Symmetries and alignment of biaxial nematic liquid crystals

The possible symmetries of the biaxial nematic phase are examined against the implications of the presently available experimental results. Contrary to the widespread notion that biaxial nematics have orthorhombic symmetry, our study shows that a monoclinic ($C_{2h}$) symmetry is more likely to be the case for the recently observed phase biaxiality in thermotropic bent-core and calamitc tetrapode nematic systems. The methodology for differentiating between the possible symmetries of the biaxial nematic phase by NMR and by IR spectroscopy measurements is presented in detail. The manifestations of the different symmetries on the alignment of the biaxial phase are identified and their implications on the measurement and quantification of biaxiality as well as on the potential use of biaxial nematic liquid crystals in electro-optic applications are discussed.Comment: 24 pages, 4 figure

Influence of cadmium loading on glutathione system of antioxidant protection of the bullocks’bodies

It was presented the results of studies of the cadmium effect loading on the activity of the glutathione system of antioxidant protection in young cattle, namely on the activity of glutathione peroxidase, glutathione reductase, glucose-6-phosphate dehydrogenase, the level of reduced glutathion. It was established that feeding of cadmium chloride to bullocks at a dose of 0.03 and 0.05 mg/kg body weight contributed to a decrease in both the enzyme and non-enzyme link of the glutathione antioxidant defense system. The toxic effect of cadmium contributes to a change in stationary concentrations of radical metabolites. О2˙ˉ, ˙ОН, НО2˙, which, in turn, initiate lipid peroxidation processes. The lowest level of glutathione indexes of the antioxidant defense system in the blood of young cattle was established on the sixteenth and twenty fourth day of the experiment, it was associated with enhanced activation of lipoperoxidation and an imbalance between the activity of the antioxidant system and the intensity of lipid peroxidation. The feeding of cadmium chloride to bullocks at a dose of 0.03 and 0.05 mg/kg of animal weight did not affect the activity of the glutathione antioxidant defense system in their blood. It was established that the greater the amount of cadmium chloride in the feed, the lower the activity of the glutathione system of the antioxidant defense of the body of bulls. Thus, cadmium chloride suppresses the antioxidant protection system, in particular, by reducing the activity of the enzyme link: glutathione peroxidase, glutathione reductase, glucose-6-phosphate dehydrogenase, and non-enzyme link: reduced glutathione

Flying-seed-like mesogens 6: Synthesis and mesomorphism of phthalocyanine derivatives substituted by pentafluorosulfanylphenoxy group

We have synthesized two novel phthalocyanines, (m-SF5PhO)(8)PcCu (7b) and (p-SF5PhO)(8)PcCu (7c), in order to investigate their flying-seed-like mesomorphism. Their phase transition behavior and the mesophase structure have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Very interestingly, the derivative (m-SF5PhO)(8)PcCu (7b) substituted a SF 5 group at m-position showed a Col(10)(P2(1)/a) (= p2gg) mesophase from rt to 315.0 degrees C, whereas the derivative (p-SF5PhO)(8)PcCu (7c) substituted a SF 5 group at p-position showed a crystalline (K) phase from rt to the decomposition temperature at ca. 336 degrees C without showing mesomorphism. Thus, the novel phthalocyanine derivative (m-SF5PhO)(8)PcCu (7b) substituted a strong electron withdrawing SF 5 group at m-position shows only one columnar mesophase in a very wide temperature region from rt to 315.0 degrees C. Furthermore, the Q-band wavelengths (672.2 and 672.1 nm) of the present (m-SF5PhO)(8)PcCu (7b) and (p-SF5PhO)(8)PcCu (7c) are shorter than that (680.3 nm) of the previous [(m-C-1) PhO](8)PcCu (5c) derivative. It can be attributed to strong electron withdrawing nature of the SF5 group on the phenoxy group.ArticleJOURNAL OF PORPHYRINS AND PHTHALOCYANINES. 20(7):822-832 (2016)journal articl

Flying-seed-like liquid crystals 5: Liquid crystals based on octakisphenylthiophthalocyanine and their optical properties

We have synthesized three novel flying-seed-like liquid crystals based on phthalocyaninato copper(II) (abbreviated as PcCu) substituted by bulky groups {(o-C-1)PhS (i), (m-C-1)PhS (j), [m, p(C-1)(2)]PhS (k)} instead of using long alkyl chains, in order to investigate their mesomorphism. Their phase transition behavior and the mesophase structures have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. As the results, [(o-C-1)PhS](8)PcCu (8i), [(m-C-1)PhS](8)PcCu (8j) and {[m,p-(C-1)(2)]PhS}(8)PcCu (8k) show a Col tet. o mesophase at 314.9 similar to 362.9 degrees C, a Col(ro) (P2m) mesophase at 287.4 similar to 334.2 degrees C and a Col(ro) (P2m) mesophase at 331.8 similar to 386.8 degrees C, respectively. Very interestingly, each of the derivatives thus exhibits a columnar mesophase at very high temperatures. The mesomorphism is apparently originated from the novel bulky groups (i similar to k). It is also noteworthy that the Q-bands of the present PhScontaining Pc derivatives 8i similar to 8k in THF significantly red-shift by about 35 nm in comparison with those of the corresponding PhO-containing derivatives in THF

Development of an exoglycosidase plate-based assay for detecting α1-3,4 fucosylation biomarker in individuals with HNF1A-MODY

Maturity-onset diabetes of the young due to hepatocyte nuclear factor-1 alpha variants (HNF1A-MODY) causes monogenic diabetes. Individuals carrying damaging variants in HNF1A show decreased levels of α1-3,4 fucosylation, as demonstrated on antennary fucosylation of blood plasma N-glycans. The excellent diagnostic performance of this glycan biomarker in blood plasma N-glycans of individuals with HNF1A-MODY has been demonstrated using liquid chromatography methods. Here, we have developed a high-throughput exoglycosidase plate-based assay to measure α1-3,4 fucosylation levels in blood plasma samples. The assay has been optimized and its validity tested using 1000 clinical samples from a cohort of individuals with young-adult onset diabetes including cases with HNF1A-MODY. The α1-3,4 fucosylation levels in blood plasma showed a good differentiating power in identifying cases with damaging HNF1A variants, as demonstrated by receiver operating characteristic curve analysis with the AUC values of 0.87 and 0.95. This study supports future development of a simple diagnostic test to measure this glycan biomarker for application in a clinical setting. </p

Large-scale analysis of apolipoprotein CIII glycosylation by ultrahigh resolution mass spectrometry

Apolipoprotein-CIII (apo-CIII) is a glycoprotein involved in lipid metabolism and its levels are associated with cardiovascular disease risk. Apo-CIII sialylation is associated with improved plasma triglyceride levels and its glycosylation may have an effect on the clearance of triglyceride-rich lipoproteins by directing these particles to different metabolic pathways. Large-scale sample cohort studies are required to fully elucidate the role of apo-CIII glycosylation in lipid metabolism and associated cardiovascular disease. In this study, we revisited a high-throughput workflow for the analysis of intact apo-CIII by ultrahigh-resolution MALDI FT-ICR MS. The workflow includes a chemical oxidation step to reduce methionine oxidation heterogeneity and spectrum complexity. Sinapinic acid matrix was used to minimize the loss of sialic acids upon MALDI. MassyTools software was used to standardize and automate MS data processing and quality control. This method was applied on 771 plasma samples from individuals without diabetes allowing for an evaluation of the expression levels of apo-CIII glycoforms against a panel of lipid biomarkers demonstrating the validity of the method. Our study supports the hypothesis that triglyceride clearance may be regulated, or at least strongly influenced by apo-CIII sialylation. Interestingly, the association of apo-CIII glycoforms with triglyceride levels was found to be largely independent of body mass index. Due to its precision and throughput, the new workflow will allow studying the role of apo-CIII in the regulation of lipid metabolism in various disease settings.Proteomic

Interlaboratory evaluation of plasma N-glycan antennary fucosylation as a clinical biomarker for HNF1A-MODY using liquid chromatography methods

Antennary fucosylation alterations in plasma glycoproteins have been previously proposed and tested as a biomarker for differentiation of maturity onset diabetes of the young (MODY) patients carrying a functional mutation in the HNF1A gene. Here, we developed a novel LC-based workflow to analyze blood plasma N-glycan fucosylation in 320 diabetes cases with clinical features matching those at risk of HNF1A-MODY. Fucosylation levels measured in two independent research centers by using similar LC-based methods were correlated to evaluate the interlaboratory performance of the biomarker. The interlaboratory study showed good correlation between fucosylation levels measured for the 320 cases in the two centers with the correlation coefficient (r) of up to 0.88 for a single trait A3FG3S2. The improved chromatographic separation allowed the identification of six single glycan traits and a derived antennary fucosylation trait that were able to differentiate individuals carrying pathogenic mutations from benign or no HNF1A mutation cases, as determined by the area under the curve (AUC) of up to 0.94. The excellent (r = 0.88) interlaboratory performance of the glycan biomarker for HNF1A-MODY further supports the development of a clinically relevant diagnostic test measuring antennary fucosylation levels.Horizon 2020 (H2020)72209

Definitions of basic terms relating to polymer liquid crystals (IUPAC Recommendations 2001)

The document first gives definitions of basic terms related to liquid-crystalline and mesomorphic states of matter and then terms specific to the classification of liquid-crystal polymers. The terms have been restricted to those most commonly encountered in the structural description of the latter class of materials. The terms have been selected from the recently published comprehensive document "Definitions of basic terms relating to low-molar-mass and polymer liquid crystals" [Pure and Applied Chemistry 73 (5), 845-895 (2001)] and are intended to form a readily usable guide for the reader interested in the structural description of polymer liquid crystals. The more comprehensive document should be used for terminology associated with types of mesophases and the optical and physical characteristics of liquid-crystalline materials. The advice given by representatives of the International Liquid Crystal Society for the preparation of this document is gratefully acknowledged.Fil:Barón, M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina