State- and water repellency-controllable molecular glass of pillar[5]arenes with fluoroalkyl groups by guest vapors

Molecular glasses are low-molecular-weight organic compounds that are stable in the amorphous state at room temperature. Herein, we report a state- and water repellency-controllable molecular glass by n-alkane guest vapors. We observed that a macrocyclic host compound pillar[5]arene with the C₂F₅ fluoroalkyl groups changes from the crystalline to the amorphous state (molecular glass) by heating above its melting point and then cooling to room temperature. The pillar[5]arene molecular glass shows reversible transitions between amorphous and crystalline states by uptake and release of the n-alkane guest vapors, respectively. Furthermore, the n-alkane guest vapor-induced reversible changes in the water contact angle were also observed: water contact angles increased and then reverted back to the original state by the uptake and release of the n-alkane guest vapors, respectively, along with the changes in the chemical structure and roughness on the surface of the molecular glass. The water repellency of the molecular glass could be controlled by tuning the uptake ratio of the n-alkane guest vapor

Optimized protocol for the extraction of RNA and DNA from frozen whole blood sample stored in a single EDTA tube

Cryopreservation of whole blood is useful for DNA collection, and clinical and basic research. Blood samples in ethylenediaminetetraacetic acid disodium salt (EDTA) tubes stored at − 80 °C are suitable for DNA extraction, but not for high-quality RNA extraction. Herein, a new methodology for high-quality RNA extraction from human blood samples is described. Quickly thawing frozen whole blood on aluminum blocks at room temperature could minimize RNA degradation, and improve RNA yield and quality compared with thawing the samples in a 37 °C water bath. Furthermore, the use of the NucleoSpin RNA kit increased RNA yield by fivefold compared with the PAXgene Blood RNA Kit. Thawing blood samples on aluminum blocks significantly increased the DNA yield by ~ 20% compared with thawing in a 37 °C water bath or on ice. Moreover, by thawing on aluminum blocks and using the NucleoSpin RNA and QIAamp DNA Blood kits, the extraction of RNA and DNA of sufficient quality and quantity was achieved from frozen EDTA whole blood samples that were stored for up to 8.5 years. Thus, extracting RNA from frozen whole blood in EDTA tubes after long-term storage is feasible. These findings may help advance gene expression analysis, as well as biomarker research for various diseases

Interferon signaling and hypercytokinemia-related gene expression in the blood of antidepressant non-responders

Only 50% of patients with depression respond to the first antidepressant drug administered. Thus, biomarkers for prediction of antidepressant responses are needed, as predicting which patients will not respond to antidepressants can optimize selection of alternative therapies. We aimed to identify biomarkers that could predict antidepressant responsiveness using a novel data-driven approach based on statistical pattern recognition. We retrospectively divided patients with major depressive disorder into antidepressant responder and non-responder groups. Comprehensive gene expression analysis was performed using peripheral blood without narrowing the genes. We designed a classifier according to our own discrete Bayes decision rule that can handle categorical data. Nineteen genes showed differential expression in the antidepressant non-responder group (n = 15) compared to the antidepressant responder group (n = 15). In the training sample of 30 individuals, eight candidate genes had significantly altered expression according to quantitative real-time polymerase chain reaction. The expression of these genes was examined in an independent test sample of antidepressant responders (n = 22) and non-responders (n = 12). Using the discrete Bayes classifier with the HERC5, IFI6, and IFI44 genes identified in the training set yielded 85% discrimination accuracy for antidepressant responsiveness in the 34 test samples. Pathway analysis of the RNA sequencing data for antidepressant responsiveness identified that hypercytokinemia- and interferon-related genes were increased in non-responders. Disease and biofunction analysis identified changes in genes related to inflammatory and infectious diseases, including coronavirus disease. These results strongly suggest an association between antidepressant responsiveness and inflammation, which may be useful for future treatment strategies for depression

Metal-Organic Coordination Network Thin Film by Surface-Induced Assembly

The growth of metal-organic coordination network thin films on surfaces has been pursued extensively and intensively to manipulate the molecular arrangement. For this study, the oriented multilayer thin films based on porphyrinic nano-architecture were synthesized toward metal-organic coordination networks using surface-induced assembly (SIA). Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion and porphyrin building blocks as precursors. Stepwise growth with a highly uniform layer was characterized using UV-Vis, AFM, IR, and XPS studies. The grazing incidence small angle X-ray scattering (GI-SAXS) and X-ray reflectivity (XRR) results remarkably suggested a periodic structure in in-plane (IP) direction with constant and high mass density (ca. 1.5 g/cm＾3) throughout the multilayer formation. We propose that orientation of the porphyrin macrocycle plane with a hexagonal packed model by single anchoring mode was tilted approximately 60° with respect to the surface substrate. It is noteworthy that the well-organized structure of porphyrin-based macrocyclic framework on the amine-terminated surface substrate can be achieved efficiently using a simple SIA approach under mild synthetic conditions. The synthesized thin film provides a different structure from that obtained using bulk synthesis. This result suggests that the SIA technique can control not only the film thickness, but also the structural arrangement on the surface. This report of our research provides insight into the ordered porphyrin-based metal-organic coordination network thin films, which opens up opportunities for exploration of unique thin film materials for diverse applications

SRG Inscription in Supramolecular Liquid Crystalline Polymer Film: Replacement of Mesogens

The photoinduced surface relief formation via mass transfer upon irradiation with patterned light has long been a subject of extensive investigation. In azobenzene-containing liquid crystalline materials, UV light irradiation that generates the cis isomer leads to the liquid crystal to isotropic photochemical transition. Due to this phase change, efficiency of the mass transfer to generate a surface relief grating (SRG) becomes markedly greater. We have previously indicated that azobenzene-colored SRG-inscribed film can be bleached by removing a hydrogen-bonded azobenzene mesogen. However, this process largely reduces the height feature of the SRG corrugation. Herein, we propose an extended procedure where a colorless mesogen is filled successively after the removal of the azobenzene side chain. The process involves four stages: (i) SRG inscription in a hydrogen-bonded supramolecular azobenzene material; (ii) crosslinking (insolubilization) of the SRG film; (iii) removal of azobenzene mesogen by rinsing with a solvent, and (iv) stuffing the hollow film with a different mesogen. Although the final stuffing stage was insufficient at the present stage, this work demonstrates the possibility and validity of the strategy of mesogen replacement

Hydration and OH-/Br- Conduction Properties of Fluorene-Thiophene-Based Anion Exchange Thin Films Tethered with Different Cations

After trimethylammonium (TMA) and N-methylpiperidinium (Pip) functionalized fluorene-thiophene-based anion conductive polymers were synthesized for this work, the effect of cationic groups on hydration and conduction properties of OH-/Br- form fluorene-thiophene-based thin films were investigated. Fluorene-thiophene-based thin film carrying TMA showed superior OH- conductivity to that functionalized with Pip, above 10-2 S cm-1 at 25 °C under 95% relative humidity (RH), because it had higher ion exchange capacity (IEC), lower hydrophobicity, and smaller size of TMA. In situ temperature dependence OH- conductivity measurement process for the thin film form was established under different temperatures and 90% RH. The activation energies (Ea) of OH- conduction for thin films carrying TMA and Pip are 33.2 kJ mol-1 and 35.7 kJ mol-1. The Ea of OH- conduction was independent of the cation. This is the first systematic study of hydration and OH- conduction properties of anion exchange thin films

Photoalignment and Photofixation of Chromonic Mesophase in Ionic Linear Polysiloxanes Using a Dual Irradiation System

Photoalignment technology enables macroscopic alignment of liquid crystalline molecules and their aggregates in a non-contact process by irradiating photo-responsive liquid crystalline compounds with linearly polarized light. Because photoalignment techniques prevent dust generation and uneven stretching, and accomplish fine and complex patterning, they are involved in the practical process of fabricating display panels, and continue to be applied in the research and creation of various anisotropic materials. Brilliant yellow (BY), a chromonic liquid crystal, has attracted considerable attention as the photoalignment sublayer in recent years, because of its ability to induce a high dichroic nature among many photo-responsive liquid crystalline materials. However, its dichroism is not maintained after prolonged exposure to a humid environment because of its intrinsic strong hygroscopicity of ionic BY molecules. In this study, to overcome this drawback, the photoalignment and successive photo-fixation of the BY columnar phase is proposed using UV-curable ionic polysiloxane as a matrix. Visible light was used for the photoalignment of the BY columnar phase, and UV light for photo-fixation. Consequently, the columnar chromonic phase is found to retain its orientation even after 4 h of exposure to a highly humid environment

The Effect of a Topcoat with Amorphous Polymer Layers on the Mesogen Orientation and Photoalignment Behavior of Side Chain Liquid Crystalline Polymer Films

The mesogen orientations of liquid crystals are sensitive to the nature of the contacting surface. For side chain liquid crystalline polymer (SCLCP) films, most investigations have been conducted for thin films formed on a solid substrate surface such as glass, quartz and metal oxides, and little knowledge has been accumulated for SCLCP films whose top surface is covered by amorphous polymers. This work presents the effect of a topcoat with amorphous polymers placed on SCLCP films on the mesogen orientation and photoalignment behavior. When an SCLCP film that adopts a homeotropic mesogen orientation is covered with a glass plate or polymer layer, the mesogens turns to a random planar orientation. This planar orientation is favorable for efficient in-plane photoalignment by irradiation with linear polarized light. An in-plane order parameter exceeding 0.5 is readily obtained. Unexpectedly, a significant stabilization of the liquid crystal phase by over 10 °C is observed above the isotropization temperature of the SCLCP. These fundamental sets of knowledge should be significant in the fabrication of various polymer LC devices

The Effect of a Topcoat with Amorphous Polymer Layers on the Mesogen Orientation and Photoalignment Behavior of Side Chain Liquid Crystalline Polymer Films

The mesogen orientations of liquid crystals are sensitive to the nature of the contacting surface. For side chain liquid crystalline polymer (SCLCP) films, most investigations have been conducted for thin films formed on a solid substrate surface such as glass, quartz and metal oxides, and little knowledge has been accumulated for SCLCP films whose top surface is covered by amorphous polymers. This work presents the effect of a topcoat with amorphous polymers placed on SCLCP films on the mesogen orientation and photoalignment behavior. When an SCLCP film that adopts a homeotropic mesogen orientation is covered with a glass plate or polymer layer, the mesogens turns to a random planar orientation. This planar orientation is favorable for efficient in-plane photoalignment by irradiation with linear polarized light. An in-plane order parameter exceeding 0.5 is readily obtained. Unexpectedly, a significant stabilization of the liquid crystal phase by over 10 °C is observed above the isotropization temperature of the SCLCP. These fundamental sets of knowledge should be significant in the fabrication of various polymer LC devices