高富勒烯的提取,分离和分析

采用二硫化碳重结晶富勒烯混合物或二硫化碳二次抽提烟灰以提取高富勒烯（ｈｉｇｈｅｒｆｕｌｅｒｅｎｅｓ，Ｃｎ，ｎ＞７０）。产物经高效液相色谱分析，高富勒烯的含量从１％分别提高到４％和６％；经激光飞行时间质谱证明，产物中除含主要成分Ｃ６０和Ｃ７０以外，还含有Ｃ７６、Ｃ７８、Ｃ８２、Ｃ８４以及更高碳原子的富勒烯。     

Further studies of M3(μ3-O)(μ-X)3(μ-O2CCH3)3L3 (M=Mo,W) type clusters with nine core electrons

Four new compounds having nine cluster electrons and cores of the types Mo₃OCl₃, Mo₃OBr₃, and W₃OCl₃ are reported. Compound (1) prepared by reduction of [Bu₄N][Mo₃OCl₆(OAc)₃] in THF with metallic zinc, was shown by X-ray crystallography to be Mo₃OCl₄(OAc)₃ (THF)₂ (1). It forms crystals in space groupP2₁ with unit cell dimensionsa=9.472(2) Å,b=13.546(4) Å,c=9.652(2) Å, =101.70(2)°,V=1201(1) Å₃,Z=2. The [Mo₃(₃-O)(-Cl)₃]⁴⁺ core is surrounded by three -O₂CCH₃ anions, one Cl^–, and two THF and has Mo-Mo distances of 2.620(1) Å, 2.613(1) Å, and 2.530(1) Å, with the shortest bond between the two Mo atoms to which the THF molecules are coordinated. Compounds [Bu₄N]₂ [Mo₃OBr₆(O₂CCH₃)₃] · Me₂CO, (2) and [Mo₃OBr₃(O₂CCH₃)₃(PMe₃)₃]₃ · BF₄, (3) are the first two nine-electron Mo₃ species with a [Mo₃(₃-O) Br₃]⁴⁺ core. Both were obtained by zinc reduction of [Mo₃OBr₆(O₂CCH₃)₃]^– in the presence of (NBu₄) Br (2) or PMe₃ and NaBF₄ (3), and each was characterized crystallographically. Compound (2) crystallized in space group Cc with unit cell dimensionsa=25.037(5) Å,b=12.827(2) Å,c=21.484(4) Å, =122.96(1)⁰,V=5790(3) ų,Z=4. While the anion has no crystallographically required symmetry, its virtual symmetry is C_3v . The Mo-Mo distances are 2.619(2) Å, 2.610(3) Å, 2.644(2) Å, with a mean value of 2.624[14] Å. Compound (3) crystallized in space groupP2₁/c with unit cell dimensionsa=10.846(2) Å,b=25.033(5) Å,c=12.641(5) Å, =94.74(2)⁰,V=3420(2) ų,Z=4. The cation occupies a general position but has virtual C_3v symmetry, with Mo-Mo distances of 2.601(2) Å, 2.610(2) Å, 2.627(2) Å, with a mean value of 2.613[14] Å. Thus the anionic and cationic Mo₃ clusters in (2) and (3), respectively, have average Mo-Mo distances that are equal within experimental error. Compound (4), [NEt₄]₂ [W₃OCl₆(O₂CCH₃)₃] is the first 9-electron compound of this type containing tungsten. It was prepared by reduction of [Et₄N][W₃OCl₆(OAc)₃] in benzene with Na/Hg. It crystallized in space groupP2₁2₁2₁ with unit cell dimensionsa=11.076(2) Å,b=14.345(2) Å,c=21.026(3) Å,V=3574(1) ų,Z=4. The anion resides on a general position but has virtual C_3v symmetry, with W-W distances of 2.577(1) Å, 2.612(1) Å, 2.584(1) Å and a mean value of 2.591[15] Å.     

Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

Hydrogen bonded layer-by-layer assembly of poly(2-vinylpyridine) and poly(acrylic acid): Influence of molecular weight on the formation of microporous film by post-base treatment

This article describes the buildup of hydrogen bonded multilayer film of poly(2-vinylpyridine) (P2VP) and poly(acrylic acid) (PAA), and the influence of polymer molecular weight on the formation of microporous film by post-base treatment. The formation of a microporous film involved a two-step mechanism: the release of PAA from P2VP/PAA multilayer, and the reorganization of the remaining P2VP on the substrate. Fourier transform infrared spectroscopy (FT-IR) indicated that the release of PAA from hydrogen bonded multilayer was a rapid process, which was almost independent of the molecular weight of PAA. Furthermore, the molecular weight of P2VP had a great effect on micropore formation by immersing the P2VP/PAA multilayer in basic solution. The rate of micropore formation increased with increasing molecular weight. We anticipate that a comparative study on P2VP/PAA films containing high or low molecular weight polymer provides a way to control the surface morphology, and will be helpful and constructive for the forthcoming discussion about the formation of the microporous film.     

High-yield solvothermal formation of magnetic CoPt alloy nanowires

One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes.     

Photoisomerization and photodissociation of aniline and 4-methylpyridine

Photoisomerization and photodissociation of aniline and 4-methylpyridine at 193 nm were studied separately using multimass ion imaging techniques. Photofragment translational energy distributions and dissociation rates were measured. Our results demonstrate that more than 23% of the ground electronic state aniline and 10% of 4-methylpyridine produced from the excitation by 193 nm photons after internal conversion isomerize to seven-membered ring isomers, followed by the H atom migration in the seven-membered ring, and then rearomatize to both methylpyridine and aniline prior to dissociation. The significance of this isomerization is that the carbon, nitrogen, and hydrogen atoms belonging to the alkyl or amino groups are involved in the exchange with those atoms in the aromatic ring during the isomerization.     

Two New C—21 Steroidal Glycosides from Cynanchum aurichulatum

Two new C-21 steroidal glycosides, cynanauriculoside I and cynanauriculoside Ⅱ, were isolated from the roots of Cynanchum aurichulatum. Their structures were established using spectroscopic methods including one and two-dimensional NMR.     

Reduction of 4-nitrophenol catalyzed by nitroreductase

The reduction of 4-nitrophenol catalyzed by nitroreductase in the presence of NADH was investigated in this paper.4-Amino- phenol and 4-bydroxylamino-phenol were found in the reductive products.The relationship between reaction time and the reductive ratio were studied.The similar reducing ratios of 4-nitrophenol were obtained under aerobic and anaerobic conditions.The results indicated that an oxygen-insensitive reaction was proceeded in the reduction of 4-nitrophenol and nitroreductase was an oxygen- insensitive enzyme.The reductive products of 4-nitrophenol were determined by HPLC and MS.     

Pt粒大小对PtNaY/HY体系氢溢出效应的影响

负载型金属催化剂的表面溢出效应(Spillover)是指吸附在金属上的物种可沿固体表面转移到担体上去的现象,是金属活性组分与担体相互作用的一个重要方面。近年来随着金属与担体之间强相互作用(SMSI)研究的逐渐深入,人们注意到溢出效应在SMSI中的重要作用。虽然提出溢出效应已有20多年的历史,并且人们采用不同的实验方法对此进行了广泛的研究,但对以分子筛为担体的负载型金属催化剂体系溢出效应的研究仍比较少。影     

Preparation and characterization O-lauroyl chitosan/poly (L-lactic acid) blend membranes by solution-casting approach

O-Lauroyl chitosan/poly(L-lactide) (OCS/PLLA) blend membranes with different compositions were prepared by solution-casting approach using chloroform as common solvent. The experimental results of FT-IR, DSC and WAXD indicated that inter-association hydrogen-bond interactions existed between OCS and PLLA in the blend membranes. And SEM observation confirmed that the blend membranes with suitable compositions were compatible.