Synthesis,characterization and polymerization of novel sugars based on methacrylate

The present study describes the synthesis and characterizations of polymerizable vinyl sugars. Glucose, mannose, galactose and fructose are abundant and sustainable natural compounds. As it is not possible to make many derivatives of sugars without using protective groups, first of all, diacetone derivatives [diacetone-d-glucose (1), diacetone-d-mannose (2), diacetone-d-galactose (3) and diacetone-d-fructose (4)] were synthesized according to the literature as starting compounds. The remaining free hydroxyl groups on C-3 (diacetone glucose), C-6 (diacetone galactose), C-1 (diacetone fructose) and C-1 (diacetone mannose), were reacted with epichlorohydrin (1-chloro-2,3-epoxypropane) to produce then “-O-(2′,3′-epoxypropane-1′-yl)” ether derivatives (5, 6, 7, and 8) which are epoxy sugars in the basic medium. Next, the epoxy rings of the ethers (5, 6, 7, and 8) were opened with methacrylic acid in DMF to produce new sugar based methacrylates (9, 10, 11, and 12). Finally, free radical polymerization of these sugar based methacrylate monomers was performed, producing related polymers (13, 14, 15 and 16). The polymerizations were carried out using AIBN as an initiator at 70 °C in DMF. All the products were characterized by FTIR, ¹HNMR and ¹³CNMR techniques. Thermal properties of all polymers were investigated by TG, DTG and DSC. The data obtained has suggested that thermal stability of the synthesized polymers has changed with the structure of the sugar and increase in molecular weight.     

Importance of a Conserved Lys/Arg Residue for Ligand/PDZ Domain Interactions as Examined by Protein Semisynthesis

PDZ domains are ubiquitous small protein domains that are mediators of numerous protein–protein interactions, and play a pivotal role in protein trafficking, synaptic transmission, and the assembly of signaling‐transduction complexes. In recent years, PDZ domains have emerged as novel and exciting drug targets for diseases (in the brain in particular), so understanding the molecular details of PDZ domain interactions is of fundamental importance. PDZ domains bind to a protein partner at either a C‐terminal peptide or internal peptide motifs. Here, we examined the importance of a conserved Lys/Arg residue in the ligand‐binding site of the second PDZ domain of PSD‐95, by employing a semisynthetic approach. We generated six semisynthetic PDZ domains comprising different proteogenic and nonproteogenic amino acids representing subtle changes of the conserved Lys/Arg residue. These were tested with four peptide interaction partners, representing the two different binding modes. The results highlight the role of a positively charged amino acid in the β1–β2 loop of PDZ domains, and show subtle differences for canonical and noncanonical interaction partners, thus providing additional insight into the mechanism of PDZ/ligand interaction.     

Effect of composition on the matrix transformation of the Co-Re-Cr-Ta-C alloys

Neutron diffraction measurement was performed in-situ at high temperatures on Co-Re-Ta-C alloys with and without Cr addition. This included alloys containing different C content with the C/Ta ratio varying between 0.5 and 1.0. The Co-Re-solid solution matrix of the experimental alloys is polymorphic (like in pure cobalt) and transformed from low temperature hexagonal ? phase to high temperature cubic γ phase on heating. This transformation is reversible and show hysteresis. The main alloying addition, Re, stabilizes the ? Co-phase and increases the transformation temperature to above 1273 K. The onset of the \(\varepsilon \rightleftharpoons \gamma\) transformation during heating and cooling was found to differ depending on the alloy composition. In alloys without Cr addition the transformation was not completed on cooling and the high temperature γ phase was partly retained at room temperature in metastable state with the amount depending on the cooling rate from high temperature. The diffraction and microstructural results showed that Cr is ? stabilizer (similar as Re) but the role of Ta is not clear. The C/Ta ratio has no direct effect on the matrix phase transformation. Nevertheless, it influences indirectly by determining the amount of Ta which is freely available in the matrix.     

Organochlorine Formation in Tertiary Amine Catalyzed Pulp Bleaching

An oxygen delignified eucalyptus kraft pulp was bleached by applying a catalytic amount of a tertiary amine, 1,4-diazabicyclo[2,2,2]octane, and hypochlorous acid at varying pH, temperature, and time. The bleaching filtrate was analyzed for chloroform and AOX and the pulp for residual lignin, hexenuronic acid, and OX. In comparison with chlorine dioxide bleaching, the novel catalytic bleaching (pH < 6) generated only traces of chloroform and low contents of AOX and OX. Separate catalytic oxidations of authentic hexenuronic acid showed that it was a major precursor of chloroform. The results demonstrate a practical way to reduce organochlorine formation in pulp bleaching and provide new understanding on the reaction pathways that yield chloroform.     

Differential Impact of Hyperglycemia in Critically Ill Patients: Significance in Acute Myocardial Infarction but Not in Sepsis?

Hyperglycemia is a common condition in critically ill patients admitted to an intensive care unit (ICU). These patients represent an inhomogeneous collective and hyperglycemia might need different evaluation depending on the underlying disorder. To elucidate this, we investigated and compared associations of severe hyperglycemia (>200 mg/dL) and mortality in patients admitted to an ICU for acute myocardial infarction (AMI) or sepsis as the two most frequent admission diagnoses. From 2006 to 2009, 2551 patients 69 (58–77) years; 1544 male; 337 patients suffering from type 2 diabetes (T2DM)) who were admitted because of either AMI or sepsis to an ICU in a tertiary care hospital were investigated retrospectively. Follow-up of patients was performed between May 2013 and November 2013. In a Cox regression analysis, maximum glucose concentration at the day of admission was associated with mortality in the overall cohort (HR = 1.006, 95% CI: 1.004–1.009; p < 0.001) and in patients suffering from myocardial infarction (HR = 1.101, 95% CI: 1.075–1.127; p < 0.001) but only in trend in patients admitted to an ICU for sepsis (HR = 1.030, 95% CI: 0.998–1.062; p = 0.07). Severe hyperglycemia was associated with adverse intra-ICU mortality in the overall cohort (23% vs. 13%; p < 0.001) and patients admitted for AMI (15% vs. 5%; p < 0.001) but not for septic patients (39% vs. 40%; p = 0.48). A medical history of type 2 diabetes (n = 337; 13%) was not associated with increased intra-ICU mortality (15% vs. 15%; p = 0.93) but in patients with severe hyperglycemia and/or a known medical history of type 2 diabetes considered in combination, an increased mortality in AMI patients (intra-ICU 5% vs. 13%; p < 0.001) but not in septic patients (intra-ICU 38% vs. 41%; p = 0.53) could be evidenced. The presence of hyperglycemia in critically ill patients has differential impact within the different etiological groups. Hyperglycemia in AMI patients might identify a sicker patient collective suffering from pre-diabetes or undiagnosed diabetes with its’ known adverse consequences, especially in the long-term. Hyperglycemia in sepsis might be considered as adaptive survival mechanism to hypo-perfusion and consecutive lack of glucose in peripheral cells. AMI patients with hyperglycemic derailment during an ICU-stay should be closely followed-up and extensively screened for diabetes to improve patients’ outcome.     

Geothermal use of an Alpine aquifer—Davos pilot study

Grundwasser - Topographically induced Alpine regional groundwater flow systems below the unconsolidated valley fillings constitute a&nbsp;substantial unused geothermal resource. Within the...     

Sanierung eines PCE-Schadens in einem makroskopisch oxischen Grundwasserleiter durch Stimulation anaerober dehalogenierender Bakterien

Grundwasser - Eine erfolgreiche biologische In-situ-Sanierung von PCE-kontaminierten Grundwasserleitern erfordert hinreichend reduzierende Bedingungen sowie die Anwesenheit von molekularem...