Acylwanderungen am 3(5)-Amino-pyrazol

Acyl Migrations on 3(5)-Amino-pyrazole 3(5)-Amino-pyrazole 1 form 3 isomeric monoacylation products, 4 diacylation products and 3 triacylation products by reaction with electrophiles like cyanates, isocyanates or carboxylic and chlorides, respectively. Acyl migrations are observed depending on the reaction temperature and the structure of the acyl residue. The structures of the acyl derivatives of 3(5)-amino-pyrazole were characterized by nmr-spectroscopy.     

Synthesis and reactivity of 4-chloro-3,3,4-trifluoro-methoxycarbonyl cyclobutene (CTMC)

An improved synthesis of CTMC is described. This cyclobutene is thermally stable towards electrocyclic ring opening. Its reactivity is explored and a number of radical adducts are described. A more complicated picture is observed with various nucleophiles. The strong dienophilic character of CTMC is illustrated by numerous examples. CTMC reacts well as a dipolarophile with diphenylnitrone, diphenylnitrilimine and diazoalkanes. The high reactivity of this cyclobutene is due to its inherent polarity and strain.     

Studies on the base-catalyzed Solvolysis of Propane-2-sulphonic Acid p-Cresylester

Products of the reaction of propane-2-sulphonic acid p-cresylester with sodium butoxide in butanol are the sodium salt of propan-2-sulphonic acid, di-n-butyl ether, p-cresyl-n-butyl ether and p-cresol. The reaction proceeds via propane-2-sulphonic acid n-butylester which is formed from the starting compound by an elimination-addition (sulphene) mechanism. The elimination step is an E1-cB reaction.     

Improved thin film stability of differently formulated,printed, and crosslinked polymer layers against successive solvent printing

Interface control remains a top challenge of solution-processed organic light emitting diodes (OLED) stacks since the device performance heavily relies on it. Film stability of an inkjet deposited and crosslinked layer against subsequent exposure to a suitable inkjet printed solvent has been investigated. Impact of processing solvent (solvent used to prepare the polymer layer) on solution-cast thin film properties has already been shown for polymer films. To our knowledge, this study is the first one analyzing thin films stability against solvent exposure using technology relevant materials processed via inkjet printing (IJP). The outcome of this research showed that the stability of the crosslinked films is affected by the solvent used for ink formulation. These findings are of great interest for multilayered semiconductors devices, such as OLEDs, field-effect transistors and dye-sensitized solar cells. Differential scanning calorimetry (DSC) was used to quantify the efficiency of the polymer crosslinking reaction in pure powder and in thin films, as processed from different solvents. Crosslinking efficiency measured by DSC correlated well with the deformation induced by the solvent and observed on layer surfaces. The interaction in solution between polymer and solvent has also been evaluated to explain its impact on thin film stability against successive solvent printing. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48895.     

The Consumption of Food Products from Linseed-Fed Animals Maintains Erythrocyte Omega-3 Fatty Acids in Obese Humans

Based on mechanistic and epidemiological data, we raise the question of the relationship between qualitative dietary polyunsaturated fatty acids (PUFA) changes and increase in obesity. In this double-blind trial, we studied the effects on 160 overweight volunteers (body mass index, BMI >30) of a 90 days experimental diet rich principally in animal fat with a low PUFA/saturated fatty acid (SFA) ratio but a low n-6/n-3 ratio, using animal products obtained from linseed-fed animals. The control diet provided less animal fat, a higher PUFA/SFA ratio and a higher n-6/n-3 ratio. Both diets excluded seafood. In the experimental group, we observed a significant increase in red blood cell (RBC) α-linolenic acid content and a slight increase in EPA and DHA derivatives, while in the control group we observed a significant reduction in EPA and DHA content. Between groups now, the difference in the three n-3 fatty acids changes in RBC was significant. This demonstrates that plasma EPA and DHA levels can be maintained without fish if products from linseed-fed animals are used. During the diets, we noted a significant reduction in weight, BMI and hip circumference within both groups of volunteers. However, no significant difference was observed between the control group and the experimental group. Interestingly, 150 days after the end of the trial (i.e., day 240), we noted a significant weight gain in the control group, whereas no significant weight gain was observed in the experimental group. This was also observed for the BMI and hip circumference. Moreover, significant differences in BMI (P < 0.05) and weight (P = 0.05) appeared between the two groups, showing in both cases a smaller increase in the experimental group. During the 90 days trial, we did not observe any differences between groups in terms of total cholesterol, HDL cholesterol, LDL cholesterol or triglycerides, suggesting that the saturate content and the P/S ratio are not as important as the n-6 and n-3 fatty acid composition.     

Transformation of Free and Dipeptide‐Bound Glycated Amino Acids by Two Strains of Saccharomyces cerevisiae

The yeast Saccharomyces cerevisiae transforms branched‐chain and aromatic amino acids into higher alcohols in the Ehrlich pathway. During microbiological culturing and industrial fermentations, this yeast is confronted with amino acids modified by reducing sugars in the Maillard reaction (glycation). In order to gain some preliminary insight into the physiological “handling” of glycated amino acids by yeasts, individual Maillard reaction products (MRPs: fructosyllysine, carboxymethyllysine, pyrraline, formyline, maltosine, methylglyoxal‐derived hydroimidazolone) were administered to two strains of S. cerevisiae in a rich medium. Only formyline was converted into the corresponding α‐hydroxy acid, to a small extent (10 %). Dipeptide‐bound pyrraline and maltosine were removed from the medium with concomitant emergence of several metabolites. Pyrraline was mainly converted into the corresponding Ehrlich alcohol (20–60 %) and maltosine into the corresponding α‐hydroxy acid (40–60 %). Five specific metabolites of glycated amino acids were synthesized and characterized. We show for the first time that S. cerevisiae can use glycated amino acids as a nitrogen source and transform them into new metabolites, provided that the substances can be transported across the cell membrane.     

硅烷膏体浸渍剂在保护混凝土中的实际应用

渗透型有机硅成功用于保护混凝土在国外已有数十年的历史。用于保护钢筋混凝土，它可防止水分及氯离子的渗透，从而对于防止混凝土的腐蚀与破坏起到关键的作用。这种浸渍剂一般都由硅烷或硅氧烷组成。通常情况下，由于这些低粘度的液体非常容易挥发。尤其在桥梁底面及立面施工时，有效成分大量流失。为了避免出现这种情况，德国瓦克化学有限公司成功开发了一种新型的硅烷乳膏状产品。这种材料施工简单，只需一步完成，具有很高的遮盖率，由于不流淌，活性组分不会损失。与混凝土表面接触时间长，保证了在高等级混凝土中的渗透深度，而且在其表面不会残留任何痕迹。     

Redox processes in pressurised smoked salmon studied by resonance Raman spectroscopy

Non-thermal food preservation technology is based on the application of high pressures up to 600 MPa. Here we report a resonance Raman (RR) spectroscopic analysis of smoked salmon meat after high pressure processing. High quality spectra, which can be obtained even from packed salmon without spectral interference of the packing foil, allow determining pressure-dependent irreversible changes of the main RR-active components of salmon meat, astaxanthin and myoglobin/haemoglobin. High pressure-treatment causes a decrease of the relative RR intensities of astaxanthin as probed with 514 nm excitation which is in line with a slight attenuation of the originally intense red colour of the salmon meat. 413-nm excited RR spectra indicate a heterogeneous broadening of astaxanthin bands accompanied by the formation of deoxy-myoglobin or deoxy-haemoglobin. The results suggest that pressure-treatment facilitates the oxidative degradation of astaxanthin coupled to the reduction of metmyoglobin (methaemoglobin).