DFT study on low molecular weight α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide bridged derivatives

The equilibrium geometries of α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene (DBDT) and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide (DBDTO) were studied at the DFT level of theory with a standard 6-311G* basis set. The molecular structures of the DBDT series were more planar than the corresponding DBDTO series, as revealed by dihedral angles. The UV-visible absorption calculated at TD-DFT/6-311G* showed two absorption peaks for all the molecules except C=S and C=O bridged molecules. In DBDTOs, C=S and C=O bridged molecules showed three and four absorption peaks, respectively. The DBDTOs had lower band gaps and longer wavelengths compared to the corresponding DBDTs.

On line pre-concentration for simultaneous determination of low molecular weight organic acids and inorganic anions in Amazonian river water samples employing ion chromatography with conductivity detection

An ion chromatography procedure, employing an IonPac AC15 concentrator column was used to investigate on line preconcentration for the simultaneous determination of inorganic anions and organic acids in river water. Twelve organic acids and nine inorganic anions were separated without any interference from other compounds and carry-over problems between samples. The injection loop was replaced by a Dionex AC15 concentrator column. The proposed procedure employed an auto-sampler that injected 1.5 ml of sample into a KOH mobile phase, generated by an Eluent Generator, at 1.5 mL min-1, which carried the sample to the chromatographic columns (one guard column, model AG-15, and one analytical column, model AS15, with 250 x 4mm i.d.). The gradient elution concentrations consisted of a 10.0 mmol l-1 KOH solution from 0 to 6.5 min, gradually increased to 45.0 mmol l-1 KOH at 21 min., and immediatelly returned and maintained at the initial concentrations until 24 min. of total run. The compounds were eluted and transported to an electro-conductivity detection cell that was attached to an electrochemical detector. The advantage of using concentrator column was the capability of performing routine simultaneous determinations for ions from 0.01 to 1.0 mg l-1 organic acids (acetate, propionic acid, formic acid, butyric acid, glycolic acid, pyruvate, tartaric acid, phthalic acid, methanesulfonic acid, valeric acid, maleic acid, oxalic acid, chlorate and citric acid) and 0.01 to 5.0 mg l-1 inorganic anions (fluoride, chloride, nitrite, nitrate, bromide, sulfate and phosphate), without extensive sample pretreatment and with an analysis time of only 24 minutes.

Humoral response to low molecular weight antigens of Mycobacterium tuberculosis by tuberculosis patients and contacts

Much effort has been devoted to the identification of immunologically important antigens of Mycobacterium tuberculosis and to the combination of target antigens to which antibodies from serum of tuberculous patients could react specifically. We searched for IgG antibodies specific for antigens of 45 to 6 kDa obtained after sonication of the well-characterized wild M. tuberculosis strain in order to detect differences in the antibody response to low molecular weight antigens from M. tuberculosis between patients with pulmonary tuberculosis and contacts. Specific IgG antibodies for these antigens were detected by Western blot analysis of 153 serum samples collected from 51 patients with confirmed pulmonary tuberculosis. Three samples were collected from each patient: before therapy, and after 2 and 6 months of treatment. We also analyzed 25 samples obtained from contacts, as well as 30 samples from healthy individuals with known tuberculin status, 50 samples from patients with other lung diseases and 200 samples from healthy blood donors. The positive predictive value for associated IgG reactivity against the 6-kDa and 16-kDa antigens, 6 and 38 kDa, and 16 and 38 kDa was 100% since simultaneous reactivity for these antigens was absent in healthy individuals and individuals with other lung diseases. This association was observed in 67% of the patients, but in only 8% of the contacts. The humoral response against antigens of 16 and 6 kDa seems to be important for the detection of latent tuberculosis since the associated reactivity to these antigens is mainly present in individuals with active disease.

Reversal of the anticoagulant and anti-hemostatic effect of low molecular weight heparin by direct prothrombin activation

Lopap, found in the bristles of Lonomia obliqua caterpillar, is the first exogenous prothrombin activator that shows serine protease-like activity, independent of prothrombinase components and unique lipocalin reported to interfere with hemostasis mechanisms. To assess the action of an exogenous prothrombin activator reversing the anticoagulant and antihemostatic effect induced by low molecular weight heparin (LMWH), male New Zealand rabbits (N = 20, weighing 3.8-4.0 kg) allocated to 4 groups were anticoagulated with 1800 IU/kg LMWH (iv) over 2 min, followed by iv administration of saline (SG) or recombinant Lopap (rLopap) at 1 µg/kg (LG1) or 10 µg/kg (LG10), 10 min after the injection of LMWH, in a blind manner. Control animals (CG) were treated only with saline. The action of rLopap was assessed in terms of activated partial thromboplastin time (aPTT), prothrombin fragment F1+2, fibrinogen, and ear puncture bleeding time (BT) at 5, 10, 15, 17, 20, 30, 40, 60, and 90 min after initiation of LMWH infusion. LG10 animals showed a decrease of aPTT in more than 50% and BT near to normal baseline. The level of prothrombin fragment F1+2 measured by ELISA had a 6-fold increase with rLopap treatment (10 µg/kg) and was inversely proportional to BT in LMWH-treated animals. Thus, Lopap, obtained in recombinant form using E. coli expression system, was useful in antagonizing the effect of LMWH through direct prothrombin activation, which can be a possible strategy for the reversal of bleeding and anticoagulant events.

Colonization by Helicobacter pylori of leprosy patients in Spain: immunomodulation to low molecular weight antigens of H. pylori

We studied the prevalence of Helicobacter pylori in patients with leprosy and the effects of co-infection on the immune response to Helicobacter antigens in the polar groups of leprosy (lepromatous and tuberculoid). We showed that there is no difference in the prevalence of H. pylori in patients with leprosy as compared to a non-leprosy population. We also demonstrated that the immune response to low molecular weight H. pylori antigens (35, 26 and 19 kDa) differs in patients with lepromatous as compared to those with tuberculoid leprosy. In lepromatous leprosy, we show that there is a higher prevalence of the 35 and 26 kDa antigens, but a lower prevalence of the 19 kDa antigen. These immunological results are consistent with previous histopathological studies illustrating a more severe gastrointestinal inflammation in lepromatous patients; importantly, a response to the 35 kDa antigen is recognized as a marker for the development of ulcerative disease.

Effect of high and low molecular weight glutenin subunits, and subunits of gliadin on physicochemical parameters of different wheat genotypes

Identification of functional properties of wheat flour by specific tests allows genotypes with appropriate characteristics to be selected for specific industrial uses. The objective of wheat breeding programs is to improve the quality of germplasm bank in order to be able to develop wheat with suitable gluten strength and extensibility for bread making. The aim of this study was to evaluate 16 wheat genotypes by correlating both glutenin subunits of high and low molecular weight and gliadin subunits with the physicochemical characteristics of the grain. Protein content, sedimentation volume, sedimentation index, and falling number values were analyzed after the grains were milled. Hectoliter weight and mass of 1000 seeds were also determined. The glutenin and gliadin subunits were separated using polyacrylamide gel in the presence of sodium dodecyl sulfate. The data were evaluated using variance analysis, Pearson's correlation, principal component analysis, and cluster analysis. The IPR 85, IPR Catuara TM, T 091015, and T 091069 genotypes stood out from the others, which indicate their possibly superior grain quality with higher sedimentation volume, higher sedimentation index, and higher mass of 1000 seeds; these genotypes possessed the subunits 1 (Glu-A1), 5 + 10 (Glu-D1), c (Glu-A3), and b (Glu-B3), with exception of T 091069 genotype that possessed the g allele instead of b in the Glu-B3.

Evidence for the presence of a kininogen-like species in a case of total deficiency of low and high molecular weight kininogens

Low and high molecular weight kininogens (LK and HK), containing 409 and 626 amino acids with masses of ~65 and 120 kDa after glycosylation, respectively, are coded by a single gene mapped to the human chromosome 3 by alternative splicing of the transcribed mRNA. The NH2-termini Glu1-Thr383 region, identical in LK and HK, contains bradykinin (BK) moieties Arg363-Arg371. LK, HK and their kinin products Lys-BK and BK are involved in several biologic processes. They are evolutionarily conserved and only 7 patients, all apparently normal, have been reported to lack them. In one of these patients (Williams' trait), a codon mutation (Arg178 ® stop) has been blamed for the absence of LK and HK. However, using Western blots with 2 monoclonal anti-HK antibodies, one that recognizes the region common to LK and HK and the other that recognizes only HK, I detected ~110-kDa bands in the plasma of this LK/HK-deficient patient vs ~120-kDa bands in normal human and ape plasmas. With polyclonal anti-Lys-BK antibody, which strongly detects BK cleaved at its COOH-terminus in purified HK, I detected ~110-kDa bands in the normal and the deficient plasmas. Western blots with a monoclonal anti-prekallikrein (PK) antibody showed that surface activation of PK and distribution of PK activation products, both dependent on HK, were similar in these plasmas. These findings suggest that a mutant gene yielded a kininogen-like species possibly involving aberrant mRNA splicing - structurally different from normal HK, but apparently with the capacity to carry out seemingly vital HK functions.

Infant mortality and low birth weight in cities of Northeastern and Southeastern Brazil

OBJECTIVE: To compare estimates of low birth weight (LBW), preterm birth, small for gestational age (SGA), and infant mortality in two birth cohorts in Brazil. METHODS: The two cohorts were performed during the 1990s, in São Luís, located in a less developed area in Northeastern Brazil, and Ribeirão Preto, situated in a more developed region in Southeastern Brazil. Data from one-third of all live births in Ribeirão Preto in 1994 were collected (2,839 single deliveries). In São Luís, systematic sampling of deliveries stratified by maternity hospital was performed from 1997 to 1998 (2,439 single deliveries). The chi-squared (for categories and trends) and Student t tests were used in the statistical analyses. RESULTS: The LBW rate was lower in São Luís, thus presenting an epidemiological paradox. The preterm birth rates were similar, although expected to be higher in Ribeirão Preto because of the direct relationship between preterm birth and LBW. Dissociation between LBW and infant mortality was observed, since São Luís showed a lower LBW rate and higher infant mortality, while the opposite occurred in Ribeirão Preto. CONCLUSIONS: Higher prevalence of maternal smoking and better access to and quality of perinatal care, thereby leading to earlier medical interventions (cesarean section and induced preterm births) that resulted in more low weight live births than stillbirths in Ribeirão Preto, may explain these paradoxes. The ecological dissociation observed between LBW and infant mortality indicates that the LBW rate should no longer be systematically considered as an indicator of social development.

Which factors could explain the low birth weight paradox?

OBJECTIVE: Low birth weight children are unusual among well-off families. However, in Brazil, low birth weight rate was higher in a more developed city than in a less developed one. The study objective was to find out the reasons to explain this paradox. METHODS: A study was carried out in two municipalities, Ribeirão Preto (Southeastern Brazil) and São Luís (Northeastern Brazil), which low birth weight rates were 10.7% and 7.6% respectively. Data from two birth cohorts were analyzed: 2,839 newborns in Ribeirão Preto in 1994 and 2,439 births in São Luís in 1997-1998. Multiple logistic regression analysis was performed, adjusted for confounders. RESULTS: Low birth weight risk factors in São Luís were primiparity, maternal smoking and maternal age less than 18 years. In Ribeirão Preto, the associated variables were family income between one and three minimum wages, maternal age less than 18 and equal to or more than 35 years, maternal smoking and cesarean section. In a combined model including both cohorts, Ribeirão Preto presented a 45% higher risk of low birth weight than São Luís. When adjusted for maternal smoking habit, the excess risk for low birth weight in Ribeirão Preto compared to São Luís was reduced by 49%, but the confidence interval was marginally significant. Differences in cesarean section rates between both cities contributed to partially explain the paradox. CONCLUSIONS: Maternal smoking was the most important risk factor for explaining the difference in low birth weight between both cities. The other factors contributed little to explain the difference in low birth weight rates.

The epidemiologic paradox of low birth weight in Brazil

OBJECTIVE: To examine whether the low birth weight (LBW) paradox exists in Brazil. METHODS: LBW and cesarean section rates between 1995 and 2007 were estimated based on data from SINASC (Brazilian Live Births Database). Infant mortality rates (IMRs) were obtained using an indirect method that correct for underreporting. Schooling information was obtained from census data. Trends in LBW rate were assessed using joinpoint regression models. The correlations between LBW rate and other indicators were graphically assessed by lowess regression and tested using Spearman's rank correlation. RESULTS: In Brazil, LBW rate trends were non-linear and non-significant: the rate dropped from 7.9% in 1995 to 7.7% in 2000, then increased to 8.2% in 2003 and remained nearly steady thereafter at 8.2% in 2007. However, trends varied among Brazilian regions: there were significant increases in the North from 1999 to 2003 (2.7% per year), and in the South (1.0% per year) and Central-West regions (0.6% per year) from 1995 to 2007. For the entire period studied, higher LBW and lower IMRs were seen in more developed compared to less developed regions. In Brazilian States, in 2005, the higher the IMR rate, the lower the LBW rate (p=0.009); the lower the low schooling rate, the lower the LBW rate (p=0.007); the higher the number of neonatal intensive care beds per 1,000 live births, the higher the LBW rate (p=0.036). CONCLUSIONS: The low birth weight paradox was seen in Brazil. LBW rate is increasing in some Brazilian regions. Regional differences in LBW rate seem to be more associated to availability of perinatal care services than underlying social conditions.

Late onset sepsis and intestinal bacterial colonization in very low birth weight infants receiving long-term parenteral nutrition

INTRODUCTION: The purpose of this study was to establish the late onset sepsis (LOS) rate of our service, characterize the intestinal microbiota and evaluate a possible association between gut flora and sepsis in surgical infants who were receiving parenteral nutrition (PN). METHODS: Surveillance cultures of the gut were taken at the start of PN and thereafter once a week. Specimens for blood culture were collected based on clinical criteria established by the medical staff. The central venous catheter (CVC) tip was removed under aseptic conditions. Standard laboratory methods were used to identify the microorganisms that grew on cultures of gut, blood and CVC tip. RESULTS: 74 very low birth weight infants were analyzed. All the infants were receiving PN and antibiotics when the gut culture was started. In total, 21 (28.4%) infants experienced 28 episodes of LOS with no identified source. Coagulase negative staphylococci were the most common bacteria identified, both in the intestine (74.2%) and blood (67.8%). All infections occurred in patients who received PN through a central venous catheter. Six infants experienced episodes of microbial translocation. CONCLUSIONS: In this study, LOS was the most frequent episode in neonates receiving parenteral nutrition who had been submitted to surgery; 28.6% of this infection was probably a gut-derived phenomenon and requires novel strategies for prevention.

Intraventricular hemorrhage in very low birth weight infants: associated risk factors and outcome in the neonatal period

Intraventricular hemorrhage (IVH) is a severe complication in very low birth weight (VLBW) newborns (NB). With the purpose of studying the incidence of IVH, the associated risk factors, and the outcomes for these neonates, we studied all the VLBW infants born in our neonatal unit. Birth weight, gestational age, presence of perinatal asphyxia, mechanical ventilation, length of hospitalization, apnea crisis, hydrocephalus, and periventricular leukomalacia were analyzed. The diagnosis of IVH was based on ultrasound scan studies (Papile's classification) performed until the tenth day of life and repeated weekly in the presence of abnormalities. Sixty-seven/101 neonates were studied. The mortality rate was 30.6% (31/101) and the incidence of IVH was 29.8% (20/67) : 70% grade I, 20% grade III and 10% grade IV. The incidence of IVH in NB <1,000 g was 53.8% (p = 0.035) and for gestational age <30 weeks was 47.3% (p = 0.04), both considered risk factors for IVH. The length of hospitalization (p = 0.00015) and mechanical ventilation (p = 0.038) were longer in IHV NB. The IVH NB had a relative risk of 2.3 of developing apnea (p = 0.02), 3.7 of hydrocephalus (p = 0.0007), and 7.7 of periventricular leukomalacia (p < 0.00001). The authors emphasize the importance of knowing the risk factors related to IVH so as to introduce prevention schemes to reduce IVH and to improve outcomes of affected newborns.

Espectrometria de massas com ionização por "electrospray": processos químicos envolvidos na formação de íons de substâncias orgânicas de baixo peso molecular

An overview of the current literature on the chemical processes involved in the ion formation from low molecular weight organic compounds by electrospray ionization mass spectrometry is given.

Removal of high-molecular weight polycyclic aromatic hydrocarbons

Alternatives for the removal of high-molecular weight polycyclic aromatic hydrocarbons (HWM-PAH) from soil were tested by adding fertilizer or glycerol, as well as the combination of both. Experiments were carried out for 60 days in reactors containing a HWM-PAH-contaminated soil (8030 μg kg-1), accompanied by pH monitoring, humidity control and quantification of total heterotrophic bacteria and total fungus. Fertilizer addition removed 41.6% of HWM-PAH. Fertilizer and glycerol in combination removed 46.2%. When glycerol was added individually, degradation reached 50.4%. Glycerol also promoted the increase of degradation rate during the first 30 days suggesting the HMW-PAH removal occurred through cometabolic pathways.