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.     

Highly Stable,Water‐Dispersible Metal‐Nanoparticle‐Decorated Polymer Nanocapsules and Their Catalytic Applications

A facile synthesis of highly stable, water‐dispersible metal‐nanoparticle‐decorated polymer nanocapsules (M@CB‐PNs: M=Pd, Au, and Pt) was achieved by a simple two‐step process employing a polymer nanocapsule (CB‐PN) made of cucurbit[6]uril (CB[6]) and metal salts. The CB‐PN serves as a versatile platform where various metal nanoparticles with a controlled size can be introduced on the surface and stabilized to prepare new water‐dispersible nanostructures useful for many applications. The Pd nanoparticles on CB‐PN exhibit high stability and dispersibility in water as well as excellent catalytic activity and recyclability in carbon–carbon and carbon–nitrogen bond‐forming reactions in aqueous medium suggesting potential applications as a green catalyst.     

Isolation of Anti-Diabetic Active Compounds from Benincasae Exocarpium and Development of Simultaneous Analysis by HPLC-PDA

Diabetes is a chronic metabolic disease that is a constant problem. Previous studies have reported that Benincasa cerifera Savi. extracts are effective in treating diabetes and its complications. Benincasae Exocarpium (BE) is a fruit peel of B. cerifera that has been reported to be used for the prevention and treatment of metabolic diseases such as hyperglycemia, obesity, and hyperlipidemia. However, there are not enough studies on the compounds and bioassays to support the efficacy of BE. The inhibitory activity of the BE extracts and fractions against advanced glycation end-products (AGE) formation and α-glucosidase activity was evaluated. These assays are relevant for the treatment of type 2 diabetes and its complications. Based on these results, compounds 1–11 were isolated through bioassay-guided isolation. In addition, we developed a high-performance liquid chromatography (HPLC) method that can simultaneously analyze these 11 compounds. Activity evaluation of the compounds was also conducted, and eight compounds exhibited significant activity. Among these, flavonoid compounds showed strong activity. A quantitative evaluation of eight bioactive compounds (2, 5–11) was conducted. In conclusion, this study demonstrated the potential of BE for prevention and treatment of type 2 diabetes and its complications.     

Synthesis of chitin derivatives and their metal complexes

Thiosemicarbazide, phosphoric acid and amidoxime derivatives of chitosan were synthesized and their ability for metal ion adsorptions was discussed. Thiosemicarbazide derivative, synthesized by treating chlorodeoxychitosan with ammonium thiocyanate followed by treatment with hydrazine, was considered to have cross-linked network structure. Phosphoric acid derivative containing both N-phosphonic acid and phosphoric acid groups was synthesized by cyanoethylation of chitosan using acrylonitrile, followed by treatment with hydroxylamine. These derivatives were found to adsorb effectively infinitesimal concentration (ppb order) of uranyl ion in seawater. Stability constants of some metal ion chitosan chelates were determined. To improve the selectivity in the adsorption of metal ions, a novel method utilizing metal ion as a template was adopted, and the results are discussed.     

Stereocontrolled enantioselective addition of diethylzinc to aldehydes using new chiral aminoalcohols

The new chiral β-aminoalcohols of indolinylmethanols ( 1 ) and their reduced derivatives ( 2 ) were synthesized from (S)-indoline-2-carboxylic acid. Both (R) and (S) enantiomers of the optically active secondary alcohols have been successfully obtained in high enantiomeric excess from the stereoselective addition of diethylzinc to the aldehydes catalyzed by the chiral aminoalcohols ( 1 and 2 ). The sense of the asymmetric induction and the degrees of enantioselectivities turned out to be highly dependent on the structure of the catalysts: The presence of the catalyst 1 afforded the (S)-configuration of the corresponding alcohols; on the other hand, the presence of 2 afforded the (R)-configuration of the alcohols in high enantiomeric selectivity.     

Electro chemical properties of porous PVdF-HFP membranes prepared with different nonsolvents

Porous poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) membranes were prepared by solvent–nonsolvent evaporation technique. Morphology and porosity of the membranes were varied with different nonsolvents and had an effect on electrochemical properties. The porous membranes were functionalized with different liquid electrolyte solutions such as p-toluene sulfonic acid/phosphoric acid/sulfuric acid. Maximum electrolyte uptake and minimal electrolyte leakage were tailored by the optimized porosity of the membranes. Thermal behavior obtained in this study ensures the complete evaporation of nonsolvents and ensures its thermal stability. The pTSA-activated PVdF-HFP/THF membrane exhibited high ionic conductivity of about 27.27 mS/cm and a lower methanol permeability in the range of 9.7 × 10⁻⁸ cm²/s. High compatibility between pTSA solution and porous PVdF-HFP polymer electrolyte membrane enhances its electro chemical behavior than that of conventional liquid electrolytes.     

Redox equilibria of iron oxides in aqueous-based magnetite dispersions: effect of pH and redox potential

The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.     

Electrochemistry, electrogenerated chemiluminescence, and excimer formation dynamics of intramolecular π-stacked 9-naphthylanthracene derivatives and organic nanoparticles

We report the electrochemical characterization and the observation of excimer emission from a series of 9-naphthylanthracene-based dimer- and trimer-bridged high steric hindrance aromatic groups during photoluminescence (PL) measurements in the solid state and in solution electrogenerated chemiluminescence (ECL) measurements. Cyclic voltammetry of 4,4'-bis(9-(1-naphthyl)anthracen-10-yl)biphenyl (4A) and 1,3,5-tris(9-(1-naphthyl)anthracen-10-yl)benzene (4C) showed two or three reversible, closely spaced one-electron transfers on oxidation in dichloromethane. The ECL emission spectra of 4A and 4C resulting from the annihilation reaction in benzonitrile showed two bands: one at the same wavelength as the PL peak in the solution state, and a broad band at longer wavelength. With a coreactant, such as peroxydisulfate, ECL spectra showed a single peak that was less broad in shape. PL measurement in the solid state and measurement of representative time traces of PL intensity, lifetimes, and picosecond time-correlated single-photon counting confirmed excimer emission at long wavelength. A reprecipitation method was used to prepare well-dispersed organic nanoparticles (NPs) of 4A in both aqueous and acetonitrile solutions. The smallest stable size of NPs produced was ~15 ± 6 nm, as analyzed by transmission electron microscopy. These organic NPs produced stable and weak ECL emission from the annihilation reaction in both aqueous and MeCN solutions. With a coreactant, such as peroxydisulfate, the ECL signal on reduction was sufficiently strong to obtain an ECL spectrum.     

Label‐Free Biosensing over a Wide Concentration Range with Photonic Force Microscopy

We present a label‐free biosensor that measures molecular interactions between biomolecules on the surface of a probe bead and substrate over a wide concentration range. This system is capable of detecting target biomolecules with concentrations varying from 10 nM to 0.1 pM , with high selectivity and sensitivity.