Molecular crystals are among the states of matter containing the largest number of thermodynamic degrees of freedom concerning spin, charge, orbital, and structure. However, many of them cannot be fully controlled to realize the unique physical properties and novel electronic states because of the thermodynamic instability of the molecular crystals. We will review here the evidence that optical excitation is a powerful tool, independent of thermodynamic conditions, to realize unique physical properties and electronic states otherwise unrealized.
Over 150 different types of modifications have been found in nucleic acids so far. The modification in nucleic acids now is recognized as a new layer in regulating gene expression. Elucidation of the functional roles of these modifications is critical to understand living organisms and the molecular mechanism of diseases. The abundance of most of the modifications is extremely low. Thus, deciphering the biological roles of these modifications requires sensitive analytical methods. In recent years, substantial advances have been achieved in the development of analytical strategies and methods for determining and quantifying nucleic acid modifications. Owing to the good detection sensitivity and capability in qualitative analysis of modifications, mass spectrometry (MS) has been widely employed in studying nucleic acid modifications. Here we review the recent MS-based methodological advances, with more focus on the chemical derivatization in conjugation with MS detection for analyzing nucleic acid modifications.
Porous polyurea films were synthesized by vapor deposition polymerization via ionic liquid (IL) nano thin films with different thicknesses, and the water contact angles (WCAs) on the polyurea films were measured. The promotion of polymerization and its accompanying porous structural formation became detectable for IL thicknesses above ∼20 nm. The WCA tended to increase with an increase of surface roughness of the porous polyurea films. The mechanism of such IL-assisted polymerization and porous structural formation will be discussed.
Boron-doped diamond powder (BDDP) was prepared using various sizes of diamond powder (DP) core (300–2600 nm), and the electrochemical properties of a screen-printed electrode obtained using the BDDP ink were investigated. The use of larger DP cores led to faster growth rate of the BDD layer on the DP core surface and lower sp2 carbon impurities content. Screen-printed electrodes prepared using large BDDPs showed wide potential window, low background current, and good electrochemical response, including direct oxidation of bovine serum albumin.
The new inclusion compound [(CH3)2NH2][CuZn(CN)4]·nH2O, whose host is a 3-D coordination polymer net formed with tetrahedral Cu(I) and Zn(II), as well as bridging cyanido ligands, exhibited a new type of structural transformation upon desorption/absorption of the guest water. This consisted of a reversible reconstruction of the host between a cristobalite-like and tridymite-like net. 63Cu solid-state NMR showed the conservation of the orientation of the cyanido bridges during the structural transformation, which required the breaking and reforming of the coordination bonds.
Inspired by the lotus leaf, a kind of superhydrophobic and oleophilic ceramic membrane was prepared through a simple ZnO nano sol coating and subsequent hexadecyltrimethoxysilane (HDTMS) grafting. The surface morphology and chemical composition analysis confirm the presence of HDTMS-ZnO coating on ceramic membrane surface. Contact angle tests confirm the superhydrophobic membrane surface. The prepared membranes also show stable performance for efficient dewatering of water-in-oil emulsions, which has potential practical value in industrial applications and environmental protection.
Two-photon absorption behavior of dispersion of solid solution nanocrystals of ZnS-AgInS2 was investigated, the measured maximum two-photon absorption cross-section of this nanoparticle being 3900 GM (1 GM = 10−50 cm4 s photon−1 mol(particle)−1) at 850 nm. The two-photon excited red photoluminescence was observed even by using a femtosecond fiber laser oscillating at 1030 nm.
Phosphorene has great potential in many applications. Here in this work, we succeed in exfoliating phosphorene directly in water by using sonication and microwave without additives, wherein violent oscillation generated by sonication facilitates intercalation of water into black phosphorus interlayers, and then the microwave further exfoliates the black phosphorus into phosphorene. The result demonstrates that this exfoliation method offers outstanding exfoliation efficiency. More importantly, the phosphorene dispersions exfoliated by our method may be directly used for future applications development.
In this work, Pt/TiO2 catalysts were synthesized by a simple sol-gel method at different calcination temperatures. TEM study revealed 5 nm particles of Pt/TiO2 calcined at 400 °C. BET surface area decreased with an increase in the calcination temperature of Pt/TiO2 catalysts. The catalytic order for the hydrogen-iodide decomposition reaction was as follows: Pt/TiO2-400 > Pt/TiO2-500 > Pt/TiO2-600. Pt/TiO2-400 achieved equilibrium conversions at 500–550 °C. This catalyst also showed a good stability for a time period of 3 h.
A Cu(I) complex of bisamidine-type sp2N bidentate ligand, Naph-diPIM, catalyzes coupling between 1,3-dicarbonyl compounds and simple cyclic alkenes using (t-BuO)2, providing the corresponding C-allylation products with up to >99:1 diastereomer ratio together with easily removable t-BuOH coproduct. The first success in dehydrogenative C-allylation in the clean and simple reaction system has been extended to the asymmetric C-allylation giving up to 81:19 enantiomer ratio.
The effect of deuterium oxide (D2O) on the stabilization of membrane structure in human erythrocytes was examined on the basis of hemolysis under high pressure and extraction of cytoskeletal proteins from the membrane under hypotonic conditions. Pressure-induced hemolysis was suppressed by D2O, which strengthens the membrane-cytoskeleton interaction.
Time-dependent density functional theory (TD-DFT) calculations were performed on eighty-six fundamental organic compounds to examine the prediction performance for refractive indices and wavelength dispersions in the visible wavelength region of three hybrid functionals, B3LYP, CAM-B3LYP, and ωB97XD with ten kinds of Pople-type basis set functions ranging from 6-31G(d) to 6-311++G(2d,2p). The refractive indices were estimated using calculated values of wavelength-dependent molecular polarizabilities and experimental densities based on the Lorentz-Lorenz formula. Geometry optimization with CAM-B3LYP/6-31G(d,p) followed by a polarizability calculation with CAM-B3LYP/6-31+G(2d,p) gave sufficiently reliable results within a reasonable amount of computation time.
Extracellular matrix (ECM) plays important roles in the maintenance of neural stem cell (NSC) stemness. However, it remains unclear how ECM maintains NSC stemness comprehensively. Here, ECM was formed by the adherent MEB5 culture, and a murine NSC line and formed ECM was prepared as a culture substrate by decellularization. The prepared substrates can support MEB5 adhesion and growth and might influence neural differentiation. The prepared ECM model might be used as an in vitro ECM model in NSC niche.
An instantaneously usable fully printed paper-based three-electrode system was developed for use as cost-effective and disposable biosensors and ion sensors. The three-electrode system was composed of a carbon working electrode, counter electrode, and an integrated Ag/AgCl reference electrode with an inner saturated KCl layer and a liquid junction. The potential stability of the reference electrode was approximately 99 h. The setup time was less than 1 min.
Effective light-driven conversion of CO2 to formic acid with a hybrid system consisting of photocatalyst TiO2 nanoparticle (P25), methylviologen (MV2+) as an electron mediating molecule and biocatalyst formate dehydrogenase (FDH) in the presence of triethanolamine (TEOA) as an electron donating molecule was investigated. After 120 min irradiation with a Xe lamp (>300 nm), 152 µM of formic acid was produced in a CO2 saturated buffer solution containing TEOA (300 mM), TiO2 nanoparticles (6.8 mg·L−1), MV2+ (0.5 mM) and FDH (7.5 µM).
2-Methacryloyloxyethyl choline phosphate (MCP) was synthesized by a ring-opening reaction of cyclic phosphates with 2-(dimethylaminoethyl methacrylate). The crude MCP consisted of an endo-cyclic desired product and an exo-cyclic byproduct. The exo-cyclic byproduct was completely removed by anion-exchange and subsequent open-column chromatography. We successfully obtained pure MCP without the exo-cyclic byproduct, and synthesized MCP polymers by free radical polymerization.
Effects of nine incorporated n-alkane derivatives on molecular packing and phase behavior of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayers were investigated using wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The incorporation commonly resulted in closer packing of the lipid alkyl chains in the ordered phase and shift of the thermal anomaly due to the main transition to a higher temperature. These common features suggest that effects of incorporated molecules on structure and phase behavior of DPPC bilayers can be classified by their shape.
An easily segregated adsorbent for highly efficient removal of mercuric (Hg(II)) ions from aqueous media remains a great challenge. Herein, A novel Fe3O4@MoS2 core-shell magnetism nanocomposite with rich sulfur in the shell was fabricated through a facile in-situ hydrothermal method, which has high adsorption efficiency and good selectivity for Hg(II) ions and can be easily removed by magnetic separation. Thus, Fe3O4@MoS2 can act as a potential adsorbent for highly efficient removal of Hg(II) ions from aqueous media.
Amphiphilic block copolymers composed of polyacrylamide (PAAm) bearing maltose (Mal) moieties, poly(N-tert-butylacrylamide) (PTBAAm) segments, and a terminal acryloyl group were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene reaction. The resulting glycopolymer-type macromonomers were used to prepare Mal-decorated polymer particles by dispersion copolymerization of the Mal-bearing block copolymers with styrene. The carbohydrate-decorated polymer particles in aqueous suspension were specifically recognized by the lectin Concanavalin A (Con A).
Novel environmentally friendly inorganic orange pigments based on Ca14(Al1−xFex)10Zn6O35 (0 ≤ x ≤ 0.30) were synthesized using a solid-state reaction method. The Fe3+-doped samples strongly absorbed visible light at wavelengths from 380 to 490 nm due to the d–d (6A1→4E) transition of Fe3+. In addition, the optical absorption around 600 nm, corresponding to the 6A1→4T2 transition of Fe3+, also increased with increasing the Fe3+ concentration. The sample color gradually turned from yellow to orange as the Fe3+ content increased.
Ba2In2O5 (BG 3.0 eV) with a brownmillerite structure has arisen as a novel photocatalyst for water splitting under UV irradiation. Ba2−xLaxIn2O5+0.5x (x = 0.04) with a brownmillerite structure had the same band gap as Ba2In2O5 and showed higher activity for water splitting than Ba2In2O5. Ba2−xLaxIn2O5+0.5x (x = 0.5, 0.66, 0.75) possessed a perovskite structure and absorption bands in a visible light region. Although the water splitting activities decreased by La-substitution, they showed activities for sacrificial H2 evolution in visible light.
An ammonium–proton exchange in double-four-ring (D4R) spherosilicate [Si8O20][NMe4]8 with Meldrum’s acid in N,N-dimethylacetamide afforded the corresponding silanol [Si8O12][OH]8 (1), which was purified successively by gel permeation chromatography and recrystallization. The single-crystal X-ray diffraction analysis of 1, which is the first of its kind, unambiguously revealed the structure of 1. Silanol 1 obtained via this procedure does not contain water and could thus be treated with the moisture-sensitive chlorosilane Me2HSiCl to afford the corresponding silylated product [Si8O12][OSiMe2H]8.
We report on the preparation and characterization of a thiazole-fused polycyclic compound containing an s-indacene chromophore, which has the characteristics of an antiaromatic system. X-ray analysis showed that the fused π-conjugated backbone has a planar structure. Theoretical investigations indicate that the introduction of thiazole rings contributes to decreasing the frontier orbital energy level while permitting the antiaromatic character of the compound to be retained. Physical measurements indicate that the characteristic properties and structures originates from the antiaromatic framework. This study provides an effective method for the chemical modification of s-indacene chromophores with a high electron affinity.
Twelve selected compounds were evaluated for their MIC values against Propionibacterium acnes and Staphylococcus aureus by broth microdilution method. The highest antibacterial activities were observed from 4 with MIC values of 0.50 and 0.99 µg/mL, followed by 5 at 1.88 and 0.94 µg/mL, respectively. The synergistic effect of those selected compounds with tetracycline was evaluated by chekerboard method. Their activity enhancement with tetracycline in combination was observed compared with using a single compound. The combination of 6 with tetracycline displayed the most potent synergistic effect to enhance the antibacterial activity against P. acnes while the combination of 9 and tetracycline revealed the most competent against S. aureus.
We herein report the oxidation efficiency of different concentration ammonia waters via a complex photocatalyst of zeolite and TiO2 under UV light. The generated NO2− and NO3− concentrations were highest when a high concentration of ammonia was oxidized by zeolite–TiO2. The prepared photocatalyst was characterized via X-ray diffraction, and Brunauer–Emmett–Teller surface area measurement.
A confocal X-ray diffractometer that can investigate depth distributions of the crystal phases inside materials was developed. Diffraction was measured by scanning the polycapillary focusing optics that receive scattering X-rays while maintaining the confocal point with the polycapillary of the incident X-rays. It was possible to acquire information corresponding to the thickness and depth of each constituent material, distinguish between the surface and the interior of the materials, and observe chemical changes that depend on the depth in the material.