Transition metal ion directed supramolecular assembly of one- and two-dimensional polyrotaxanes incorporating cucurbituril

This paper reports a synthetic strategy to construct one- and two-dimensional (1D and 2D) polyrotaxanes, in which a number of rings are threaded onto a coordination polymer, by the combination of self-assembly and coordination chemistry. Our approach to construct polyrotaxanes with high structural regularity involves threading a cucurbituril (CB) "bead" with a short "string" to form a stable pseudorotaxane, followed by linking the pseudorotaxanes with metal ions as "linkers" to organize into a 1D or 2D polyrotaxane. A 4- or 3-pyridylmethyl group is attached to each end of 1,4-diaminobutane or 1,5-diaminopentane to produce the short "strings", which then react with the cucurbituril "bead" to form stable pseudorotaxanes. The reaction of the pseudorotaxanes with various transition metal ions including CuII, CoII, NiII, AgI, and CdII produces 1D or 2D polyrotaxanes, in which many molecular "beads" are threaded onto 1D or 2D coordination polymers as confirmed by X-ray crystallography. The overall structure of a polyrotaxane is the result of interplay among various factors that include the coordination preferences of the metal ion, spatial disposition of the donor atoms with respect to the CB beads in the pseudorotaxane, and the size and coordination ability of the counteranion.     

Visualization of natural convection heat transfer on horizontal cylinders

Natural convection heat transfer phenomena on horizontal cylinders were investigated experimentally in order to explore the applicability of analogy experimental method using the copper electroplating system and to visualize the local heat transfer depending on the angular position and the diameter of the horizontal cylinder. The diameters of the cylinders are varied from 0.01 to 0.15 m, which correspond to the Rayleigh numbers of 1.73 × 10⁷–5.69 × 10¹¹. The measured mass transfer coefficients show good agreements with the existing heat transfer correlations. The patterns of copper plated on the aluminum cathodes for various Rayleigh numbers reveal and visualize the local heat transfer depending on the angular position and show good agreement with the works of Kitamura et al. The hydrogen bubbles produced at higher applied potential visualize the plumes appeared on top region of the cylinders.     

A compact finite difference method for solving Burgers' equation

In this paper, a high‐order accurate compact finite difference method using the Hopf–Cole transformation is introduced for solving one‐dimensional Burgers' equation numerically. The stability and convergence analyses for the proposed method are given, and this method is shown to be unconditionally stable. To demonstrate efficiency, numerical results obtained by the proposed scheme are compared with the exact solutions and the results obtained by some other methods. The proposed method is second‐ and fourth‐order accurate in time and space, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

DNA methylome and single-cell transcriptome analyses reveal CDA as a potential druggable target for ALK inhibitor–resistant lung cancer therapy

Acquired resistance to inhibitors of anaplastic lymphoma kinase (ALK) is a major clinical challenge for ALK fusion-positive non-small-cell lung cancer (NSCLC). In the absence of secondary ALK mutations, epigenetic reprogramming is one of the main mechanisms of drug resistance, as it leads to phenotype switching that occurs during the epithelial-to-mesenchymal transition (EMT). Although drug-induced epigenetic reprogramming is believed to alter the sensitivity of cancer cells to anticancer treatments, there is still much to learn about overcoming drug resistance. In this study, we used an in vitro model of ceritinib-resistant NSCLC and employed genome-wide DNA methylation analysis in combination with single-cell (sc) RNA-seq to identify cytidine deaminase (CDA), a pyrimidine salvage pathway enzyme, as a candidate drug target. CDA was hypomethylated and upregulated in ceritinib-resistant cells. CDA-overexpressing cells were rarely but definitively detected in the naïve cell population by scRNA-seq, and their abundance was increased in the acquired-resistance population. Knockdown of CDA had antiproliferative effects on resistant cells and reversed the EMT phenotype. Treatment with epigenome-related nucleosides such as 5-formyl-2′-deoxycytidine selectively ablated CDA-overexpressing resistant cells via accumulation of DNA damage. Collectively, our data suggest that targeting CDA metabolism using epigenome-related nucleosides represents a potential new therapeutic strategy for overcoming ALK inhibitor resistance in NSCLC.Subject terms: Gene expression, Epigenomics, Non-small-cell lung cancer     

Homogeneous alignment of liquid crystals on low-temperature solution-derived gallium oxide films via IB irradiation method

In this paper, solution-derived gallium oxide (GaO) films are fabricated for the homogeneous alignment of liquid crystals (LCs) after an ion-beam (IB) irradiation process. GaO thin films are prepared under a variety of temperatures and different IB irradiation intensities, and the physicochemical performances of the fabricated GaO thin films are analysed using a UV-vis spectrometer, an atomic force microscope, and X-ray photoelectron spectroscopy. A higher transmittance of 85.40% from GaO thin film is obtained compared with that of polyimide (PI) film (83.52%), which indicates the feasibility for a GaO thin layer to substitute for a conventional PI layer as an alignment layer. LCs are found to align on the GaO thin film after pre-baking at 100°C and homogeneous and uniform low-IB intensity irradiation. We also determined the electro-optical (EO) characteristics of the twisted nematic (TN) cells fabricated with GaO thin layers and found them to be similar to those of cells fabricated with PI layers. Overall, GaO films achieved via the IB irradiation method are promising LC alignment layers due to the method’s low-temperature solution-derived process.     

Mitochondrial pyruvate dehydrogenase phosphatase 1 regulates the early differentiation of cardiomyocytes from mouse embryonic stem cells

Mitochondria are crucial for maintaining the properties of embryonic stem cells (ESCs) and for regulating their subsequent differentiation into diverse cell lineages, including cardiomyocytes. However, mitochondrial regulators that manage the rate of differentiation or cell fate have been rarely identified. This study aimed to determine the potential mitochondrial factor that controls the differentiation of ESCs into cardiac myocytes. We induced cardiomyocyte differentiation from mouse ESCs (mESCs) and performed microarray assays to assess messenger RNA (mRNA) expression changes at differentiation day 8 (D8) compared with undifferentiated mESCs (D0). Among the differentially expressed genes, Pdp1 expression was significantly decreased (27-fold) on D8 compared to D0, which was accompanied by suppressed mitochondrial indices, including ATP levels, membrane potential, ROS and mitochondrial Ca²⁺. Notably, Pdp1 overexpression significantly enhanced the mitochondrial indices and pyruvate dehydrogenase activity and reduced the expression of cardiac differentiation marker mRNA and the cardiac differentiation rate compared to a mock control. In confirmation of this, a knockdown of the Pdp1 gene promoted the expression of cardiac differentiation marker mRNA and the cardiac differentiation rate. In conclusion, our results suggest that mitochondrial PDP1 is a potential regulator that controls cardiac differentiation at an early differentiation stage in ESCs.     

Absorption and photoluminescence of PbS QDs in glasses

Optical properties of PbS quantum dots (QDs) precipitated inside the oxide glass matrix were investigated. Photoluminescence (PL) from the PbS QDs showed peak wavelengths located at 1170–1680 nm with widths of 150–550 nm. Radii of QDs in glasses were 2.3–4.7 nm depending upon the thermal treatment. Peak wavelengths of PL bands shifted as much as 70 nm as the temperatures and excitation irradiances increased. Calculated effective local temperatures indicated that these shifts of PL spectra were associated with local heating induced by the temperatures and laser beam.     

Conformation‐Specific Circular Dichroism Spectroscopy of Cold,Isolated Chiral Molecules

The CD spectroscopy of a chiral compound in solution yields an average CD value derived from all of the conformations of a chiral molecule. By contrast, CD spectroscopy of cold chiral molecules in the gas phase distinguishes specific conformers of a chiral molecule, but the weak CD effect has limited the practical application of this technique. Reported herein is the first resonant two‐photon ionization CD spectra of ephedrines in a supersonic jet using circularly polarized laser pulses, which were generated by synchronizing the oscillation of the photoelastic modulator with the laser firing. The spectra exhibited well‐resolved CD bands which were specific for the conformations and vibrational modes of each enantiomer. The CD signs and magnitudes of the jet‐cooled chiral molecules were very sensitive to their conformations and thus offered crucial information for determining the three‐dimensional structures of chiral species, as conducted in combination with quantum chemical calculations.