Self-assembly of highly oriented one-dimensional h-WO3 nanostructures

A new self-assembled and highly oriented one-dimensional single-crystal nanostructure of WO3 with hexagonal form was successfully prepared by a mild, solution-based colloidal approach.     

Radical mediated synthesis of 6-arylphenanthridines via benzotriazole ring-opening

Lithiation of diarylbenzotriazol-1-ylmethanes followed by addition of copper( I ) iodide gave 6-arylphenanthridine derivatives in moderate yields. When the two aryl groups were the same or contained very different electron densities, only one product was obtained. However, when the two aryl groups exhibited electron densities of similar magnitude, two isomers were afforded. According to the substituent effect, we believe that the reactions proceed via radical intermediates formed by copper( I ) iodide.     

笼形聚偕胺肟树脂的研究—酚处理对树脂吸附贵金属性能的影响

研究了笼形聚偕胺肟树脂（CAO）和酸式（ACAO）及碱式（BCAO）树脂对于苯酚、对-氨基酚、对-硝基酚、对-甲氨基酚和对-苯二酚的吸附和吸留作用，测定了酚处理树脂的中和当量。它反映了笼形树脂吸留外来物的特性。酚处理树脂有效地吸附Ag 、AuCl4－、PtCl62-、PdCl42-和IrCl62-等贵金属离子，吸附方式似乎与溶液的pH值有关。SEM观察表明，Ag 、Au－Cl4-和IrCl62-离子在吸附过程中被还原为零价态，在树脂表面生成形态各异的结晶。     

Photoinduced reactions of chloranil with 1,1-diarylethenes and product photochemistry-intramolecular

Photoinduced reactions of chloranil (CA) with 1,1-diarylethenes 1 [(p-X-Ph)(2)C=CH(2), X = F, Cl, H, Me] in benzene afforded products 4-14, respectively, with the bicyclo[4.2.0]oct-3-ene-2,5-diones 4, the 6-diarylethenylcyclohexa-2,5-diene-1,4-diones 5, and 2,3,5, 6-tetrachlorohydroquinone 13 as the major primary products. The cyclobutane products 4 are formed via a triplet diradical intermediate without involvement of single electron transfer (SET) between the two reactants, while 5 is derived from a reaction sequence with initial SET interaction between (3)CA and the alkene. The 9-arylphenanthrene-1,4-diones 6 and its 10-hydroxy-derivatives 7 are secondary photochemical products derived from 5. The isomeric cage products 9-11 are formed from 4 via intramolecular benzene-alkene [2 + 2] (ortho-)photocycloadditions induced by the triplet excited enedione moiety. The relative amount of the two groups of products (4 and its secondary products 9-11 via non-SET route vs 5 and its secondary products 6, 7, 8, 12, and 14 via SET route) shows a rather regular change, with the ratio of non-SET route products gradually increasing with the increase in oxidation potential of the alkenes and in the positive free energy change for electron transfer (DeltaG(ET)) between (3)CA and the alkene, at the expense of the ratio of the products from the SET route. The competition between the SET and non-SET routes was also found to be drastically influenced by solvent polarity, with the SET pathways more favored in polar solvent. Photo-CIDNP investigations suggest the intermediacy of exciplexes or contact ion radical pairs in these reactions in benzene, while in acetonitrile, SET process led to the formation of CA(*)(-) and cation radical of the alkene in the form of solvent separated ion radical pairs and free ions.     

Dynamics of photodissociation of 3,3,3-d(3)-propene at 157 nm: site effect and hydrogen migration

In a preceding paper [Lee et al., J. Chem. Phys. 119, 827 (2003)], we measured the kinetic-energy distributions P(E(t)) and branching ratios of products from photolysis of propene at 157 nm using time-of-flight spectroscopy combined with photoionization. In the present work, hydrogen migration before fragmentation and a site effect on P(E(t)) and branching ratios were revealed from the photodissociation of CD(3)CHCH(2). Labeling of the methyl group with deuterium enabled us to differentiate between elimination of atomic and molecular hydrogen from the vinyl moiety and from the methyl moiety; the P(E(t)) and relative yields for the formation of H, D, H(2), HD, and D(2) were measured. Deuterium labeling allowed us to also differentiate the fragmentation after hydrogen transfer from that before hydrogen migration. The observation of isotopic variants of CD(3) and C(2)H(3) radicals in the C-C bond cleavage provides evidence for hydrogen transfer of propene because of site specificity. The fraction of fragmentation after hydrogen transfer is estimated to be 25%. The isotope-specific branching ratios for five dissociation pathways of CD(3)CHCH(2) were evaluated.     

Does core size matter in the kinetics of ligand exchanges of monolayer-protected Au clusters?

This paper compares the kinetics of exchanges of phenylethanethiolate ligands (PhC2S-) of the monolayer-protected clusters (MPCs) Au(38)(SC2Ph)(24) and Au(140)(SC2Ph)(53) with p-substituted arylthiols (p-X-PhSH), where X = NO(2), Br, CH(3), OCH(3), and OH. First-order rate constants at 293 K for exchange of the first ca. 25% of the ligands on the molecule-like Au(38)(SC2Ph)(24) MPC, measured using (1)H NMR, vary linearly with the in-coming arythiol concentration; ligand exchange is an overall second-order reaction. Remarkably, the second-order rate constants for ligand exchange on Au(38)(SC2Ph)(24) are very close to those of corresponding exchange reactions on the larger nanoparticle Au(140)(SC2Ph)(53) MPCs. These are the first results that quantitatively show that the chemical reactivity of different sized nanocrystals is almost independent of size; presumably, this is because the locus of the initial ligand exchanges is a common kind of site, thought to be the nanocrystal vertexes. The rates of later stages of exchange (beyond ca. 25%) differ for Au(38) and Au(140) cores, the latter being much slower presumably due to its larger terrace-like surface atom content. The reverse exchange reaction was studied for Au(38)(p-X-arylthiolate)(24) MPCs (X = NO(2), Br, and CH(3)), where the in-coming ligand is now phenylethanethiol. Remarkably, the rate constants of both forward and reverse exchanges display identical substituent effects, which implies a concurrent bonding of both in-coming and leaving ligands to the Au core in the rate-determining step, as in an associative mechanism. X = NO(2) gives the fastest rates, and the ratio of forward and reverse rate constants gives an equilibrium constant of K(EQ,PE) = 4.0 that is independent of X.     

Versatile photosensitization system for 1O2-mediated oxidation of alkenes based on nafion-supported platinum(II) terpyridyl acetylide complex

[structure: see text] Platinum(II) terpyridyl acetylide complex (1) was incorporated into Nafion membranes as a photosensitizer, and the Nafion was immersed in an aqueous or organic solution of 7-dehydrocholesterol, alpha-pinene, or cyclopentadiene. This photosensitizer system can generate singlet oxygen ((1)O(2)) in high quantum yield to oxidize the alkenes in the solution outside the Nafion and can be easily removed from the reaction vessel at the end of the photooxidation.     

Effects of BaCl_2 on slow vacuolar ion channels on radish by patch-clamp

Effects of BaCl2 on slow vacuolar ion channels on radish by patch-clamp YANG Pin (杨 频) & ZHANG Liping (张丽平) Institute of Molecular Science, Shanxi University, Taiyuan 030006, China Correspondence should be addressed to Yang Pin (email: yangpin@sxu.edu.cn)     

Theoretical study of structure and stability of fullerene derivative: C50O

A total of eight possible isomers of C₅₀O, an oxide of fullerene C₅₀ (D_5h), have been investigated by B3LYP/3‐21G calculations. The isomer, which has an annulene‐like structure with oxygen bridging across a [5,6] type C? C bond at the site between the pole and the equatorial belt, is found being the ground state of C₅₀O. Four isomers are relatively more stable and the energy differences between them are not large. This result indicates that more than one C₅₀O isomer will coexist once C₅₀O is synthesized. The relative stabilities of the C₅₀O isomers may be determined mainly by the strain release and by the formation of the cyclic phenylene substructure at the equatorial belt of the cage. The calculated nucleus independent chemical shifts (NICS) of the C₅₀O isomers will be useful because from them one can expect outstanding NMR properties that can lead to their identification and characterization. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

纤维素基磁性聚偕胺肟树脂的研究──(NH_4)_2IrCl_6在树脂上的吸附

碱式纤维素基磁性聚偕胺肟树脂（ＢＭＡＯ）吸附（ＮＨ４）２ＩｒＣｌ６是快速过程，属超当量吸附。吸附结果生成ＡＯ－Ｉｒ和ＡＯ２－Ｉｒ３络合物，随后Ｉｒ（Ⅳ）被偕胺肟基还原为Ｉｒ（０），聚集成球状晶簇附着在树脂表面。