Preparation of helical liquid crystal electrolyte with L-isoleucine derivatives and molecular asymmetric imprinting polymerization in liquid crystal to produce electro-optically coloration active polymers having chiral charge carrier chiralions

Molecular asymmetric imprinting polymerization in the cholesteric liquid crystal was carried out. An L-isoleucine derivative with fluorine was synthesized for a chiral inducer to induce the cholesteric liquid crystal from the nematic liquid crystal. A substance with multiple asymmetric centers can be obtained conveniently to use amino acid as chiral substance. The L-isoleucine derivative induced helical structure for 4-cyano-4'-hexylbiphenyl (6CB). Electrochemical preparation of π-conjugated polymers was carried out in the cholesteric liquid crystal. Fingerprint texture derived from the cholesteric liquid crystal was transcribed to the polymers. UV-vis and circular dichroism (CD) spectra of oxidized (doped) for and reduced (dedoped) form of the polymer were measured. Electrochemical polymerization in the helical liquid crystal produced the molecular aggregation imprinted chiral polymers, which have liquid crystal-like aggregation form, chirality with no stereogenic center via formation of polymer atropisomer, and electrochemical driven change in optical activity, as a form of electro-optically coloration active polymers. Finally, the polarons and bipolarons are in the form of chiral structure. These charge carriers in the polymers can be determined as chiral charge carrier “chiralions”.</p

Molecular Order Imprint Polymerization of Furan–Thiophene-Based Monomers with Electrochemical Polymerization in Chiral Liquid Crystals

A polymerization reaction in chiral liquid crystal produced electro-optically active polymers from achiral furan–thiophene-based monomers. The set of polymers prepared in this study had characteristics of liquid crystal molecular order and organic semiconductors. The optically active aromatic copolymers were synthesized via an electrochemical method in cholesteric liquid crystals (Ch-LCs). Electrical properties and chirality can be tuned to choose suitable monomer units. The polymers obtained were evaluated by polarizing optical microscopy (POM), circular dichroism, UV–vis spectroscopy, cyclic voltammetry, reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. POM observations of the products showed a vortex-type fingerprint texture. Polymerization of the monomers containing only two active polymerization sites produced the resultant compounds with good transcription of the fingerprint texture and chirality from the Ch-LC electrolyte solution. The membrane-forming behavior can be improved by introducing furans at the edges of monomers. The absorption bands derived from polarons and bipolarons as charge carriers of conducting polymers can be tuned by an electrical redox process and hydrazine vaporization treatment. Electrical control for the optical activity of the furan–thiophene-based polymers was achieved

Horizontal and Vertical Orientation of Polythiophenes by Electrochemical Polymerization in Magnetically Aligned Smectic Liquid Crystal

Macroscopically highly oriented polythiophene derivative films are synthesized by electrochemical polymerization in a smectic liquid crystal reaction medium. Control of orientation direction of conjugated main chains is performed by use of magnetic field which is applied parallel, obliquely, and perpendicularly to the substrate electrodes to align the liquid crystal reaction medium

Defective autophagy in vascular smooth muscle cells enhances cell death and atherosclerosis

<p>Macroautophagy/autophagy is considered as an evolutionarily conserved cellular catabolic process. In this study, we aimed to elucidate the role of autophagy in vascular smooth muscle cells (SMCs) on atherosclerosis. SMCs cultured from mice with SMC-specific deletion of the essential autophagy gene <i>atg7</i> (<i>Atg7cKO</i>) showed reduced serum-induced cell growth, increased cell death, and decreased cell proliferation rate. Furthermore, 7-ketocholestrerol enhanced apoptosis and the expression of CCL2 (chemokine [C-C motif] ligand 2) with the activation of TRP53, the mouse ortholog of human and rat TP53, in SMCs from <i>Atg7cKO</i> mice. In addition, <i>Atg7cKO</i> mice crossed with <i>Apoe</i> (apolipoprotein E)-deficient mice (<i>apoeKO; Atg7cKO:apoeKO</i>) showed reduced medial cellularity and increased TUNEL-positive cells in the descending aorta at 10 weeks of age. Intriguingly, <i>Atg7cKO: apoeKO</i> mice fed a Western diet containing 1.25% cholesterol for 14 weeks showed a reduced survival rate. Autopsy of the mice demonstrated the presence of aortic rupture. Analysis of the descending aorta in <i>Atg7cKO:apoeKO</i> mice showed increased plaque area, increased TUNEL-positive area, decreased SMC-positive area, accumulation of macrophages in the media, and adventitia and perivascular tissue, increased CCL2 expression in SMCs in the vascular wall, medial disruption, and aneurysm formation. In conclusion, our data suggest that defective autophagy in SMCs enhances atherosclerotic changes with outward arterial remodeling.</p

One year follow-up after a randomized controlled trial of a 130 g/day low-carbohydrate diet in patients with type 2 diabetes mellitus and poor glycemic control

<div><p>Background & aims</p><p>Recently, we conducted a prospective randomized controlled trial (RCT) showing that a 6-month 130g/day low-carbohydrate diet (LCD) reduced HbA1c and BMI more than a calorie restricted diet (CRD). [<a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0188892#pone.0188892.ref001" target="_blank">1</a>] To assess whether the benefits of the LCD persisted after the intensive intervention, we compared HbA1c and BMI between the LCD and CRD groups at 1 year after the end of the 6-month RCT.</p><p>Methods</p><p>Following the end of the 6-month RCT, patients were allowed to manage their own diets with periodic outpatient visits. One year later, we analyzed clinical and nutrition data.</p><p>Results</p><p>Of the 66 participants in the original study, 27 in the CRD group and 22 in the LCD group completed this trial. One year after the end of the original RCT, the carbohydrate intake was comparable between the groups (215 [189–243]/day in the CRD group and 214 (176–262) g/day in the LCD group). Compared with the baseline data, HbA1c and BMI were decreased in both groups (CRD: HbA1c -0.4 [-0.9 to 0.3] % and BMI -0.63 [-1.20 to 0.18] kg/m²; LCD: HbA1c -0.35 [-1.0 to 0.35] % and BMI -0.77 [-1.15 to -0.12] kg/m²). There were no significant differences in HbA1c and BMI between the groups.</p><p>Conclusions</p><p>One year after the diet therapy intervention, the beneficial effect of the LCD on reduction of HbA1c and BMI did not persist in comparison with CRD. However, combining the data of both groups, significant improvements in HbA1c and BMI from baseline were observed. Although the superiority of the LCD disappeared 1 year after the intensive intervention, these data suggest that well-constructed nutrition therapy programs, both CRD and LCD, were equally effective in improving HbA1c for at least 1 year.</p><p>Trial registration</p><p>University Hospital Medical Information Network (UMIN) <a href="https://clinicaltrials.gov/ct2/show/ID000010663" target="_blank">ID000010663</a></p></div

Characteristics of 49 patients at the RCT baseline, and changes in medication dosages at the end of 1-year follow-up.

<p>Characteristics of 49 patients at the RCT baseline, and changes in medication dosages at the end of 1-year follow-up.</p

Study flow chart.

<p>The baseline data of the study subjects are shown in Tables <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0188892#pone.0188892.t001" target="_blank">1</a> and <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0188892#pone.0188892.t002" target="_blank">2</a>. Except for age and fat intake, other data were well-matched.</p

Data at baseline, 6 months, and 18 months for 49 patients in the calorie-restricted diet (CRD) group and the low-carbohydrate diet (LCD) group.

<p>Data at baseline, 6 months, and 18 months for 49 patients in the calorie-restricted diet (CRD) group and the low-carbohydrate diet (LCD) group.</p