|
| ||
|
|
||
Bu
Selected AbstractsThe relationship of behavioural undercontrol to alcoholism in higher-functioning adultsDRUG AND ALCOHOL REVIEW, Issue 5 2006MARC A. SCHUCKIT Abstract Externalising behaviours, including the personality characteristics of behavioural undercontrol (BU), represent one of several genetically influenced domains that impact on the alcoholism risk. Because genes explain only about 60% of the vulnerability toward alcohol use disorders (AUDs), an optimal understanding of how such behaviours affect the risk requires evaluation of their impact in the context of additional influences. Few studies have addressed this question regarding BU among relatively well-functioning adults. This paper presents results from testing a BU-based mediational model of risk in men from the San Diego Prospective Study. Structured research instruments were used with 430 adult Caucasian males to evaluate the performance of BU in predicting AUDs at the 15-year follow-up using Pearson product-moment correlations among domains and an AMOS-based structural equation model (SEM). While both the family history of AUDs (FHalc) and BU predicted alcohol-related outcome, BU by itself did not mediate the relationship of the FH to alcohol disorders. The impact of BU on alcohol problems was mediated by alcohol expectancies, peer drinking and by coping. The SEM explained 42% of the variance for AUDs. The current results indicate that BU contributed to the risk for alcohol-related problems, even among more highly functional subjects and after excluding the impact of the antisocial personality disorder, but by itself did not mediate the relationship of FH to outcome in these subjects. [source] The Status of Bedside Ultrasonography Training in Emergency Medicine Residency ProgramsACADEMIC EMERGENCY MEDICINE, Issue 1 2003Francis L. Counselman MD Abstract Bedside ultrasonography (BU) is rapidly being incorporated into emergency medicine (EM) training programs and clinical practice. In the past decade, several organizations in EM have issued position statements on the use of this technology. Program training content is currently driven by the recently published "Model of the Clinical Practice of Emergency Medicine," which includes BU as a necessary skill. Objective: The authors sought to determine the current status of BU training in EM residency programs. Methods: A survey was mailed in early 2001 to all 122 Accreditation Council for Graduate Medical Education (ACGME)-accredited EM residency programs. The survey instrument asked whether BU was currently being taught, how much didactic and hands-on training time was incorporated into the curriculum, and what specialty representation was present in the faculty instructors. In addition, questions concerning the type of tests performed, the number considered necessary for competency, the role of BU in clinical decision making, and the type of quality assurance program were included in the survey. Results: A total of 96 out of 122 surveys were completed (response rate of 79%). Ninety-one EM programs (95% of respondents) reported they teach BU, either clinically and/or didactically, as part of their formal residency curriculum. Eighty-one (89%) respondents reported their residency program or primary hospital emergency department (ED) had a dedicated ultrasound machine. BU was performed most commonly for the following: the FAST scan (focused abdominal sonography for trauma, 79/87%); cardiac examination (for tamponade, pulseless electrical activity, etc., 65/71%); transabdominal (for intrauterine pregnancy, ectopic pregnancy, etc., 58/64%); and transvaginal (for intrauterine pregnancy, ectopic pregnancy, etc., 45/49%). One to ten hours of lecture on BU was provided in 43%, and one to ten hours of hands-on clinical instruction was provided in 48% of the EM programs. Emergency physicians were identified as the faculty most commonly involved in teaching BU to EM residents (86/95%). Sixty-one (69%) programs reported that EM faculty and/or residents made clinical decisions and patient dispositions based on the ED BU interpretation alone. Fourteen (19%) programs reported that no formal quality assurance program was in place. Conclusions: The majority of ACGME-accredited EM residency programs currently incorporate BU training as part of their curriculum. The majority of BU instruction is done by EM faculty. The most commonly performed BU study is the FAST scan. The didactic component and clinical time devoted to BU instruction are variable between programs. Further standardization of training requirements between programs may promote increasing standardization of BU in future EM practice. [source] Absence of veno-occlussive disease in a cohort of multiple myeloma patients undergoing autologous stem cell transplantation with targeted busulfan dosageEUROPEAN JOURNAL OF HAEMATOLOGY, Issue 1 2006A. Clopés Abstract:,Background:,Plasma concentrations of oral busulfan (BU) were measured in multiple myeloma (MM) patients undergoing autologous peripheral blood stem cell transplantation (ASCT) with a double alkylating conditioning protocol in order to individualise doses of BU based on individual pharmacokinetic parameters and to reduce toxicities related to BU exposure. Patients and methods:,Forty-four consecutive patients with MM participating in the co-operative Spanish protocol were prospectively evaluated. Conditioning regimen prior to autologous infusion consisted of BU followed by melphalan. BU pharmacokinetic parameters were estimated for each patient after the first dose based on measured concentrations and subsequent doses were modified as necessary to achieve target exposure. Results:,Mean BU exposure (AUCss) (±DS) before dosage modification range from 3192 to 12 180 ng h/mL. Twenty-six out of 44 (59%) patients required dose adjustment. None of the patients developed hepatic veno-occlusive disease (VOD). Grade , II oropharyngeal mucositis was observed in the majority of patients (95%) and the severity of mucositis increased with increasing average steady-state BU plasma concentration. There were four treatment-related deaths: two patients died from multiorgan failure and two of respiratory infections. Of the remaining 40 patients, 15 were in complete remission with negative immunofixation, 21 in partial remission and four in stable disease 3 months after ASCT. Conclusions:,The results of the present study show the variability in BU pharmacokinetic parameters and suggest the possible relationship between toxicities and BU exposure. Individualising BU dosage in MM patients undergoing ASCT we observed the absence of VOD. [source] Low-dose immune tolerance induction for paediatric haemophilia patients with factor VIII inhibitorsHAEMOPHILIA, Issue 2 2008A. UNUVAR Summary., The development of an inhibitor against factor VIII (FVIII) is a serious complication in children with haemophilia A. Immune tolerance induction (ITI) therapy is generally considered to be the best approach to eradicate the inhibitor. In this paper, the low-dose (,50 IU kg,1 twice or three times weekly with plasma-derived factor concentrates) ITI regimen used in Turkey is discussed. This regimen was given to 21 haemophilia A patients with high titer inhibitors. The median age at the beginning of ITI was 9 years and exposure days were 25. The median pre-ITI historical peak inhibitor titer, and inhibitor titer when ITI started were 80 BU (range 6.0,517), 19.2 BU (range 3.6,515), respectively. Complete immune tolerance was defined as the time at which at least two negative inhibitor assays was obtained with no anamnestic response. Our two cases were not reached in follow-up period. Immune tolerance could be achieved in 5 of 19 (26.3%) patients within a median time of 6 months. Partial tolerance was obtained in 7 patients while treatment failed in spite of significant decreased inhibitor levels in the other patients. A relapse developed in one immune-tolerized patient, one year later. The level of inhibitor titer at the beginning of ITI (,10 BU), the pre-ITI historical peak inhibitor titer (<50 BU), and the time between the first diagnosis inhibitor to starting ITI (<12 months) were main factors in the success (complete or partial tolerance) of ITI. In conclusion, the outcome of low-dose ITI protocol was not satisfactory in this retrospective study. [source] Tyr2105Cys mutation in exon 22 of FVIII gene is a risk factor for the development of inhibitors in patients with mild/moderate haemophilia AHAEMOPHILIA, Issue 4 2006M. FRANCHINI Summary., We report the case of a patient with mild haemophilia A, due to a Tyr2105Cys mutation in exon 22 of the C1 domain, who developed a high-titre factor VIII inhibitor (maximum titre 1600 BU) with recurrent severe haemorrhages and fatal intracranial bleeding. Based on published data, it appears that although this mutation occurs rarely in patients with mild or moderate haemophilia A, it is frequently associated with the development of high-titre inhibitors. [source] Acquired haemophilia: management of bleeds and immune therapy to eradicate autoantibodiesHAEMOPHILIA, Issue 5 2005P. A. Holme Summary., Acquired haemophilia is a rare, but often severe bleeding disorder caused by autoantibodies against a coagulation factor, usually factor VIII (FVIII). Between 1997 and 2004 we observed 14 patients (mean age of 78 years) with acquired haemophilia. The aim of the present study was to investigate the effect of activated prothrombin complex concentrate (aPCC) for bleeds and the response to corticosteroids and cyclophosphamide to eradicate the offending autoantibodies. The most common clinical presentations were severe profuse bruising (12) and haematuria (5). Ten patients were classified as idiopathic. At the time of diagnosis all patients had a very low FVIII level, and one patient also showed factor IX < 1%. High levels of antibodies to FVIII varying from 10 to 1340 Bethesda units (BU) and prolonged activated partial thromboplastin time were disclosed in all patients. Eight severe bleeds were treated with aPCC (FEIBA®) at a dosage of 70 IU kg,1 every 8 h until haemostasis. Ten patients received corticosteroids and cyclophosphamide as immunomodulatory therapy. Effective haemostasis was achieved in all bleeds after aPCC. Ten of 11 patients responded either completely or partially to the immunomodulatory regime within 6 months. Five patients achieved complete response (CR) whereas partial responses were seen in five patients. The anti-CD20 monoclonal antibody rituximab was given to two patients in conventional doses and a CR was seen in one patient. aPCC is effective in treating acute bleeds in patients with acquired haemophilia with high inhibitor levels. The combination of oral corticosteroids and cyclophosphamide seems to be effective to eradicate the inhibitor. [source] Inhibitor development in patients receiving recombinant factor VIII (Recombinate rAHF/Bioclate®): a prospective pharmacovigilance studyHAEMOPHILIA, Issue 5 2004B. M. Ewenstein Summary., Clinical trials to date have not been adequately powered to assess comparatively infrequent events such as inhibitor development in previously treated patients (PTPs). Comprehensive large-scale pharmacovigilance studies can be useful for this purpose. We prospectively collected inhibitor development reports worldwide among recipients of Recombinate rAHF recombinant factor VIII (rFVIII), also formerly distributed under the product name Bioclate®, for the entire postlicensure period from 1993 through 2002. To determine level of exposure to rFVIII we also compiled the Recombinate rAHF/Bioclate International Units (IU) distributed annually. To estimate inhibitor incidence separately for previously untreated or minimally treated patients (PUPs) with 1,50 exposure days and PTPs with >50 exposure days, we used haemophilia A incidence and prevalence data and pooled mean annual rFVIII consumption per PUP and PTP from international multicentre prospective clinical trials. Documented inhibitor cases totalled 89, and the total quantity of Recombinate rAHF/Bioclate rFVIII distributed was 6.48 ×109 IU. No lot association or other clustering of inhibitor events was evident in PTPs. The incidence of all reported inhibitors, expressed as a percentage of patients treated, was 11.9% (CI: 5.05,28.0%) for PUPs when compared with 0.123% (CI: 0.030,0.512%) for PTPs. The rates for high-titre inhibitors (>5 BU) only were 5.96% (CI: 3.00,11.8%) for PUPs and 0.0554% (CI: 0.0113,0.271%) for PTPs. Thus, incidence rates for both all inhibitors and high-titre inhibitors in PTPs were 1% of the corresponding rates in PUPs. Data from prospective PUP clinical trials involving intensive active monitoring suggest that true inhibitor incidence may be approximately twice that estimated in this pharmacovigilance study. Nevertheless, inhibitor development in PTPs receiving Recombinate rAHF/Bioclate is infrequent. [source] Successful use of recombinant factor VIIa in a patient with inhibitor secondary to severe factor XI deficiencyHAEMOPHILIA, Issue 2 2002P. LAWLER Factor XI (FXI) inhibitors are a rare complication of inherited FXI deficiency. We report the successful use of recombinant factor VIIa (FVIIa) in a patient with a high-responding inhibitor undergoing cataract extraction. At the time of surgery there were limited available data on the optimal management of patients with FXI deficiency. A 62-year-old Ashkenazi Jewish woman had a lifelong history of excessive bleeding secondary to severe FXI deficiency (2 U dL,1), and received FXI concentrate (FXI:C) when she underwent a colposuspension procedure. She was subsequently diagnosed with a FXI inhibitor of 16 Bethesda units (BU) when she developed a poor response to FXI:C at the time of total hip replacement. Two months later she was admitted for cataract extraction. The FXI level was < 1 U dL,1 with an inhibitor titre of 48 BU. She received 90 ,g kg,1 of FVIIa immediately preoperatively followed by continuous infusion at a rate of 20 ,g kg,1 h,1 for 24 h. The cataract extraction was successful and there was no excess bleeding during surgery or in the postoperative period. Mutation analysis of the FXI gene showed that the patient was homozygous for the type II genotype [exon 5, Glu117,Ter]. The reason for the low prevalence of inhibitor formation in patients with FXI deficiency is unclear but may reflect a number of factors including reporting bias, the rarity of absent circulating FXI:C activity, and the infrequent use of FXI replacement therapy. [source] Porcine factor VIII in the treatment of high-titre inhibitor patientsHAEMOPHILIA, Issue 2002M.B. Garvey Development of an inhibitor against factor VIII (FVIII) is an important complication of haemophilia. It occurs in approximately 25,30% of patients with haemophilia A [1]. FVIII inhibitors may also occur as autoantibodies. The latter occur in nonhaemophiliacs and, although rare (occurring in approximately one per million of the population), are frequently associated with life-threatening bleeding. Inhibitors are considered low level if they are < 5 Bethesda Units (BU) or high level if they are > 10 BU. The former usually remain low and rarely give anamnestic response, the latter do so frequently. Despite various approaches to their management, the presence of inhibitors remains a major cause of morbidity and mortality. The effectiveness of porcine FVIII (pFVIII) in treating patients with both auto- and alloantibodies to FVIII has been well demonstrated when adequate circulating levels of FVIII are obtained [2,10]. However, pFVIII therapy may give rise to antibodies to the pFVIII and the utility of this treatment in the presence of high levels of porcine antibody is less well recognized and understood. Nonetheless, pFVIII under these circumstances may be useful in a select group of patients where management is difficult. [source] Classification of protein content and technological properties of eighteen wheat varieties grown in IranINTERNATIONAL JOURNAL OF FOOD SCIENCE & TECHNOLOGY, Issue 2006Mohammad Ali Sahari Summary The best method for wheat planning and its food industrial usage is evaluation of its technological properties. Classification of protein content and some technological properties of eighteen important Iranian wheat cultivars were investigated. Statistical analysis revealed, highest protein content (11%), protein quality (SDS = 35.6 mL), hardness degree (63%), in Rooshan of Karaj (I), Zagroos of Ahvaz (K) and Marvdasht of Karaj (O) varieties, respectively. On the basis of the quality, the Zagross of Ahvaz (K), Zarrine of Aurumieh (L), Rooshan of Karaj (I), and Chamran of Ahvaz (D) varieties were recognized for their farinograph and extensograph characteristics (water absorption = 61,65%, dough development time = 2.3,5.3 min, dough stability to break down = 15,19.3 min, mixing tolerance index = 22.3,32.3 BU, valorimetry index = 55,64.3 Unit, maximum resistance to extension = 134,450 BU, dough energy = 11.3,100.3 cm2 and extensibility = 156,179 mm). The dendrogram was classified into four groups and in general, the wheat cultivar K was the most separated from the other cultivars, followed by L and I. [source] Solvent effects on chemical processes: new solvents designed on the basis of the molecular,microscopic properties of (molecular solvent,+,1,3-dialkylimidazolium) binary mixturesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 2 2008P. M. Mancini Abstract The purpose of this work was to analyze the microscopic feature of binary solvent systems formed by a molecular solvent (acetonitrile or dimethylformamide or methanol) and an ionic liquid (IL) cosolvent [1-(1-butyl)-3-methylimidazolium tetrafluoroborate or 1-(1-butyl)-3-methylimidazolium hexafluorophosphate]. The empirical solvatochromic solvent parameters ET(30), ,*, ,, and , were determined from the solvatochromic shifts of adequate indicators. The behavior of the solvent systems was analyzed according to their deviation from ideality. The study focused on the identification of solvent mixtures with relevant solvating properties in order to select mixed solvents with particular characteristics. The comparison of the molecular,microscopic solvent parameters corresponding to the selected binary mixtures with both ILs considered at similar mixed-solvent composition revealed that the difference is centered on the basic character of them. A kinetic study of a nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene (FDNB) and 1-butylamine (BU) developed in (acetonitrile or dimethylformamide,+,IL) solvent mixtures is presented in order to investigate and compare the solvent effects on a chemical process. For the explored reactive systems the solvation behavior is dominated by both the dipolarity/polarizability and the basicity of the media, contributing these solvent properties to accelerating the chemical process. Copyright © 2007 John Wiley & Sons, Ltd. [source] COOKING BEHAVIOR OF RICE AND BLACK GRAM IN THE PREPARATION OF IDLI, A TRADITIONAL FERMENTED PRODUCT OF INDIAN ORIGIN, BY VISCOGRAPHYJOURNAL OF TEXTURE STUDIES, Issue 1 2009BONG KYUNG KOH ABSTRACT Pasting profile of coarse rice, fine rice as well as black gram was carried out individually, in combination, in flour as well as in batter form, before and after fermentation by Brabender Viscoamylograph. Lowest gelatinization temperature was seen in black gram among the three commodities studied. Coarse rice registered a peak viscosity (PV) of 1,300 BU, fine rice 1,030 BU and black gram 1,080 BU. Cold paste viscosity (CPV) was highest in fine rice, lowest in black gram and intermediate in coarse rice. Breakdown (BD) was least in fine rice, highest in coarse rice and black gram lay in between. Values of total setback indicated the strong reason for use of coarse rice in parboiling as well as in idli and dosa preparations. Physical combination of black gram, with fine as well as coarse rice, reduced PV on an average to an extent of 26,30%. CPV was highest in fine rice and black gram combination compared with that of coarse rice and black gram. BD was high in the physical mix of coarse rice and black gram. In comparison with physical mix of fine rice and black gram, in the batter form before fermentation, the PV and CPV reduced by 23 and 34%, respectively, but there was no BD in this mix, indicating restricted swelling behavior in the batter before fermentation. Almost all viscographic parameters reduced before fermentation in coarse rice and black gram compared with their physical combination. Highest relative BD (BDr) was noticed in the pasting profile of black gram alone, probably because of the presence of mucilaginous principle. BDr values increased in batter form to various extents, before and after fermentation, compared with physical combination of rice and black gram. After fermentation, in coarse rice and black gram, the BDr value was low compared with that in fine rice and black gram. PRACTICAL APPLICATIONS Fermented products are commonly ingested in India, especially in the southern states. Nowadays, batter is sold in public for the sake of convenience, as it is a common breakfast preparation. The practice is to use coarse rice for the preparation of idli, a steamed fermented product. It is generally not known how the rice behaves before and after fermentation while cooking. Hence, this work was planned, and results indicated the scientific basis for the usage of coarse rice in the preparation of rice products. The behavior of batter prepared from fine rice has also been described, although it is not an economically viable option. [source] Functional properties and retrogradation behaviour of native and chemically modified starch of mucuna bean (Mucuna pruriens)JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 15 2003Kayode O Adebowale Abstract Mucuna bean (Mucuna pruriens) starch was isolated and subjected to chemical modification by oxidation and acetylation. The proximate analysis of the non-starch components of the native starch on a dry weight basis was 92 g kg,1 moisture, 5 g kg,1 ash, 2 g kg,1 fat, 7 g kg,1 crude fibre and 19 g kg,1 protein. Chemical modification reduced the values for all the non-starch components except the moisture level. For all the samples, swelling power and solubility increased as the temperature increased in the range 50,90 °C. The swelling power of mucuna native starch (MNS) and mucuna acetylated starch (MAS) increased with increasing acidity and alkalinity, while that of mucuna oxidised starch (MOS) only increased with increasing pH in the acidic range. The maximal solubility of all the starches was observed at pH 12. All the starch samples absorbed more oil than water. The lowest gelation concentration followed the trend MAS < MNS < MOS. Chemical modification reduced the gelatinisation temperature (Tp), while peak viscosity (Pv), hot paste viscosity (Hv) and cold paste viscosity (Cv) decreased after oxidation but increased following acetylation. The setback tendency of the native starch was reduced significantly after chemical modification. However, the breakdown value of MNS, 65 BU (Brabender units), was lower than that of MOS (78 BU) but higher than that of MAS (40 BU). Differential scanning calorimetry studies of gelatinisation and retrogradation revealed that chemical modification reduced the onset temperature (To), peak temperature (Tp) and conclusion temperature (Tc). Oxidation and acetylation reduced the gelatinisation and retrogradation enthalpies of the native starch. The enthalpy of retrogradation of the starches increased as the length of storage increased. Copyright © 2003 Society of Chemical Industry [source] Reduced intensity conditioning regimen with fludarabine, busulfan, and low-dose TBI (Flu-BU2-TBI): Clinical efficacy in high-risk patients,AMERICAN JOURNAL OF HEMATOLOGY, Issue 4 2010Mutsumi Takahata Reduced intensity conditioning (RIC) regimens are widely used in allogeneic stem cell transplantation (SCT). In this study, we retrospectively investigated the clinical outcomes of RIC with fludarabine (Flu; 180 mg/m2), intravenous busulfan (BU; 6.4 mg/kg) or oral BU (8 mg/kg), and low-dose total body irradiation (TBI; 4 Gy) (Flu-BU2-TBI) in 66 patients (median age: 54.5 years) with various hematological malignancies. Thirty-eight patients (58%) were high-risk patients (median age: 56 years). The overall survival rate at 2 years of the high-risk patients was 64.5%, which was comparable to the survival rate of 70.9% in standard-risk patients (P = 0.68). The relapse rates at 2 years in the standard-risk and high-risk patients were 16 and 28%, respectively, and day 100 treatment-related mortality rates were 0 and 6%, respectively. The Flu-BU2-TBI regimen for high-risk patients showed therapeutic effects equivalent to those for standard-risk patients and favorable outcomes compared with those of other previous RIC regimens. Am. J. Hematol., 2010. © 2010 Wiley-Liss, Inc. [source] Eight new and three recalculated orbits for binariesASTRONOMISCHE NACHRICHTEN, Issue 3 2010Z. Cvetkovi Abstract In this paper new orbital elements are given for eleven binaries. For eight of them, WDS 00003,4417 = I 1477, WDS 00106,7313 = I 43 AB, WDS 00366+5609 = A 914, WDS 00519,4343 = I 47, WDS 01315+1521 = BU 506, WDS 01577+4434 = A 1526, WDS 08144,4550 = FIN 113 AB and WDS 08291,4756 = FIN 315 Aa-Ab, the orbital elements are calculated for the first time. For three of them, WDS 04422+2257 = MCA 16 Aa-Ab, WDS 08275,5501 = FIN 116 and WDS 14567,6247 = FIN 372, the orbital elements are recalculated. One of the eleven binaries, MCA 16 Aa-Ab, was discovered by McAlister in 1980 by speckle interferometry and four pairs were discovered by Finsen between 1929 and 1960. For these five pairs, all measured separations are less than 0,.4 and most of the observations were done by using the interferometric techniques. The orbital periods calculated here are between 39 and 270 years. The remaining six pairs were discovered between 1878 and 1926 and most of the observations are visual. They have longer orbital periods, between 384 and 1637 years. In addition to the orbital elements the masses, dynamical parallaxes, absolute magnitudes and ephemerides for the next five years are also given in this paper (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] The local immune response in ulcerative lesions of Buruli diseaseCLINICAL & EXPERIMENTAL IMMUNOLOGY, Issue 3 2006A. E. Kiszewski Summary Buruli disease (BU) is a progressive necrotic and ulcerative disease of the skin and subcutaneous tissue caused by Mycobacterium ulcerans. BU is considered the third most common mycobacterial disease after tuberculosis and leprosy. Three clinical stages of the cutaneous lesions have been described in BU: pre-ulcerative, ulcerative and healed lesions. In this study we used immunohistochemistry and automated morphometry to determine the percentage of macrophages and of CD4/CD8 lymphocytes and their expression of interferon (IFN)-,, interleukin (IL)-10, tumour necrosis factor (TNF)-, and transforming growth factor (TGF)-,. Expression of these cytokines was correlated with the inflammatory response evaluated by histopathology. All the studied BU ulcerative cases showed extensive necrosis and chronic inflammation. The most important feature was the presence or absence of granulomas co-existing with a mixed pro-inflammatory/anti-inflammatory cytokine balance. When granulomas were present significantly higher expression of IFN-, was seen, whereas in ulcerative lesions without granulomas there was increased expression of IL-10 and significantly higher bacillary counts. These features correlated with the chronicity of the lesions; longer-lasting lesions showed granulomas. Thus, granulomas were absent from relatively early ulcerative lesions, which contained more bacilli and little IFN-,, suggesting that at this stage of the disease strong suppression of the protective cellular immune response facilitates proliferation of bacilli. [source] Hantzsch 1,4-dihydropyridines containing a nitrooxyalkyl ester moiety to study calcium channel antagonist structure,activity relationships and nitric oxide releaseDRUG DEVELOPMENT RESEARCH, Issue 4 2000Jeffrey-Tri Nguyen Abstract A group of 3-nitrooxyalkyl 5-alkyl 1,4-dihydro-2,6-dimethyl-4-(pyridyl)-3,5-pyridinedicarboxylates were prepared using a modified Hantzsch reaction that involved the condensation of a nitrooxyalkyl acetoacetate with an alkyl 3-aminocrotonate and a pyridinecarboxaldehyde. 1H NMR nuclear Overhauser enhancement (nOe) studies for 3-(3-nitrooxypropyl) 5-isopropyl 1,4-dihydro-2,6-dimethyl-4-(2-pyridyl)-3,5-pyridinedicarboxylate (17) indicates a predominant rotamer exists in solution where the pyridyl nitrogen atom is orientated above the 1,4-DHP ring system, and the pyridyl nitrogen atom is antiperiplanar to the 1,4-DHP ring H-4 proton. Variable temperature 1H NMR studies (,30 to +60°C) showed the 1,4-DHP NH proton in 17 is H-bonded in CHCl3 solution. This interaction is believed to be due to intermolecular H-bonding between the pyridyl nitrogen free electron pair and the 1,4-DHP NH proton. In vitro calcium channel antagonist (CCA) activities were determined using a muscarinic-receptor-mediated Ca+2 -dependent contraction of guinea pig ileal longitudinal smooth muscle assay. This class of compounds exhibited lower CCA activity (IC50 = 5.3 × 10,6 to 3.5 × 10,8 M range) than the reference drug nifedipine (IC50 = 1.4 × 10,8 M). For compounds having C-3 ,CH2CH2ONO2 and C-4 pyridyl substituents, the C-5 alkyl was a determinant of CCA (i -Pr > the approximately equipotent i -Bu, t -Bu, and Et analogs). The point of attachment of the isomeric C-4 pyridyl substituent was a determinant of CCA when C-3 ,CH2CH2ONO2 and C-5 i -Pr substituents were present providing the potency profile 2-pyridyl , 3-pyridyl > 4-pyridyl. CCA with respect to the C-3 nitrooxyalkyl substituent was inversely dependent on the length of the alkyl spacer. The percent nitric oxide (·NO) released in vitro by this group of compounds (range of 0.03,0.43%/ONO2 group), quantified as nitrite by reaction with the Griess reagent, was lower than that for the reference drug glycerol trinitrate (3.81%/ONO2 group). Nitric oxide release studies showed that the %·NO released was dependent on the number of ONO2 groups/molecule. A QSAR study for this group of compounds showed a correlation between the specific polarizability descriptor (SpPol) and %·NO release. Drug Dev. Res. 51:233,243, 2000. © 2001 Wiley-Liss, Inc. [source] Reductive Activation of tripod Metal Compounds: Identification of Intermediates and Preparative Application,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2008Jürgen Mautz Abstract [tripodCoCl2] {tripod = CH3C(CH2PPh2)3} when treated with KC8 in THF solution under an argon atmosphere produces a reactive species ["tripodCo0"] (A) which undergoes oxidative additions with stannanes, [tripodCo(H)2(SnBu3)] (4), formed, for example, by addition of Bu3SnH. Silanes, R3SiH, undergo the same type of reaction producing [tripodCo(H)2(SiR3)] (R = Et: 5a; R = Ph: 5b). The solid-state structures of all the compounds [tripodCo(H)2(ER3)] (E = Si, R = Ph; E = Sn, R = Ph, Bu) are rather similar. While they contain six-coordinate cobalt with the formal oxidation state of cobalt being +III the coordination geometry is not octahedral: the heteroelement E deviates from the position which it would have in octahedral coordination by around 40° while the other five ligands, three phosphorus and two hydrogen, have the expected interligand angles of around 90° and 180°, respectively. The deviation of the heteroelement E is such that it approaches the metal bonded hydrogen atoms leading to short H···E contacts of only about 190 pm (E = Si) and 230 pm (E = Sn), respectively. The generation of a reactive species ["tripodCo0"] (A) was transferred to the synthesis of a reactive tripodnickel(0) species by treating a THF solution of [(DME)NiBr2] with KC8 in the presence of tripod. This species reacts with two electron donor ligands L to produce the pseudo tetrahedral compounds [tripodNi(L)] {L = PPh3 (6), AsPh3 (7), cHexNC (8), tBuNC (9), C2H4 (10)}. The identity of the reactive nickel(0) species as unequivocally deduced from NMR experiments is [tripod4Ni3] (12). All compounds were characterised by the usual analytic techniques including X-ray analysis where applicable.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Structural Characterization of N -Methylpyridoxine (MePN; PN = Vitamin B6) and Its Diorganotin Complexes [SnR2(MePN-H)]I (R = Me, Et, Bu and Ph)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2003José S. Casas Abstract For comparison with the corresponding pyridoxine complexes we have prepared dimethyl-, diethyl-, dibutyl- and diphenyltin(IV) complexes of N -methylpyridoxine (MePN). The compounds [SnMe2(MePN,H)]I (1), [SnEt2(MePN,H)]I (2), [SnBu2(MePN,H)]I (3) and [SnPh2(MePN,H)]I·H2O (4) were isolated and characterized by IR, Raman, Mössbauer, 1H, 13C and 119Sn NMR spectroscopy, and by EI and FAB mass spectrometry. The crystal structures of [HMePN]I and of compounds 1, 2·2H2O and 3 were determined by X-ray diffractometry. Their lattices contain dimeric [SnR2(MePN,H)]22+ units (R = Me, Et, Bu) in which two bridging-chelating methylpyridoxinato anions link pentacoordinate Sn atoms with coordination polyhedra closer to square pyramids than to trigonal bipyramids. NMR results show that the dimeric cations persist in (CD3)2SO. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Preparation of Functional Hybrid Glass Material from Platinum (II) Complexes for Broadband Nonlinear Absorption of LightADVANCED FUNCTIONAL MATERIALS, Issue 2 2009Roman Zieba Abstract The synthesis of trans -di(arylalkynyl)diphosphine platinum(II) complexes bearing trialkoxysilane groups is described, as well as the preparation of siloxane-based hybrid materials from organometallic chromophores through a modified sol,gel process. Glass materials prepared from trans -[P(n,Bu)3]2Pt[(C,C,p,C6H4,C,C,p,C6H4,CH2O(CO)NH(CH2)3Si(OC2H5)3]2 generally show spectral transmittance, absorption and luminescence similar to that of solutions reported in the literature. Measurements of optical power limiting for the hybrid glass are carried out, and show broadband nonlinear absorption throughout the whole visible wavelength range with clamping values in the range 0.2,7,µJ at 120,mM chromophore concentration. The sol,gel process using urethane-propyltriethoxysilane-functionalized chromophores as precursors appears to be a valid method for formation of robust silicate materials with grafted diarylethynyl Pt(II) complexes for OPL devices. [source] Preparation of ,2 -Amino Acid Derivatives (,2hThr, ,2hTrp, ,2hMet, ,2hPro, ,2hLys, Pyrrolidine-3-carboxylic Acid) by Using DIOZ as Chiral Auxiliary,HELVETICA CHIMICA ACTA, Issue 8 2005Francois Gessier The title compounds were prepared from valine-derived N -acylated oxazolidin-2-ones, 1,3, 7, 9, by highly diastereoselective (,,90%) Mannich reaction (,,4,6; Scheme,1) or aldol addition (,,8 and 10; Scheme,2) of the corresponding Ti- or B-enolates as the key step. The superiority of the ,5,5-diphenyl-4-isopropyl-1,3-oxazolidin-2-one' (DIOZ) was demonstrated, once more, in these reactions and in subsequent transformations leading to various t -Bu-, Boc-, Fmoc-, and Cbz-protected ,2 -homoamino acid derivatives 11,23 (Schemes,3,6). The use of , -bromo-acyl-oxazolidinones 1,3 as starting materials turned out to open access to a variety of enantiomerically pure trifunctional and cyclic carboxylic-acid derivatives. [source] Allylsilane-Modified Amino Acids from the Claisen RearrangementHELVETICA CHIMICA ACTA, Issue 12 2002Mustafa Mohamed The Claisen rearrangement of the N -protected, silylated allyl glycinates 11 and 12 led to the formation of allyl/silyl-functionalized amino acids 13 and 14 in yields up to 80%. The diastereoisomer ratio varied from 2,:,1 to 29,:,1 for 11mb, and from 2,:,1 to 46,:,1 (syn/anti) for 12mb, depending on reaction conditions, as shown by X-ray crystallographic analysis of 14mb. The relationship between the size of the alkyl groups on the chlorosilane reagent (Me2R,SiCl, R,=Cl, Me, t -Bu, Ph) used as an enolate trap and the observed stereoselectivity was investigated in the case of the Ireland,Claisen variant. Me3SiCl gave the best results. However, the size of the alkyl groups on the silylated ester (Me2R,Si, R=Me, t -Bu, Ph, i-Pr) did not exert a significant effect on the diastereoselectivity or yield of the rearrangement. [source] Synthesis, characterization, and in vitro antimicrobial activities of organotin(IV) complexes of Schiff bases with ONO-type donor atomsHETEROATOM CHEMISTRY, Issue 6 2010Gülgün Yeni, ehirli A new series of diorganotin complexes of the type R2SnL (L1: N -(2-hydroxy-5-chlorophenyl)- 3-ethoxysalicylideneimine, R = Me, (Me2SnL1), R = n -Bu, (n -Bu2SnL1), R = Ph, (Ph2SnL1), L2: N -(2-hydroxy-4-nitro-5-chlorophenyl)-3-ethoxysalicylideneimine, R = Ph, Ph2SnL2, L3: N -(2-hydroxy-4-nitrophenyl)-3-methoxysalicylideneimine, R = Me, (Me2SnL3), R = n -Bu, (n -Bu2SnL3), L4: N -(2-hydroxy-4-nitrophenyl)-3-ethoxysalicylideneimine, R = Me, (Me2SnL4), R = n -Bu, (n -Bu2SnL4)) were synthesized and characterized by elemental analysis, infrared (IR), 1H, and 13C NMR mass spectroscopic techniques, and electrochemical measurements. Ph2SnL1 and Ph2SnL2 were also characterized by X-ray diffraction analysis and were found to show a fivefold C2NO2 coordination geometry nearly halfway between a trigonal bipyramidal and distorted square pyramidal arrangement. The CSnC angles in the complexes were calculated using Lockhart's equations with the 1J(117/119Sn- 13C) and 2J(117/119Sn- 1H) values from the 1H NMR and 13C NMR spectra. Biocidal activity tests against several micro-organisms and some fungi indicate that all the complexes are mildly active against Gram (+) bacteria and the fungi, A. niger and inactive against Gram (,) bacteria. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:373,385, 2010; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20628 [source] Erratum: Synthesis of functional phosphines with ortho-substituted aryl groups: 2-RC6H4PH2 and 2-RC6H4P(SiMe3)2 (R = i -Pr- or t -Bu)HETEROATOM CHEMISTRY, Issue 5 2010Julien Dugal-Tessier The synthesis and characterization of 2-i-PrC6H4PCl2 (3), 2-t-BuC6H4PCl2 (4), 2-i-PrC6H4PH2 (5), 2-t-BuC6H4PH2 (6), 2-i-PrC6H4P(SiMe3)2 (7), and 2-t-BuC6H4P(SiMe3)2 (8) are described. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:355,360, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20619, [source] Palladium/Tris(tert -butyl)phosphine-Catalyzed Suzuki Cross- Couplings in the Presence of WaterADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Sha Lou Abstract Dipalladiumtris(dibenzylideneacetone)/tris(tert -butyl)phosphonium tetrafluoroborate/potassium fluoride dihydrate [Pd2(dba)3/[HP(t- Bu)3]BF4/KF,2,H2O] serves as a mild, robust, and user-friendly method for the efficient Suzuki cross-coupling of a diverse array of aryl and heteroaryl halides with aryl- and heteroarylboronic acids. [source] Highly Efficient Ligands for the Palladium-Assisted Double N -Arylation of Primary Amines for One-Sep Construction of CarbazolesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2010Yibo Zhou Abstract A highly efficient one-pot synthesis of carbazoles via palladium-catalyzed double N -arylation of primary amines with 2,2,-dihalobiphenyls is described using a catalyst system comprised of tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3) and the proazaphosphatrane P(i -BuNCH2CH2)3N (8) or its derivative (t- Bu)2PNP(i- BuNCH2CH2)3N (9a) as the ligand. The process is effective for double N -arylation of 2,2,-biphenyl dibromide, diiodide, and even dichloride with a variety of primary amines including neutral, electron-rich, electron-deficient, and sterically hindered anilines as well as aliphatic amines. [source] Silica-Supported Zirconium Complexes and their Polyoligosilsesquioxane Analogues in the Transesterification of Acrylates: Part 1.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Characterization, Synthesis Abstract Various silica-supported acetylacetonate and alkoxy zirconium(IV) complexes have been prepared and characterized by quantitative chemical measurements of the surface reaction products, quantitative surface microanalysis of the surface complexes, in situ infrared spectroscopy, CP-MAS 13C,NMR spectroscopy and EXAFS. The complex (SiO)Zr(acac)3 (acac=acetylacetonate ligand) (1) can be obtained by reaction of zirconium tetraacetylacetonate [Zr(acac)4] with a silica surface previously dehydroxylated at 500,°C. The complexes (SiO)3Zr(acac) (2) and (SiO)3Zr(O- n- Bu) (n- Bu=butyl ligand) (3) can be synthesized by reaction of (SiO)3ZrH with, respectively, acetylacetone and n -butanol at room temperature. The spectroscopic data, including EXAFS spectroscopy, confirm that in compound 1 the zirconium is linked to the surface by only one SiOZr bond whereas in the case of compounds 2 and 3 the zirconium is linked to 3 surface oxygen atoms which are sigma bonded. EXAFS data indicate also that the acetylacetonate ligands behave as chelating ligands leading to a hepta-coordination around the zirconium atom in 1 and a penta-coordination in 2. In order to provide a molecular analogue of 1, the synthesis of the following polyoligosilsesquioxane derivative (c -C5H9)7Si8O12(CH3)2Zr(acac)3 (1,) was achieved. The compound 1, is obtained by reacting (c -C5H9)7Si8O11(CH3)2(OH), 4, with an equimolecular amount of Zr(acac)4. In the same manner, syntheses of complexes (c -C5H9)7Si7O12Zr(acac) (2,) and of (c-C5H9)7Si7O12Zr(O- n- Bu) (3,) were achieved by reaction of the unmodified trisilanol, (c -C5H9)7Si7O9(OH)3, with respectively Zr(acac)4 and Zr(O- n- Bu)4 at 60,°C in tetrahydrofuran. Compounds 1,, 2, and 3, can be considered as good models of 1, 2 and 3 since their spectroscopic properties are comparable with those of the surface complexes. The synthetic results obtained will permit us to study the catalytic properties of these surface complexes and of their molecular analogues with the ultimate goal of delineating clear structure-activity relationships. [source] Silica-Supported Zirconium Complexes and their Polyoligosilsesquioxane Analogues in the Transesterification of Acrylates: Part 2.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Activity, Recycling, Regeneration Abstract The catalytic activity of both supported and soluble molecular zirconium complexes was studied in the transesterification reaction of ethyl acrylate by butanol. Two series of catalysts were employed: three well defined silica-supported acetylacetonate and n -butoxy zirconium(IV) complexes linked to the surface by one or three siloxane bonds, (SiO)Zr(acac)3 (1) (SiO)3Zr(acac) (2) and (SiO)3Zr(O- n -Bu) (3), and their soluble polyoligosilsesquioxy analogues (c -C5H9)7Si8O12(CH3)2Zr(acac)3 (1,), (c -C5H9)7Si7O12Zr(acac) (2,), and (c -C5H9)7Si7O12Zr(O- n -Bu) (3,). The reactivity of these complexes were compared to relevant molecular catalysts [zirconium tetraacetylacetonate, Zr(acac)4 and zirconium tetra- n -butoxide, Zr(O- n- Bu)4]. Strong activity relationships between the silica-supported complexes and their polyoligosilsesquioxane analogues were established. Acetylacetonate complexes were found to be far superior to alkoxide complexes. The monopodal complexes 1 and 1, were found to be the most active in their respective series. Studies on the recycling of the heterogeneous catalysts showed significant degradation of activity for the acetylacetonate complexes (1 and 2) but not for the less active tripodal alkoxide catalyst, 3. Two factors are thought to contribute to the deactivation of catalyst: the lixivation of zirconium by cleavage of surface siloxide bonds and exchange reactions between acetylacetonate ligands and alcohols in the substrate/product solution. It was shown that the addition of acetylacetone to the low activity catalyst Zr(O- n- Bu)4 produced a system that was as active as Zr(acac)4. The applicability of ligand addition to heterogeneous systems was then studied. The addition of acetylacetone to the low activity solid catalyst 3 produced a highly active catalyst and the addition of a stoichiometric quantity of acetylacetone at each successive batch catalytic run greatly reduced catalyst deactivation for the highly active catalyst 1. [source] Facile, Efficient Copolymerization of Ethylene with Bicyclic, Non-Conjugated Dienes by Titanium Complexes Bearing Bis(,-Enaminoketonato) LigandsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009Jing-yu Liu Abstract Copolymerizations of ethylene with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene under the action of various titanium complexes bearing bis(,-enaminoketonato) chelate ligands of the type, [R1NC(R2)CHC(R3)O]2TiCl2 (1, R1=Ph, R2=CF3, R3=Ph; 2, R1=C6H4F- p, R2=CF3, R3=Ph; 3, R1=Ph, R2=CF3, R3=t- Bu; 4, R1=C6H4F- p, R2=CF3, R3=t- Bu; 5, R1=Ph, R2=CH3, R3=CF3; 6, R1=C6H4F- p, R2=CH3, R3=CF3), have been shown to occur with the regioselective insertion of the endocyclic double bond of the monomer into the copolymer chain, leaving the exocyclic vinyl double bond as a pendant unsaturation. The ligand modification strongly affects the copolymerization behaviour. High catalytic activities and efficient co-monomer incorporation can be easily obtained by optimizing the catalyst structures and polymerization conditions. [source] Improved Protocols for Molybdenum- und Tungsten-Catalyzed HydrostannationsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009Alexander Abstract A series of (isonitrile)tungsten carbonyl complexes of type W(CO)m(CNR)n has been synthesized and evaluated as hydrostannation catalysts. The results are compared with those obtained by the previously reported tri(tert -butylisonitrile)molybdenum tricarbonyl catalyst, Mo(CO)3(CN- t- Bu)3 (=MoBI3). The yields and selectivities strongly depend on the isonitriles used, and with certain substrates better results are obtained compared to the molybdenum catalyst. No side products are observed in hydrostannations under microwave irradiation or when the reactions are carried out under an atmosphere of carbon monoxide. Based on these findings, a mechanistic rational is given, explaining the different pathways responsible for the formation of hydrostannation or distannation products. [source] | ||||||||||||||||||||||||||||||||||