22 resultados para BON-9-B
em Deakin Research Online - Australia
Resumo:
The condensation of [Ph2(OH)Sn(CH2)nSn(OH)Ph2] (1-3; n = 1-3) with HO3SCF3 and HO2PPh2 provided [Ph2Sn(CH2)nSnPh2(OH)](O3SCF3) (4-6; n = 1-3) and [Ph2(O2PPh2)Sn(CH2)nSn(O2PPh2)Ph2] (10-12; n = 1-3), respectively. The reaction of [Ph2Sn(CH2)nSnPh2(OH)](O3SCF3) (4-6; n = 1-3) with HO2PPh2 and NaO2PPh2 gave rise to the formation of [Ph2Sn(CH2)nSnPh2(O2PPh2)](O3SCF3) (7-9; n = 1-3) and [Ph2(OH)Sn(CH2)nSn(O2PPh2)Ph2] (13-15; n = 1-3), respectively. In the solid state, compounds 4-9 comprise ion pairs of cationic cyclo-[Ph2SnCH2SnPh2(OH)]22+, cyclo-[Ph2Sn(CH2)nSnPh2(OH)]+ (n = 2, 3), and cyclo-[Ph2Sn(CH2)nSnPh2(O2PPh2)]+ (n = 1-3) and triflate anions. In MeCN, the eight-membered-ring system cyclo-[Ph2SnCH2SnPh2(OH)]22+ appears to be in equilibrium with the four-membered-ring system cyclo-[Ph2SnCH2SnPh2(OH)]+. In contrast, compounds 10-15 show no ionic character. Compounds 1-15 were characterized by multinuclear NMR spectroscopy in solution and in the solid state, IR spectroscopy, conductivity measurements, electrospray mass spectrometry, osmometric molecular weight determinations, and X-ray crystallography (4, 5, 7, and 12).
Resumo:
The bis(arylene silanes) p,p'-HMe2SiC6H4EMe2C6H4SiMe2H (E = C (10), Si (11), Ge (12), Sn(13)) were prepared by the in situ Grignard reaction of p,p'-BrC6H4CMe2C6H4Br, Mg turnings, and HSiMe2Cl (for 10) and the Grignard reaction using p-HMe2SiC6H4Br, Mg turnings, and Me2ECl2 (E = Si for 11, Ge for 12, Sn for 13). The oxidation of 10-13 using Pearlman's catalyst, Pd(OH)2/C, in aqueous THF provided the bis(arylene silanols) p,p'-HOMe2SiC6H4EMe2C6H4SiMe2OH (E = C (14), Si (15), Ge (16), Sn(17)). The HCl-catalyzed condensation of 14-17 in highly diluted solutions of acetone/water afforded the siloxane-bridged paracyclophanes cyclo-[p,p'-Me2SiC6H4EMe2C6H4SiMe2O]2 (6-9) that incorporate the group 14 elements E = C, Si, Ge, and Sn. Compounds 6-17 were investigated by multinuclear solution and solid-state NMR spectroscopy and 6 and 9 also by X-ray crystallography.
Resumo:
The reaction of Me3SiCH2Cl2Sn(CH2)3SnCl2Ph (6) with (tBu2SnO)3 gave a statistical mixture of the corresponding tetraorganodistannoxanes whereas the reaction of the spacer-bridged ditin tetrachlorides RCl2Sn(CH2)4SnCl2R (3, R = Me3CCH2; 4, R = Me2CHCH2; 10, R = Me3SiCH2) with the polymeric spacer-bridged ditin oxides [R(O)Sn(CH2)4Sn(O)R]n (7, R = Me2CHCH2; 8, R = Me3CCH2; 11, R = Me3SiCH2) provided the mixed double ladder compounds {[R(Cl)Sn(CH2)4Sn(Cl)R][R(Cl)Sn(CH2)4Sn(Cl)R']O2}2 (9, R = Me3CCH2, R' = Me2CHCH2; 12, R = Me3CCH2, R' = Me3SiCH2) in almost quantitative yield. In solution, 9 and 12 are in equilibrium with their corresponding dimers, as was evidenced by 119Sn NMR spectroscopy, molecular mass determination, and electrospray mass spectrometry. The molecular structures of 9 and 12 were established by single crystal X-ray diffraction.
Resumo:
Background/Aims
Familial clustering of hepatitis B virus (HBV) infection is related to perinatal transmission, and is the main cause of familial-type hepatocellular carcinoma (HCC). The route of HBV transmission differs between the children and siblings of patients with HCC. This study examined the differences in HBV carrier rates and HCC-related mortality between two generations in HCC families.
Methods
From 1992 to 1997, relatives of individuals with HCC were screened prospectively with ultrasonography, alpha-fetoprotein, liver biochemistry tests and viral markers. Total HCC-related deaths during a 9-year period were compared between the generations of index patients and their children.
Results
The study included a total of 13 676 relatives in two generations. More HCC-related deaths occurred in the index patient generation than in the child generation. Furthermore, children of female index patients had higher rates of liver cancer related mortality than children of male index patients. The same was true when the analysis was limited to male HBV carriers. The prevalence of HBsAg in the offspring of HBsAg positive mothers was 66% in the child generation and 72% in the index patient generation. These high prevalences indicated high maternal HBV replication status.
Conclusions
Perinatal transmission and maternal viral load are important risk factors in hepatocarcinogenesis.
Resumo:
Members of the matrix metalloproteinase (MMP) family are important for the remodeling of the extracellular matrix in a number of biological processes including a variety of immune responses. Two members of the family, MMP2 and MMP9, are highly expressed in specific myeloid cell populations in which they play a role in the innate immune response. To further expand the repertoire of molecular reagents available to study zebrafish myeloid cell development, the matrix metalloproteinase 9 (mmp9) gene from this organism has been identified and characterized. The encoded protein is 680 amino acids with high homology to known MMP9 proteins, particularly those of other teleost fish. Maternal transcripts of mmp9 are deposited in the oocyte and dispersed throughout the early embryo. These are replaced by specific zygotic transcripts in the notochord from 12 h post fertilization (hpf) and also transiently in the anterior mesoderm from 14 to 16 h post fertilization. From 24 h post fertilization, mmp9 expression was detected in a population of circulating white blood cells that are distinct from macrophages, and which migrate to the site of trauma, and so likely represent zebrafish heterophils. In the adult, mmp9 expression was most prominent in the splenic cords, a site occupied by mature myeloid cells in other species. These results suggest that mmp9 will serve as a useful marker of mature myeloid cells in the zebrafish.
Resumo:
Objective: To document patterns of measured weight and waist circumference (WC) change and the increase in overweight and obesity over a 9-year period. Subjects/Methods: A total of 1044 subjects from two age-defined cohorts aged 39 and 59 in 1991. Height, weight and WC were measured in 1991, 1995 and 2000 and body mass index (BMI) was calculated. Pattern of weight and WC change was studied over approximately 9 years. Results: The prevalence of overweight and obesity increased markedly and the younger cohort showed greater increases in weight and WC than the older cohort. There was no significant difference in mean BMI and/or mean 9-year weight change between men and women in either age cohort, and mean weight gain was similar for all occupational groups. Only 20% of subjects maintained a stable weight (plusminus2 kg), while 42.2 and 17.6% gained greater than 5 and 10 kg over the 9-year period, respectively. The rate of weight gain appeared to be relatively steady over the 9 years among younger subjects but declined in the older subjects in the second half of the observation period. Conclusions: Health promotion strategies to prevent weight gain need to be population-based, targeting all social and age groups, but particularly those in their early middle-age.
Resumo:
Tumor necrosis factor (TNF) plays a role in the pathogenesis of chronic hepatitis B (CHB) and chronic hepatitis C (CHC). The difference in the cytokine responses between hepatitis B virus (HBV) and hepatitis C virus (HCV) infections may have implications in the pathogenesis of these diseases. We performed a comparative study to examine the possible differences in the TNF-TNF receptor (TNFR) response between CHB and CHC. We studied the cytokine levels of 38 patients with CHB, 40 patients with CHC and 9 patients with dual hepatitis B and C, and compared them with the baseline levels of 12 healthy controls. The plasma levels of TNF-, interferon-, interleukin (IL)-2, IL-4, IL-10 and soluble TNFR-1 and 2 (sTNFR-1 and 2) were quantified by enzyme-linked immunosorbent assays. The expression of TNFR-1 and 2 in liver tissues was examined in 30 cases of CHB and 15 cases of CHC by semiquantitative reverse transcription polymerase chain reaction. The results showed that sTNFR-1 levels correlated with liver inflammation in all patients, whereas this correlation was not found with sTNFR-2 or other cytokines. Liver inflammation indicators were higher in HCV RNA+ than in HCV RNA– CHC. Most significantly, sTNFR-1 levels correlated with liver inflammation in CHB, but not in CHC. However, the expression of TNFR-1 and 2 in liver was similar between CHB and CHC. These findings suggest that the TNFR signal transduction pathway is modulated differently in HBV and HCV infection.
Resumo:
Summary. There is little recent data of the seroprevalence of hepatitis B in Australia. We have surveyed a large cohort of endoscopy patients attending a teaching hospital in central Sydney, and related the presence of hepatitis B virus (HBV) markers with putative risk factors for exposure using the SAS statistical package. Of the 2115 patients tested: 2.1% (45/2115) were HBV surface antigen positive, 0.75% (14/2115) viraemic, 9.5% (200/2115) anti-HBs and anti-HBc positive, 20.1% (430/2115) vaccinated (anti-HBs only) and the remaining 70% were susceptible. The adjusted OR of HBV infection was significantly increased in patients who had been diagnosed with human immunodeficiency virus (36.3-fold), born in Asia or Pacific islands (12.4-fold), born in North Africa, Middle East & Mediterranean countries (6-fold) or born abroad elsewhere in the world (2.7-fold), had household contact with someone diagnosed with hepatitis between 1980 and 1990 (3.9-fold), injected drugs between 1980 and 1990 (4.4-fold), resided in a military establishment for 3 months (2.3-fold) or in a hospital for 3 months (2.2-fold), never been vaccinated for hepatitis B (2.8-fold), received blood transfusion due to an accident and/or a haemorrhage (1.92-fold) and finally been a male gender (1.59-fold). The prevalence of HBV in this hospital population was higher than predicted on the basis of notifications to the passive surveillance scheme. Most HBV patients had multiple risk factors for infection, but the hierarchy of odds ratios provides a rational basis for targeted programmes to identify asymptomatic HBV carriers who might benefit from treatment.
Resumo:
Hev b 6.01 is a major allergen of natural rubber latex with sensitization of 70–86% of latex glove-allergic subjects. Recently, we mapped the immunodominant T cell sites of Hev b 6.01 to the highly IgE-reactive hevein (Hev b 6.02) domain. Hev b 6.01 contains 14 cysteine residues with multiple disulphide bridges stabilizing tertiary conformation. With the goal of a standardized specific immunotherapy we developed hypoallergenic Hev b 6.01 mutants by site-directed mutagenesis of selected cysteine residues (3, 12, 17, and 41) within the Hev b 6.02 domain. Peptides corresponding to the Hev b 6.02 domain of two of the mutants were also synthesized. These mutants and peptide variants showed markedly decreased or ablated latex-allergic patient serum IgE binding by immunoblotting and ELISA. Basophil activation testing confirmed markedly decreased activation with successive cysteine substitutions of the mutants and complete abrogation with the Hev b 6.02 (Cys 3, 12, 17, 41 Ala) peptide. Retention of T cell reactivity is crucial for effective specific immunotherapy and all mutants and peptide variants maintained their latex-specific T cell reactivity. The ablated allergenicity but retained T cell reactivity of the Hev b 6.02 (Cys 3, 12, 17, 41 Ala) peptide suggests this peptide is a suitable candidate for inclusion in a latex immunotherapy preparation.
Resumo:
Background: Both folate and betaine are important predictors of total homocysteine (tHcy) during pregnancy. However, studies to date have only been undertaken in populations with Western dietary patterns.
Objective: We investigated the predictors of tHcy in pregnant women recruited in the Seychelles, a population where access to fortified foods is limited and where women habitually consume diets rich in fish, eggs, rice, and fruit.
Design: Pregnant women (n = 226) provided blood samples at enrollment, at week 28 of gestation, and at delivery. Cord blood was obtained from a subset of participants (n = 135).
Results: As in other studies, maternal tHcy was lower during pregnancy than at delivery, whereas folate and vitamin B-12 status declined significantly to delivery. Despite low maternal folate status at delivery (median: 9.0 nmol/L), with 35% of women in the deficient range (serum folate: <6.8 nmol/L), cord blood folate status (median: 40.2 nmol/L) was similar to concentrations reported in Western populations. Folate was a significant predictor of tHcy at all time points (P < 0.001). In contrast with previous studies, betaine was only a significant predictor of maternal tHcy (P < 0.001) when the essential amino acid methionine was low.
Conclusions: The current study reports 2 important findings. First, fetal requirements for folate are paramount, such that cord blood folate status is maintained, even when maternal status is low. Second, betaine is a significant predictor of tHcy in pregnant women with low serum folate and low serum methionine concentrations.
Resumo:
The matrix metalloproteases (MMPs) and the ADAMs (A Disintegrin And Metalloprotease domain) are proteolytic enzyme families containing a catalytic zinc ion, that are implicated in a variety of normal and pathological processes involving tissue remodeling and cancer. Synthetic MMP inhibitors have been designed for applications in pathological situations. However, a greater understanding of substrate binding and the catalytic mechanism is required so that more effective and selective inhibitors may be developed for both experimental and clinical purposes. By modeling a natural substrate spanning P4-P4‘ in complex with the catalytic domains, we aim to compare substrate-specificities between Stromelysin-1 (MMP-3), ADAM-9 and ADAM–10, with the aid of molecular dynamics simulations. Our results show that the substrate retains a favourable antiparallel beta-sheet conformation on the P-side in addition to the well-known orientation of the P'-region of the scissile bond, and that the primary substrate selectivity is dominated by the sidechains in the S1' pocket and the S2/S3 region. ADAM-9 has a hydrophobic residue as the central determinant in the S1' pocket, while ADAM-10 has an amphiphilic residue, which suggests a different primary specificity. The S2/S3 pocket is largely hydrophobic in all three enzymes. Inspired by our molecular dynamics calculations and supported by a large body of literature, we propose a novel, hypothetical, catalytic mechanism where the Zn-ion polarizes the oxygens from the catalytic glutamate to form a nucleophile, leading to a tetrahedral oxyanion anhydride transition state.
Resumo:
Background
Clinical guidelines advise screening for depression in patients with diabetes. The Patient Health Questionnaire (PHQ-9) and the depression subscale of the Hospital Anxiety and Depression Scale (HADS-D) are commonly used in primary care.
Aim
To compare the efficacy of HADS-D and PHQ-9 in identifying moderate to severe depression among primary care patients with type 2 diabetes.
Design of study
Self-report postal survey, clinical records assessed by GPs.
Setting
Seven metropolitan and rural general practices in Victoria, Australia.
Method
Postal questionnaires were sent to all patients with diabetes on the registers of seven practices in Victoria. A total of 561 completed postal questionnaires were returned, giving a response rate 47%. Surveys included demographic information, and history of diabetes and depression. Participants completed both the PHQ-9 and HADS-D. Clinical data from patient records included glycosylated hemoglobin (HbA1c) levels and medications.
Results
The proportion of the total sample completing HADS-D was 96.8% compared with 82.4% for PHQ-9. Level of education was unrelated to responses on the HADS-D but was related to completion of the PHQ-9. Using complete data (n = 456) from both measures, 40 responders showed HADS-D scores in the moderate to severe range, compared with 103 cases identified by PHQ-9. Only 35 cases were classified in the moderate to severe category by both the PHQ-9 and HADS-D. Items with the highest proportions of positive responses on the PHQ-9 were related to tiredness and sleeping problems and, on the HADS-D, feeling slowed down.
Conclusion
It may be that the items contributing to the higher prevalence of moderate to severe depression using the PHQ-9 are due to diabetes-related symptoms or sleep disorders.