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Selected AbstractsStrain-engineered novel III,N electronic devices with high quality dielectric/semiconductor interfacesPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2003M. Asif Khan Abstract Since the early demonstration of 2D-electron gas [M. A. Khan et al., Appl. Phys. Lett. 60, 3027 (1992)] and a heterojunction field effect transistor (HFET) [M. Asif Khan et al., Appl. Phys. Lett. 63, 1214 (1993)] in III,N materials, rapid progress has been made to improve the DC and RF performance of GaN,AlGaN based HFETs. Stable and impressive microwave powers as high as 4,8 W/mm have been reported for device operation frequencies from 10 to 35 GHz. The key reason for these high performance numbers is an extremely large sheet carrier densities (>1 × 1013 cm,2) that can be induced at the interfaces in III,N hetereojunction [A. Bykhovsk et al., J. Appl. Phys. 74, 6734 (1993); M. Asif Khan et al., Appl. Phys. Lett. 75, 2806 (1999)]. These are instrumental in screening the channel dislocations thereby retaining large room temperature carrier mobilities (>1500 cm2/Vs) and sheet resistance as low as 300 ,/sq. These numbers and the high breakdown voltages of the large bandgap III,N material system thus enable rf-power approximately 5,10 times of that possible with GaAs and other competitor's technologies. We have recently introduced a unique pulsed atomic layer epitaxy approach to deposit AlN buffer layers and AlN/AlGaN superlattices [J. Zhang et al., Appl. Phys. Lett. 79, 925 (2001); J. P. Zhang et al., Appl. Phys. Lett. 80, 3542 (2002)] to manage strain and decrease the dislocation densities in high Al-content III,N layers. This has enabled us to significantly improve GaN/AlGaN hetereojunctions and the device isolation. The resulting low defect layers are not only key to improving the electronic but also deep ultraviolet light-emitting diode devices. For deep UV LED's they enabled us to obtain peak optical powers as high as 10 mW and 3 mW for wavelengths as short as 320 nm and 278 nm. Building on our past work [M. Asif Khan et al., Appl. Phys. Lett. 77, 1339 (2000); X. Hu et al., Appl. Phys. Lett. 79, 2832 (2001)] we have now deposited high quality SiO2/Si3N4 films over AlGaN with low interface state densities. They have then been used to demonstrate III,N insulating gate transistors (MOSHFET (SiO2) and MISHFET (Si3N4) with gate leakage currents 4,6 order less than those for conventional GaN,AlGaN HFETs. The introduction of the thin insulator layers (less then 100 Ĺ) under the gate increases the threshold voltage by 2,3 V. In addition, it reduces the peak transconductance gm. However the unity cut-off frequency, the gain and the rf-powers remain unaffected as the gm/Cgs (gate-source capacitance) ratio remains unchanged. In addition to managing the defects and gate leakage currents we have also employed InGaN channel double heterojunction structures (AlInGaN,InGaN,GaN) to confine the carriers thereby reducing the spillover into trappings states. These InGaN based MOS-DHFETs exhibited no current-collapse, extremely low gate leakage currents (<10,10 A/mm) and 10,26 GHz rf-powers in excess of 6 W/mm. We have also demonstrated the scalability and stable operation of our new and innovative InGaN based insulating gate heterojunction field effect transistor approach. In this paper we will review the III,N heterojunction field-effect transistors progress and pioneering innovations including the excellent work from several research groups around the world. (© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Oxidation of PCE with a UV LED Photocatalytic ReactorCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 1 2005D. H. Chen Abstract This paper is the first to investigate photocatalysis using a cutting-edge and energy-efficient solid-state light source: Ultraviolet (UV) Light Emitting Diodes (LED's). UV LED's do not involve mercury vapor, can be driven with direct current (DC), and have a long lifetime of 100,000 hours. UV LED's with a peak wavelength of 375,nm were tested for perchloroethylene (PCE) photocatalytic oxidation over Degussa P,25 TiO2. At a UV light output of only 49,,W/cm2, the designed reactor delivers a PCE conversion of up to 43,%. If the UV LED price continues to drop, it is very likely that UV LED's will replace UV lamps as the favored light source in photocatalysis applications. [source] Etiology, pathogenesis and prevention of neural tube defectsCONGENITAL ANOMALIES, Issue 2 2006Rengasamy Padmanabhan ABSTRACT Spina bifida, anencephaly, and encephalocele are commonly grouped together and termed neural tube defects (NTD). Failure of closure of the neural tube during development results in anencephaly or spina bifida aperta but encephaloceles are possibly post-closure defects. NTD are associated with a number of other central nervous system (CNS) and non-neural malformations. Racial, geographic and seasonal variations seem to affect their incidence. Etiology of NTD is unknown. Most of the non-syndromic NTD are of multifactorial origin. Recent in vitro and in vivo studies have highlighted the molecular mechanisms of neurulation in vertebrates but the morphologic development of human neural tube is poorly understood. A multisite closure theory, extrapolated directly from mouse experiments highlighted the clinical relevance of closure mechanisms to human NTD. Animal models, such as circle tail, curly tail, loop tail, shrm and numerous knockouts provide some insight into the mechanisms of NTD. Also available in the literature are a plethora of chemically induced preclosure and a few post-closure models of NTD, which highlight the fact that CNS malformations are of hetergeneitic nature. No Mendelian pattern of inheritance has been reported. Association with single gene defects, enhanced recurrence risk among siblings, and a higher frequency in twins than in singletons indicate the presence of a strong genetic contribution to the etiology of NTD. Non-availability of families with a significant number of NTD cases makes research into genetic causation of NTD difficult. Case reports and epidemiologic studies have implicated a number of chemicals, widely differing therapeutic drugs, environmental contaminants, pollutants, infectious agents, and solvents. Maternal hyperthermia, use of valproate by epileptic women during pregnancy, deficiency and excess of certain nutrients and chronic maternal diseases (e.g. diabetes mellitus) are reported to cause a manifold increase in the incidence of NTD. A host of suspected teratogens are also available in the literature. The UK and Hungarian studies showed that periconceptional supplementation of women with folate (FA) reduces significantly both the first occurrence and recurrence of NTD in the offspring. This led to mandatory periconceptional FA supplementation in a number of countries. Encouraged by the results of clinical studies, numerous laboratory investigations focused on the genes involved in the FA, vitamin B12 and homocysteine metabolism during neural tube development. As of today no clinical or experimental study has provided unequivocal evidence for a definitive role for any of these genes in the causation of NTD suggesting that a multitude of genes, growth factors and receptors interact in controlling neural tube development by yet unknown mechanisms. Future studies must address issues of gene-gene, gene-nutrient and gene,environment interactions in the pathogenesis of NTD. [source] Lactate kinetics in human tissues at rest and during exerciseACTA PHYSIOLOGICA, Issue 4 2010Gerrit Van Hall Abstract Lactate production in skeletal muscle has now been studied for nearly two centuries and still its production and functional role at rest and during exercise is much debated. In the early days skeletal muscle was mainly seen as the site of lactate production during contraction and lactate production associated with a lack of muscle oxygenation and fatigue. Later it was recognized that skeletal muscle not only played an important role in lactate production but also in lactate clearance and this led to a renewed interest, not the least from the Copenhagen School in the 1930s, in the metabolic role of lactate in skeletal muscle. With the introduction of lactate isotopes muscle lactate kinetics and oxidation could be studied and a simultaneous lactate uptake and release was observed, not only in muscle but also in other tissues. Therefore, this review will discuss in vivo human: (1) skeletal muscle lactate metabolism at rest and during exercise and suggestions are put forward to explain the simultaneous lactate uptake and release; and (2) lactate metabolism in the heart, liver, kidneys, brain, adipose tissue and lungs will be discussed and its potential importance in these tissues. [source] The Use of Midodrine in Patients With Advanced Heart FailureCONGESTIVE HEART FAILURE, Issue 3 2009Ramzan M. Zakir MD In many patients, the treatment of heart failure (HF) cannot be optimized because of pre-existing or treatment-induced hypotension. Midodrine, a peripheral ,1-adrenergic agonist may allow for up-titration of neurohormonal antagonist therapy leading to improved outcomes. Ten consecutive patients with HF due to systolic dysfunction and symptomatic hypotension interfering with optimal medical therapy were started on midodrine. After a 6-month follow-up, a higher percentage of patients were on optimal HF therapy (angiotensin-converting enzyme inhibitor/angiotensin receptor blocker mg % of optimal dose 20% vs 57.5%; P<.001) (,-blockers mg % optimal dose 37.5% vs 75%; P<.001) (spironolactone/eplerenone mg % 43.7% vs 95%; P<.001). This led to an improvement in left ventricular ejection fraction (baseline 24±9.4 vs 32.2±9.9; P<.001) and clinical outcomes, with a significant reduction in total hospital admissions (32 vs 12; P=.02) and total hospital days (150 vs 58; P=.02). [source] What really happens with the electron gas in the famous Franck-Hertz experiment?CONTRIBUTIONS TO PLASMA PHYSICS, Issue 3-4 2003F. Sigeneger Abstract The interpretation of the anode current characteristics obtained in the famous Franck-Hertz experiment of 1914 led to the verification of Bohr's predictions of quantised atomic states. This fundamental experiment has been often repeated, and nowadays is generally part of the curriculum in modern physics education. However, the interpretation of the experiment is typically based upon significant simplifying assumptions, some quite unrealistic. This is the case especially in relation to the kinetics of the electron gas, which is in reality quite complex, due mainly to non-uniformities in the electric field, caused by a combination of accelerating and retarding components. This non-uniformity leads to a potential energy valley in which the electrons are trapped. The present state of understanding of such effects, and their influence upon the anode characteristics, is quite unsatisfactory. In this article a rigorous study of a cylindrical Franck-Hertz experiment is presented, using mercury vapour, the aim being to reveal and explain what really happens with the electrons under realistic experimental conditions. In particular, the anode current characteristics are investigated over a range of mercury vapour pressures appropriate to the experiment to clearly elaborate the effects of elastic collisions (ignored in typical discussions) on the power budget, and the trapping of electrons in the potential energy valley. [source] An appreciation of Ronnie Mac Keith (1978)DEVELOPMENTAL MEDICINE & CHILD NEUROLOGY, Issue 2 2008Martin Bax DM It is 100 years since Ronnie Mac Keith's birth and 50 years since he started the Journal Developmental Medicine & Child Neurology (DMCN; initially called The Cerebral Palsy Bulletin), the first number being a reprint of William Little's original article. Scope, then The Spastics Society, had just begun to raise significant sums of money and Ronnie persuaded them not only to put some money into medical research, which they did, funding the research laboratories at Guy's, but also, uniquely, to spend some money on educating and informing doctors. This led to financial backing, happily still continuing, to the publishers of DMCN, now the Mac Keith Press. Initially, it was published under the title Spastics International Medical Publications but this was a clumsy and difficult title because of the unfortunate use of the word 'spastics'and soon after Ronnie's death, who was then senior editor, the Mac Keith Press Board were delighted that his family agreed that the Press would be named after him. In the late 1950s and early 1960s, Ronnie was collecting a team around him to develop the Journal and the books, and contacted me because he knew I had literary interests. I didn't really want to edit a medical journal but I was interested in paediatrics so in the end I got involved! I worked very closely with Ronnie, both clinically and at the Mac Keith Press, and also with the Medical Education Information Unit of the Spastics Society on the meetings he ran. When he died, I tried to pull together something of Ronnie's nature in this personal memoir below, which supplemented the more formal statements about his life and career which can be found in the relevant number of the Journal.1 One hopes that Ronnie would be pleased with what we have done and I know that he would be hoping that we would continue for another 50 years developing ideas and approaches which were essentially developed by Ronnie Mac Keith. [source] Effects of physical exercise versus rosiglitazone on endothelial function in coronary artery disease patients with prediabetesDIABETES OBESITY & METABOLISM, Issue 9 2010S. Desch We conducted a three-arm, parallel-group, randomized, controlled trial to compare the effects of rosiglitazone and physical exercise on endothelial function in patients with coronary artery disease and impaired fasting glucose or impaired glucose tolerance over a 6-month period. Group A received rosiglitazone tablets 8 mg daily (n = 16), group B underwent a structured physical exercise programme (n = 15) and group C served as a control group (n = 12). At baseline and after 6 months, brachial artery ultrasound imaging was performed to assess reactive flow-mediated dilation (FMD). Rosiglitazone treatment and exercise both led to significant improvements in insulin resistance at 6 months, whereas no change was observed in control patients. FMD improved significantly in physical exercise patients, whereas no change could be observed in patients receiving rosiglitazone or in the control group. Between-group comparisons also showed a significant relative improvement in FMD in exercise patients compared with rosiglitazone. [source] Some historical aspects of diabetic foot diseaseDIABETES/METABOLISM: RESEARCH AND REVIEWS, Issue S1 2008Henry Connor Abstract During the 19th century and for much of the 20th century, disease of the lower limb in diabetic patients was conceptualized not, as it is now, as ,the diabetic foot' or as ,a diabetic foot ulcer' but as ,gangrene in the diabetic foot' or as ,diabetic gangrene'. The prognostically and therapeutically important distinction between gangrene due to vascular insufficiency and gangrene due to infection in a limb with a normal or near normal blood supply was not made until about 1893. The advent of aseptic surgery improved the survival of amputation flaps, but surgery remained a hazardous undertaking until the discovery of insulin. Although insulin therapy reduced the risk of surgical intervention, diabetic foot disease now replaced hyperglycaemic coma as the major cause of diabetic mortality. The increasing workload attributable to diabetic foot disease after the introduction of insulin is reflected in the publications on diabetes in the 1920s. In some hospitals in North America this led to initiatives in prophylactic care and patient education, the importance of which were only more widely appreciated some 60 years later. A continuing emphasis on ischemia and infection as the major causes of diabetic foot disease led to a neglect of the role of neuropathy. In consequence, the management of diabetic neuropathic ulceration entered a prolonged period of therapeutic stagnation at a time when significant advances were being made in the management of lepromatous neuropathic ulceration. Reasons for the revival of progress in the management of diabetic neuropathic ulceration in the 1980s will be discussed. Copyright © 2008 John Wiley & Sons, Ltd. [source] The influence of host plant variation and intraspecific competition on oviposition preference and offspring performance in the host races of Eurosta solidaginisECOLOGICAL ENTOMOLOGY, Issue 1 2000Timothy P. Craig Summary 1. A series of experiments was conducted to measure the impact of plant genotype, plant growth rate, and intraspecific competition on the oviposition preference and offspring performance of the host races of Eurosta solidaginis (Diptera: Tephritidae), a fly that forms galls on Solidago altissima and Solidago gigantea (Asteraceae). Previous research has shown that both host races prefer to oviposit on their own host plant where survival is much higher than on the alternate host plant. In this study, neither host race showed any relationship between oviposition preference and offspring performance in choosing among plants of their natal host species. 2. The larval survival of both host races differed among plant genotypes when each host race oviposited on its natal host species. In one experiment, altissima host race females showed a preference among plant genotypes that was not correlated with offspring performance on those genotypes. In all other experiments, neither the altissima nor gigantea host race demonstrated a preference for specific host plant genotypes. 3. Eurosta solidaginis had a preference for ovipositing on rapidly growing ramets in all experiments, however larval survival was not correlated with ramet growth rate at the time of oviposition. 4. Eurosta solidaginis suffered high mortality from intraspecific competition in the early larval stage. There was little evidence, however, that females avoided ovipositing on ramets that had been attacked previously. This led to an aggregated distribution of eggs among ramets and strong intraspecific competition. 5. There was no interaction among plant genotype, plant growth rate, or intraspecific competition in determining oviposition preference or offspring performance. [source] An integrated map of the murine hippocampal proteome based upon five mouse strainsELECTROPHORESIS, Issue 13 2006Daniela D. Pollak Abstract With the advent of proteomics technologies it is possible to simultaneously demonstrate the expression of hundreds of proteins. The information offered by proteomics provides context-based understanding of cellular protein networks and has been proven to be a valuable approach in neuroscience studies. The mouse hippocampus has been a major target of analysis in the search for molecular correlates to neuronal information storage. Although human and rat hippocampal samples have been successfully subjected to proteomic profiling, no elaborate analysis providing the fundamental experimental basis for protein-expression studies in the mouse hippocampus has been carried out as yet. This led us to construct a master map generated from the individual hippocampal proteomes of five different mouse strains. A proteomic approach, based upon 2-DE coupled to MS (MALDI-TOF/TOF) has been chosen in an attempt to establish a comprehensive reference database of proteins expressed in the mouse hippocampus. 469 individual proteins, represented by 1156 spots displaying various functional states of the respective gene products were identified. Proteomic profiling of the hippocampus, a brain region with a pivotal role for neuronal information processing and storage may provide insight into the characteristics of proteins serving this highly sophisticated function. [source] Transcriptional control of the pvdS iron starvation sigma factor gene by the master regulator of sulfur metabolism CysB in Pseudomonas aeruginosaENVIRONMENTAL MICROBIOLOGY, Issue 6 2010Francesco Imperi Summary In the Gram-negative pathogen Pseudomonas aeruginosa, the alternative sigma factor PvdS acts as a key regulator of the response to iron starvation. PvdS also controls P. aeruginosa virulence, as it drives the expression of a large set of genes primarily implicated in biogenesis and transport of the pyoverdine siderophore and synthesis of extracellular factors, such as protease PrpL and exotoxin A. Besides the ferric uptake regulatory protein Fur, which shuts off pvdS transcription under iron-replete conditions, no additional regulatory factor(s) controlling the pvdS promoter activity have been characterized so far. Here, we used the promoter region of pvdS as bait to tentatively capture, by DNA-protein affinity purification, P. aeruginosa proteins that are able to bind specifically to the pvdS promoter. This led to the identification and functional characterization of the LysR-like transcription factor CysB as a novel regulator of pvdS transcription. The CysB protein directly binds to the pvdS promoter in vitro and acts as a positive regulator of PvdS expression in vivo. The absence of a functional CysB protein results in about 50% reduction of expression of PvdS-dependent virulence phenotypes. Given the role of CysB as master regulator of sulfur metabolism, our findings establish a novel molecular link between the iron and sulfur regulons in P. aeruginosa. [source] A metagenomic analysis of soil bacteria extends the diversity of quorum-quenching lactonasesENVIRONMENTAL MICROBIOLOGY, Issue 3 2008Kashif Riaz Summary A metagenomic library of 10 121 clones, generated from bacteria inhabiting a pasture soil from France, was screened for the presence of fosmids conferring either N -acylhomoserine lactone (NAHL) synthesis or NAHL degradation ability upon their Escherichia coli host. No clone producing NAHLs was identified whereas one, containing a 31 972 bp insert in fosmid p2H8, allowed NAHL degradation. This led to the cloning and identification of a gene, qlcA, encoding an NAHL-lactonase activity, as judged by lactone-ring closure and HPLC/MS analyses of NAHL degradation products. The qlcA gene efficiently quenched quorum-sensing regulated pathogenic functions when expressed in Pectobacterium carotovorum. The QlcA peptide belongs to the family of zinc-dependent metallohydrolases and appears to be distantly related to other NAHL-lactonases discovered in Agrobacterium, Bacillus, Photorhabdus and Rhizobium. In-silico analysis of the metagenomic insert revealed the occurrence of 20 orf, with a constant GC% and codon usage, suggesting a unique bacterial origin. Nine out of these 20 orf were homologous to genes encoding biosynthesis of arginine; they were clustered with an unusual succession argFJADBCRGH. The fosmid p2H8 is able to complement the argA, argB and argC mutants in E. coli. Phylogenetic analysis showed that 9 orf out of 20 were related to sequences from members of the Acidobacteria, supporting the hypothesis that the analysed insert might be originated from an organism related to this phylum. [source] A longitudinal study of cannabis use and mental health from adolescence to early adulthoodADDICTION, Issue 4 2000Rob McGee Aims. To examine the longitudinal association between cannabis use and mental health. Design. Information concerning cannabis use and mental health from 15 to 21 years was available for a large sample of individuals as part of a longitudinal study from childhood to adulthood. Participants. Participants were enrolled in the Dunedin Multidisciplinary Health and Development Study, a research programme on the health, development and behaviour of a large group of New Zealanders born between 1 April 1972 and 31 March 1973. Measurements. Cannabis use and identification of mental disorder was based upon self-report as part of a general assessment of mental health using a standard diagnostic interview. Daily smoking and alcohol use at age 15 were assessed by self-report. Indices of family socio-economic status, family climate and parent - child interaction were formed using information gathered from parent report and behavioural observations over early childhood. Childhood behaviour problems were assessed by parent and teacher report. Attachment to parents was assessed in adolescence. Findings. Cross-sectional associations between cannabis use and mental disorder were significant at all three ages. Both outcome variables shared similar pathways of low socio-economic status and history of behaviour problems in childhood, and low parental attachment in adolescence. Mental disorder at age 15 led to a small but significantly elevated risk of cannabis use at age 18; by contrast, cannabis use at age 18 elevated the risk of mental disorder at age 21. The latter association reflected the extent to which cannabis dependence and other externalizing disorders at age 21 were predicted by earlier level of involvement with cannabis. Conclusions. The findings suggest that the primary causal direction leads from mental disorder to cannabis use among adolescents and the reverse in early adulthood. Both alcohol use and cigarette smoking had independent associations with later mental health disorder. [source] AgC10, a mucin from Trypanosoma cruzi, destabilizes TNF and cyclooxygenase-2 mRNA by inhibiting mitogen-activated protein kinase p38EUROPEAN JOURNAL OF IMMUNOLOGY, Issue 6 2004Pilar Alcaide Abstract Secretion of proinflammatory mediators by activated macrophages plays an important role in the immune response to Trypanosoma cruzi. We have previously reported that AgC10, a glycosylphosphatidylinositol-anchored mucin from T. cruzi, inhibits TNF secretion by activated macrophages (de Diego, J., Punzon, C., Duarte, M. and Fresno, M., Alteration of macrophage function bya Trypanosoma cruzi membrane mucin. J. Immunol. 1997. 159: 4983,4989). In this report we have further investigated the molecular mechanisms underlying this inhibition. AgC10 inhibited TNF, IL-10 and cyclooxygenase-2 (COX-2) synthesis by macrophages activated with LPS or LPS plus IFN-, in a dose-dependent manner. AgC10 did not affect other aspects of macrophage activation induced by LPS, such as inducible nitric oxide synthase (iNOS) expression. AgC10 also had no effect on TNF or COX-2 transcription or the induction of their promoters but inhibited the stability of TNF and COX-2 mRNA, which are regulated post-transcriptionally by the mitogen-activated protein kinase (MAPK) p38 pathway. AgC10 was found to inhibit both the activation and the activity of p38 MAPK, since MAPK activated protein kinase-2 (MAPKAP-K2 or MK-2) phosphorylation was also strongly inhibited. This led to TNF and COX-2 mRNA destabilization. In contrast, AgC10 did not affect p38 activation induced by TNF. Furthermore, AgC10 inhibition must lie upstream in the MAPK activation pathway by LPS, since this mucin also inhibited extracellularly regulated kinase (ERK) and Jun kinase (JNK)activation. [source] Aluminium Complexes of a Phenoxyimine Ligand with a Pendant Imidazolium Moiety: Synthesis, Characterisation and Evidence for Hydrogen Bonding in SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2008Stefano Milione Abstract Novel alkylaluminium complexes (phim)AlMe2 (1) and(phimid)AlR2+Br, [R = Me (2), R = iBu (3)] bearing the Schiff base ligands 3,5- tBu2 -2-(OH)C6H2CH=NiPr (phim -H) and3,5- tBu2 -2-(OH)C6H2CH=NCH2CH2[CH(NCHCHNiPr)]Br(phimid -H·Br) have been prepared and fully characterised. Complexes 1,3 each have a tetrahedral structure, with the aluminium atom surrounded by the oxygen and nitrogen atoms of the chelating ligand and two alkyl groups. The structures of phimid -H·Br and of complex 1 have been determined by X-ray diffraction studies. Investigation of the solution structures of 1,3 by 1H NMR spectroscopy revealed that the coordinated phimid ligand is involved in hydrogen bonding with bromide anion. Treatment of 1 with B(C6F5)3 led smoothly to (phim)Al(C6F5)Me (4) by transfer of a C6F5 group from MeB(C6F5)3, to the initially formed coordinatively unsaturated cationic intermediate. In contrast, treatment of 2 with one equiv. of B(C6F5)3 afforded the cationic monomethyl species (phimid)AlMeBr+,MeB(C6F5)3, (5), stabilised by the coordination of the bromide anion acting as a Lewis base.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Chemical and Electrochemical Behaviours of a New Phenolato-Bridged Complex [(L)MnIIMnII(L)]2+.EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2006Dinuclear Mono-µ-Oxido [(L)MnIII(µ-O)MnIII/IV(L)]2+/3+ Species, Pathways to Mononuclear Chlorido [(L)MnII/III/IVCl]0/1/2+ Abstract The X-ray structure of a new dinuclear phenolato-bridged Mn2II complex abbreviated as [(L)MnMn(L)]2+ (1), where LH is the [N4O] phenol containing ligand N,N -bis(2-pyridylmethyl)- N, -salicylidene-ethane-1,2-diamine ligand, is reported. A J value of ,3.3 cm,1 (H = ,J,1·,2) was determined from the magnetic measurements and the 9.4 GHz EPR spectra of both powder and frozen acetonitrile solution samples were analyzed with temperature. The cyclic voltammetry of 1 displays a reversible anodic wave at E1/2 = 0.46 V vs. SCE associated with the two-electron oxidation of 1 yielding the dinuclear Mn2III complex [(L)MnMn(L)]4+ (2). The easy air oxidation of 1 gives the mono-,-oxido Mn2III complex [(L)Mn(, - O)Mn(L)]2+ (3). A rational route to the formation of the mixed-valence Mn2III,IV complex [(L)Mn(, - O)Mn(L)]3+ (4) starting from 1 by bulk electrolysis at EP = 0.75 V vs. SCE in the presence of one equiv. of base per manganese ion is also briefly reported. Addition of chloride ions to 1 led to the cleavage of the phenolato bridges to give the mononuclear MnII complex [(L)MnCl] (5). Cyclic voltammetry of 5 displays two reversible anodic waves at E1/2 = 0.21 and E1/2 = 1.15 V vs. SCE, assigned to the two successive one-electron abstractions giving the MnIII and MnIV species [(L)MnCl]+ (6) and [(L)MnCl]2+ (7), respectively. The electronic signatures from UV/Visible and EPR spectroscopy of the electrochemically prepared samples of 6 and 7 confirmed the respective oxidation states. For instance, 7 displays a broad and intense absorption band characteristic of a phenolato to MnIV charge-transfer transition at 690 nm (2000 M,1,cm,1) and its 9.4 GHz EPR spectrum shows a strong transition at g = 5.2 consistent with a rhombically distorted S = 3/2 system with a zero-field splitting dominating the Zeeman effect. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis of L -Furanomycin and Its Analogues via Furoisoxazolines,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2005Peter J. Zimmermann Abstract The 1,3-dipolar cycloaddition of nitrile oxides and 2-methylfuran has provided suitable precursors for ,-amino acids such as L -furanomycin (1) that contain a dihydrofuran ring. By using a chiral nitrile oxide derived from D -glyceraldehyde, the enantiomerically pure furoisoxazolines 9 and 10 were obtained. Owing to the bicyclic, bowl-shaped structure of furoisoxazoline 9 highly stereoselective additions were feasible, in particular, the epoxidation of 9 with dimethyldioxirane provided the required (5'S) configuration in 1 after epoxide reduction. Hydroboration of 9 led to the (5'R) epimer 2 and nucleophilic addition of a methyl Grignard reagent to epoxyfuroisoxazoline 11 gave rise to 5'-methylfuranomycin (3). Further, catalytic hydrogenation of the dihydrofuran intermediate 22, derived from 11, afforded the tetrahydrofuranyl derivative 31 from which dihydrofuranomycin (4) was obtained in enantiomerically pure form. The biological activities of these ,-amino acids showed an extremely narrow structure,activity profile, the natural product being the only compound of this series with high activities. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] O -Glycosyl Amino Acids by 2-Nitrogalactal Concatenation , Synthesis of a Mucin-Type O -GlycanEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2003Gottfried A. Winterfeld Abstract Base-promoted Michael-type addition of N -Boc- and N -Fmoc-protected serine and threonine esters to 2-nitrogalactal derivatives 2 and 26 led highly selectively to ,-glycosides 4a,d and 27a,c, respectively. Ensuing transformation of threonine derivative 4d and serine derivatives 4a,b resulted in compounds useful as lysine and dipeptide mimetics. 6- O -Desilylation of 27a,c, then 6- O -sialylation, and transformation of the nitro group of the galactose moiety into a 2-acetamido functionality, afforded N -Boc-protected serine and threonine tert -butyl esters 31a,c carrying the O -protected STN -antigen at the hydroxy group. The threonine derivative 31c was then transformed into the N -Fmoc-protected amino acid building block 33, which was employed for the synthesis of mucin repeating unit partial structure Ac-GS(STN)-TAPPAHG-NH2 (1). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Choice of comparisons in intergroup settings: the role of temporal information and comparison motivesEUROPEAN JOURNAL OF SOCIAL PSYCHOLOGY, Issue 5 2006Rupert J. Brown Three studies investigated comparison choices in intergroup settings, a neglected but important topic for theories of intergroup relations. Two main questions were addressed: What is role of comparison motives in determining comparison choices in intergroup contexts? How important are temporal comparisons (of the ingroup in the past or future) in intergroup settings? In Study 1 (N,=,115), motives for Assessment or Enhancement were primed in a multi-group performance context. Compared to Controls, Assessment priming encouraged both upward and downward comparisons, while Enhancement encouraged mainly downward comparisons. In general, temporal comparisons were as prevalent as comparisons with other groups. Study 2 (N,=,199) employed a real-world setting in which members of a mid-ranking university indicated their interest in comparing with other higher or lower status universities or with their own university in the past. Temporal comparisons were once more much in evidence, and manipulating enhancement motives again encouraged downward comparisons. In Study 3 (N,=,40), set in the context of inter-nation student comparisons, Improvement motives were primed implicitly. This led to an increase in interest in an outgroup just above the ingroup but to a decrease in interest in future-oriented comparisons. Copyright © 2006 John Wiley & Sons, Ltd. [source] Analysis of nubbin expression patterns in insectsEVOLUTION AND DEVELOPMENT, Issue 5 2004Hua Li Summary Previous studies have shown that the gene nubbin (nub) exhibits large differences in expression patterns between major groups of arthropods. This led us to hypothesize that nub may have evolved roles that are unique to particular arthropod lineages. However, in insects, nub has been studied only in Drosophila. To further explore its role in insects in general, we analyzed nub expression patterns in three hemimetabolous insect groups: zygentomans (Thermobia domestica, firebrat), dyctiopterans (Periplaneta americana, cockroach), and hemipterans (Oncopeltus fasciatus, milkweed bug). We discovered three major findings. First, observed nub patterns in the ventral central nervous system ectoderm represent a synapomorphy (shared derived feature) that is not present in other arthropods. Furthermore, each of the analyzed insects exhibits a species-specific nub expression in the central nervous system. Second, recruitment of nub for a role in leg segmentation occurred early during insect evolution. Subsequently, in some insect lineages (cockroaches and flies), this original role was expanded to include joints between all the leg segments. Third, the nub expression in the head region shows a coordinated change in association with particular mouthpart morphology. This suggests that nub has also gained an important role in the morphological diversification of insect mouthparts. Overall, the obtained data reveal an extraordinary dynamic and diverse pattern of nub evolution that has not been observed previously for other developmental genes. [source] NO synthase isoforms specifically modify peroxynitrite reactivityFEBS JOURNAL, Issue 19 2010Amandine Maréchal Nitric oxide synthases (NOSs) are multi-domain hemothiolate proteins that are the sole source of nitric oxide (NO) in mammals. NOSs can also be a source or a sink for peroxynitrite (PN), an oxidant that is suspected to be involved in numerous physiopathological processes. In a previous study, we showed that the oxygenase domain of the inducible NOS (iNOSoxy) reacts with PN and changes its oxidative reactivity [Maréchal A, Mattioli TA, Stuehr DJ & Santolini J (2007) J Biol Chem282, 14101,14112]. Here we report a similar analysis on two other NOS isoforms, neuronal NOS (nNOS) and a bacterial NOS-like protein (bsNOS). All NOSs accelerated PN decomposition, with accumulation of a similar heme intermediate. The kinetics of PN decomposition and heme transitions were comparable among NOSs. However, their effects on PN reactivity differ greatly. All isoforms suppressed PN two-electron oxidative activity, but iNOSoxy enhanced PN one-electron oxidation and nitration potencies, the oxygenase domain of nNOS (nNOSoxy) affected them minimally, and bsNOS abolished all PN reactivities. This led to the loss of both NOS and PN decomposition activities for nNOSoxy and iNOSoxy, which may be linked to the reported alterations in their electronic absorption spectra. Bacterial bsNOS was affected to a lesser extent by reaction with PN. We propose that these differences in PN reactivity among NOSs might arise from subtle differences in their heme pockets, and could reflect the physiological specificity of each NOS isoform, ranging from oxidative stress amplification (iNOS) to detoxification (bsNOS). [source] ,- d -Mannopyranosyl-(1,2)-,- d -glucopyranosyl-(1,2)-glycerate in the thermophilic bacterium Petrotoga miotherma , structure, cellular content and functionFEBS JOURNAL, Issue 12 2007Carla D. Jorge The intracellular accumulation of low molecular mass organic compounds in response to stressful conditions was investigated in the thermophilic bacterium Petrotoga miotherma, a member of the order Thermotogales. This led to the discovery of a new solute, whose structure was established as ,- d -mannopyranosyl-(1,2)-,- d -glucopyranosyl-(1,2)-glycerate (MGG) by MMR spectroscopy and MS. Under optimum growth conditions (3% NaCl; 55 °C), MGG was the major solute [up to 0.6 µmol·(mg protein),1]; ,-glutamate and proline were also present but in minor amounts [below 0.08 µmol·(mg protein),1]. The level of MGG increased notably with the salinity of the growth medium up to the optimum NaCl concentration. At higher NaCl concentrations, however, the level of MGG decreased, whereas the levels of proline and ,-glutamate increased about five-fold and 10-fold, respectively. MGG plays a role during low-level osmotic adaptation of Petrotoga miotherma, whereas ,-glutamate and, to a lesser extent, proline are used for osmoprotection under salt stress. MGG is not part of the cell strategy for coping with heat or oxidative stress. Nevertheless, MGG was an efficient protector of pig heart malate dehydrogenase against heat inactivation and freeze-drying, although mannosylglycerate was better. This is the first report on the occurrence of MGG in living systems. [source] Glucose sensing in the intestinal epitheliumFEBS JOURNAL, Issue 16 2003Jane Dyer Dietary sugars regulate expression of the intestinal Na+/glucose cotransporter, SGLT1, in many species. Using sheep intestine as a model, we showed that lumenal monosaccharides, both metabolisable and nonmetabolisable, regulate SGLT1 expression. This regulation occurs not only at the level of transcription, but also at the post-transcriptional level. Introduction of d -glucose and some d -glucose analogues into ruminant sheep intestine resulted in >,50-fold enhancement of SGLT1 expression. We aimed to determine if transport of sugar into the enterocytes is required for SGLT1 induction, and delineate the signal-transduction pathways involved. A membrane impermeable d -glucose analogue, di(glucos-6-yl)poly(ethylene glycol) 600, was synthesized and infused into the intestines of ruminant sheep. SGLT1 expression was determined using transport studies, Northern and Western blotting, and immunohistochemistry. An intestinal cell line, STC-1, was used to investigate the signalling pathways. Intestinal infusion with di(glucos-6-yl)poly(ethylene glycol) 600 led to induction of functional SGLT1, but the compound did not inhibit Na+/glucose transport into intestinal brush-border membrane vesicles. Studies using cells showed that increased medium glucose up-regulated SGLT1 abundance and SGLT1 promoter activity, and increased intracellular cAMP levels. Glucose-induced activation of the SGLT1 promoter was mimicked by the protein kinase A (PKA) agonist, 8Br-cAMP, and was inhibited by H-89, a PKA inhibitor. Pertussis toxin, a G-protein (Gi)-specific inhibitor, enhanced SGLT1 protein abundance to levels observed in response to glucose or 8Br-cAMP. We conclude that lumenal glucose is sensed by a glucose sensor, distinct from SGLT1, residing on the external face of the lumenal membrane. The glucose sensor initiates a signalling pathway, involving a G-protein-coupled receptor linked to a cAMP,PKA pathway resulting in enhancement of SGLT1 expression. [source] The stress response protein Gls24 is induced by copper and interacts with the CopZ copper chaperone of Enterococcus hiraeFEMS MICROBIOLOGY LETTERS, Issue 1 2010Jivko V. Stoyanov Abstract Intracellular copper routing in Enterococcus hirae is accomplished by the CopZ copper chaperone. Under copper stress, CopZ donates Cu+ to the CopY repressor, thereby releasing its bound zinc and abolishing repressor,DNA interaction. This in turn induces the expression of the cop operon, which encodes CopY and CopZ, in addition to two copper ATPases, CopA and CopB. To gain further insight into the function of CopZ, the yeast two-hybrid system was used to screen for proteins interacting with the copper chaperone. This led to the identification of Gls24, a member of a family of stress response proteins. Gls24 is part of an operon containing eight genes. The operon was induced by a range of stress conditions, but most notably by copper. Gls24 was overexpressed and purified, and was shown by surface plasmon resonance analysis to also interact with CopZ in vitro. Circular dichroism measurements revealed that Gls24 is partially unstructured. The current findings establish a novel link between Gls24 and copper homeostasis. [source] Residual compressive behavior of alkali-activated concrete exposed to elevated temperaturesFIRE AND MATERIALS, Issue 1 2009Maurice Guerrieri Abstract This paper reports the effect of elevated temperature exposures, up to 1200°C , on the residual compressive strengths of alkali-activated slag concrete (AASC) activated by sodium silicate and hydrated lime; such temperatures can occur in a fire. The strength performance of AASC in the temperature range of 400,800°C was similar to ordinary Portland cement concrete and blended slag cement concrete, despite the finding that the AASC did not contain Ca(OH)2 , which contributes to the strength deterioration at elevated temperatures for Ordinary Portland Cement and blended slag cement concretes. Dilatometry studies showed that the alkali-activated slag (AAS) paste had significantly higher thermal shrinkage than the other pastes while the basalt aggregate gradually expanded. This led to a higher thermal incompatibility between the AAS paste and aggregate compared with the other concretes. This is likely to be the governing factor behind the strength loss of AASC at elevated temperatures. Copyright © 2008 John Wiley & Sons, Ltd. [source] Predator-released compounds, ambient temperature and competitive exclusion among differently sized Daphnia speciesFRESHWATER BIOLOGY, Issue 4 2006JACOBUS VIJVERBERG Summary 1. We studied the effects of fish water and temperature on mechanisms of competitive exclusion among two Daphnia species in flow-through microcosms. The large-bodied D. pulicaria outcompeted the medium sized D. galeata × hyalina in fish water, but not in the control treatment. Daphnia galeata × hyalina was competitively displaced 36 days earlier at 18 °C than at 12 °C. 2. It is likely that the high phosphorus content of fish water increased the nutritional value of detrital seston particles by stimulating bacterial growth. Daphnia pulicaria was presumably better able to use these as food and hence showed a more rapid somatic growth than its competitor. This led to very high density of D. pulicaria in fish water, but not in the controls. The elevated D. pulicaria density coincided with high mortality and reduced fecundity in D. galeata × hyalina, resulting in competitive displacement of the hybrid. 3. It is clear that the daphnids competed for a limiting resource, as grazing caused a strong decrease in their seston food concentration. However, interference may also have played a role, as earlier studies have shown larger Daphnia species to be dominant in this respect. The high density of large-bodied D. pulicaria in fish water may have had an allelopathic effect on the hybrid. Our data are inconclusive with respect to whether the reached seston concentration was below the threshold resource level (R*) of the hybrid, where population growth rate and mortality exactly balance, as it would be set in the absence of interference, or whether interference actually raised the hybrid's R* to a value above this equilibrium particle concentration. 4. Our results do clearly show that fish-released compounds mediated competitive exclusion among zooplankton species and that such displacement occurred at a greatly enhanced rate at an elevated temperature. Fish may thus not only structure zooplankton communities directly through size-selective predation, but also indirectly through the compounds they release. [source] Polyphase evolution and reaction sequence of compositional domains in metabasalt: a model based on local chemical equilibrium and metamorphic differentiationGEOLOGICAL JOURNAL, Issue 3-4 2000T. M. Toóth Abstract Eclogitic garnet amphibolite samples from the Southern Steep Belt of the Central Alps show evidence of several stages of metamorphic evolution and exhumation. A method for unravelling this evolution is presented and applied to these samples. It involves a combination of detailed petrographic analysis and microchemical characterization with quantitative models of the thermodynamically stable phase relations for specific compositional domains of each sample. Preserved mineral relics and textural evidence are compared to model predictions to identify the important irreversible reactions. The interpretation of the exhumation history is thus based on the consistency of a wide spectrum of observations with predicted phase diagrams, leading to robust reconstruction of a pressure,temperature (P,T) path even where the mineralogical relics in samples are insufficient, due to retrogression, to warrant application of multi-equilibrium thermobarometric techniques. The formation of compositionally different domains in the metabasalt samples studied is attributed to prograde growth of porphyroblasts (e.g. garnet, plagioclase, zoisite) in the matrix, implying substantial metamorphic differentiation at the scale of a few millimetres. Chemical interaction among different domains during the subsequent P,T evolution is shown to have been very limited. This led to different reaction sequences during exhumation, in which relics preserved in different domains reflect a range of continually changing P,T conditions. For samples from a single outcrop, we deduce a Barrovian prograde path to eclogite facies (23,±,3,kbar, 750,±,50°C), followed by (rapid) decompression to 8,±,1,kbar and 675,±,25°C, and a final heating phase at similar pressures reaching 750,±,40°C. This evolution is attributed to the Alpine cycle involving subduction,collision and slab breakoff,extrusion of tectonic fragments that make up the Southern Steep Belt of the Central Alps. Copyright © 2000 John Wiley & Sons, Ltd. [source] Metabolism of Deuterated erythro -Dihydroxy Fatty Acids in Saccharomyces cerevisiae: Enantioselective Formation and Characterization of HydroxylactonesHELVETICA CHIMICA ACTA, Issue 6 2008Leif-A. Abstract Epoxides of fatty acids are hydrolyzed by epoxide hydrolases (EHs) into dihydroxy fatty acids which are of particular interest in the mammalian leukotriene pathway. In the present report, the analysis of the configuration of dihydroxy fatty acids via their respective hydroxylactones is described. In addition, the biotransformation of (±)- erythro -7,8- and -3,4-dihydroxy fatty acids in the yeast Saccharomyces cerevisiae was characterized by GC/EI-MS analysis. Biotransformation of chemically synthesized (±)- erythro -7,8-dihydroxy(7,8- 2H2)tetradecanoic acid ((±)- erythro - 1) in the yeast S. cerevisiae resulted in the formation of 5,6-dihydroxy(5,6- 2H2)dodecanoic acid (6), which was lactonized into (5S,6R)-6-hydroxy(5,6- 2H2)dodecano-5-lactone ((5S,6R)- 4) with 86% ee and into erythro -5-hydroxy(5,6- 2H2)dodecano-6-lactone (erythro - 8). Additionally, the , -ketols 7-hydroxy-8-oxo(7- 2H1)tetradecanoic acid (9a) and 8-hydroxy-7-oxo(8- 2H1)tetradecanoic acid (9b) were detected as intermediates. Further metabolism of 6 led to 3,4-dihydroxy(3,4- 2H2)decanoic acid (2) which was lactonized into 3-hydroxy(3,4- 2H2)decano-4-lactone (5) with (3R,4S)- 5=88% ee. Chemical synthesis and incubation of (±)- erythro -3,4-dihydroxy(3,4- 2H2)decanoic acid ((±)- erythro - 2) in yeast led to (3S,4R)- 5 with 10% ee. No decano-4-lactone was formed from the precursors 1 or 2 by yeast. The enantiomers (3S,4R)- and (3R,4S)-3,4-dihydroxy(3- 2H1)nonanoic acid ((3S,4R)- and (3R,4S)- 3) were chemically synthesized and comparably degraded by yeast without formation of nonano-4-lactone. The major products of the transformation of (3S,4R)- and (3R,4S)- 3 were (3S,4R)- and (3R,4S)-3-hydroxy(3- 2H1)nonano-4-lactones ((3S,4R)- and (3R,4S)- 7), respectively. The enantiomers of the hydroxylactones 4, 5, and 7 were chemically synthesized and their GC-elution sequence on Lipodex®E chiral phase was determined. [source] Oligonucleotide Analogues with Integrated Bases and Backbone.HELVETICA CHIMICA ACTA, Issue 5 2007Part 1 Abstract The self-complementary (Z)-configured U*[ce]A(*) dinucleotide analogues 6, 8, 10, 12, 14, and 16, and the A*[ce]U(*) dimers 19, 21, 23, 25, 27, and 29 were prepared by partial hydrogenation of the corresponding ethynylene linked dimers. Photolysis of 14 led to the (E)-alkene 17. These dinucleotide analogues associate in CDCl3 solution, as evidenced by NMR and CD spectroscopy. The thermodynamic parameters of the duplexation were determined by van't Hoff analysis. The (Z)-configured U*[ce]A(*) dimers 14 and 16 form cyclic duplexes connected by Watson,Crick H-bonds, the (E)-configured U*[ce]A dimer 17 forms linear duplexes, and the U*[ce]A(*) allyl alcohols 6, 8, 10, and 12 form mixtures of linear and cyclic duplexes. The C(6/I)-unsubstituted A*[ce]U allyl alcohols 19 and 23 form linear duplexes, whereas the C(6/I)-substituted A*[ce]U* allyl alcohols 21 and 25, and the C(5,/I)-deoxy A*[ce]U(*) dimers 27 and 29 also form minor amounts of cyclic duplexes. The influence of intra- and intermolecular H-bonding of the allyl alcohols and the influence of the base sequence upon the formation of cyclic duplexes are discussed. [source] | ||||||||||||||||||||||||||||||||||||||||||||||||||||