[reaction: see text] The side product from homocoupling reaction of two terminal acetylenes in the Sonogashira reaction can be reduced to about 2% using an atmosphere of hydrogen gas diluted with nitrogen or argon. Terminal arylethynes, diarylethynes, and a few new arylpyridylethynes with donor substituents have been synthesized in very good yields. Comparative control experiments suggest that the homocoupling yield is determined by concentration of both catalyst and oxygen.
An attempt to tune the electronic properties of pyrene (Py) by coupling it with a strong electron donor (-PhNMe2, DMA)/acceptor (anthronitrile, AN) through an ethynyl bridge has been undertaken. A moderate electron donor (iPrOPh-, IPP)/acceptor (2-quinolinyl, 2Q) has also been incorporated, and all four molecules were studied with reference to a neutral molecule, namely, 1-phenylethynylpyrene (PhEPy). All the arylethynylpyrenes (ArEPy's) have been thoroughly characterized, and their electronic properties were studied by absorption and emission spectral properties of these ArEPy's. The electrochemical characteristics were also studied for arriving at the electrochemical band gap which has been compared with the HOMO-LUMO energy gap derived from the photophysical measurements and theoretical calculations performed by density functional theory (DFT) using B3LYP/6-31G basis sets. The results obtained from experimental and theoretical studies are critically discussed.
γ‐(D,L)‐Polyglutamic acid [γ‐(D,L)‐PGA, or γ‐PGA] produced by Bacillus subtilis (natto) both on laboratory and pilot scale fermenter systems has been characterized. γ‐PGA in its free acid form (H+) is insoluble in water. The salt forms of K+, Na+, NH4+, Ca2+, and Mg2+ of γ‐polyglutamates are fully soluble in water. The structural characteristics of the salts of γ‐Polyglutamates (Na+, K+, NH4+, Ca2+, and Mg2+) were determined with 1H‐ and 13C‐NMR spectroscopy and FT‐IR spectroscopy. The thermal properties were determined with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The typical physical and chemical properties including pH‐titration curve, concentration‐dependent viscosity temperature‐dependent viscosity, and heavy metal binding properties with Pb2+, Cd2+, and Cu2+ were also determined. The biological functionalities were partially characterized with in vivo feeding studies with broilers and egg‐layers, and activation of GTF (Glucose tolerance factor) activity with rat 3T3‐L1 cell culture studies. γ‐(D,L)‐Polyglutamic acid [γ‐(D,L)‐PGA] appears to have five different conformations depending on the environmental conditions. They are the α‐helix, β‐sheet, helix‐to‐random coil transition, random‐coil and enveloped aggregate. The conformational states, hydrogen bonding and polyanionic nature make γ‐PGA a versatile multi‐functional biopolymer possessing many useful biological functionalities.
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