bluuebunny/crossref_metadata_2025 huggingface dataset:
Differential Production of Systemic and Intralesional Gamma Interferon and Interleukin-10 in Nodular and Ulcerative Forms of Buruli Disease
Authors: Prévot Ghislaine , Bourreau Eliane , Pascalis Herve , Pradinaud Roger , Tanghe Audrey , Huygen Kris , Launois Pascal
Published: January 2004

Buruli disease, caused byMycobacterium ulcerans, is the third most important mycobacterial disease in humans besides tuberculosis and leprosy. We have compared systemic and intralesional cytokine production in patients presenting with a nodular form and a necrotizing, ulcerative form of the disease. Gamma interferon (IFN-γ) levels in response to wholeM. ulceransandMycobacterium bovisBCG bacilli and in response to purified Ag85 protein from BCG were lower in peripheral blood mononuclear cells (PBMC) cultures from Buruli disease patients than in PBMC from healthy purified protein derivative-positive contacts. Interleukin-4 (IL-4) and IL-13 content was below the detection threshold in these PBMC cultures. IFN-γ production after stimulation withM. ulceranswas significantly lower (P< 0.05) in PBMC cultures from patients with ulcers than in those from patients with nodules. On the other hand, PBMC from Buruli disease patients produced significant levels of IL-10 in response toM. ulcerans(but not toM. bovisBCG) and production was highest in patients with the ulcerative form. Third, semiquantitative reverse transcription-PCR analysis demonstrated a similar difference in the local, intralesional cytokine profile for the two forms of the disease: high IFN-γ but low IL-10 mRNA levels in nodular lesions and high IL-10 but low IFN-γ mRNA levels in ulcerative lesions. Intralesional IL-4 and IL-13 mRNA levels were low and only detected in patients with the ulcerative form. Our results indicate, although they do not formally prove, that production of IL-10 rather than production of IL-4 or IL-13 by Th2-type T cells may be involved in the lowM. ulcerans-specific IFN-γ response in Buruli disease patients.
Willem Heda and the edition of his Historia episcoporum Ultrajectensium
Authors: Van Der Horst Koert
Published: January 2004

When Willem Heda concluded his Latin history of the Utrecht bishops on 1 May 1521 with a dedicatory epistle to the Utrecht Cathedral Chapter, he probably could not have expected it would take almost a century before the work was actually printed. That he assumed his history would soon be on the press is apparent from a sentence in the dedication itself: '. . . iussistis ut . . . etiam gesta ac vitas sanctorum, . . . ea in lucem proferentes publicis impensis novis formis excudenda traderemus, . . . [You, canons of the cathedral, commissioned us . . . to publish also the history and lives of the saints (the bishops of Utrecht) and present it to be printed at your expense (at the expense of public funds), "novis formis": in the new letters (type faces)]'.
N-acetylcysteine decreases lactate signal intensities in liver tissue and improves liver function in septic shock patients, as shown by magnetic resonance spectroscopy: extended case report
Authors: Hein Ortrud Vargas , Öhring Renate , Schilling Andreas , Oellerich Michael , Armstrong Victor W , Kox Wolfgang J , Spies Claudia
Published: January 2004

Background

N-acetylcysteine (NAC) has been shown to improve splanchnic blood flow in experimental studies. This report evaluates the effects of NAC on liver perfusion and lactate signal intensities in the liver tissue of septic shock patients using proton magnetic resonance imaging and spectroscopy. Furthermore, the monoethylglycinexylidide (MEGX) test was used to investigate hepatic function.

Methods

Five septic shock patients received 150 mg/kg body weight NAC as an intravenous bolus injection over 15 min. Lidocaine was injected both prior to and following NAC administration in order to determine MEGX formation. Measurements (hemodynamics, oxygen transport-related variables, blood samples for lactate, liver-related markers) were performed 1 hour before and 1 hour after NAC injection. In addition to the proton magnetic resonance imaging patients received two proton magnetic resonance spectra, one prior to and one 30 min subsequent to the onset of the NAC infusion at a 1.5 Tesla clinical scanner, for measurement of liver perfusion and liver lactate signal intensity.

Main findings

Following NAC infusion, the lactate signal intensity in the liver tissue showed a median decrease of 89% (11–99%), there was a median increase in liver perfusion of 41% (-14 to 559%), and the MEGX serum concentration increased three times (1.52–5.91).

Conclusions

A decrease in the lactate signal intensity in the liver tissue and an increase in the MEGX serum concentration and in liver perfusion might indicate improved liver function as a result of NAC administration. Patients with compromised hepatosplanchnic function, such as patients with septic shock due to peritonitis, may therefore benefit from NAC therapy.
Railways: How they may contribute to a sustainable future
Authors: Smith R. A.
Published: January 2004

A combination of a rapidly increasing world population and an increasing energy-intensive lifestyle has led to doubts about the sufficiency of natural resources. The waste products of these economic activities have become large enough to change the climate of the globe. The demand for transport is characterized by an exponential increase and a tendency to choose faster modes. These facts give rise to concerns about the sustainability of present transport practices.

While railways presently offer significant environmental advantages over other modes of transport, particularly the car, in many areas the gap is closing quickly. Cars are much safer, more energy efficient and less polluting than a decade ago. Trains in the future will have to contend with reducing hydrocarbon fuel supplies and much stricter legislation limiting emissions, particularly diesel particulates. Because the energy environmental performance of trains depends on the passenger load factor, the areas in which railways excel are high-speed intercity and commuting. Both these activities are well served by electric traction.

With very few exceptions railway companies have not yet responded to significant environmental challenges. The oft-stated complacent view, that railways are environmentally superior to other modes of transport, fails to recognize that the competition is rapidly eroding their lead.
Research of European railway operators to reduce the environmental impact of high-speed trains
Authors: Schulte-Werning B
Published: January 2004

This article presents the results of several research projects to reduce the environmental impact of high-speed traffic on rails. The most prominent keywords relating to environmental friendliness are energy saving and noise reduction. To follow national as well as European Union (EU) requirements and to empower the environmental friendliness of the European railway traffic, the railway companies and manufacturers are joining together more and more to perform research projects in this area.

At about 280km/h travelling speed flow-induced noise becomes important, so areas with flow separation on the train must be avoided, thus reducing the aerodynamic drag of the train at the same time. Bogie fairings lead both to a reduction in aerodynamic resistance and locally generated aerodynamic noise resulting from the high level of turbulence in the bogie area. In a similar way, streamlining of the frame structure of the pantograph leads to a reduction of the noise generated at high velocities.

A high-speed train entering a tunnel generates a pressure wave. When it is reflected at the tunnel exit a part of the pressure wave is audibly emitted into the surrounding environment. A number of technical solutions were advanced to circumvent noise annoyance. In situ tests showed that an acoustically soft head of a sound barrier works very well and that the barrier effect can be improved.
High-speed rail and air passenger transport: A comparison of the operational environmental performance
Authors: Janic M
Published: January 2004

This paper presents an overview of the environmental performance of high-speed rail (HSR) and air passenger transport (APT) in the European Union (EU). This performance embraces the direct environmental burdens/emissions such as energy consumption, air pollution, noise, land-take and land use, safety and congestion.

A comparison of the marginal values of particular burdens/emissions and their costs (externalities) is carried out. The results have shown that significant mitigation of the impacts and savings of costs could be achieved by substitution of air passenger transport by high-speed rail. The substitution can be carried out through competition and complementarity of operations of both modes.
Application of lifecycle assessment to Shinkansen vehicles and cross ties in Japan
Authors: Ueda H , Miyauchi T , Tsujimura T
Published: January 2004

Recently, environmental protection has become one of the most critical concerns on a global scale. Currently, it is widely recognized that lifecycle assessment (LCA) is a very effective instrument used to evaluate the environmental impact of various products quantitatively across their whole lifecycle. A basic LCA survey of Shinkansen vehicles and cross ties was conducted as a case study for the railway system. Through this study, the following results were confirmed. For any type of vehicle, more than 95 per cent of lifecycle energy consumption (LCE) and lifecycle CO2 emission LCCO2 is attributable to vehicle running. Lightweight vehicles, reduction of running resistance and the use of regenerative brakes contribute to energy saving in vehicle running. Regarding the CO2 emission from four types of ties (wood, concrete, synthetic and steel), wood ties emit the least amount of CO2 and synthetic ties the most. When the effect throughout the lifetime is considered, however, wood ties are by no means insignificant in terms of the environmental load. As a result of this survey, useful knowledge for applying LCA to railways was obtained.
Recyclability of stainless steel railway vehicles
Authors: Matsuoka S
Published: January 2004

Current trends in environmental issues mean that manufacturers are now required to take responsibility for the recycling of their products. In the railway industry, the recycling of mild steel vehicles has been carried out and recycling of aluminium vehicles has been tried and tested but not stainless steel vehicles. This paper describes a field test used to find out the recyclability of a stainless steel vehicle. The costs of disassembly and recycling for several types of vehicle are compared and it is demonstrated that the recycling of stainless steel vehicles is the cheapest.
Bioremediation of polychlorinated biphenyl contaminated sludge and ballast
Authors: Shimura M , Hayakawa T , Kyotani T , Ushiogi T , Kimbara K
Published: January 2004

Incineration had been the only authorized method for polychlorinated biphenyl (PCB) decomposition in Japan. However, because of the objection of Japanese people to the construction of PCB incineration facilities, no progress was made in detoxifying PCBs for decades. In the late 1990s, the Japanese Ministry of Health and Welfare authorized several alternative methods to promote PCB detoxification. Most of the methods authorized are for liquid PCBs and PCB containers, while only a few are for the kind of PCB wastes resulting from an accidental PCB spill.

Here the detoxification of PCB contaminated sludge and ballast is examined. Microbial treatment of PCB contaminated sludge removed 90 per cent of the PCBs in 60 days of treatment. However, neither microbial treatment nor solvent treatment effectively removed PCBs from ballast.
The application of fuel cell technology to rail transport operations
Authors: Hillmansen S
Published: January 2004

Fuel cell technology has in recent years undergone a period of rapid development. This evolution has been driven by the requirements of developed countries to reduce the emission of greenhouse gases, with particular emphasis placed on reducing CO2 emissions. This article discusses the possibility of using fuel cell technology for rail vehicle propulsion, with the United Kingdom chosen as a case study. A brief review of fuel cell technology and its application within the UK is presented. It is concluded that, although the technology for fuel cell power will be suitable within the next few years, its adoption by mainline UK rail operators will be delayed considerably until existing diesel vehicles have reached the end of their useful life. By this time the technology of fuel cells will be well proven within other transport markets and its transfer to rail markets will be facilitated. This will be augmented at this time by increasing diesel fuel prices. However, the adoption of fuel cell technology for light rail/tram systems does offer advantages in terms of infrastructure development and aesthetics which could make it a serious option for new and upgraded light rail/tram schemes.
Peptide and Protein Presenting Materials for Tissue Engineering
Authors: Hirano Y. , Mooney D. J.
Published: January 2004

Tissue engineering aims to create new tissues and organs to replace those lost to disease, trauma, or congenital defects. However, considerable instruction must be given to the cells forming these new tissues if one is to create a tissue structurally and functionally similar to the native tissue. Materials are ideal for the local presentation of various peptides and proteins that can bind to cell surface receptors and regulate cell function. An overview of techniques to present peptides and proteins from materials, and the utility of these systems in engineering tissues in vitro and in vivo is presented.
Nanoporous Ultra‐Low‐κ Films Prepared from Fluorinated Polyimide with Grafted Poly(acrylic acid) Side Chains
Authors: Wang W.‐C. , Vora R. H. , Kang E.‐T. , Neoh K.‐G. , Ong C.‐K. , Chen L.‐F.
Published: January 2004

Thermal decomposition of labile poly(acrylic acid) (PAAc) side chains grafted onto fluorinated polyimide backbones (see Figure) is used to prepare nanoporous ultra‐low‐κ fluorinated polyimide films. The dielectric constant of the nanoporous fluorinated polyimide film can be varied by altering the graft concentration of the labile side chains.
Self‐Assembled In2O3 Nanocrystal Chains and Nanowire Networks
Authors: Lao J. Y. , Huang J. Y. , Wang D. Z. , Ren Z. F.
Published: January 2004

The synthesis of self‐assembled In2O3 nanocrystal chains and networks (see Figure) on SiO2‐covered Si substrates by a thermal evaporation and condensation method is reported. Au catalyst is required for the growth. The chains and networks can be used for the fabrication of complex nanoelectronic devices and toward a better understanding of nanodevice physics.
Indium‐Assisted Growth of Aligned Ultra‐Long Silica Nanotubes
Authors: Li Y. , Bando Y. , Golberg D.
Published: January 2004

Well‐aligned silica nanotubes with lengths up to 0.9–1.0 mm have been prepared via a vapor–liquid–solid process. The nanotubes are either partially filled with indium or hollow (see Figure). The thermal expansion behavior of a liquid indium column inside a silica nanotube, a prospective novel inorganic nanotube‐based nanothermometer, is analyzed in a transmission electron microscope.
Demonstration of Flexible Freestanding All‐Polymer Integrated Optical Ring Resonator Devices
Authors: Huang Y. , Paloczi G. T. , Poon J. K. S. , Yariv A.
Published: January 2004

A simple method to fabricate thin freestanding all‐polymer integrated optical devices and the transfer of the devices to various substrates, such as the curved surfaces of capillary tubes, is reported. A passive microring resonator optical filter device (see Figure) with a –27 dB notch extinction for wavelengths in the telecommunication band, which is within the range of requirements for practical telecommunications applications, is also shown.
Carbon Nanotube/CdS Core–Shell Nanowires Prepared by a Simple Room‐Temperature Chemical Reduction Method
Authors: Cao J. , Sun J.‐Z. , Hong J. , Li H.‐Y. , Chen H.‐Z. , Wang M.
Published: January 2004

A facile solution‐phase reaction has been developed to fabricate carbon nanotube/CdS core–shell nanowires (see Figure). The thickness of the CdS sheath can be controlled by varying the concentration of the precursors. The obtained heterostructures demonstrate an enhanced surface photovoltage response, which is associated with the efficient photoinduced charge transfer from the CdS shell to the carbon nanotube core.
Emulsion‐Templated Gold Beads Using Gold Nanoparticles as Building Blocks
Authors: Zhang H. , Hussain I. , Brust M. , Cooper A. I.
Published: January 2004

Highly porous gold beads have been synthesized from gold nanoparticle “building blocks” using emulsion‐ templated polymer beads as scaffolds (see Figure and cover for scanning electron microscopy images). The distribution of the nanoparticles throughout the scaffold can be controlled, which in turn allows a variety of complex structures to be produced.
Fabrication of Large‐Area Silicon Nanowire p–n Junction Diode Arrays
Authors: Q. Peng K. , P. Huang Z. , Zhu J.
Published: January 2004

Large‐area silicon nanowire p–n junction diode arrays (see Figure) have been fabricated by chemical etching of planar silicon p–n junction wafers in aqueous HF solution that contains appropriate amounts of silver nitrate near room temperature. The I–V characteristics have been measured using current‐sensing atomic force microscopy, and nonlinear and rectifying electrical transport behavior has been observed.
Generische herkunftsbezogene Namen für Polymere
Authors: Meisel Ingrid
Published: January 2004

Es gibt bereits Empfehlungen zur Bildung herkunftsbezogener Namen für lineare Copolymere und nichtlineare Polymere, die jedoch in einigen Fällen nicht zu eindeutigen Bezeichnungen führen. Hier werden deshalb Nomenklaturregeln zur Erzeugung generischer herkunftsbezogener Namen vorgestellt, die dieses Problem beseitigen und eindeutigere herkunftsbezogene Namen liefern. Ein generischer herkunftsbezogener Name besteht aus zwei Teilen: dem Namen der Polymerklasse (generisch), gefolgt von einem Doppelpunkt, und dem/den Namen des/der (hypothetischen) Monomers/Monomere, die im Fall eines Copolymers durch einen Bindestrich getrennt werden. Im Folgenden werden bei allen Beispielen die Strukturformel, der von der Struktur abgeleitete Name (“systematisch”), der von den Ausgangsstoffen abgeleitete Name (“herkunftsbezogen”) und der generische herkunftsbezogene Name angegeben. Wenn ein Polymer mehr als einen Namen hat oder wenn es durch eine Folge von Reaktionsschritten über Zwischenstufen erhalten wurde, dann ist nur der generische herkunftsbezogene Namen eindeutig. Die Nomenklaturregeln gelten im Wesentlichen für Polymere mit einer oder mehreren funktionellen Gruppen oder mit heterocyclischen Einheiten in der Hauptkette. In gewissem Maß sind sie aber auch auf Polymere mit Seitenketten, reinen Kohlenwasserstoffhauptketten – wie in Vinyl‐ oder Dienpolymeren –, auf Spiropolymere und cyclische Polymere sowie auf Netzwerke anwendbar.
Titelbild: σ‐Bond Stretching: A Static Approach for a Dynamic Process (Angew. Chem. 5/2004)
Authors: Scheschkewitz David , Amii Hideki , Gornitzka Heinz , Schoeller Wolfgang W. , Bourissou Didier , Bertrand Guy
Published: January 2004

Der filmische Ablauf einer chemischen Umwandlung lässt sich aus femtosekundenspektroskopischen Momentaufnahmen montieren. G. Bertrand et al. erläutern in ihrer Zuschrift auf S. 595 ff., wie das Reaktionsprofil der Inversion von Bicyclo[1.1.0]butan – einschließlich der im Titelbild illustrierten Dehnung der B‐B‐Bindung – durch eine Serie von Bor‐Phosphor‐Analoga modelliert werden kann.
New Catalytic Approaches in the Stereoselective Friedel–Crafts Alkylation Reaction
Authors: Bandini Marco , Melloni Alfonso , Umani‐Ronchi Achille
Published: January 2004

After more than 125 years, the Friedel–Crafts alkylation is still one of the most studied and most utilized reactions in organic synthesis. What is the secret of this astonishing success? Perhaps the great versatility in scope and applicability continues to justify its crucial role in the synthesis of more and more complex molecules. However, it has taken more than a century for asymmetric catalytic versions of this reaction to be developed and subsequently extended to a range of aromatic compounds and alkylating agents. Herein we review recent developments in the design and use of catalytic and stereoselective strategies for the alkylation of aromatic systems and synthesis of a wide range of polyfunctionalized enantiomerically enriched compounds.
How adhesion, migration, and cytoplasmic calcium transients influence interleukin‐1β mRNA stabilization in human monocytes
Authors: Pomorski P. , Watson J.M. , Haskill S. , Jacobson K.A.
Published: January 2004

We investigated the mechanisms by which primary human monocyte migration and the production of important cytokines are co‐regulated. Motile monocytes underwent cyclic morphologic and adhesive changes that were associated with intracellular free calcium changes; in such cells, cytokine transcripts were unstable and translationally repressed. Agents that activate monocytes, including lipopolysacharrides (LPS), cytomegalovirus (CMV), and tumor necrosis factor (TNFα), have been shown to de‐repress translation and these agents stabilize adhesion‐induced transcripts for IL‐lβ and IL‐8 and markedly diminish cell migration in the presence of autologous serum. LPS suppressed Rho A activity and either this agent or C3 transferase elevated intracellular free calcium, stabilized transcripts, and, in tandem, inhibited cell migration by preventing tail retraction, a prerequisite for cell translocation. These results, therefore, suggest that monocyte activating agents inhibit the RhoA pathway and continuously elevate intracellular calcium leading to a concomitant decrease in monocyte migration and stabilization of cytokine transcripts prior to translation. Cell Motil. Cytoskeleton 57:143–157, 2004. © 2004 Wiley‐Liss, Inc.
Characterisation of chicken TES and its role in cell spreading and motility
Authors: Griffith Elen , Coutts Amanda S. , Black Donald M.
Published: January 2004

Previously we identified TES as a candidate tumour suppressor gene that is located at human chromosome 7q31.1. More recently, we and others have shown TES to encode a novel LIM domain protein that localises to focal adhesions. Here, we present the cloning and functional analysis of the chicken orthologue of TES, cTES. The TES proteins are highly conserved between chicken and human, showing 89% identity at the amino acid level. We show that the cTES protein localised at focal adhesions, actin stress fibres, and sites of cell‐cell contact, and GST‐cTES can pull‐down zyxin and actin. To investigate a functional role for cTES, we looked at the effect of its overexpression on cell spreading and cell motility. Cells overexpressing cTES showed increased cell spreading on fibronectin, and decreased cell motility, compared to RCAS vector transfected control cells. The data from our studies with cTES support our previous findings with human TES and further implicate TES as a member of a complex of proteins that function together to regulate cell adhesion and additionally demonstrate a role for TES in cell motility. Cell Motil. Cytoskeleton 57:133–142, 2004. © 2004 Wiley‐Liss, Inc.
Positioning and capture of cell surface‐associated microtubules in epithelial tendon cells that differentiate in primary embryonic Drosophila cell cultures
Authors: Tucker John B. , Mackie John B. , Cottam Deborah M. , Rogers‐Bald Margaret M. , Macintyre John , Scarborough Julie A. , Milner Martin J.
Published: January 2004

Using primary embryonic Drosophila cell cultures, we have investigated the assembly of transcellular microtubule bundles in epidermal tendon cells. Muscles attach to the tendon cells of previously undescribed epidermal balls that form shortly after culture initiation. Basal capture of microtubule ends in cultured tendon cells is confined to discrete sites that occupy a relatively small proportion of the basal cell surface. These capturing sites are associated with hemiadherens junctions that link the ends of muscle cells to tendon cell bases. In vivo, muscle attachment and microtubule capture occur across the entire cell base. The cultured tendon cells reveal that the basal ends of their microtubules can be precisely targeted to small, pre‐existing, structurally well‐defined cortical capturing sites. However, a search and capture targeting procedure, such as that undertaken by kinetochore microtubules, cannot fully account for the precision of microtubule capture and positioning in tendon cells. We propose that cross‐linkage of microtubules is also required to zip them into apicobasally oriented alignment, progressing from captured basal plus ends to apical minus ends. This involves repositioning of apical minus ends before they become anchored to an apical set of hemiadherens junctions. The proposal is consistent with our finding that hemiadherens junctions assemble at tendon cell bases before they do so at cell apices in both cultures and embryos. It is argued that control of microtubule positioning in the challenging spatial situations found in vitro involves the same procedures as those that operate in vivo. Cell Motil. Cytoskeleton 57:175–185, 2004. © 2004 Wiley‐Liss, Inc.
High temperature arsenic doping of CdHgTe epitaxial layers
Authors: Vlasov A. , Bogoboyashchyy V. , Bonchyk O. , Barcz A.
Published: January 2004

Experimental results on solid‐state arsenic doping of the n‐type bulk and ISOVPE epitaxial CdXHg1‐XTe (X = 0.19 ÷ 0.3) alloys are presented. The arsenic doped thin epitaxial CdxHg1‐xTe films (nAs ≈ 5 · 1016 ÷ 1 · 1020 cm‐3; d = 2 ÷ 5 μm) obtained by RF sputtering in a mercury glow discharge were used as As diffusion sources. The arsenic diffusion and activation were carried out at temperatures T = 500 ÷ 600 °C under Hg vapour pressure. Immediately after the high temperature treatment all samples were annealed to annihilate point defects. The SIMS analysis was used for determination of the quantitative admixture distribution of As in the diffusion area. The arsenic electrical activity has been evaluated by means of differential Hall, resistivity and thermoemf measurements. The analysis of experimental data obtained as well as their comparison with previously obtained results has been performed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Metastability and crystal growth kinetics on L‐arginine phosphate
Authors: Arunmozhi G. , de M. Gomes E.
Published: January 2004

Stability of saturated L‐Arginine Phosphate (LAP) solution studied as a function of supercooling rate and crystal growth kinetics investigated as a function of supersaturation are reported in this communication. Solution stability was studied by observing the metastable zone width at different cooling rates employing a polythermal method. Analysis of the experimental data yielded the kinetic constant of nucleation and the order of nucleation. Crystal growth rates studied on small seed crystals with regular morphology, under normal growth conditions and at different supersaturation levels were found to satisfy BCF surface diffusion model. Crystal growth rates were investigated normal to the (100), (010) and (00$ \bar 1 $) faces. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
X‐ray diffraction studies of bone apatite under acid demineralization
Authors: Danilchenko S. N. , Moseke C. , Sukhodub L. F. , Sulkio‐Cleff B.
Published: January 2004

The analysis of the X‐ray diffraction line broadening used to determine bone apatite crystallite size and lattice microstrain can provide information about the substructure of the bone mineral under differing real or simulated conditions. The paper discusses modifications in the bioapatite crystals observed in the bone subjected to demineralization in a 0.1 N HCl solution. Planar oriented specimens of mature bone with the analyzed surface normal to the longer bone axis were treated for varied immersion times. The crystallite size and the lattice microstrain were determined simultaneously by Fourier analysis of the X‐ray diffraction line profiles. Both were observed to decrease during the acid demineralization. These findings support the idea that the distribution of lattice imperfections in the bulk of bioapatite crystals is highly nonuniform, with crystallite surface regions richer in imperfections dissolving more readily. In addition, an approach is proposed suitable for rough estimation of the reaction front advancement by demineralization‐induced variations in the integrated intensity or shift in the position of the (002) and (004) diffraction lines. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Synthesis and structure of 2D‐ and 3D‐ inorganic‐organic coordination polymers: based on Ag‐hmt subunit
Authors: Lu Sheming , Qin Shoubo , Ke Yanxiong , Li Jianmin , Pei Hongxia , Zhou Shuxi , Wu Xintao , Du Wenxin
Published: January 2004

Two new inorganic‐organic complexes, namely, [Ag2(hmt)2]Cr2O7·H2O (1) and [Ag(hmt)(tar)0.5]·H2O (2), (hmt = hexamethylenetetramine, Tar = tartarate,), have been synthesized in H2O/CH3CN solvent at room temperature. Both molecules have the common [Ag3hmt3]3+ layers. Compound 1 is a two‐dimensional structure, and Complex 2 shows three‐dimensional topology. In complex 2, the tartarate molecules are connected with adjacent layers to form parallelogram pores of 18.55×7.44 Å, which are occupied by two water molecules. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Pyridine‐2‐sulfonates as Versatile Ligands for the Synthesis of Novel Coordinative and Hydrogen‐Bonded Supramolecules
Authors: Lobana Tarlok S. , Kinoshita Isamu , Kimura Kentaro , Nishioka Takanori , Shiomi Daisuke , Isobe Kiyoshi
Published: January 2004

The reactions of 3‐methylpyridine‐2‐sulfonic acid (3‐mpSO3H) with CuII and 4‐methylpyridine‐2‐sulfonic acid (4‐mpSO3H) with ZnII in water formed one‐dimensional infinite coordination polymers, [Cu(3‐mpSO3)2]n (1) and [Zn(4‐mpSO3)2]n (2). Similarly, two‐dimensional hydrogen‐bonded supramolecules of stoichiometries, [ML2(H2O)2] [L = 3‐methylpyridine‐2‐sulfonate (3‐mpSO3), M = Mn (3), Fe (4), Co (5), Zn (6); L = 5‐methylpyridine‐2‐sulfonate (5‐mpSO3), M = Zn (7); L = pyridine‐2‐sulfonate (PySO3), M = Zn (8); L = 4‐mpSO3, M = Co (9)], [Ni(3‐mpSO3)2(H2O)2]·H2O (10) and the one‐dimensional hydrogen‐bonded network [VO(acac)(3‐mpSO3)(H2O)] (11) (acac = acetylacetonate) have been prepared. The ligands are tridentate [N,O‐chelating‐Cu‐μ‐O‐bridging] in 1 and 2, while in all the other compounds the N,O‐chelating and uncoordinated O atoms are engaged in intermolecular hydrogen bonding leading to the formation of hydrogen‐bonded networks. The geometry around each metal center is octahedral (9) or distorted octahedral (1−8, 10 and 11). The compounds 3−8, and 10 showed novel π−π stacking interactions, not shown by 9 and 11. The magnetic behavior of 3 and 11 indicates lack of any intermolecular magnetic interactions. The position of the substituents in the pyridyl ring and Jahn−Teller effect (CuII) appear to determine the stacking interactions as well as the density of ligands with regard to the formation of coordinative and hydrogen‐bonded supramolecules. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Role of the 2,6‐Bis(trifluoromethyl)phenyl Group on the Acidity of the Corresponding Phosphane
Authors: Miqueu Karinne , Sotiropoulos Jean‐Marc , Pfister‐Guillouzo Geneviève , Rudzevich Valentyn , Romanenko Vadim , Bertrand Guy
Published: January 2004

The proton affinities of PhPH− (1) and ArfPH− (2) were calculated using the B3LYP hybrid functional and the 6‐31+G(d,p) basis set. For both anions a net difference was observed. The study of the structural and electronic properties of the anionic species and the corresponding phosphanes PhPH2 (3) and ArfPH2 (4) allowed us to unsderstand this results and point out the specific role of the 2,6‐bis(trifluoromethyl)phenyl (Arf) substituent. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Gold and Silver Complexes with the Ligands N‐[Bis(isopropoxy)thiophosphoryl]thiobenzamide and N‐[Bis(isopropoxy)thiophosphoryl]N′‐phenylthiourea
Authors: Crespo Olga , Brusko Vasiliy V. , Gimeno M. Concepción , Tornil M. Loreto , Laguna Antonio , Zabirov Nail G.
Published: January 2004

Gold and silver complexes with the N‐[bis(isopropoxy)thiophosphoryl]thiobenzamide (HL1) and N‐[bis(isopropoxy)thiophosphoryl]‐N′‐phenylthiourea (HL2) ligands are reported. The compounds [M(HL)(PPh3)]TfO, [Ag(HL)(TfO)] and [Ag(HL)(PPh3)2]TfO were obtained by the reaction of both ligands with the corresponding trifluoromethanesulfonate salts. The (acetylacetonato)gold and ‐silver materials [M(acac)(PPh3)] or [Au(acac)(C6F5)2] cause deprotonation of the ligands and afford [ML(PPh3)] or [AuL(C6F5)2], whereas the reaction of [Au(TfO)(PPh3)] with HL1 in a 2:1 molar ratio in KOH/MeOH affords [Au2(L1)(PPh3)2]TfO. The first homoleptic anionic metal compounds [AuIL2]− are also reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Reactivity of [Cp2Ti(CO)2] towards Nitrile and Water Adducts of B(C6F5)3: Formation of [Cp2Ti(η2‐F3CC6H4CN)·B(C6F5)3] and [Cp2Ti][HOB(C6F5)3] with a Ti···F Interaction
Authors: Choukroun Robert , Lorber Christian , Vendier Laure
Published: January 2004

The reaction of [Cp2Ti(CO)2] with borane adducts CF3C6H4CN·B(C6F5)3 and [H2O·B(C6F5)3] has afforded the titanaazirine [Cp2Ti(η2‐C,N‐F3CC6H4CN)·B(C6F5)3] (1) and the TiIII salt [Cp2Ti][HOB(C6F5)3] (2), respectively. In both cases, a Ti···F interaction between the titanium centre and an ortho‐fluorine atom of the tris(perfluorophenyl)borane is observed in the X‐ray structure determination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
X‐ray Crystallographic Study of Copper(II), Cobalt(II) and Silver(I) Complexes of Ligands Containing Two Oxine Subunits Linked by Xylylene Spacer Groups
Authors: Al‐Mandhary Muna R. A. , Steel Peter J.
Published: January 2004

X‐ray crystal structures are reported for six transition‐metal complexes of the ligands 1,2‐bis(8‐quinolyloxymethyl)benzene (3) and 1,3‐bis(8‐quinolyloxymethyl)benzene (4). In three mononuclear copper(II) and cobalt(II) complexes, 3 acts as a chelating ligand with either N,O,N′‐tridentate or N,O,O′,N′‐tetradentate coordination. A novel dinuclear silver(I) complex of 3 is shown to be stabilised by a number of weak metal−ligand contacts and multiple intramolecular π−π stacking interactions. In two dinuclear copper(II) nitrate complexes of 4, the ligand adopts very different bridging modes of coordination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Mercury−Chalcogenide Clusters: Synthesis and Structure of [Hg10Te4(SePh)12(PPhnPr2)4], [Hg10Te4(TePh)12(PPhnPr2)4] and [Hg34Te16(SePh)36(PPhnPr2)4]
Authors: Eichhöfer Andreas , Deglmann Peter
Published: January 2004

The reaction of HgCl2 with PPhnPr2, Te(SinBu3)2 and PhESiMe3 (E = Se, Te) in DME at −30 °C results in the formation of yellow octahedral crystals of [Hg10Te4(SePh)12(PPhnPr2)4] and [Hg10Te4(TePh)12(PPhnPr2)4] respectively. The molecular structures of the clusters are similar to those of other [M10Se4(SePh)12(PR3)4] (M = Cd, Zn; R = org. group) cluster compounds, but are the first of this type with tellurium as the group 16 metal atom. Dissolution of [Hg10Te4(SePh)12(PPhnPr2)4] in benzene/toluene at 5 °C leads to the formation of the larger cluster [Hg34Te16(SePh)36(PPhnPr2)4] which displays a new structure type for group 12−16 cluster molecules. The “Hg34Te16Se36” cluster core can be considered as an idealized tetrahedral fragment, 15 Å in diameter, of the cubic sphalerite lattice with a vacancy in the center. Theoretical investigations on the basis of density functional theory (DFT) reproduce the structural data and the measured electronic spectra for this cluster. Additionally we found that formal occupation of the vacancy by a mercury ion would lead to an ionic cluster [Hg35Te16(SeMe)36(PMe3)4]2+ which should be stable according to the results of the calculations. This suggests that the formation of the vacancy is probably driven by the absence of an appropriate counterion in the reaction which might stabilize such an ionic cluster molecule. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Syntheses and Crystal Structures of Tetrakis(arylamidine)nickel(II) Chloride and Bis[2,4‐dipyridyl‐1,3,5‐triazapentadienato]nickel(II)
Authors: Guo Jianping , Wong Wai‐Kwok , Wong Wai‐Yeung
Published: January 2004

The reaction of LiN(SiMe3)2 with arylnitrile, followed by the addition of anhydrous NiCl2 gives ionic complexes of the general formula [Ni{H2NC(Ar)=NH}4]Cl2 (Ar = Ph 1, p‐tolyl 2). When the above reaction is carried out with cyanopyridine instead of arylnitrile under the same reaction conditions, neutral complexes of the general formula [{HN=C(Py)N=C(Py)NH}2Ni] (Py = 4‐pyridyl, 3; 3‐pyridyl, 4] are obtained. Compound 1 undergoes a metathesis reaction with sodium benzoate to give the neutral complex [(PhCO2)2Ni {H2NC(Ph)=NH}4] (5). Magnetic susceptibility measurements show that 1−4 are diamagnetic and that 5 is paramagnetic with two unpaired electrons. These results suggest that 1−4 are d8 square‐planar complexes and 5 is an octahedral complex. The solid state structures of compounds 1−5 were determined by X‐ray crystallography. Structural analyses reveal that 1 and 2 form a one‐dimensional network through charge‐assisted hydrogen bonds; whereas 5 forms a one‐dimensional network through hydrogen bonds only. In complexes 3 and 4, the 2,4‐dipyridyl‐1,3,5‐triazapentadienyl ligand behaves as a bidentate ligand forming a six‐membered ring with the metal ion. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
η1‐Pbasal Coordination of P4X3 (X = S, Se) Molecules toward 16e Ruthenium Fragments
Authors: Di Vaira Massimo , de los Rios Isaac , Mani Fabrizio , Peruzzini Maurizio , Stoppioni Piero
Published: January 2004

Ruthenium(II) pentamethylcyclopentadienyl complexes [Ru(η5‐C5Me5)Cl(L−L)] [L−L = 1,2‐bis(diphenylphosphanyl)ethane, dppe (1), bis(diphenylphosphanyl)methane, dppm, cis‐1,2‐bis(diphenylphosphanyl)ethylene, dppet, and (1‐diphenylarsanyl‐2‐diphenylphosphanyl)ethane, dpadppe] treated with a stoichiometric amount of P4X3 (X = S, Se) in THF have yielded the compounds [Ru(η5‐C5Me5)(L−L)(P4X3)]BPh4 (X = S, Se). In the P4Se3 derivatives the heptatomic cage is bound to the metal through a basal phosphorus atom. The P4S3 derivatives have been obtained as pairs of coordination isomers, with the cage linked either through the apical or through one of the basal P atoms, the latter form predominating (95% abundance), irrespective of the L−L ligand. The monometal complex [Ru(η5‐C5Me5)(dppe)(η1Pbasal‐P4Se3)]BPh4 reacts with 1 to afford the dimetal compound [{Ru(η5‐C5Me5)(dppe)}2(μ,η1:1‐Pbasal‐Papical‐P4Se3)](BPh4)2, where the cage exhibits both modes of bonding. The compounds have been characterized by NMR spectra (1H, 13C and 31P) and elemental analyses. A theoretical analysis of the bonding properties of the two coordination isomer types is also presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Cyano‐Bridged Dimetallic Polynuclear Cu6Cr, Cu6Cr6, Cu2W, and CuW Arrays: Synthesis, Crystal Structure, and Magnetism
Authors: Kou Hui‐Zhong , Zhou Bei Chuan , Si Shu‐Feng , Wang Ru‐Ji
Published: January 2004

The synthesis, structure, and properties of the dimetallic complexes [CuLCr(CN)6]6·[{CuL(H2O)}6Cr(CN)6](ClO4)3· 16H2O (1), [CuLCr(CN)5(NO)]6·[{CuL(H2O)}6Cr(CN)5(NO)](ClO4)3·16H2O (2) and [CuL]3[W(CN)8]2·4H2O (3) {L = 3,7‐bis(2‐aminoethyl)‐1,3,5,7‐tetraazabicyclo[3.3.2]decane} are presented. The structures of 1 and 2 are isomorphous and consist of novel cyano‐bridged [CuL(μ‐CN)2Cr(CN)4]6 dodecanuclear units and [CuL(H2O)(μ‐CN)]6Cr heptanuclear moieties. Every cyclic dodecanuclear Cu6Cr6 group embeds a ClO4− anion. The heptanuclear and the dodecanuclear units are connected through hydrogen bonds to generate a vacant hole, in which another ClO4− anion is accommodated. Complex 3 contains cyano‐bridged Cu2W trimers and CuW dimers. Magnetic studies have shown that the three complexes display ferromagnetic coupling across the Cr−CN−Cu or W−CN−Cu linkages. The best fit to the magnetic data gave for complex 1 JCuCr = +2.40 cm−1, gCr = 1.99, gCu = 2.09, and an intermolecular coupling constant θ = +0.23 K while for complex 2 JCuCr = +12 cm−1, g = 2.13, and θ = −0.49 K. Ferromagnetic CuII‐WV coupling is operative in complex 3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
The Construction of (N2S2)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C4‐Paddlewheel Structure
Authors: Golden Melissa L. , Jeffery Stephen P. , Miller Matthew L. , Reibenspies Joseph H. , Darensbourg Marcetta Y.
Published: January 2004

In pursuit of an analogy between bidentate diphosphane ligands and cis‐dithiolato nickel complexes, the easily prepared [bis(mercaptoethane)diazacycloheptane]nickel complex, Ni‐1′, has been treated with PdII and NiII sources. With the latter, trinickel species are observed with typical slant‐chair structures; for palladium(II) chloride, a basket‐type structure is realized in which the floor of the basket is a PdS4 unit and the sides are N2S2 units. One chloride atom is held within the basket at a Pd···Cl distance of 3.26 Å. With Pd(NO3)2 as a palladium source, a hexanuclear aggregate in the form of a C4‐paddlewheel structure is obtained. In this structure, the N2S2Ni complex serves as a bidentate ligand which bridges two Pd2+ cations at a distance of 3.132 Å. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Cover Picture: Synthesis and Structural Studies of Rhenium(V) Complexes Stabilized by a Monoanionic Cyclen Ligand (Eur. J. Inorg. Chem. 2/2004)
Authors: Xavier Catarina , Paulo António , Domingos Angela , Santos Isabel
Published: January 2004

The cover picture shows the structure of the cation [ReO(cyclen‐H)I]+. This complex and the analogous [ReO(cyclen‐H)Cl]+ are the first examples of d transition metal oxo complexes anchored by a monoanionic cyclen ligand. The deprotonation of cyclen can be accounted by the enhanced Lewis acidity of the d2 rhenium center. Although the geometric contraints of cis‐octahedral cyclen could impose the cis‐ReO2 unit, the resulting cis‐dioxo complex, cis‐[ReO2(cyclen)]+, is very reactive, being readily converted into [ReO(cyclen‐H)X]+. Details are discussed in the article by I. Santos et al. on p. 243 ff.
Supramolecular Assemblies as Promoters of Iodohydrin Formation
Authors: Cerritelli Simona , Chiarini Marco , Cerichelli Giorgio , Capone Marina , Marsili Mario
Published: January 2004

Finding alternative reaction media to replace polluting organic solvents is one aim of green chemistry. The ultimate green solvent, water, is the cheapest, non‐toxic and most readily available reaction medium: three properties which make it an environmentally and economically attractive solvent. However, a fundamental problem in performing reactions in water is that many organic substrates are hydrophobic and not soluble in water. Several approaches are possible in solubilizing these compounds in aqueous media, one of which is carrying out reactions in aqueous solutions of surfactants at concentrations above their critical micellar concentration (cmc). Reactions of iodine with cyclohexene, 1‐octene and styrene in water or in the presence of cationic surfactants do not give useful amounts of iodohydrins, but reactions in anionic surfactants give good yields. Iodohydrins are important functionalizable compounds and are readily prepared in the presence of sodium dodecyl sulfate (SDS) or sodium N‐dodecanoyl sarcosinate (SANa). The critical conditions for these reactions were optimized with a rigorous statistical approach, the experimental design method. Use of these newly optimized reaction conditions gave high yields in short times for all of the alkenes examined. The use of anionic surfactants in water to form iodohydrins is a valid alternative to methods previously described. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Sarcodonins and Sarcoviolins, Bioactive Polyhydroxy‐p‐terphenyl Pyrazinediol Dioxide Conjugates from Fruiting Bodies of the Basidiomycete Sarcodon leucopus
Authors: Calì Valeria , Spatafora Carmela , Tringali Corrado
Published: January 2004

Six new polyhydroxy‐p‐terphenyl pyrazinediol dioxide conjugates (4−9) related to sarcodonin (3) have been isolated from the EtOAc extract of the fruiting bodies of the basidiomycete Sarcodon leucopus and we established their structures by spectral analysis and chemical conversions. Three of them, named sarcodonins α (4), β (5), and γ (6), afforded the same peracetate 12 upon acetylation. Compounds 7, 8, and 9 gave peracetate 13 and were characterized as the N‐oxide epimers of 3−5, respectively, and are named, accordingly, episarcodonin, episarcodonin α, and episarcodonin β. From the EtOH extract, we obtained a mixture of two violet pigments. Chemical and spectroscopic data allowed their structures to be established as the p‐terphenyl ortho‐quinones related to the sarcodonins, namely sarcoviolin α (10) and episarcoviolin α (11). Compounds 3, 4, 6, and 7 and the mixture of 10 and 11 were found to be active in assays against tumor cell cultures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Nitrosation of Amines in Non‐Aqueous Solvents − Difference Between N−N=O and O−N=O Nitroso Donors
Authors: García‐Río Luis , Leis José R. , Moreira José A. , Serantes David
Published: January 2004

A kinetic study has been carried out on nitroso group transfer from substituted N‐methyl‐N‐nitroso‐benzenesulfonamides to different secondary amines: pyrrolidine, piperidine, N‐methylpiperazine, and morpholine in cyclohexane. The observed pseudo‐first‐order rate constant kobs shows a linear and quadratic dependency on the amine concentration with the existence of a primary kinetic isotope effect. Experiments carried out at different temperatures show Arrhenius‐type behavior. Addition of isopropylamine (iPrNH2) to the reaction medium produces an increase in kobs. In the presence of a high iPrNH2 concentrations the influence of secondary amine concentration on kobs shows the disappearance of the quadratic dependency of kobs on the secondary amine. These results would be compatible with an addition‐elimination mechanism, similar to that observed for the aminolysis of the alkyl nitrites in apolar solvents. The observed behavior in the presence of 18‐crown‐6 is very different, however. Addition of crown ether catalyses the reaction of aminolysis of alkyl nitrites insofar as it does not alter the rate of the nitroso group transfer from N‐nitrososulfonamides. This behavior has been interpreted in terms of a concerted reaction mechanism through cyclical transition states, with four or six centers, involving one or two molecules of secondary amine. Addition of iPrNH2 to the reaction medium causes the appearance of a third reaction path, which emerges through a mixed transition state formed by a molecule of a secondary amine and a molecule of isopropylamine. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)