functionalization reactions without loss of morphology.     

Revised model core potentials of s-block elements

We developed new model core potentials (MCPs) for s-block elements from Na to Ra, in which the outer core (n-1)s and (n-1)p electrons are treated explicitly together with the ns electrons. By adding suitable correlating functions, we demonstrated that the present MCP basis sets show excellent performance in describing the electronic structures of atoms and molecules, bringing about accurate ionization potentials of atoms and very good spectroscopic constants of ionic and covalent molecules. The results obtained with the new MCPs are very close to the ones obtained using the all-electron correlation consistent basis sets of Dunning.     

In situ micro-sized gel-forming injectable implant using biodegradable amphiphilic graft copolymer

A synthesized graft polymer is used as a biodegradable polymer for an in situ gel-forming injectable implant system. The amphiphilic character of the polymer in the graft structure lowered the viscosity of the polymer solution, which enabled easy injection. A micro-sized gel can be obtained with this system, which has not been found for previous in situ gel-forming systems with poly[(D,L-lactide)-co-glycolide] copolymer. In addition, a protein particle embedded gel exhibits good in vitro drug release performance as a result of the enhanced stability and shorter diffusion length.     

Elasticity in certain block monoids via the Euclidean table

This paper continues the study begun in [GEROLDINGER, A.: On non-unique factorizations into irreducible elements II, Colloq. Math. Soc. János Bolyai 51 (1987), 723–757] concerning factorization properties of block monoids of the form ℬ(ℤ _n , S) where S = (hereafter denoted ℬ _a (n)). We introduce in Section 2 the notion of a Euclidean table and show in Theorem 2.8 how it can be used to identify the irreducible elements of ℬ _a (n). In Section 3 we use the Euclidean table to compute the elasticity of ℬ _a (n) (Theorem 3.4). Section 4 considers the problem, for a fixed value of n, of computing the complete set of elasticities of the ℬ _a (n) monoids. When n = p is a prime integer, Proposition 4.12 computes the three smallest possible elasticities of the ℬ _a (p). Part of this work was completed while the second author was on an Academic Leave granted by the Trinity University Faculty Development Committee.     

Synthesis of 3-deoxy-3,3-difluoro-d-ribohexose from gem-difluorohomoallyl alcohol

A novel synthetic route to 3-deoxy-3,3-difluoro-d-ribohexose 1 has been developed. Dihydroxidation of gem-difluorohomoallyl alcohol followed by several steps of protection and deprotection gave key intermediate 9. Oxidation of 1,5-diol 9 with 2 equiv. trichloroisocyanuric acid and catalytic TEMPO gave lactone 10. Reduction of 10 with DIBAL-H followed by deprotections afforded the target molecule 1.     

Dynamic block GMRES: an iterative method for block linear systems

We present variants of the block-GMRES() algorithms due to Vital and the block-LGMRES(,) by Baker, Dennis and Jessup, obtained with replacing the standard QR factorization by a rank-revealing QR factorization in the Arnoldi process. The resulting algorithm allows for dynamic block deflation whenever there is a linear dependency between the Krylov vectors or the convergence of a right-hand-side occurs. implementations of the algorithms were tested on a number of test matrices and the results show that in some cases a substantial reduction of the execution time is obtained. Also a parallel implementation of our variant of the block-GMRES() algorithm, using and was tested on parallel computer, showing good parallel efficiency. This work was carried out while the author was at IM/UFRGS.     

图像序列运动检测算法的研究及其应用

探讨了监控图像序列中进行运动检测的若干基本算法 ,结合统计方法和边缘检测筛选出运动边缘点 ,对运动边缘点逐个进行了块匹配最优搜索 ,估算出其运动矢量 .此方法在数字视频监控系统中用于运动物体检测和报警 ,不但提供了智能型监控 ,而且也有效的压缩了存储数据 ,改善了系统性能 ,有较好的实用价值 .     

Modeling of the Phase Separation Behavior of Polydisperse Semi‐Flexible Diblock Copolymers

Summary: A modified random phase approximation method with a cumulant expansion for the semi‐flexible structure factor of diblock copolymers was exercised to describe the phase separation behavior of semi‐flexible and polydisperse diblock copolymers. Scattering curves and spinodal diagrams were calculated applying monomer specific input parameters. The influence of polydispersity was included applying basic concepts of mathematical statistics utilizing several probability density distributions in the case of the two single blocks. In contrast to semi‐flexibility, the main effect of polydispersity was found to shift the spinodal up, thus to enlarge the range of existence of the homogeneous phase.

Twofold Schultz‐Zimm distribution of diblock copolymers.     

Polymer Melt Intercalation in Clay Modified by Diblock Copolymers

Summary: The thermodynamic equilibrium in a melt of homopolymer C mixed with clay modified by a diblock copolymer AB is considered in theory. It is assumed that mixing is carried out in two stages. At first, the diblock copolymer penetrates into the interlayers formed by long clay sheets. Then, the clay with adsorbed diblock copolymer chains is added to the homopolymer melt. It is shown that the first process is thermodynamically favorable only if the interlayer width exceeds some threshold value that depends mostly on the difference in the adsorption energy of units A and B. A spontaneous mixing at the second stage is possible only if the enthalpic interactions between homopolymer and copolymer units are not very unfavorable. If so, the formation of an intercalated state is expected for a homopolymer of length comparable to the copolymer length, while for a long homopolymer the anticipated equilibrium state is exfoliation. The spatial distribution of A, B, and C units across the interlayer has been studied for different parameters of the system. The most readily adsorbing units A occupy almost all clay surface. However, the layer of block A is considerably swelled by both B and C units. The mutual distribution of units B and C may vary from almost homogeneous to having rather sharp boundary depending on the value of the Flory‐Huggins parameter χ_BC. The formation of a pure homopolymer layer at the center of the interlayer indicates about a tendency to exfoliate.

Interlayer profiles of the fractions of units A, B, and C, respectively.     

An Ordered Nanoporous Monolith from an Elastomeric Crosslinked Block Copolymer Precursor

Summary: An ordered nanoporous monolith was prepared from a poly(isoprene‐b‐dimethylsiloxane) (PI‐PDMS) hexagonally packed cylinder precursor. The PDMS cylinders were macroscopically aligned, the PI was crosslinked with dicumyl peroxide, and the PDMS was removed using tetrabutylammonium fluoride. The stability of the pores depended on the modulus of the matrix. At high crosslink density the pores were stable, but they collapsed at a low crosslink density. The nanoporous materials could be swollen in toluene.

A scanning electron micrograph of the end‐on view of crosslinked degraded poly(isoprene‐b‐dimethylsiloxane).