Synthesis and Characterization of Cyanobutadiene Isomers-Molecules of Astrochemical Significance.

Four cyanobutadiene isomers of considerable interest to the organic chemistry, molecular spectroscopy, and astrochemistry communities were synthesized in good yields and isolated as pure compounds: (E)-1-cyano-1,3-butadiene (E-1), (Z)-1-cyano-1,3-butadiene (Z-1), 4-cyano-1,2-butadiene (2), and 2-cyano-1,3-butadiene (3). A diastereoselective synthesis was developed to generate (E)-1-cyano-1,3-butadiene (1) (10:1 E/Z) via tandem SN2 and E2' reactions. The potential energy surfaces of the E2' reactions leading to (E)- and (Z)-1-cyano-1,3-butadiene (1) were analyzed by density functional theory calculations, and the observed diastereoselectivity was rationalized in the context of the Curtin-Hammett principle. The preparation of pure samples of these reactive compounds enables measurement of their laboratory rotational spectra, which are the critical data needed to search for these species in space by radioastronomy.

Complex sulfated galactans from hot water extracts of red seaweed Asparagopsis taxiformis comprise carrageenan and agaran structures.

Hot water extraction from the red seaweed Asparagopsis taxiformis yielded three extracts which showed sulfated galactans with a D:L-galactose ratio non consistent with carrageenan or agaran backbones. The major extract was fractionated by cetrimide precipitation and redissolution with increasing sodium chloride concentrations due to their low solubility. Seven fractions were obtained, and studied by methylation analysis, desulfation-methylation, and NMR spectroscopy of the partially hydrolyzed and the native samples. Fractions with the highest yield were those obtained at high concentrations of NaCl. They comprised both agaran and crageenan structures in considerable amounts. The main agaran structures were ß-D-galactose 4-sulfate and ß-D-galactose 2-sulfate units linked to α-L-galactose 2,3-disulfate residues, and ß-D-galactose linked to α-L-galactose 3-sulfate or 6-sulfate, or substituted with single stubs of ß-D-xylose on C3, while the carrageenan structures comprised ß-D-galactose (2-sulfate) linked to α-D-galactose 3-sulfate or 2,3-disulfate, and ß-D-galactose 2,4-disulfate linked to α-D-galactose 2,3-disulfate. Between the less sulfated fractions, the one obtained by solubilization in 0.5 M NaCl was mainly constituted by agarans, which included 3,6-anhydro-α-L-galactose units. Anticoagulant activity was assayed by general coagulation tests (aPTT and TT), showing a moderate action compared with heparin. This is the first detailed study of the sulfated galactans from the order Bonnemaisoniales.

Central Oxygen Venous Saturation and Mortality in Patients Undergoing Coronary Artery Bypass Grafting.

Purpose: Central venous oxygen saturation (ScvO2) has been reported as a prognostic marker of in-hospital mortality when it is below 60% in certain situations. Nevertheless, it has not been widely reported in patients undergoing coronary artery bypass graft (CABG). The study determined the association between ScvO2 and in-hospital mortality in patients undergoing CABG in a high-complexity health institution in Santiago de Cali, Colombia. Patients and Methods: A retrospective cohort study was conducted with patients undergoing isolated CABG. The subject sample included 515 subjects aged 18 years or older. Exposure was defined as ScvO2 <60% upon admission to the intensive care unit (ICU) following surgery. The major outcome was mortality rates after 30 days. Furthermore, exposure variables were measured at preoperative, intra-operative, and postoperative time points. Results: A total of 103 exposed and 412 unexposed subjects were included. The final model revealed a higher mortality risk in individuals with ScvO2 <60% upon ICU admission compared with those with higher saturation levels (relative risk 4.2, 95% confidence interval: 2.4-7.2; p = 0.001). Values were adjusted using variables such as age (>75 years), low socioeconomic stratum, chronic kidney failure before surgery, unstable angina before surgery, ischemia time (>60 min), and intra-operative inotrope use. The primary cause of death was cardiogenic shock (54.7%), followed by sepsis (25.0%) and postoperative bleeding (17.2%). Conclusion: The study identified an association between ScvO2 <60% and in-hospital mortality in patients undergoing CABG.

NMR spectroscopy for structural elucidation of sulfated polysaccharides from red seaweeds.

Some sulfated polysaccharides from red seaweeds are used as hydrocolloids. In addition, it is well known that there are sulfated galactans (carrageenans and agarans) and sulfated mannans, with remarkable biological properties, as antiviral, antitumoral, immunomodulating, antiangiogenic, antioxidant, anticoagulant, and antithrombotic activities, and so on. Knowledge of the detailed structure of the active compound is essential and difficult to acquire. The substitution patterns of the polymer chain, as degree of sulfation and position of sulfate groups, as well as other substituents of the backbone, determine their biological behavior. NMR spectroscopy is a powerful and versatile tool for structural determination. It can be used for elucidation of structures of polysaccharides from new algal sources with novel substitutions or to detect the already known structures from different algal sources, and it could even help to monitor the quality of the active compound on a productive scale. In this review, the available information about NMR spectroscopy of sulfated polysaccharides from red seaweeds is revised and rationalized, to help other researchers working in different fields to study their structures. In addition, considerations about the effects of different structural features, as well as some recording conditions on the chemical shifts of the signals are analyzed.

Gracilariopsis hommersandii, a red seaweed, source of agar and sulfated polysaccharides with unusual structures.

Red seaweed Gracilariopsis hommersandii produces important amounts of non-gelling galactans, which were extracted with hot water (GrC, yield, 37%, viscosity average molecular weight, Mv 109 kDa), comprising agarose and sulfated galactan structures. The alkali modified derivative, GrCTr (Mv 95 kDa), gave a galactose:3,6-anhydrogalactose molar ratio of 1.0:0.9, and a more regular structure, favouring gelation (melting and gelling temperatures 64 and 14 °C, respectively). The rheological properties of this product suggest possible applications as hydrocolloid. G. hommersandii also biosynthesizes non gelling sulfated galactan fractions with diads constituted by ß-d-galactose and partially cyclized α-l-galactose units or non-cyclized α-d-galactose residues. Sulfation was mainly detected on C6 or C4 of the ß-d-galactose units, and on C6 and, in minor amounts, on C3 of the α-l-galactose units. The presence of ß-apiuronic acid was demonstrated for these fractions as side chains of the galactan backbone. Carrageenan structures were found for the first time in an agarophyte of the Gracilariales.

Widespread distribution of a newly found point mutation in voltage-gated sodium channel in pyrethroid-resistant Aedes aegypti populations in Vietnam.

BACKGROUND: Resistance of Aedes aegypti to photostable pyrethroid insecticides is a major problem for disease-vector control programs. Pyrethroids target the voltage-gated sodium channel on the insects' neurons. Single amino acid substitutions in this channel associated with pyrethroid resistance are one of the main factors that cause knockdown resistance in insects. Although kdr has been observed in several mosquito species, point mutations in the para gene have not been fully characterized in Ae. aegypti populations in Vietnam. The aim of this study was to determine the types and frequencies of mutations in the para gene in Ae. aegypti collected from used tires in Vietnam. METHODS AND FINDINGS: Several point mutations were examined that cause insensitivity of the voltage-gated sodium channel in the insect nervous system due to the replacement of the amino acids L1014F, the most commonly found point mutation in several mosquitoes; I1011M (or V) and V1016G (or I), which have been reported to be associated to knockdown resistance in Ae. aegypti located in segment 6, domain II; and a recently found amino acid replacement in F1269 in Ae. aegypti, located in segment 6, domain III. Among 756 larvae from 70 locations, no I1011M or I1011V nor L1014F mutations were found, and only two heterozygous V1016G mosquitoes were detected. However, F1269C mutations on domain III were distributed widely and with high frequency in 269 individuals among 757 larvae (53 collection sites among 70 locations surveyed). F1269C frequencies were low in the middle to north part of Vietnam but were high in the areas neighboring big cities and in the south of Vietnam, with the exception of the southern mountainous areas located at an elevation of 500-1000 m. CONCLUSIONS: The overall percentage of homozygous F1269C seems to remain low (7.4%) in the present situation. However, extensive and uncontrolled frequent use of photostable pyrethroids might be a strong selection pressure for this mutation to cause serious problems in the control of dengue fever in Vietnam.