Mesomorphism and luminescence properties of platinum(II) complexes with tris(alkoxy)phenyl-functionalized pyridyl pyrazolate chelates

A series of new mesomorphic platinum(II) complexes 1 – 4 bearing pyridyl pyrazolate chelates are reported herein. In this approach, pyridyl azolate ligands have been strategically functionalized with tris(alkoxy)phenyl groups with various alkyl chain lengths. As a result, they are ascribed to a class of luminescent metallomesogens that possess distinctive morphological properties, such as their intermolecular packing arrangement and their associated photophysical behavior. In CH₂Cl₂, independent of the applied concentration in the range 10^?6–10^?3 M , all Pt^II complexes exhibit bright phosphorescence centered at around 520 nm, which is characteristic for monomeric Pt^II complexes. In stark contrast, the single‐crystal X‐ray structure determination of [Pt(C4pz)₂] ( 1 ) shows the formation of a dimeric aggregate with a notable Pt???Pt contact of 3.258 Å. Upon heating, all Pt^II complexes 1 – 4 melted to form columnar suprastructures, for which similar intracolumnar Pt???Pt distances of approx. 3.4–3.5 Å are observed within an exceptionally wide temperature range (>250 °C), according to the powder XRD data. Upon casting into a neat thin film at RT, the luminescence of 1 – 4 is dominated by a red emission that spans 630–660 nm, which originates from the one‐dimensional, chainlike structure with Pt–Pt interaction in the ground state. Taking complex 4 as a representative, the emission intensity and wavelength were significantly decreased and blueshifted, respectively, on heating from RT to 250 °C. Further heating to liquefy the sample alters the red emission back to the green phosphorescence of the monomer. The results highlight the pivotal role of tris(alkoxy)phenyl groups in the structural versus luminescence behavior of these Pt^II complexes.     

Two new phenylalkanoids from the rhizomes of Zingiber officinale

Two new phenylalkanoids, 5-hydroxy-1-(4',5'-dihydroxy-3'-methoxy-phenyl)-decan-3-one and 1-(4',5'-dihydroxy-3'-methoxy-phenyl)-dec- 4-en-3-one, were isolated from the rhizomes of Chinese ginger (Zingiber officinale Roscoe (Zingiberaceae)). The structures of these new phenylalkanoids were elucidated by chemical and physical evidence.     

A priori estimate for non-uniform elliptic equations

A priori estimate for non-uniform elliptic equations with periodic boundary conditions is concerned. The domain considered consists of two sub-regions, a connected high permeability region and a disconnected matrix block region with low permeability. Let ? denote the size ratio of one matrix block to the whole domain. It is shown that in the connected high permeability sub-region, the Hölder and the Lipschitz estimates of the non-uniform elliptic solutions are bounded uniformly in ?. But Hölder gradient estimate and Lp estimate of the second order derivatives of the solutions in general are not bounded uniformly in ?.     

Isocratic Separation of Dansylated Biogenic Amines on a C8‐Bonded Silica Column under the LC Elution of Methanol‐Based Mobile Phase

Under the elution of methanol‐based mobile phase, the isocratic resolution of 12 biogenic amines, including 1 aromatic, 2 heterocyclic and 9 aliphatic amines, as the dansylated derivatives has been accomplished in less than 25 minutes on a 15 cm C₈‐bonded column. The resolution can not be reproduced on other examined alkyl‐bonded phases (e.g., C₄ and C₁₈) under the same chromatographic conditions, or in the reversed‐phase mode. The retention, mainly as a result of hydrophobic interaction between analyte and stationary phase, can be adjusted by varying the percentage of methanol in the mobile phase. Also, incorporating acetic acid as additive to the mobile phase to protonate the analyte and silanol groups that are little shielding on the surface of silica gel reduces the dipole‐dipole interaction, and thus the retention scale, which in turn deteriorates the resolution. Furthermore, the elution reversal is plausible for some of analytes as a greater percent of acetic acid is used in the elution. Values of correlation coefficients (R²) range between 0.9995 and 0.9996, indicating good linearity.     

Hammett correlations in the chemistry of 3-phenylpropyl radicals

The energetics and kinetics of the reaction of variously substituted benzyl radicals with a model alkene were calculated at the G3(MP2)-RAD//B3-LYP/6-31G(d) level of theory to determine whether such reactions are amenable to Hammett analysis. The reactions were studied both in the gas phase and in toluene solution in the temperature range 298-353 K; calculations include 1D-hindered rotor corrections for low frequency torsional modes, and the solvation energies were calculated using COSMO-RS at the BP/TZP level of theory. The addition reaction was found to be dominated by radical stabilization effects, but under circumstances where olefin substituent effects were decoupled from aryl substituent effects, a modest polar effect comes into play, which is enhanced by solvation. Reasonable correlations with empirical substituent parameters such as Hammett σ and σ(?) are observed for the enthalpy of activation, but additional entropic factors act to decrease the degree of correlation with respect to free energies and rate coefficients, confirming hypotheses from earlier experimental work. Substituent effects on the reverse β-fragmentation reaction, and potential cyclization of the 3-phenylpropyl radicals formed by addition are also discussed.     

Synthesis of cationic quantum dots via a two-step ligand exchange process

A new class of quaternary ammonium derivatives has been used to synthesize cationic CdSe/ZnS quantum dots with exceptional stability in water as well as in biological media.     

Antibacterial characteristics and activity of water-soluble chitosan derivatives prepared by the Maillard reaction

The antibacterial activity of water-soluble chitosan derivatives prepared by Maillard reactions against Staphylococcus aureus, Listeria monocytogenes, Bacillus cereus, Escherichia coli, Shigella dysenteriae, and Salmonella typhimurium was examined. Relatively high antibacterial activity against various microorganisms was noted for the chitosan-glucosamine derivative as compared to the acid-soluble chitosan. In addition, it was found that the susceptibility of the test organisms to the water-soluble chitosan derivative was higher in deionized water than in saline solution. Metal ions were also found to reduce the antibacterial activity of the water-soluble chitosan derivative on S. aureus. The marked increase in glucose level, protein content and lactate dehydrogenase (LDH) activity was observed in the cell supernatant of S. aureus exposed to the water-soluble chitosan derivative in deionized water. The results suggest that the water-soluble chitosan produced by Maillard reaction may be a promising commercial substitute for acid-soluble chitosan.     

Synthesis of hexagonal ZnO clubs with opposite faces of unequal dimensions for the photoanode of dye-sensitized solar cells

Novel sub-micro sized hexagonal clubs of ZnO (HC-ZnO), which are coated as a scattering layer (SL) for the photoanode of a DSSC, are synthesized. X-ray diffraction (XRD) patterns of the ZnO clubs show clear peaks corresponding to wurtzite crystal phase of ZnO. Scanning electron microscopic (SEM) images show that each club has two opposite hexagonal faces (parts) of unequal dimensions. High resolution transmission electron microscopic (HR-TEM) image of a single ZnO club reveals that the ZnO is single crystalline and has wurtzite crystal structure; the image indicates a lattice spacing (d) of 0.26 nm; this is ascribed to the (002) planar spacing of the hexagonal ZnO. A solar-to-electricity conversion efficiency (η) of 3.36% is achieved for the cell with the double layer (DL) film, which is 16% higher than that of the cell with only transparent layer (TL) of commercial ZnO (2.89%) and far higher than that of the cell with SL (0.05%). The η of the cell with the DL (3.36%) could further be improved to 4.28% through the modification of the DL surface with TiO(x). Incident photo-to-current conversion efficiency (IPCE) curves, UV-vis absorption spectra, energy dispersive X-ray (EDX) spectra, and electrochemical impedance spectra (EIS) are also used to substantiate the results.     

On the Congruences of Some Combinatorial Numbers

In this paper, we apply Lucas' theorem to evaluate the congruences of several combinatorial numbers, including the central Delannoy numbers and a class of Apéry-like numbers, the numbers of noncrossing connected graphs, the numbers of total edges of all noncrossing connected graphs on n vertices, etc. One of these results verifies a conjecture given by Deutsch and Sagan recently. In the end, we use an automaton to explain the idea of our approach.