Anion coordination and molecular assembly in C2-substituted thiamine-anion systems: effects of the anion and molecular conformation

The compounds (het)(PtCl6)2H(2)O 1, (het)(HgI4).H2O 2 (het = 2-(alpha-hydroxyethyl)thiamine) and (hpt)(Hg2Br6) 3 (hpt = 2-(alpha-hydroxypropyl)thiamine) have been prepared and structurally characterized by X-ray crystallography in order to study the influence of the anion and molecular conformation on the formation of supramolecular architectures that adsorb anionic species. Both het and hpt molecules adopt the usual S conformation for C2-substituted thiamine but differ from the F conformation for C2-free thiamine derivatives. Two types of characteristic ligand-anion complexation are observed, being of the forms C(6')-H...anion...thiazolium-ring (in 1 and 2) and N(4'1)-H...anion...thiazolium-ring (in 3). The reaction of het with PtCl62- or HgI42- gives a 1-D double-chain in 1, consisting of two hydrogen-bonded het chains, which are cross-linked by anions through hydrogen bonding and anion...aromatic-ring interactions, or a cationic 3-D framework in 2 formed by the stacking of hydrogen-bonded sheets with anion-and-water-filled channels. In the case of 3, hydrogen-bonded hpt dimers and HgBr62- anions form alternate cation-anion columns. A comparison with the cases of C2-free thiamine-anion complexes indicates that the change in molecular conformation results in novel supramolecular assemblies in 1 and 2 and an analogous architecture in 3, which also depends on the nature of the anions.

Synthesis, crystal structure, and magnetic properties of {[Cu(oxbe)]Mn(H2O)[Cu(oxbe)(DMF)]}(n)center dot nDMF center dot nH(2)O: From dissymmetrical mononuclear entities to a 3D heterometallic supramolecular coordination polymer

Self-assembly of the building block [Cu(oxbe)](-) with Mn(II) led to a novel coordination polymer {[Cu(oxbe)]Mn(H2O)(Cu(oxbe)(DMF)]}(n).nDMF.nH(2)O, where H(3)oxbe is a new dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)-oxamido and DMF = dimethylformamide. The crystal forms in the triclinic system, space group P(1)over-bar, with a = 9.260(4) angstorm, b = 12.833(5) angstrom, c = 15.274(6) angstrom , alpha = 76.18(3)degrees, beta = 82.7(3)degrees, gamma = 82.31(3)degrees, and Z = 2. The crystal structure of the title complex reveals that the two-dimensional bimetallic layers are constructed of (CuMnII)-Mn-II-Cu-II chains linked together by carboxylate bridge and hydrogen bonds help to produce a novel three-dimensional channel-like structure. The magnetic susceptibility measurements (5-300 K) were analyzed by means of the Hamiltonian (H)over-cap = -2J(S)over-cap (Mn)((S)over-cap(Cu1) + (S)over-cap(Cu2)), leading to J = -17.4 cm(-1).

Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: Synthesis, structure, and fluorescent properties of [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (DNBA=3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo6O192-, has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.

From dissymmetrical mononuclear entities to centrosymmetrical heterotrinuclear complex with 2D supramolecular structure: synthesis, characterization, crystal structure, and magnetic properties

A new centrosymmetrical heterotrinuclear complex, {[Cu(oxbe)](2)Co(H2O)(2)}.2DMF.DMA with 2D supramolecular structure, has been obtained by the self-assembly of a dissymmetrical building block [Cu(oxbe)](-) with bivalent metal ion Co2+, where H(3)oxbe is dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)oxamido, DMF = dimethylformamide, DMA = dimethylamine. Its structure was determined by single crystal X-ray analysis. The molecular structure is centrosymmetrical with the cobalt atom lying on an inversion center. Through the hydrogen bonds and d-pi stacking interactions, a 2D supramolecular structure is formed. This study exemplifies a new method for the assembly of supramolecular structure using a dissymmetrical brick. Magnetic susceptibility measurements (5-300 K) indicate that the central cobalt and terminal copper metal ions are antiferromagnetically coupled with J = -23.1 cm(-1).

Oxamido-bridged heterobinuclear copper(II)-nickel(II) complex and homotrinuclear nickel(II) complex with 2D supramolecular structure: synthesis, crystal structure, magnetic and spectroscopic properties

The oxamido-bridged heterobinuclear copper(II)-nickel(II) complex, [Cu(oxbe)Ni(phen)(2)]ClO4.3H(2)O (1) and homotrinuclear nickel(11) complex {[Ni(oxbe)](2)Ni(H2O)(2)}.2.5DMF (2) have been synthesized and characterized by means of elemental analysis, IR, EPR. and electronic spectra and magnetic susceptibility, where H(3)oxbe is dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)ox-amido, phen = 1.10-phenanthroline, DMF = dimethylformamide. Complex I has an extended oxamido-bridged structure consisting of planar copper(II) and octahedral nickel(II) ions. The chi(M) and mu(eff) versus T plots of 1 is typical of an antiferromagnetically coupled Cu(II)-Ni(II,) pair with a spin-doublet ground state, and magnetic analysis leads to J = -57.1 cm(-1). The molecular structure of 2 is centrosymmetrical, with one octahedral nickel atom lying at an inversion center and two terminal Ni(II) atoms in approximately square planar environment. Through the hydrogen bonds and pi- pi stacking interactions, a 2D supramolecular structure is formed.

Encapsulation and luminescence of the nanostructured supramolecular material [Eu(Phen)(4)](NO3)(3)/(CH3)(3)Si-MCM-41

The nanostructured material (NSM) of pure silica MCM-41 molecular sieve was synthesized with tetraethyl orthosilicate (TEOS) as the source of silica and cetyltrimethylammonium bromide (CTMABr) as the template under supersonic wave condition. Then NSM of (CH3)(3)Si-MCM-41 was obtained by introducing trimethylsilyl to MCM-41. (CH3)(3)Si-MCM-41 showed the similar TEM and XRD photographs with the normal crystal of MCM-41 and the diameter of the NSM crystallites with a hexagon shape is of about 10-40 nm. The dispersivity of (CH3)(3)Si-MCM-41 prevails over the NSM of MCM-41 as its hydrophobicity. The fluorescent intensity of (CH3)(3)Si-MCM-41 is 3.4 times as that of the MCM-41. The luminescent functional supramolecular nanostructured material was prepared in EtOH, and characterized by TEM, HRTEM, XRD, TG, IR, and elemental analysis. The results showed that the [Eu(Phen)(4)](NO3)(3) had entered into the channels of nanosized mesoporous sieve of (CH3)(3)Si-MCM-41, forming discrete centers of luminescence. The energy transferring of the host to guest, superficial effect of NSM, quanta tunnel effect, and discrete luminescent center result in the fluorescent intensity of the supramolecule enhancement.

Molecular and supramolecular deformations and disclinations in a liquid crystalline copolyether thin films under an electrostatic field

An alignment study of a liquid crystalline copolyether TPP-7/11(5/5) thin films has been carried out in a 10 kV . cm(-1) electrostatic field parallel to the thin film surface normal. This copolyether possesses a negative dielectric anisotropy. The chain molecules are homogeneously aligned in the electric field and they form two-dimensionally ordered lamellae in a tilted columnar phase when the samples were cooled to room temperature. It is observed that the chain molecules are splayed to form bent lamellae and the chain direction is perpendicular to the tangential direction of the lamellar surfaces. These lamellae thus become replicas of the chain orientation, Due to the flexoelectric effect and density fluctuation on the thin film free surface, disclinations having topological strength s = 1, c = pi /4 and defect walls form. These s = 1 disclinations possesses both left- and right-handednesses. Discussion of the defect formations have been attempted.

The crystal structure and supramolecular chain of [La(NO3)(3)(OH2)(2)(phen)]center dot 15-crown-5

[La(NO3)(3)(OH2)(2)(phen)]. 15-crown-5 is hexagonal, P6(5), with a = 10.955(2), c = 43.769(9) Angstrom, and D-calc = 1.668 g cm(-3) for Z = 6. In the complex, two nitrogen atoms (from phen) and eight oxygen atoms (six from three bidentate nitrate anions and two from water molecules) are coordinated to the central La(III) ion, forming a coordination polyhedron which is approximately a bicapped square antiprism. The coordinated water molecules donate hydrogen bonds to the oxygen atoms of the crown ether, forming polymeric hydrogen bonded chains which wrap helically along the unit cell direction c.

Response of chlorophyll fluorescence to dynamic light in three alpine species differing in plant architecture

A study was carried out to examine the effect of dynamic photosynthetically active photon flux density (PPFD) on photoinhibition and energy use in three herbaceous species, prostrate Saussurea superba, erect-leaved S. katochaete, and half-erect-leaved Gentiana straminea, from the Qinghai-Tibet Plateau. Chlorophyll fluorescence response was measured under each of three sets of high-low PPFD combinations: 1700-0, 1400-300, and 1200-500 mu mol m(-2) s(-1), illuminating in four dynamic frequencies: 1, 5, 15, and 60 cycles per 2 h. The total light exposure time was 2h and the integrated PPFD was the same in all treatments. The highest frequency of PPFD fluctuation resulted in the lowest photochemical activity, the highest level of non-photochemical quenching, and the greatest decrease of F-v/F-m (maximal photochemical efficiency of PSII). The 5 and 15 cycles per 2h treatments resulted in higher photochemical activity than the 1 cycle per 2h treatment. The 1700-0 PPFD combination led to the lowest photochemical activity and more serious photoinhibition in all species. S. superba usually exhibited the highest photochemical activity and CO2 uptake rate, the lowest reduction of F-v/F-m,F- and the smallest fraction of energy in thermal dissipation. With similar fractions of thermal dissipation, S. katochaete had relatively less photoinhibition than G. straminea owing to effective F-o quenching. The results suggest that high frequency of fluctuating PPFD generally results in photoinhibition, which is more serious under periods of irradiation with high light intensity. (c) 2005 Elsevier B.V. All rights reserved.

Photosynthetic depression in relation to plant architecture in two alpine herbaceous species

The Qinghai-Tibet Plateau is characterized by extremely high radiation, which may induce down-regulation of photosynthesis in plants living in this alpine ecosystem. To clarify whether photoinhibition occurs in the alpine environment and to discern its underlying mechanisms, we examined photosynthetic gas exchange and fluorescence emission in response to the changes in photosynthetic photon flux density (PPFD) and leaf temperature under natural regimes for two herbaceous species: prostrate Saussurea superba and erect-leaved Saussurea katochaete from altitude 3250 m on the Qinghai-Tibet Plateau. S. superba intercepted a higher maximum PPFD and experienced much higher leaf temperature than the erect-leaved S. katochaete. S. superba exhibited a much higher light saturation point for photosynthesis than S. katochaete. Under controlled conditions, the former species had higher CO2 uptake rates and neither species showed obvious photosynthetic down-regulation at high PPFD. Under natural environmental conditions, however, apparent photoinhibition, indicated by reduced electron transport rate (ETR), was evident at high PPFD for both species. After a night frost, the photochemistry of S. katochaete was depressed markedly in the early morning and recovered by mid-day. After a frost-free night, it was high in the morning and low at noon due to high radiation. S. superba did not respond to the night frost in terms of daytime photochemical pattern. In both species, photochemical depression was aggravated by high leaf temperature and the erect species was more sensitive to high temperature. This study suggests that the high radiation on the Qinghai-Tibet Plateau is likely to induce rapidly reversible photoinhibition, which is related closely to plant architecture. Photochemistry in the prostrate species seems able to tolerate higher PPFD, without obvious suppression, than the erect species. (C) 2003 Elsevier Science B.V. All rights reserved.

Message-Driven Processor Architecture: Verson 11

The Message-Driven Processor is a node of a large-scale multiprocessor being developed by the Concurrent VLSI Architecture Group. It is intended to support fine-grained, message passing, parallel computation. It contains several novel architectural features, such as a low-latency network interface, extensive type-checking hardware, and on-chip memory that can be used as an associative lookup table. This document is a programmer's guide to the MDP. It describes the processor's register architecture, instruction set, and the data types supported by the processor. It also details the MDP's message sending and exception handling facilities.

Towards an Example-Based Image Compression Architecture for Video-Conferencing

This paper consists of two major parts. First, we present the outline of a simple approach to very-low bandwidth video-conferencing system relying on an example-based hierarchical image compression scheme. In particular, we discuss the use of example images as a model, the number of required examples, faces as a class of semi-rigid objects, a hierarchical model based on decomposition into different time-scales, and the decomposition of face images into patches of interest. In the second part, we present several algorithms for image processing and animation as well as experimental evaluations. Among the original contributions of this paper is an automatic algorithm for pose estimation and normalization. We also review and compare different algorithms for finding the nearest neighbors in a database for a new input as well as a generalized algorithm for blending patches of interest in order to synthesize new images. Finally, we outline the possible integration of several algorithms to illustrate a simple model-based video-conference system.

New Timber Architecture in Scotland.

New Timber Architecture in Scotland illustrates 90 exemplar projects and demonstrates clearly that there is no single building type unsuited to the use of this adaptable, variable and infinitely renewable material. Too long out of fashion, timber is now widely specified and has become an important design element in some of the most innovative projects being built today. The projects selected for inclusion are not the work of a few superstar architects: they represent the output of a significant percentage of architectural practices in Scotland and illustrate a burgeoning confidence in timber as an exciting, contemporary construction material. New Timber Architecture in Scotland aims to stimulate others to follow their lead.

Indian Architecture: Social and Political Challenges

The objective of this paper is to reassess the central factors which have shaped the Indian architecture. The author puts forward the concept of plurality introduced by Western art historians and argues that the diversity of the Indian architecture should not be explained in terms of religious differences, but in terms of the socio-economical situation in South Asia. He also elaborates on the Hindu caste system and its impact on the Indian architecture.