bluuebunny/crossref_metadata_2025_split huggingface dataset:
Relationship between In Vitro Lipopolysaccharide-Induced Cytokine Response in Whole Blood, Angiographic In-Stent Restenosis, and Toll-Like Receptor 4 Gene Polymorphisms
Authors: Rittersma Saskia ZH , Kremer Hovinga Johanna A , Koch Karel T , Boekholdt S Matthijs , van Aken Benien E , Scheepmaker Arko , Bax Matthijs , Schotborgh Carl E , Piek Jan J , Tijssen Jan GP , Reitsma Pieter H , de Winter Robbert J 
Published: January 2005

Abstract
Background: In coronary in-stent restenosis (ISR), a substantial contribution of inflammation is assumed. We evaluated the association between polymorphisms in the Toll-like receptor 4 (TLR4) gene and cytokine response after lipopolysaccharide (LPS) challenge and the development of ISR.
Methods: Patients were included after successful elective stent placement in a native coronary artery and were scheduled for follow-up angiography after 6 months. Quantitative coronary analysis was performed off-line. Patient whole blood was challenged with LPS for 24 h. Baseline and stimulated concentrations of interleukin (IL)-1β, IL-6, tumor necrosis factor-α, and IL-10 were assessed by ELISA. Two cosegregating single-nucleotide polymorphisms in the TLR4 gene (Asp299Gly and Thr399Ile) were analyzed by allele-specific PCR amplification of genomic DNA.
Results: A total of 236 consecutive patients were included, and 40 (17%) developed ISR. Median baseline and stimulated cytokine concentrations did not differ between patients with and without ISR. In multivariate analysis, male sex, unstable angina, hypertension, and chronic total occlusion were predictors of ISR. TLR4 genotypes were not associated with baseline or stimulated cytokine concentrations or with angiographic variables at follow-up.
Conclusions: In vitro cytokine response to LPS challenge is not increased in patients with ISR. Functionality of the TLR4 Asp299Gly polymorphism could not be demonstrated in this setting, and this polymorphism was not associated with angiographic outcome, calling into question its role in the progression of neointimal tissue growth.
Grignard Reactions
Authors: Rakita Philip E. 
Published: January 2005

Abstract

The term
Grignard reaction
refers to both the preparation of a class of organomagnesium halide compounds and their subsequent reaction with a wide variety of organic and inorganic substrates.

The general sequence of the reactions is now embodied in the following generic forms, where RX = an organic halide (most typically a chloride or bromide, although fluorides can be induced to react); S = a coordinating solvent (such as an ether or an amine); and AZ = a substrate with an electronegative group, Z: RX + Mg +
n
S → RMgX·S

n

RMgX·S

n

+ AZ → RAZMgX·S

n

RAZMgX·S

n

→ RA + ZMgX·S

n

.

The development of improved industrial procedures, including the substitution of tetrahydrofuran (THF) for diethyl ether and the demonstration that the less reactive, but significantly less expensive, vinyl and aryl chlorides could be successfully used, has greatly expanded the commercial possibilities of this reaction. In the flavor, fragrance, pharmaceutical, and fine chemical industries, its use can generally be regarded as routine.
The great value of the Grignard reaction to the synthetic chemist is its general applicability as a building block for an impressive range of structures and functional groups.
Ag‐Functionalized Carbon Molecular‐Sieve Membranes Based on Polyelectrolyte/Polyimide Blend Precursors
Authors: Barsema J. N. , van der Vegt N. F. A. , Koops G. H. , Wessling M. 
Published: January 2005

AbstractWe prepared dense flat‐sheet Ag‐functionalized carbon molecular‐sieve (CMS) membranes from blends of P84 co‐polyimide and a sulfonated poly(ether ether ketone) with a Ag+ counterion (AgSPEEK). These blends offer the possibility of producing new functionalized precursor structures, which were previously not possible, such as integrally skinned asymmetric hollow fibers. Membranes prepared at a pyrolysis end temperature of 800 °C showed a maximum permeability for all tested gases at a Ag content of approximately 2.5 wt.‐% (He permeability PHe = 465 Barrer (1 Barrer = 7.5 × 10–18 m2 s–1 Pa–1), P = 366 Barrer, P = 91.8 Barrer, P = 10.3 Barrer). The maximum achieved selectivity for O2 over N2 with CMS membranes based on these blends was α = 13.5 (Ag content: 4.5 wt.‐%, P = 52.7 Barrer). The CO2 over N2 selectivity reached a value of 48.9 (Ag content: 4.5 wt.‐%, P = 191 Barrer). These observations are explained by the formation of selective bypasses around Ag nanoclusters in the CMS matrix.
Air‐Pulse‐Drive Fabrication of Photonic Crystal Films of Colloids with High Spectral Quality
Authors: Kanai T. , Sawada T. , Toyotama A. , Kitamura K. 
Published: January 2005

AbstractA fast and highly controllable method of fabricating large films of photonic crystals of colloids is reported. A charge‐stabilized colloidal suspension was run in a flat capillary driven by a pressure‐regulated air pulse. The colloidal crystal texture formed in the capillary was a sensitive function of air pressure. Above a critical pressure, the entire capillary was filled with a uniform single‐domain texture whose transmittance spectrum showed a high quality as a photonic crystal, i.e., excellent opacity at a photonic bandgap and high transparency at other wavelengths. The present method is easily applicable to industrial processes for mass production.
Enhancement of Field‐Effect Mobility Due to Surface‐Mediated Molecular Ordering in Regioregular Polythiophene Thin Film Transistors
Authors: Kim D. H. , Park Y. D. , Jang Y. , Yang H. , Kim Y. H. , Han J. I. , Moon D. G. , Park S. , Chang T. , Chang C. , Joo M. , Ryu C. Y. , Cho K. 
Published: January 2005

AbstractWith the aim of enhancing the field‐effect mobility by promoting surface‐mediated two‐dimensional molecular ordering in self‐aligned regioregular poly(3‐hexylthiophene) (P3HT) we have controlled the intermolecular interaction at the interface between P3HT and the insulator substrate by using self‐assembled monolayers (SAMs) functionalized with various groups (–NH2, –OH, and –CH3). We have found that, depending on the properties of the substrate surface, the P3HT nanocrystals adopt two different orientations—parallel and perpendicular to the insulator substrate—which have field‐effect mobilities that differ by more than a factor of 4, and that are as high as 0.28 cm2 V–1 s–1. This surprising increase in field‐effect mobility arises in particular for the perpendicular orientation of the nanocrystals with respect to the insulator substrate. Further, the perpendicular orientation of P3HT nanocrystals can be explained by the following factors: the unshared electron pairs of the SAM end groups, the π–H interactions between the thienyl‐backbone bearing π‐systems and the H (hydrogen) atoms of the SAM end groups, and interdigitation between the alkyl chains of P3HT and the alkyl chains of the SAMs.
From Blue to Red: Syntheses, Structures, Electronic and Electroluminescent Properties of Tunable Luminescent N,N Chelate Boron Complexes
Authors: Liu Q. D. , Mudadu M. S. , Thummel R. , Tao Y. , Wang S. 
Published: January 2005

AbstractA comprehensive study of a series four‐coordinate boron compounds with the general formula of BPh2(N,N), where N,N are bidentate chelate ligands containing both neutral and negatively charged nitrogen donor atoms has been conducted. The structures of the boron complexes were examined via single‐crystal X‐ray diffraction. The series of molecules display bright luminescence with emission maxima λmax ranging from blue to red, depending on the nature of the N,N chelate ligand. The electronic effects and their consequences on the luminescent properties of the complexes due to the CH replacement of the chelate ligand by a nitrogen atom, the increase of conjugation, or the change of substituents on the chelate ligand have been examined using electrochemical analysis, UV‐visible, and fluorescence spectroscopic methods, and by molecular orbital calculations (Gaussian 98). Experimental data and MO calculation results established that the emission of this class of compounds is caused by π–π* transitions centered on the chelate ligand. Furthermore, the experimental and theoretical results consistently and conclusively established that electron withdrawing groups on the negatively charged N‐donor portion of the chelate ligand causes a decrease in the highest occupied molecular orbital (HOMO) energy level, thus increasing the energy gap. The CH replacement by a nitrogen atom on the negatively charged portion of the chelate ligand causes a dramatic decrease of the HOMO energy level, and the increase of conjugation in the chelate ligand significantly decreases the energy gap. Blue and red electroluminescent (EL) devices were fabricated successfully using two representative boron compounds from the series. The new boron compounds have been found to be able to function as both emitters and electron transport materials in EL devices.
Primary Cell Adhesion on RGD‐Functionalized and Covalently Crosslinked Thin Polyelectrolyte Multilayer Films
Authors: Picart C. , Elkaim R. , Richert L. , Audoin F. , Arntz Y. , Da Silva Cardoso M. , Schaaf P. , Voegel J.‐C. , Frisch B. 
Published: January 2005

AbstractPolyelectrolyte multilayers (PEMs) are now widely used for biomedical applications. In this work, we investigated the primary osteoblast adhesion properties of PEMs of poly(L‐lysine) (PLL), poly(L‐glutamic acid) (PGA), poly(alginic acid) (Palg), and poly(galacturonic acid) (Pgal). In order to compensate for the poor adhesion of the as‐synthesized films, two kinds of film modifications were achieved: a purely physical modification by film crosslinking, and a chemical modification by grafting a arginine–glycine–aspartic acid (RGD) peptide to PGA. Crosslinking was performed using a water‐soluble carbodiimide in combination with N‐hydroxysulfosuccinimide (sulfo‐NHS) to induce amide formation. This reaction was followed by Fourier‐transform IR spectroscopy. For film functionalization, a 15‐amino‐acid peptide was grafted to PGA and deposited as the top layer of the film. PLL/PGA, PLL/Palg, and PLL/Pgal films were crosslinked or functionalized. The films were tested for both short‐term adhesion properties and long‐term proliferation of primary osteoblasts. Whereas the effect of film crosslinking on short‐term adhesion was moderate, it was much more important for the RGD‐functionalized films. On the other hand, the long‐term proliferation was the same or even higher for the crosslinked films as compared with the functionalized films. This effect was particularly enhanced for the PLL/Palg and PLL/Pgal films. Finally, we functionalized PLL/PGA that had been crosslinked prior to PGA‐RGD deposition. These architectures exhibited even higher short‐term adhesion and proliferation. These results clearly show the important role of the physical properties of the films, besides their chemical properties, for the modulation of primary cell‐adhesion behavior.
Solar‐Energy Conversion in TiO2/CuInS2 Nanocomposites
Authors: Nanu M. , Schoonman J. , Goossens A. 
Published: January 2005

AbstractThe search for low‐cost thin‐film solar cells, to replace silicon multi‐crystalline cells in due course, calls for new combinations of materials and new cell configurations. Here we report on a new approach, based on semiconductor nanocomposites, towards what we refer to as the three‐dimensional (3D) solar‐cell concept. Atomic layer chemical vapor deposition is employed for infiltration of CuInS2 inside the pores of nanostructured TiO2. In this way it is possible to obtain a nanometer‐scale interpenetrating network between n‐type TiO2 and p‐type CuInS2. X‐ray diffraction, Raman spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, transmission electron microscopy, and current–voltage measurements are used to characterize the nanostructured devices. The 3D solar cells obtained show photovoltaic activity with a maximum monochromatic incident photon‐to‐current conversion efficiency of 80 % and have an energy‐conversion efficiency of 4 %.
Growth Control and Optics of Organic Nanoaggregates
Authors: Balzer F. , Rubahn H.‐G. 
Published: January 2005

AbstractLight‐emitting organic nanofibers made of phenyl molecules like para‐hexaphenyl (p‐6P) and grown on muscovite mica form a model system well‐suited for the study of optics in the sub‐wavelength regime. We demonstrate that p‐6P nanofibers can be grown with high control of the morphology of individual nanoaggregates and also of the mutual alignment of aggregates by the use of appropriate growth conditions and substrate surfaces. The nanofibers can be detached from the substrate, thus allowing one to study the optical response under a huge variety of fundamentally different conditions, from individual floating aggregates to dense bunches of interacting aggregates. We show examples of linear and nonlinear optical properties of the blue‐light‐emitting aggregates and mention possible applications in future submicrometer‐sized optoelectronics.
Covalent Surface Chemistry of Single‐Walled Carbon Nanotubes
Authors: Banerjee S. , Hemraj‐Benny T. , Wong S. S. 
Published: January 2005

AbstractIn this review article, we explore covalent chemical strategies for the functionalization of carbon‐nanotube surfaces. In recent years, nanotubes have been treated as chemical reagents (be it inorganic or organic) in their own right. Indeed, from their inherent structure, one can view nanotubes as sterically bulky, π‐conjugated ligands, or conversely as electron‐deficient alkenes. Hence, herein we seek to understand, from a structural perspective, the breadth and types of reactions single‐walled nanotubes (SWNTs) can undergo in solution phase, not only at the ends and defect sites but also along the sidewalls. Controllable chemical functionalization suggests that the unique electronic and mechanical properties of SWNTs can be tailored in a determinable manner. Moreover, prevailing themes in nanotube functionalization have been involved with dissolution of tubes.
Induction period of CaCO3 interpreted by the Smoluchowski's coagulation theory
Authors: Tai C. Y. , Chien W. C. , Hsu J. P. 
Published: January 2005

AbstractSmoluchowski's coagulation theory is adopted to estimate the induction period for the formation of the critical nuclei of CaCO3 in a supersaturated CaCl2‐Na2CO3 aqueous solution. The effects of the presence of impurity and crystal seeds, degree of supersaturation and operating temperature on the induction period are discussed. The association coefficient between two clusters is found to depend on both the degree of supersaturation and the temperature. The estimated activation energy for the association between two clusters is about 200 J/mol, which implies that the association between two clusters is of physical nature. It is found that the increase in the induction period with the presence of Mg2+ may be caused by an increase in the solid‐liquid interfacial energy, and a decrease in the association coefficient. Due to van der Waals attraction, the addition of crystal seeds increases the concentration of clusters near seed surface, and, thus, yields a shorter induction period. © 2005 American Institute of Chemical Engineers AIChE J, 51: 480–486, 2005
The Dihydroxyacetone Unit—A Versatile C3Building Block in Organic Synthesis
Authors: Enders Dieter , Voith Matthias , Lenzen Achim 
Published: January 2005

AbstractNature employs dihydroxyacetone phosphate (DHAP) as the donor component in various enzyme‐catalyzed aldol reactions. Probably the most significant example in this regard is photosynthesis, in whichD‐glucose, the most widespread natural product, is formed in just a few steps from DHAP. In recent years a number of synthetic equivalents of DHAP have been reported that deserve particular attention, as their applicability in organic synthesis is not limited to (stereoselective) aldol reactions. The power of these reagents has also been demonstrated convincingly in numerous other asymmetric electrophilic α‐substitution reactions in target‐oriented syntheses. Furthermore, the related 1,3‐dioxins are useful equivalents of 2‐substituted acrolein derivatives.
Investigation of oxidative stress during fracture healing in the rats
Authors: Yeler Hasan , Tahtabas Filiz , Candan Ferda 
Published: January 2005

AbstractOne of the most damaging effects of reactive oxygen species (ROS) is lipid peroxidation, the end‐product of which is malondialdehyde (MDA). This study was aimed to evaluate erythrocyte MDA levels during fracture healing in rats. Thirty male rats were used and the rats were divided into two groups to serve as controls and tests. Six rats were used as a control group that was not subject to fracture. The remaining 24 rats were divided into four groups and erythrocyte MDA levels were examined on days 5, 10, 20 and 30 post fracture. The right fibulas of rats were broken by manual angulation in the experimental group. The erythrocyte malondialdehyde level was measured in the experimental and control groups. The difference between malondialdehyde levels of control and experimental groups was statistically significant ( p < 0.05). Oxidative stress clearly increases during fracture healing in rats. Copyright © 2005 John Wiley & Sons, Ltd.
Ruthenium‐Catalyzed Propargylic Substitution Reactions of Propargylic Alcohols with Oxygen‐, Nitrogen‐, and Phosphorus‐Centered Nucleophiles
Authors: Nishibayashi Yoshiaki , Milton Marilyn Daisy , Inada Youichi , Yoshikawa Masato , Wakiji Issei , Hidai Masanobu , Uemura Sakae 
Published: January 2005

AbstractThe scope and limitations of the ruthenium‐catalyzed propargylic substitution reaction of propargylic alcohols with heteroatom‐centered nucleophiles are presented. Oxygen‐, nitrogen‐, and phosphorus‐centered nucleophiles such as alcohols, amines, amides, and phosphine oxide are available for this catalytic reaction. Only the thiolate‐bridged diruthenium complexes can work as catalysts for this reaction. Results of some stoichiometric and catalytic reactions indicate that the catalytic propargylic substitution reaction proceeds via an allenylidene complex formed in situ, whereby the attack of nucleophiles to the allenylidene Cγ atom is a key step. Investigation of the relative rate constants for the reaction of propargylic alcohols with several para‐substituted anilines reveals that the attack of anilines on the allenylidene Cγ atom is not involved in the rate‐determining step and rather the acidity of conjugated anilines of an alkynyl complex, which is formed after the attack of aniline on the Cγ atom, is considered to be the most important factor to determine the rate of this catalytic reaction. The key point to promote this catalytic reaction by using the thiolate‐bridged diruthenium complexes is considered to be the ease of the ligand exchange step between a vinylidene ligand on the diruthenium complexes and another propargylic alcohol in the catalytic cycle. The reason why only the thiolate‐bridged diruthenium complexes promote the ligand exchange step more easily with respect to other monoruthenium complexes in this catalytic reaction should be that one Ru moiety, which is not involved in the allenylidene formation, works as an electron pool or a mobile ligand to another Ru site. The catalytic procedure presented here provides a versatile, direct, and one‐step method for propargylic substitution of propargylic alcohols in contrast to the so far well‐known stoichiometric and stepwise Nicholas reaction.
Polymers of Intrinsic Microporosity (PIMs): Bridging the Void between Microporous and Polymeric Materials
Authors: McKeown Neil B. , Budd Peter M. , Msayib Kadhum J. , Ghanem Bader S. , Kingston Helen J. , Tattershall Carin E. , Makhseed Saad , Reynolds Kevin J. , Fritsch Detlev 
Published: January 2005

AbstractNovel types of microporous material are required for chemoselective adsorptions, separations and heterogeneous catalysis. This concept article describes recent research directed towards the synthesis of polymeric materials that possess microporosity that is intrinsic to their molecular structures. These polymers (PIMs) can exhibit analogous behaviour to that of conventional microporous materials, but, in addition, may be processed into convenient forms for use as membranes. The excellent performance of these membranes for gas separation and pervaporation illustrates the unique character of PIMs and suggests immediate technological applications.
Electron‐Donating Alkoxy‐Group‐Driven Synthesis of Heteroleptic Tris(phthalocyaninato) Lanthanide(III) Triple‐Deckers with Symmetrical Molecular Structure
Authors: Zhu Peihua , Pan Na , Li Renjie , Dou Jianmin , Zhang Ying , Cheng Diana Y. Y. , Wang Daqi , Ng Dennis K. P. , Jiang Jianzhuang 
Published: January 2005

AbstractReaction of heteroleptic bis(phthalocyaninato) lanthanide compounds [(Pc)M{Pc(OC8H17)8}] [H2Pc=unsubstituted phthalocyanine; H2Pc(OC8H17)8=2,3,9,10,16,17,23,24‐octakis(octyloxy)phthalocyanine] with monomeric complexes [(Pc)M(acac)] (Hacac=acetylacetone), both of which generated in situ, led to the isolation of heteroleptic phthalocyaninato‐[2,3,9,10,16,17,23,24‐octakis(octyloxy)phthalocyaninato] lanthainde(III) triple‐decker complexes [(Pc)M{Pc(OC8H17)8}] (M=Gd–Lu) (1–8) as the sole product. Heterodinuclear analogues [(Pc)Lu{Pc(OC8H17)8}M(Pc)] (M=Gd–Yb) (9–15) were obtained in a similar manner from the reaction of [(Pc)M{Pc(OC8H17)8}] (M=Gd–Yb) and [(Pc)Lu(acac)]. The molecular structures of the herterodinuclear compound [(Pc)Lu{Pc(OC8H17)8}Er(Pc)] (13) and its homodinuclear counterparts [(Pc)M{Pc(OC8H17)8}M(Pc)] (M=Er, Lu) (5, 8) have been determined by X‐ray diffraction analysis; these structures exhibit a symmetrical molecular structure with one inner planar Pc(OC8H17)8 ligand and two outer domed Pc ligands. In addition to various spectroscopic analyses, the electrochemistry of these compounds has also been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods, revealing the gradually enhanced π–π interactions among the phthalocyanine rings in the triple‐deckers along with the lanthanide contraction.
New Types of Blue, Red or Near IR Luminescent Phosphonate‐Decorated Lanthanide Oxalates
Authors: Song Jun‐Ling , Mao Jiang‐Gao 
Published: January 2005

AbstractHydrothermal reactions of the lanthanide chlorides with MeN(CH2CO2H)(CH2PO3H2), (H3L1) (or Me2NCH2PO3H2, H2L2) and sodium oxalate lead to seven new lanthanide oxalate phosphonate hybrids with three types of 3D network structures, namely, [Ln(C2O4){MeNH(CH2CO2)(CH2PO3H)}]⋅0.5 H2O (Ln=Nd: 1; Eu: 2; Gd: 3), [Ln4(C2O4)5(Me2NHCH2PO3)2(H2O)4]⋅2 H2O (Ln=La: 4, Nd: 5), [Ln3(C2O4)4(Me2NHCH2PO3)(H2O)6]⋅6 H2O (Gd: 6, Er: 7). Their structures have been established by X‐ray single‐crystal diffraction. Complexes 1–3 are isostructural and feature a 3D network formed by the interconnection of 3D network of {Ln(H2L1)}2+ with 1D chains of {Ln(C2O4)}+. Complexes 4 and 5 are isostructural and feature a complex 3D network built from 3D network of lanthanide oxalate and {Ln4(HL2)2} units. The isostructural 6 and 7 form another type of 3D network composed of porous lanthanide–oxalate network inserted by 1D chains of lanthanide–oxalate phosphonate. Compounds 1, 5 and 7 are luminescent materials in the near IR region. Compounds 3 and 6 exhibit a broad blue fluorescent emission band at 451 and 467 nm, respectively. Compound 2 displays very strong and sharp emission bands at 592, 616 and 699 nm with a long luminescent lifetime of 1.13 ms.