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

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

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

Reduction in Predator Defense in the Presence of Neighbors in a Colonial Fish

Predation pressure has long been considered a leading explanation of colonies, where close neighbors may reduce predation via dilution, alarming or group predator attacks. Attacking predators may be costly in terms of energy and survival, leading to the question of how neighbors contribute to predator deterrence in relationship to each other. Two hypotheses explaining the relative efforts made by neighbors are byproduct-mutualism, which occurs when breeders inadvertently attack predators by defending their nests, and reciprocity, which occurs when breeders deliberately exchange predator defense efforts with neighbors. Most studies investigating group nest defense have been performed with birds. However, colonial fish may constitute a more practical model system for an experimental approach because of the greater ability of researchers to manipulate their environment. We investigated in the colonial fish, Neolamprologus caudopunctatus, whether prospecting pairs preferred to breed near conspecifics or solitarily, and how breeders invested in anti-predator defense in relation to neighbors. In a simple choice test, prospecting pairs selected breeding sites close to neighbors versus a solitary site. Predators were then sequentially presented to the newly established test pairs, the previously established stimulus pairs or in between the two pairs. Test pairs attacked the predator eight times more frequently when they were presented on their non-neighbor side compared to between the two breeding sites, where stimulus pairs maintained high attack rates. Thus, by joining an established pair, test pairs were able to reduce their anti-predator efforts near neighbors, at no apparent cost to the stimulus pairs. These findings are unlikely to be explained by reciprocity or byproduct-mutualism. Our results instead suggest a commensal relationship in which new pairs exploit the high anti-predator efforts of established pairs, which invest similarly with or without neighbors. Further studies are needed to determine the scope of commensalism as an anti-predator strategy in colonial animals