CFD Process Modeling of the Industrial Calcination of Diatomite

Calcination of diatomite is an expensive process frequently resulting in products with unpredictable structure. Alternatively, calcination in swirling flow is an energy‐saving option. Computational fluid dynamics modeling of an experimental calcination process unit is presented. Experimental results and systematic collection of process data were used to define boundary condition for steady‐state and transient simulation runs. The comparison of experimental and simulation results shows the complexity of the calcination process. The results can be used for further process optimization.     

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.     

Hydroxyoctadecadienoic Acids Regulate Apoptosis in Human THP‐1 Cells in a PPARγ‐Dependent Manner

Macrophage apoptosis, a key process in atherogenesis, is regulated by oxidation products, including hydroxyoctadecadienoic acids (HODEs). These stable oxidation products of linoleic acid (LA) are abundant in atherosclerotic plaque and activate PPARγ and GPR132. We investigated the mechanisms through which HODEs regulate apoptosis. The effect of HODEs on THP‐1 monocytes and adherent THP‐1 cells were compared with other C18 fatty acids, LA and α‐linolenic acid (ALA). The number of cells was reduced within 24 hours following treatment with 9‐HODE (p < 0.01, 30 μM) and 13 HODE (p < 0.01, 30 μM), and the equivalent cell viability was also decreased (p < 0.001). Both 9‐HODE and 13‐HODE (but not LA or ALA) markedly increased caspase‐3/7 activity (p < 0.001) in both monocytes and adherent THP‐1 cells, with 9‐HODE the more potent. In addition, 9‐HODE and 13‐HODE both increased Annexin‐V labelling of cells (p < 0.001). There was no effect of LA, ALA, or the PPARγ agonist rosiglitazone (1μM), but the effect of HODEs was replicated with apoptosis‐inducer camptothecin (10μM). Only 9‐HODE increased DNA fragmentation. The pro‐apoptotic effect of HODEs was blocked by the caspase inhibitor DEVD‐CHO. The PPARγ antagonist T0070907 further increased apoptosis, suggestive of the PPARγ‐regulated apoptotic effects induced by 9‐HODE. The use of siRNA for GPR132 showed no evidence that the effect of HODEs was mediated through this receptor. 9‐HODE and 13‐HODE are potent—and specific—regulators of apoptosis in THP‐1 cells. Their action is PPARγ‐dependent and independent of GPR132. Further studies to identify the signalling pathways through which HODEs increase apoptosis in macrophages may reveal novel therapeutic targets for atherosclerosis.     

Development of organosilicone–polyurethanes as stone preservation and consolidation materials

Two organosilicone-modified polyurethanes are investigated as potential materials for the conservation and consolidation of natural stones. The materials are low molecular weight oligomers at the application stage and react with the humidity of the air to give polymers, forming continuous microlayers. The two differ in the length of the organosilicone chain, resulting in pronounced differences in their physical state: one forms a brittle glassy material (T_g ≈ 70°C). and the other, a soft rubbery material (T_g ≈ −100°C). The rate of the polymerization of the prepolymers was investigated at different conditions, showing a strong dependence on the presence of a catalyst and air humidity. Both these favorable conditions exist probably in the natural stone pores, enhancing the formation of the protective hydrophobic internal microlayer. © 1996 John Wiley & Sons, Inc.     

Solid-Phase Microextraction (SPME) of Pyrazines in Model Reaction Systems

Headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) was used for isolating and analysing pyrazines formed in a model system. This system consisted of an aqueous mixture of glucose, glycine and sodium hydroxide. Pyrazine formation was accelerated by heating in a microwave oven. Results were compared with our earlier ones using conventional techniques for isolation of pyrazines. HS-SPME-GC showed several advantages over traditional methods. The method is rapid, sensitive, easy to use and reproducible. Headspace and liquid of the model reaction were extracted and the results obtained using headspace sampling showed good agreement with the methylene chloride extraction method. In all cases, coefficients of variation of 5% or lower were obtained when the SPME extraction time was consistent.     

Synthese und Reaktionen chiraler,von (R)-(−)-bzw. (S)-(+)-2-Methoxymethylpyrrolidin abgeleiteter Dithiocarbamate

Synthesis and Reactions of Chiral Dithiocarbamates Derived from (R)-(−)- or (S)-(+)-2- The synthesis, diastereoselective alkylation reactions, dithiocarboxylation, and aldol condensation of several substituted methyl (R¹ CH₂) (S)-2-(methoxymethyl)-pyrrolidine-1-dithiocarboxylates (S)- 2 and of the corresponding (R)-derivatives (R)- 2 are described. The new enantiomeric dithiocarbamates (S) -2a – e , and (R) -2a – d are obtained by reaction of (S)-(+)-[(S) -1 ] or (R)-(−)-2-(methoxymethyl)-pyrrolidine [(R) -1 ], respectively, with carbon disulfide in dry methanol/anhydrous sodium acetate and the appropriate alkylating agent. The cyclic ketene dithioacetals (S) -3 and (R) -3 are formed by dithiocarboxylation procedure of (S) -2a and (R) -2a whereas (S) -6 and (R) -6 are obtained by aldol reaction with isobutyraldehyde. (S)- 2c , d and (R) -2c , d react in a diastereoselective manner after deprotonation with n-BuLi or LiTMP/LiBr at −78°C in THF with alkyl halides to the enantiomeric compounds 4a /ent -4a, 4b /ent -4b and 5 /ent -5 , respectively.