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1.
TBPY‐5‐34‐(Butane‐1,4‐diyl)(2‐{[1‐(2‐oxidophenyl)ethylidene‐κO]amino‐κN}ethanolato‐κO)silicon, C14H19NO2Si, crystallizes in two modifications. The monoclinic form, (IIm), was obtained by crystallization over a period of 2 d at room temperature; the orthorhombic form, (IIo), crystallized overnight at 248 K. The main difference between the two molecular structures involves the angles in the equatorial plane of the trigonal bipyramid around silicon. Form (IIm) has an O—Si—O angle of ca 121° and O—Si—C angles of ca 121 and 116°. In form (IIo), the corresponding angles are ∼123, 124 and 111°. There are also significant differences in the packing: (IIm) shows π stacking, whereas (IIo) does not.  相似文献   
2.
Conductance measurements are reported for LiPi, NaPi, KPi, RbPi, CsPi, Bu4NPi, Bu4NBr, Bu4NClO4, Bu4NNO3, and Bu4NBBu4 at 25°C in -butyrolactone-sulfolane mixtures. In these mixtures of solvents that are practically homomorphous, isodielectic and with comparable dipole moments, the ion pair association and ionic mobilities of large ions conform to the expectations of the primitive model. Electrolytes containing lithium or sodium ions show anomalies indicating that other factors besides shape, dipole moment, and polarizability of the solvent molecules are involved in the association and transport processes of these ions.  相似文献   
3.
Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl2)2((ch)230S4O6)] ( 1 ), [HgCl2(mn21S2O5)] ( 2 ), [HgCl2(ch18S2O4)] ( 3 ) and [HgI(meb12S2O2)]2[Hg2I6] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl2)2((ch)230S4O6)] two HgCl2 units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)230S4O6) forming a binuclear complex. HgCl2 forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S2O5) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S2O4) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S2O2) ligand gave with two equivalents HgI2 the compound [HgI(meb12S2O2)]2[Hg2I6]. In the cation [HgI(meb12S2O2)]+ meb12S2O2 forms with the cation HgI+ a half‐sandwich complex.  相似文献   
4.
Reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with LiR reagents containing functional groups readily yields meso substituted derivatives suitable for further transformations with residues such as -p-C6H5Br, -p-C6H5-CCH, -p-C6H5-NH2 or -(CH2)3-CHCH2. Similar reactions of tetrabenzoporphyrin with alkyllithium reagents afforded the first entry into meso mono- and dialkylsubstituted tetrabenzoporphyrins while reaction of bicyclo[2.2.2]oct-type masked isoindole precursors with LiR followed by in situ retro-Diels-Alder reaction also afforded the 5-phenyl and 5,10-diphenyltetrabenzoporphyrins in high purity.  相似文献   
5.
Three new Mn(III) porphyrin catalysts of O2.-dismutation (superoxide dismutase mimics), bearing ether oxygen atoms within their side chains, were synthesized and characterized: Mn(III) 5,10,15,20-tetrakis[N-(2-methoxyethyl)pyridinium-2-yl]porphyrin (MnTMOE-2-PyP(5+)), Mn(III)5,10,15,20-tetrakis[N-methyl-N'-(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTM,MOE-2-ImP(5+)) and Mn(III) 5,10,15,20-tetrakis[N,N'-di(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTDMOE-2-ImP(5+)). Their catalytic rate constants for O2.-dismutation (disproportionation) and the related metal-centered redox potentials vs. NHE are: log k(cat)= 8.04 (E(1/2)=+251 mV) for MnTMOE-2-PyP(5+), log k(cat)= 7.98 (E(1/2)=+356 mV) for MnTM,MOE-2-ImP(5+) and log k(cat)= 7.59 (E(1/2)=+365 mV) for MnTDMOE-2-ImP(5+). The new porphyrins were compared to the previously described SOD mimics Mn(III) 5,10,15,20-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP(5+)), Mn(III) 5,10,15,20-tetrakis(N-n-butylpyridinium-2-yl)porphyrin (MnTnBu-2-PyP(5+)) and Mn(III) 5,10,15,20-tetrakis(N,N'-diethylimidazolium-2-yl)porphyrin (MnTDE-2-ImP(5+)). MnTMOE-2-PyP(5+) has side chains of the same length and the same E(1/2), as MnTnBu-2-PyP(5+)(k(cat)= 7.25, E(1/2)=+ 254 mV), yet it is 6-fold more potent a catalyst of O2.-dismutation , presumably due to the presence of the ether oxygen. The log k(cat)vs. E(1/2) relationship for all Mn porphyrin-based SOD mimics thus far studied is discussed. None of the new compounds were toxic to Escherichia coli in the concentration range studied (up to 30 microM), and protected SOD-deficient E. coli in a concentration-dependent manner. At 3 microM levels, the MnTDMOE-2-ImP(5+), bearing an oxygen atom within each of the eight side chains, was the most effective and offered much higher protection than MnTE-2-PyP(5+), while MnTDE-2-ImP(5+) was of very low efficacy.  相似文献   
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7.
We study the interplay between Auger effects and ionization processes in the limit of strong electronic confinement in core/shell CdSe/ZnS semiconductor nanocrystal quantum dots. Spectrally resolved fluorescence decay measurements reveal a monotonic increase of the photoluminescence decay rate on excitation density. Our results suggest that Auger recombination accelerates ionization processes that lead to the occupation of dark, nonemissive nanocrystal states. A model is proposed in the quantized Auger regime describing these experimental observations and providing an estimate of the Auger assisted ionization rates.  相似文献   
8.
Hair color changes and protein damage caused by ultraviolet radiation   总被引:12,自引:0,他引:12  
Ultraviolet and visible radiations are known to damage hair. However, quantitative data relating damage to hair type, proteins and color to the radiation wavelength are missing. We studied the effect of UV plus visible, UVA plus visible, visible mercury-vapor lamp radiation and sunlight on (blended) virgin dark-brown, blond and red hair and (one head) virgin black and curly dark-brown hair. All hair types showed a substantial increase in protein loss in water after lamp and sun irradiation. The damaging effect of UVB was about 2-5 times higher than that of UVA plus visible radiation, depending on the hair type. Significant color changes were also observed in every hair type, after lamp and sun irradiation, being more pronounced for the light colored hairs. The luminosity difference parameter was the major contributor to the hair color changes, but significant changes in the red-green and yellow-blue parameters of every hair were observed. In this case, the damaging effect is ascribable mainly to UVA radiation. No significant changes in the mechanical properties or topography were observed in any case. We discuss these results in terms of hair type and composition and melanin types.  相似文献   
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