bluuebunny/crossref_metadata_2025 huggingface dataset:
Solution growth and comparative characterization of L‐HFB single crystals
Authors: Sinha N. , Sahas  , Singh B. K. , Kumar K. , Singh N. , Gupta M. K. , Budakoti G. C. , Kumar B.
Published: August 2008

Single crystals of L‐histidine tetrafluoroborate (C6H10N3O2BF4, L‐HFB) were grown by solution growth method using two different temperature profiles: conventional, in which the growth temperature was kept constant at 30°C and rapid, in which it was increased in steps of 1 K per day while keeping the other growth conditions same. Crystals grew in nearly 30 and 10 days in the two methods, respectively. The crystals were transparent and showing its characteristic morphology. Both types of crystals were characterized by XRD for their structural comparison. Surface morphology and growth features of the crystals were studied by SEM. Features of two dimensional layer growth steps, rectangular etch pits, slip lines and bands, etc. were observed. The presence of various functional groups and their bonding were studied by FTIR in the range 4000‐400 cm‐1. Thermal stability of the crystals was determined by thermo‐gravimetric and differential thermal analysis. The generation of green light due to second harmonic generation for fundamental λ =1064 nm has been confirmed in both cases. Dielectric constant measurement was carried out in the range 20Hz‐2MHz. In the UV‐Vis studies, high transmittance and a shorter ‘lower cut off' value (232 nm) were observed. The effect of rapid growth on the structural, morphological and optical properties of the crystals were studied and compared to those of crystals grown in conventional way. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Time‐dependent dielectric behaviour in incommensurate TlInS2 crystal
Authors: Mikailov F. A.
Published: August 2008

The results of measurements of temperature and time dependencies of the dielectric constant of TlInS2 in the temperature interval of successive incommensurate and commensurate phase transitions have been presented. Considerable decrease of the dielectric constant in a temperature interval including successive phase transitions was observed after annealing the sample at a fixed temperature in the ferroelectric state. Additionally, it has been revealed that the time dependencies of the real part of dielectric susceptibility and dielectric losses angle tangent of TlInS2 crystal in the incommensurate phase exhibits an unusual behaviour, which is accompanied by exponential decreasing of the dielectric constant and increasing of dielectric losses angle tangent by time. The observed effects are qualitatively explained using defect‐density‐wave model and phenomenological theory of incommensurate systems containing discommensurations undergoing nucleation and evolution processes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A comparative study of pure and potassium doped cadmium mercury thiocyanate single crystals grown in silica gel
Authors: Kumari P. Nisha Santha , Margaret M. Beatrice , Kalainathan S.
Published: August 2008

Pure and potassium doped cadmium mercury thiocyanate single crystals have been obtained from silica gel by the process of diffusion. The X‐ray diffraction studies reveal the crystal lattice of both pure and doped crystals to be tetragonal. The crystalline perfection of the grown crystals were investigated by high resolution X‐ray diffraction analysis and the quality of the crystals are found to be extremely good. Transmission and Fourier transform infrared spectra were recorded for the grown crystals. The TG/DTA analyses show that the crystals are highly thermally stable. The mechanical strength of the crystals were studied by Vickers microhardness test and a study of their second harmonic generation efficiency in comparison with urea has been made by performing Kurtz powder test. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Low temperature hydrothermal growth and optical properties of ZnO nanorods
Authors: Yang J. H. , Zheng J. H. , Zhai H. J. , Yang L. L.
Published: August 2008

Well‐faceted hexagonal ZnO nanorods have been synthesized by a simple hydrothermal method at relative low temperature (90°C) without any catalysts or templates. Zinc oxide (ZnO) nanorods were grown in an aqueous solution that contained Zinc chloride (ZnCl2, Aldrich, purity 98%) and ammonia (25%). Most of the ZnO nanorods show the perfect hexagonal cross section and well‐faceted top and side surfaces. The diameter of ZnO nanorods decreased with the reaction time prolonging. The samples have been characterized by X‐ray powder diffraction (XRD) and scanning electron microscopy (SEM) measurement. XRD pattern confirmed that the as‐prepared ZnO was the single‐phase wurtzite structure formation. SEM results showed that the samples were rod textures. The surface‐related optical properties have been investigated by photoluminescence (PL) spectrum and Raman spectrum. Photoluminescence measurements showed each spectrum consists of a weak band ultraviolet (UV) band and a relatively broad visible light emission peak for the samples grown at different time. It has been found that the green emission in Raman measurement may be related to surface states. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Synthesis and crystallographic characterization of a six coordinate Cu(II) complex based on hexamethylenetetramine ligand
Authors: Yawen Xuan , Wen Wu , Shujing Li
Published: August 2008

The title compound, Cu(H2O)6]Cl2.2{(CH2)6N4}.4H2O (1), has been prepared under mild hydrothermal conditions. Each CuII atom, located on a centre of symmetry, is coordinated by six water molecules in distorted octahedral coordination geometry. The hexamethylenetetramine molecule does not coordinate to the Cu atom but links with the Cu complex via three O—H…N hydrogen bonds. The remaining N atom of the hexamethylenetetramine is hydrogen‐bonded to the solvent water molecule. In the crystal structure, intermolecular O—H…O, O—H…N and O—H…Cl hydrogen bonds link the components into a three‐dimensional network. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Co nanoclusters as origin of ferromagnetism in sol‐gel synthesized Zn1‐xCoxO (x = 0.05, 0.10 and 0.15) samples
Authors: Sharma V. K. , Varma G. D.
Published: August 2008

We report on the structural and magnetic properties of the polycrystalline samples of Zn1‐xCoxO (x = 0.05, 0.10 and 0.15) synthesized via sol‐gel route. The air sintered samples of all compositions exhibit paramagnetic behaviour at room temperature, on the other hand the same samples on annealing in Ar/H2 atmosphere show room temperature ferromagnetism (RTFM) with enhanced magnetization. The value of magnetization increases with the Co concentration (x) in both the air sintered and Ar/H2 annealed samples. The observed ferromagnetism in the Ar/H2 annealed Zn1‐xCoxO (x = 0.05, 0.10 and 0.15) samples is attributed to the presence of Co nanoclusters as detected by XRD and FESEM‐EDAX. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A flow‐cytometry method for analyzing the composition of membrane rafts
Authors: Morales‐García M. Guadalupe , Fournié Jean‐Jacques , Moreno‐Altamirano M. Maximina Bertha , Rodríguez‐Luna Gabriela , Flores Ricardo‐Mondragón , Sánchez‐García F. Javier
Published: August 2008

Membrane rafts are involved in a broad variety of biological processes. Their protein composition under growth factor stimulation, anti‐inflammatory or proinflammatory microenvironments, or in the course of pathogenic infections still remains to be determined. However, current techniques aimed at the identification of particular proteins on membrane rafts are not devoid of pitfalls. Membrane rafts were obtained by detergent‐free based differential centrifugation from Jurkat T cells and J774 macrophages. Membrane rafts were labeled with fluorochrome‐labeled antibodies directed against different cell membrane molecules, and with fluorochrome‐labeled cholera toxin B that targets GM1 and analyzed by flow cytometry. CD3, CD11a, and GM1 were shown to be differentially expressed on Jurkat T cell‐derived membrane rafts, indicating heterogeneity in membrane rafts composition. On the other hand, it was shown in J774 cell‐derived membrane rafts that most but not all CD14 is present in the GM1‐containing membrane fragments, thus confirming the heterogeneity of membrane rafts composition in other cell lines. The method described here allows the fluorometric assessment of the relative expression of more than one membrane raft component at a time, and at a single vesicle level in a fast and sensitive manner. This method seems to be a suitable approach to evaluate the molecular heterogeneity in membrane rafts composition. © 2008 International Society for Advancement of Cytometry
Contamination of synthetic HuD protein spanning peptide pools with a CMV‐encoded peptide
Authors: de Graaf Marieke T. , de Beukelaar Janet W. , Burgers Peter C. , Luider Theo M. , Kraan Jaco , Smitt Peter A. Sillevis , Gratama Jan W.
Published: August 2008

To detect HuD‐specific T cells in patients with Hu‐antibody associated paraneoplastic neurological syndromes (Hu‐PNS), we used short‐term stimulation assays with HuD protein spanning peptide pools (PSPP) with purities of at least 70% and found reproducible false‐positive CD8+ T‐cell responses in three of 127 individuals (two healthy controls and one Hu‐PNS patient), which all shared HLA‐A*2402 and HLA‐B*1801. After testing the 15‐mer peptides of the HuD antigen separately, we discovered that the same three 15‐mers yielded the CD8+ T cell response in those three individuals. This highly unusual result could not be reproduced when using new batches of peptides with a higher level of purity (>82% and >95%). Therefore, we assumed this response was not directed against the HuD peptides and analyzed the HuD 15‐mers by Fourier transform ion cyclotron resonance (FT‐ICR) tandem mass spectrometry (MS/MS), which showed the presence of a cytomegalovirus (CMV)‐encoded peptide (AIAEESDEEEAIVAY) as a contaminant. The three responding individuals all were CMV‐seropositive and the contaminating peptide appeared to fit in the binding groove of HLA‐B*18. Our data reveal that synthetic PSPP may contain immunogenic contaminations which may cause false positive results in T‐cell stimulation assays. © 2008 International Society for Advancement of Cytometry
The use of receiver operating characteristic analysis for detection of minimal residual disease using five‐color multiparameter flow cytometry in acute myeloid leukemia identifies patients with high risk of relapse
Authors: Al‐Mawali Adhra , Gillis David , Lewis Ian
Published: August 2008

Background:

Multiparameter flow cytometry (MFC) has been shown to be a useful approach for detection of minimal residual disease (MRD). The aim of the study was to determine the optimal threshold that can separate patients into two groups in terms of leukemic residual cells and relapse status after induction and consolidation chemotherapy.

Methods:

Five‐color MFC and receiver operating characteristics (ROC) analysis were used to determine the optimal threshold. This study analyzed 54 acute myeloid leukemia (AML) patients.

Results:

LAPs were detected in 51/54 (94%) patients. MRD was evaluated in the bone marrow (BM) in morphologic complete remission from 25 and 22 patients after induction and consolidation, respectively. The threshold discriminating MRD− from MRD+ cases was set at 0.15% residual leukemic cells, a level that allowed optimal sensitivity and specificity for prediction of relapse, both at postinduction (P = 0.05) and postconsolidation (P = 0.009) time points using ROC analysis. MRD level postinduction not only influenced relapse‐free survival (RFS) (P = 0.004) but also overall survival (OS) (P = 0.003). Multivariate analysis showed that MRD level postinduction was a powerful independent prognostic factor for both RFS (P = 0.037) and OS (P = 0.026).

Conclusions:

Using the ROC analysis, the threshold of 0.15% was defined as the optimal value in discriminating risk categories in AML, and postinduction MRD assessment is able to better predict disease outcome than consolidation. Therefore, MRD analysis by MFC could be used for refining the selection of therapeutic strategies and improving clinical outcome in individual patients. © 2008 Clinical Cytometry Society
Berechnungsvorschlag zur Bestimmung der Schubtragfähigkeit von Aussteifungsscheiben aus Mauerwerk
Authors: Kranzler Thomas , Graubner Carl‐Alexander
Published: August 2008

Im Rahmen des EU‐Forschungsvorhabens ESECMaSE (Enhanced Safety and Efficient Construction of Masonry Structures in Europe) wurde am Institut für Massivbau der TU Darmstadt ein innovatives Modell zur Berechnung der Schubtragfähigkeit von Aussteifungsscheiben aus unbewehrtem Mauerwerk entwickelt. Ein neuer integraler Berechnungsvorschlag, welcher die wesentlichen Einflussgrößen auf die Schubtragfähigkeit von Mauerwerksscheiben beinhaltet und durch entsprechende FE‐Analysen verifiziert wurde, basiert auf den Ergebnissen einer detaillierten Analyse, Bewertung und Erweiterung der aus der Literatur bekannten Nachweisverfahren. Die Güte des neuen Vorschlages kann durch eine Gegenüberstellung der rechnerischen Traglasten mit experimentellen Ergebnissen gezeigt werden.
Chancen und Möglichkeiten von ESECMaSE – Konsequenzen für die Modellierung von Mauerwerksgebäuden
Authors: Jäger Wolfram , Fehling Ekkehard , Schermer Detleff , Stürz Jochen , Schöps Peter
Published: August 2008

Die Einführung der neuen Erdbeben‐ und Windlastnormen und die Entwicklungen auf dem Materialsektor haben zu zahlreichen Untersuchungen zur Schubtragfähigkeit von Mauerwerk geführt. Es ging im Wesentlichen darum, die Bemessungsgleichungen zur Bestimmung der Schubfestigkeit von Mauerwerk bzw. der Tragfähigkeit einer einzelnen Wand zu optimieren und mit Versuchsergebnissen in Übereinstimmung zu bringen. Damit sollten die Verluste aus den verschärften Einwirkungen und dem Teil sicherheitskonzept kompensiert werden. Trotz Ausnutzung des nichtlinearen Verhaltens haben jedoch diese Bemühungen Grenzen. Vergleichende Untersuchungen zur Tragfähigkeit von Gebäuden zeigten erhebliche Reserven bei der Interaktion im Bauteilverbund, die es durch eine verbesserte Modellierung als System zukünftig zu nutzen gilt. Im Folgenden sollen einige dieser Ergebnisse vorgestellt, die Konsequenzen erläutert und ein Ausblick auf die zukünftige Vorgehensweise bei der Modellierung gegeben werden.
Pseudo‐dynamische Großversuche an Reihenmittelhäusern
Authors: Meyer Udo , González Antonio Caballero
Published: August 2008

Im Rahmen des Europäischen Forschungsvorhabens ESECMaSE wurden im Forschungslabor ELSA in ISPRA (Italien) zwei pseudo‐dynamische Großversuche im Maßstab 1:1 an Reihenhaushälften durchgeführt. Die Versuche zeigen eindrucksvoll, dass übliche Reihenhausgrundrisse bei den in Deutschland zu erwartenden Erdbeben lasten nahezu rissfrei bleiben.

Die Versuche bilden zusammen mit den vorhergehenden Untersuchungen im Rahmen des Projekts die Grundlage für eine nachhaltige Optimierung der bislang gängigen Bemessungsannahmen und ‐modelle, mit denen die Leistungsfähigkeit von Mauerwerkbauten zur Zeit noch deutlich unterschätzt wird.
Klimaschutz mit wirtschaftlichem Augenmaß – zur Novellierung der Energieeinsparverordnung (EnEV) 2009/2012
Authors: Herholz Ronny
Published: August 2008

Die Bundesregierung hat am 5. Dezember 2007 im Nachgang zur Sitzung von Meseberg die Eckpunkte für ein Integriertes Energie‐ und Klimaprogramm (IKEP) beschlossen. Das ehrgeizige Programm sieht vor, bis 2020 schädliche Emissionen des Treibhausgases Kohlendioxid um 40% gegenüber 1990 zu verringern. Aktuell werden so viele neue gesetzliche Rahmenbedingungen für fast alle energierelevanten Alltagsbereiche erarbeitet wie in den letzten 10Jahren zusammen nicht. Wenn auch jetzt noch eine Reihe wichtiger Fragen nicht geklärt ist, bereits am 21. Mai 2008 wurde das IKEPII im Bundeskabinett beschlossen. Ab 2009 gilt eine erneut verschärfte Energieeinsparverordnung (EnEV).
False Hyperglycemies in Diabetic Patients Using Icodextrin in Peritoneal Dialysis
Authors: Ramos Rosa , González Teresa , Fulladosa Xavier , Castelao Alberto M. , Grinyó Josep M.
Published: August 2008

BACKGROUND

Monitoring blood glucose is an important part of integral management of peritoneal dialysis (PD) patients with diabetes. Nowadays, several systems of glucometers are commercially available, and practically all are based on 3 enzymatic reactions. The two systems used most often are glucose oxidase (GOD) and glucose dehydrogenase using pyrroloquinolinequinone cofactor (GDH/PQQ). On the other hand, icodextrin (Extraneal) is an isosmotic PD solution containing glucose polymers. Accumulation in the systemic circulation of icodextrin metabolites may lead to a disparity between fi nger‐stick and formal blood glucose measurement.

METHODS

We analyzed the possible interference of icodextrin metabolites with various glucose assays in 9 diabetic patients undergoing PD using icodextrin.

RESULTS

The simple regression test showed a good association between central laboratory values and the Ascensia Breeze II (Bayer) glucometer:GOD (r = 0.928; p < 0.0001), the One Touch Ultra (Johnson and Johnson): GOD (r = 0.911; p < 0.0002), and the Glucocard Memory 2 (Menarini):GOD (r = 0.966; p < 0.00001). Nevertheless, the Accu‐chek Aviva (Roche):GDH/PQQ showed poor correlation (r = 0.353; p = 0.317) with the laboratory results. It has been suggested that maltose interferes with glucose assays that use glucose dehydrogenase with GDH/PQQ, leading to falsely increased readings. Our results confirmed that GDH/PQQ devices overestimated glucose levels in these patients

CONCLUSIONS

We concluded that patients with diabetes mellitus treated by icodextrin‐PD are at risk of having erroneous blood glucose measurements using GDH/PQQ‐based glucometers. Careful attention needs to be given to checking that the glucose devices used in these patients are based on GOD, GDH with a different PQQ cofactor, or hexokinase methods in order to minimize the risk of hypoglycemies due to an overdose of insulin.
Cross‐Modal transfer of the conditioned eyeblink response during interstimulus interval discrimination training in young rats
Authors: Brown Kevin L. , Stanton Mark E.
Published: August 2008

Eyeblink classical conditioning (EBC) was observed across a broad developmental period with tasks utilizing two interstimulus intervals (ISIs). In ISI discrimination, two distinct conditioned stimuli (CSs; light and tone) are reinforced with a periocular shock unconditioned stimulus (US) at two different CS–US intervals. Temporal uncertainty is identical in design with the exception that the same CS is presented at both intervals. Developmental changes in conditioning have been reported in each task beyond ages when single‐ISI learning is well developed. The present study sought to replicate and extend these previous findings by testing each task at four separate ages. Consistent with previous findings, younger rats (postnatal day—PD23 and 30) trained in ISI discrimination showed evidence of enhanced cross‐modal influence of the short CS–US pairing upon long CS conditioning relative to older subjects. ISI discrimination training at PD43–47 yielded outcomes similar to those in adults (PD65–71). Cross‐modal transfer effects in this task therefore appear to diminish between PD30 and PD43–47. Comparisons of ISI discrimination with temporal uncertainty indicated that cross‐modal transfer in ISI discrimination at the youngest ages did not represent complete generalization across CSs. ISI discrimination undergoes a more protracted developmental emergence than single‐cue EBC and may be a more sensitive indicator of developmental disorders involving cerebellar dysfunction. © 2008 Wiley Periodicals, Inc. Dev Psychobiol 50: 647‐664, 2008.
Expression pattern of Anosmin‐1 during pre‐ and postnatal rat brain development
Authors: Clemente Diego , Esteban Pedro F. , Del Valle Ignacio , Bribián Ana , Soussi‐Yanicostas Nadia , Silva Augusto , De Castro Fernando
Published: August 2008

Anosmin‐1 participates in the development of the olfactory and GnRH systems. Defects in this protein are responsible for both the anosmia and the hypogonadotrophic hypogonadism found in Kallmann's syndrome patients. Sporadically, these patients also manifest some neurological symptoms that are not explained in terms of the developmental defects in the olfactory system. We describe the pattern of Anosmin‐1 expression in the central nervous system during rat development using a novel antibody raised against Anosmin‐1 (Anos1). The areas with Anos1‐stained neurons and glial cells were classified into three groups: (1) areas with immunoreactivity from embryonic day 16 to postnatal day (P) 15; (2) areas with Anosmin‐1 expression only at postnatal development; (3) nuclei with immunoreactivity only at P15. Our data show that Anos1 immunoreactivity is detected in projecting neurons and interneurons within areas of the brain that may be affected in patients with Kallmann's syndrome that develop both the principal as well as sporadic symptoms. Developmental Dynamics 237:2518–2528, 2008. © 2008 Wiley‐Liss, Inc.
Adipato‐Bridged Copper(II) Complexes
Authors: Zheng Yue‐Qing , Cheng De‐Yi , Lin Jian‐Li , Li Zhi‐Feng , Wang Xian‐Wen
Published: August 2008

Reactions of Cu(ClO4)2·6H2O, adipic acid, and 2,2′‐bipyridine/1,10‐phenanthroline in aqueous methanolic solutions afforded four adipato‐bridged CuII complexes, {[Cu(phen)2]2(C6H8O4)}(ClO4)2 (1), {[Cu(phen)2]2(C6H8O4)}(ClO4)2·1.33H2O (2), [Cu2(phen)2(H2O)]2(C6H8O4)2(ClO4)4 (3), and {[Cu2(bpy)2(H2O)]2(C6H8O4)2}(ClO4)4·2H2O (4) (phen = 1,10‐phenanthroline, bpy = 2,2′‐bipyridine, C6H8O4 = adipate anion). The centrosymmetric adipato‐bridged dumbbell‐like dinuclear complex cations {[Cu(phen)2]2(C6H8O4)}2+ in 1 and 2, through aromatic stacking interactions, are assembled into supramolecular (4,4) networks, and twofold interpenetration of the networks completes the 3D supramolecular architectures with counterions as well as the lattice water molecules in voids. The characteristic secondary building units in 3 and 4 are the centrosymmetric double‐semi‐paddle‐wheel oftetranuclear {[Cu2(phen)2(H2O)]2(COO)4} and{[Cu2(bpy)2(H2O)]2(COO)4} clusters, respectively, which are interconnected by adipato ligands to form (4,4) networks. The resulting networks, through interlayer‐stacking interactions, are assembled into a 3D open framework with counterions as well as the lattice water molecules in channels. Magnetic studies of 3 and 4 suggest significant antiferromagnetic coupling interactions between CuII ions bridged by the syn–syn carboxylate groups, whereas weak ferromagnetic coupling is observed between two symmetry‐related copper(II) ions bridged by the μ2‐O atoms. Cyclic voltammograms of 3 and 4 exhibit similar redox behaviors and display two quasireversible couples. The thermal decompositions of 3 and 4 are also described.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Mechanistic Insights into Acetophenone Transfer Hydrogenation Catalyzed by Half‐Sandwich Ruthenium(II) Complexes Containing 2‐(Diphenylphosphanyl)aniline – A Combined Experimental and Theoretical Study
Authors: Bacchi Alessia , Balordi Marcella , Cammi Roberto , Elviri Lisa , Pelizzi Corrado , Picchioni Filippo , Verdolino Vincenzo , Goubitz Kees , Peschar René , Pelagatti Paolo
Published: August 2008

Several new half‐sandwich ruthenium(II) complexes containing 2‐(diphenyphosphanyl)aniline (PNH2) of formula {Ru[(κ2P,N)PNH2](p‐cymene)Cl}Y [Y = Cl (1a), PF6 (1b), BF4 (1c), BPh4 (1d), TfO (1e)] were synthesized and fully characterized both in solution (1H NMR and 31P{1H} NMR spectroscopy) and in the solid state (FTIR, X‐ray analysis on single crystal). Complexes 1a and 1b are active precatalysts in the hydrogen transfer reaction of acetophenone, leading to tof values up to 4440 h–1. In comparison, the {Ru[(κ2P,N)PNMe2](p‐cymene)Cl}Cl complex leads to a tof value of 100 h–1 under the same catalytic conditions. The mechanism through which the precatalysts operate was deeply explored by high‐resolution MS (ESI) and DFT/PCM studies. The results reveal that the complexes containing PNH2 operate through a bifunctional mechanism analogous to that proposed for diamines and amino alcohol ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
An Assessment of the Potential Relationship between the Charge of Gd–DTPA Complexes and the Exchange Rate of the Water Coordinated to the Metal
Authors: Laurent Sophie , Vander Elst Luce , Botteman François , Muller Robert N.
Published: August 2008

The residence time of coordinated water (τM), a parameter of paramount importance for relaxivity, is compared in a series of Gd–DTPA derivatives carrying different global charges. The importance of the charge in the first coordination sphere of the metal and in its vicinity is reported. Neutral bisester and bisamide complexes have significantly different τM values. The paradoxical similarity of the exchange rates of bisester complexes and Gd–DTPA, on the one hand, and the large difference between neutral bisester and bisamide complexes, on the other hand, suggest that the charge inside the first coordination sphere is not the factor dominating the water exchange rate, which seems therefore more sensitive to the steric congestion. The study of Gd–(S)‐N6–carboxymethyl–DTPA, Gd–DTPA–BHydroxamide at basic pH, and Gd–DTPA–BAlaA clearly shows that anionic groups located outside the first coordination sphere have a beneficial influence on the value of τM, but that this effect strongly decreases with an increasing distance between the anionic group and the coordinated water. These conclusions underline the influence of steric hindrance and of the charged groups present in close proximity of the first coordination sphere on the exchange rate of the coordinated water. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Di‐, Tetra‐, and Polynuclear Copper(II) Complexes: Active Catalysts for Oxidation of Toluene and Benzene
Authors: Roy Partha , Dhara Koushik , Manassero Mario , Banerjee Pradyot
Published: August 2008

Three copper(II) complexes with a binucleating N2O donor ligand, [Cu2(L1)(μ2‐pz)(CH3COO)2] (1), [Cu4(L1)2(μ4‐O)(μ2‐CH3COO)2(μ1,1‐N3)(N3)] (2), and [Cu2(L2)(μ1,1‐N3)(μ1,3‐N3)2]∞(3) [pz = pyrazolato, HL1= 2,6‐bis(morpholinomethyl)‐4‐tert‐butylphenol and HL2= 2,6‐bis(morpholinomethyl)‐4‐methylphenol] have been synthesized and characterized by elemental analysis, FTIR and UV/Vis spectroscopy, and X‐ray crystallography. X‐ray crystallographic studies revealed that a series of di‐, tetra‐, and polynuclear complexes have been formed by varying the bridging ligand, counteranion, and reaction conditions. These show effective catalytic properties for the hydrogen peroxide oxidation of toluene and benzene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Synthesis and Structures of Triorganochalcogenium (Te, Se, S) Dinitramides
Authors: Klapötke Thomas M. , Krumm Burkhard , Scherr Matthias
Published: August 2008

The syntheses of the triorganochalcogenium dinitramide salts [Ph3Te][N(NO2)2] (1), [Me3Te][N(NO2)2] (2), [Ph3Se][N(NO2)2] (3), [Me3Se][N(NO2)2] (4), [Ph3S][N(NO2)2] (5), and [Me3S][N(NO2)2] (6), their characterization by multinuclear NMR spectroscopy, vibrational spectra, and single‐crystal structures are described. The syntheses of the compounds were achieved with the help of [Ag(py)2][N(NO2)2] and [Ag(NCCH3)][N(NO2)2] as dinitramide transfer reagents. Whereas in the crystal structure of 1 different coordination modes to dinitramide moieties are present, the crystal structure of 3 shows only a single intermolecular contact to the dinitramide moiety. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Mo‐Catalyzed Cross‐Metathesis Reaction of Propynylferrocene (Eur. J. Inorg. Chem. 25/2008)
Authors: Bobula Tomáš , Hudlický Jason , Novák Petr , Gyepes Róbert , Císařová Ivana , Štěpnička Petr , Kotora Martin
Published: August 2008

The cover picture shows the reaction scheme for the cross‐metathesis of (prop‐1‐yn‐1‐yl)ferrocene with substituted propynes effected by catalysts generated from [Mo(CO)6] and halophenols, situated on a background full of typical ferrocene, autumn‐like colors. The metathesis reaction affords good yields of unsymmetric ferrocenyl alkynes, thus offering a new alternative approach toward their preparation. Also shown are the crystal structure of methyl 4‐[(ferrocenyl)ethynyl]benzoate and the orbital diagram of its solid‐state π···π stacked dimer as calculated by DFT methods. A survey of various substrates and catalysts, results of X‐ray structure analysis and DFT calculations as well as electrochemical data for a series of (phenylethynyl)ferrocenes substituted at the phenyl ring are discussed in the article by M. Kotora, P. Štěpnička et al. on p. 3911 ff.
A Practical Access to 1,2‐Diaminophytosphingolipids
Authors: Harrak Youssef , Llebaria Amadeu , Delgado Antonio
Published: August 2008

A practical approach to the synthesis of phytosphingolipids containing the 1,2‐diamino framework is described. The methodology relies on the regioselective ring‐opening of phytosphingosine‐derived N‐nosylaziridines 4 and 6 with primary or secondary amines, acylation and subsequent deprotection steps. For practical purposes, N‐substituted benzylamines were used as protected primary amine surrogates to avoid side‐reactions in the course of the N‐nosyl deprotection step.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Assessing the effect of clustered and biased multi‐stage sampling
Authors: Menezes Raquel , Tawn Jonathan
Published: August 2008

We propose a method for detecting biased multi‐stage sampling of spatial data and a method to adjust for biased clustering of samples. We assess the effect of these methods for the analysis of radioactivity contamination data from Rongelap island, with the scientific problem being the estimation of the maximum level of radioactivity over the island. These data were collected over a two‐stage process of uniform and clustered samples, which may have an impact on conclusions from a standard analysis that does not account for either of these features. Copyright © 2008 John Wiley & Sons, Ltd.
Risk assessment before and after solar photocatalytic degradation of BTEX contaminated groundwater at a gas station site in Korea
Authors: Cho Il‐Hyoung , Choi Kyungho , Kang Hojeong , Zoh Kyung‐Duk
Published: August 2008

We assessed the incremental lifetime risks due to groundwater contamination with benzene, toluene, ethylbenzene, and xylene compounds (BTEX) for residents living on the site of a former gas station. Five remedial processes were applied to examine the degradation pattern of groundwater samples under similar weather conditions in winter: H2O2/solar light (action 1), immobilized TiO2/solar light (action 2), TiO2 slurry/solar light (action 3), immobilized TiO2/solar light/H2O2 (action 4), and TiO2 slurry/solar light/H2O2 (action 5). None of the remedial actions satisfied the criteria of acceptable risk (1 × 10−6 for carcinogens) using point estimation with both central tendency exposure (CTE) and reasonable maximum exposure (RME) for all pathways via designated exposure scenarios. Regarding the total hazard index (HI) for noncarcinogens, only action 5 satisfied all the exposure scenarios, both CTE and RME, for toluene, ethylbenzene, and xylene compounds, whereas the total health risk for benzene was between 10−5 and 10−6 for carcinogens. Results of probabilistic estimation before and after the treatment of benzene with action 5 using a Monte Carlo simulation were 68.1% for males (95% CI: 5.0 × 10−7 to 3.9 × 10−6) and 74.2% for females (95% CI: 5.0 × 10−7 to 4.6 × 10−6), exceeding the criteria of acceptable risk (10−6 for carcinogens). However, no adverse health risk was posed if remedial action 5 or an increased reaction time were applied. This study is a new attempt to integrate issues of groundwater contamination based on concentration and health risk assessment associated with different ex situ remedial actions. © 2008 American Institute of Chemical Engineers Environ Prog, 2008
Spatial memory and the monkey hippocampus: Not all space is created equal
Authors: Lavenex Pamela Banta , Lavenex Pierre
Published: August 2008

Studies of the role of the monkey hippocampus in spatial learning and memory, however few, have reliably produced inconsistent results. Whereas the role of the hippocampus in spatial learning and memory has been clearly established in rodents, studies in nonhuman primates have made a variety of claims that range from the involvement of the hippocampus in spatial memory only at relatively longer memory delays, to no role for the hippocampus in spatial memory at all. In contrast, we have shown that selective damage restricted to the hippocampus (CA regions) prevents the learning or use of allocentric, spatial relational representations of the environment in freely behaving adult monkeys tested in an open‐field arena. In this commentary, we discuss a unifying framework that explains these apparently discrepant results regarding the role of the monkey hippocampus in spatial learning and memory. We describe clear and strict criteria to interpret the findings from previous studies and guide future investigations of spatial memory in monkeys. Specifically, we affirm that, as in the rodent, the primate hippocampus is critical for spatial relational learning and memory, and in a time‐independent manner. We describe how claims to the contrary are the result of experimental designs that fail to recognize, and control for, egocentric (hippocampus‐independent) and allocentric (hippocampus‐dependent) spatial frames of reference. Finally, we conclude that the available data demonstrate unequivocally that the central role of the hippocampus in allocentric, spatial relational learning and memory is conserved among vertebrates, including nonhuman primates. © 2008 Wiley‐Liss, Inc.
Distinct hippocampal regions make unique contributions to relational memory
Authors: Giovanello Kelly Sullivan , Schnyer David , Verfaellie Mieke
Published: August 2008

Neuroscientific research has shown that the hippocampus is important for binding or linking together the various components of a learning event into an integrated memory. In a prior study, we demonstrated that the anterior hippocampus is involved in memory for the relations among informational elements to a greater extent that it is involved in memory for individual elements (Giovanello et al., 2004. Hippocampus 14:5–8). In the current study, we extend those findings by further specifying the role of anterior hippocampus during relational memory retrieval. Specifically, anterior hippocampal activity was observed during flexible retrieval of learned associations, whereas posterior hippocampal activity was detected during reinstatement of study episodes. These findings suggest a functional dissociation across the long axis of human hippocampus based on the nature of the mnemonic process rather than the stage of memory processing or type of stimulus. © 2008 Wiley‐Liss, Inc.
Room‐Temperature Alkyne–Nitrile Metathesis and Unambiguous Proof for the Existence of a High‐Valent Iron‐Nitrido Dication in the Gas Phase. Short Communication
Authors: Boyd John P. , Schlangen Maria , Grohmann Andreas , Schwarz Helmut
Published: August 2008

An unprecedented alkyne–nitrile metathesis takes place when the high‐valent iron‐nitrido dication [Fe(L)N]2+, with L=2,6‐bis(2‐methyl‐1,3‐diaminopropan‐2‐yl)pyridine, is reacted with alkynes in the gas phase under thermal conditions. While the detailed role of the alkyne substrate with respect to relative rates, regioselectivities, and branching ratios remains to be elucidated, the very existence of this novel metathesis reaction provides additional experimental evidence of a genuine, long‐lived, formal iron(V)‐nitrido dication.
On the Adsorption and Reduction of the Herbicide Picloram on Mercury and Carbon Electrodes
Authors: Rodríguez Mellado Jose M. , Pintado Sara , Ruiz Montoya Mercedes
Published: August 2008

At concentrations higher than 2⋅10−4 M, and below pH 3, the cyclic voltammograms of picloram (=4‐amino‐3,5,6‐trichloropyridine‐2‐carboxylic acid) on Hg electrodes show two prepeak systems (named I and II attending to the proximity to the main reductions peak), which can be attributed to the weak adsorption of reactant and the strong adsorption of the product at the electrode surface. The system II is due to the uncharged form of picloram, and system I to the picloram protonated at the pyridine N‐atom. Small amounts of the surfactant Triton X‐100 (=α‐[4‐(1,1,3,3‐tetramethylbutyl)phenyl]‐ω‐hydroxypoly(oxyethane‐1,2‐diyl)) cause the disappearance of system I, the shift of system II, and also affect the intensities and widths of anodic and cathodic peaks but not the charge passed in each peak. Thus, the adsorption process responsible for the appearance of system I is inhibited by the presence of Triton; by contrast, the process corresponding to system II is only modified by the surfactant, becoming an electrochemical process occurring at the potentials corresponding to system II, which is more reversible than that observed in the absence of Triton. The addition of Triton permitted the analysis of the main reduction process. Convolution voltammetry of the main reduction peak is consistent with the loss of a Cl‐atom in equilibrium which occurs after a reversible electron transfer and is followed by the reductions of both species present in the equilibrium (Scheme 2). This is also the reduction mechanism on a glassy carbon electrode but the electron transfer on the carbon electrode increases with respect to the mercury electrodes; in addition, the loss of the Cl‐atom does not take place on the electrode surface. From the recording of differential capacity–potential curves, it was concluded that picloram is adsorbed on the carbon electrode; but this adsorption is too weak to induce the appearance of prepeak systems.
The ‘Azirine/Oxazolone Approach’ to the Synthesis of Aib‐Pro Endothiopeptides
Authors: Budzowski Artur , Linden Anthony , Heimgartner Heinz
Published: August 2008

The reaction of methyl N‐(2,2‐dimethyl‐2H‐azirin‐3‐yl)‐L‐prolinate (2a) with thiobenzoic acid at room temperature gave the endothiopeptide Bz‐AibΨ[CS]‐Pro‐OMe (7) in high yield. In an analogous manner, (benzyloxy)carbonyl (Z)‐protected proline was transformed into the thioacid, which was reacted with 2a to give the endothiotripeptide Z‐Pro‐AibΨ[CS]‐Pro‐OMe (12). The corresponding thioacid of 7 was prepared in situ via saponification, formation of a mixed anhydride, and treatment with H2S. A second reaction with 2a led to the endodithiotetrapeptide 9, but extensive epimerization at Pro2 was observed. Similarly, saponification of 12 and coupling with either 2a or H‐Phe‐OMe and 2‐(1H‐benzotriazol‐1‐yl)‐1,1,3,3‐tetramethyluronium tetrafluoroborate/1‐hydroxy‐1H‐benzotriazole (TBTU/HOBt) gave the corresponding endothiopeptides as mixtures of two epimers. The synthesis of the pure diastereoisomer BzΨ[CS]‐Aib‐Pro‐AibΨ[CS]‐N(Me)Ph (21) was achieved via isomerization of 7 to BzΨ[CS]‐Aib‐Pro‐OMe (16), transformation into the corresponding thioacid, and reaction with N,2,2‐trimethyl‐N‐phenyl‐2H‐azirin‐3‐amine (1a). The structures of 12 and 21 were established by X‐ray crystallography.
Two New Spirostanol Saponins from Reineckia carnea
Authors: Zhang Zhong‐Quan , Chen Jian‐Chao , Zhang Xian‐Ming , Li Zhong‐Rong , Qiu Ming‐Hua
Published: August 2008

Two new spirostanol saponins, (1β,3β,5β,25S)‐spirostan‐1,3‐diol 1‐(β‐D‐xylopyranoside) (1) and (1β,3β,5β,25S)‐spirostan‐1,3‐diol 1‐[α‐L‐rhamnopyranosyl‐(1→2)‐β‐D‐fucopyranoside] (2), along with two known compounds, (1β,3β,5β,25S)‐spirostan‐1,3‐diol 1‐[α‐L‐rhamnopyranosyl‐(1→2)‐β‐D‐xylopyranoside] (3) and (1β,3β,4β,5β,25S)‐spirostan‐1,3,4,5‐tetrol 5‐(β‐D‐glucopyranoside) (4) were isolated from the whole plant of Reineckia carnea. The structures of the new steroids were determined by detailed analysis of their 1D‐ and 2D‐NMR spectra and chemical methods, and by comparison with spectral data of known compounds. Compounds 3 and 4 were isolated from the genus Reineckia for the first time.
Discharge characteristics at the control point for rainfall runoff model application
Authors: Hwang Man H. , Maeng Seung J. , Lee Sang J. , Lee Bae S. , Koh Ick H.
Published: August 2008

To manage and distribute water resources efficiently, a rainfall runoff model must be selected and established. To determine the appropriations for this rainfall runoff model, however, accurate flow data must first be obtained. Thus, in this study, the simulated flow of Korea's Geum River was compared with the observed flow at Gongju point, a main control point, using the Streamflow Synthesis and Reservoir Regulation (SSARR) model. The results obtained showed a huge difference between the simulated and observed flows during the low flow period. To determine what caused this difference, a confidence analysis of the formula of the stage discharge curve at Gongju point, developed by the Ministry of Construction and Transportation's Geum River Flood Control Office, was conducted. The flow during the low flow period (between 2003 and 2005) was also measured, and the value obtained was compared with the simulated flow. The long‐term flow as low flow was also calculated, through runoff component analysis, to determine the hydraulic characteristics of the control point and to examine the runoff characteristics during the low flow water utilization seasons.

The study results show that during the low flow period (between 2003 and 2005), the simulated flow (based on the SSARR model) approximated the long‐term flow (based on the runoff component analysis).

The results, however, also show that the observed flow, according to the stage discharge curve formula developed by the Geum River Flood Control Office, was overestimated by about 10% up to 20% both during the normal water level and drought seasons, due to hydraulic factors caused by the spatial characteristics of Gongju point, a main control point. The results of the study reveal that the estimation of the flow must be corrected, and that such flow must be continuously monitored. Copyright © 2008 John Wiley & Sons, Ltd.
Ferritin and FasL (CD95L) mediate density dependent apoptosis in primary rat hepatocytes
Authors: Bresgen N. , Ohlenschläger I. , Wacht N. , Afazel S. , Ladurner G. , Eckl P.M.
Published: August 2008

Based on a recent description of an apoptosis stimulating property for hepatocyte derived isoferritins, this investigation demonstrates that ferritin, released in vitro from hepatocytes substantially contributes to density dependent apoptosis in primary hepatocytes and is significantly (P ≤ 0.05) inhibited by anti‐H‐ferritin antibody rH02. Furthermore, total protein release and albumin secretion rapidly decline in a time and density dependent mode under serum‐free conditions, whereas ferritin secretion, which is upregulated at initial stages of primary culture is not affected by cell density. Supplementation with dexamethasone (DEX) or proliferative stimulation by epidermal growth factor (EGF) and insulin strongly suppresses density dependent apoptosis. Both regimens have previously been shown to inhibit isoferritin mediated apoptosis in hepatocytes, most likely by interrupting proapotitc mitochondrial signalling. Finally, FasL/Fas also participates in density dependent apoptosis, since apoptosis is significantly (P ≤ 0.005) reduced in high density cultures supplemented with an anti‐FasL antibody. This antibody has also been shown to neutralise ferritin mediated apoptosis in primary hepatocytes, suggesting a linkage of ferritin and Fas in density dependent apoptosis. In conclusion, ferritin contributes to apoptosis in primary hepatocytes in an autocrine, density dependent mode, involving Fas stimulation and proapoptotic mitochondrial signalling. With respect to liver physiology, these findings may indicate that ferritin plays a yet unrecognised role as an acute phase signalling molecule in early stages of tissue repair and liver regeneration, and may also be responsible for the limited ability to propagate human hepatocytes in culture and the limited expansion of donor cells in the recipient liver upon cell transplantation. J. Cell. Physiol. 217: 800–808, 2008. © 2008 Wiley‐Liss, Inc.
“APRIL hath put a spring of youth in everything”: Relevance of APRIL for survival
Authors: Kimberley Fiona C. , Hahne Michael , Medema Jan Paul
Published: August 2008

A proliferation inducing ligand (APRIL or TALL‐2 and TRDL‐1) was first discovered as a cytokine over‐expressed in many transformed cells and with the capacity to stimulate proliferation. APRIL was shown to bind two different receptors of the TNF receptor superfamily: B cell maturation antigen (BCMA) and transmembrane activator and calcium modulator and cyclophilin ligand interactor (TACI), as well as heparan sulphate proteoglycans (HSPGs). APRIL has since been shown to play a physiological role in B cell biology, in particular the survival of plasma B cells in a specialized APRIL‐rich niche. However, aberrant expression of APRIL and the subsequent activation of pro‐survival pathways, is potentially the driving force for the survival of several B cell malignancies. APRIL has therefore become an important therapeutic target, but many questions regarding its mechanism of action still remain. It is for instance unclear what the exact physiological implications of the APRIL–HSPG interaction could be. Neither do we know the precise signals elicited by APRIL in normal or in malignant cells, and whether blocking these effects could provide real therapeutic gain in cancer patients. In this review we discuss the specific relevance of APRIL for cell survival, in terms of both its physiological role and its role in tumor biology, and highlight some of the key questions that will undoubtedly form the basis of future research in this field. J. Cell. Physiol. 218: 1–8, 2009. © 2008 Wiley‐Liss, Inc.
Internalization of EGF receptor following lipid rafts disruption in keratinocytes is delayed and dependent on p38 MAPK activation
Authors: Lambert Sylviane , Ameels Hélène , Gniadecki Robert , Hérin Michel , Poumay Yves
Published: August 2008

The receptor for epidermal growth factor (EGF) plays an important role in epidermal keratinocytes and is known to move out of lipid raft after cholesterol depletion, leading to ligand‐independent activation. Accumulation of evidence indicates the ability of EGF receptor (EGFR) to undergo internalization without participation of the ligand under the control of p38 MAPK during stress conditions. Since cholesterol depletion using methyl‐beta‐cyclodextrin is known to induce ligand‐independent activation of EGFR in keratinocytes, we investigated by confocal microscopy and ligand‐binding tests the processing and localization of EGFR following lipid raft disruption. Here, we report the dimerization and the slow internalization of the receptor accompanied by the delayed phosphorylation of tyrosine 1068 and its degradation by the proteasome. We also demonstrate the involvement of p38 MAPK during the process of internalization, which can be considered as a protective response to stress. Moreover, cholesterol‐depleted keratinocytes recover their ability to proliferate during the recovery period that follows lipid raft disruption. J. Cell. Physiol. 217: 834–845, 2008. © 2008 Wiley‐Liss, Inc.