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961.
Soriaga RA Nguyen JM Albright TA Hoffman DM 《Journal of the American Chemical Society》2010,132(51):18014-18016
The addition of 4 equiv of LiN=C-t-Bu(2) to CrCl(3), MoCl(5), and WCl(6) in diethyl ether produced the complexes M(N=C-t-Bu(2))(4) (M = Cr, Mo, W). Single-crystal X-ray diffraction studies revealed that the molecules have flattened tetrahedral geometries with virtual D(2d) symmetry in the solid state. (1)H and (13)C NMR spectra indicated that the complexes are diamagnetic, and a qualitative MO analysis showed that the orthogonal π-donor and -acceptor orbitals of the ketimide ligand cooperatively split the d(xy) and d(z2) orbitals sufficiently to allow spin pairing in the d(xy) orbital. A more sophisticated quantum-mechanical analysis of Cr(N=C-t-Bu(2))(4) using density functional/molecular mechanics methods confirmed the qualitative analysis by showing that the singlet state is 27 kcal/mol more stable than the triplet state. 相似文献
962.
Noah D. Weiss Jonathan J. Stickel Jeffrey L. Wolfe Quang A. Nguyen 《Applied biochemistry and biotechnology》2010,162(4):975-987
The biochemical conversion of cellulosic biomass to liquid transportation fuels includes the breakdown of biomass into its soluble, fermentable components. Pretreatment, the initial step in the conversion process, results in heterogeneous slurry comprised of both soluble and insoluble biomass components. For the purpose of tracking the progress of the conversion process, it is important to be able to accurately measure the fraction of insoluble biomass solids in the slurry. The current standard method involves separating the solids from the free liquor and then repeatedly washing the solids to remove the soluble fraction, a laborious and tedious process susceptible to operator variations. In this paper, we propose an alternative method for calculating the fraction of insoluble solids which does not require a washing step. The proposed method involves measuring the dry matter content of the whole slurry as well as the dry matter content in the isolated liquor fraction. We compared the two methods using three different pretreated biomass slurry samples and two oven-drying techniques for determining dry matter content, an important measurement for both methods. We also evaluated a large set of fraction insoluble solids data collected from previously analyzed pretreated samples. The proposed new method provided statistically equivalent results to the standard washing method when an infrared balance was used for determining dry matter content in the controlled measurement experiment. Similarly, in the large historical data set, there was no statistical difference shown between the wash and no-wash methods. The new method is offered as an alternative method for determining the fraction of insoluble solids. 相似文献
963.
Long Wang Lin-Chao Zhang Ingo Lieberwirth Hong-Wei Xu Chun-Hua Chen 《Electrochemistry communications》2010,12(1):52-55
A monoclinic lithium vanadium phosphate (Li3V2(PO4)3) and carbon composite thin film (LVP/C) is prepared via electrostatic spray deposition. The film is studied with X-ray diffraction, scanning and transmission electron microscopy and galvanostatic cell cycling. The LVP/C film is composed of carbon-coated Li3V2(PO4)3 nanoparticles (50 nm) that are well distributed in a carbon matrix. In the voltage range of 3.0–4.3 V, it exhibits a reversible capacity of 118 mA h g?1 and good capacity retention at the current rate of 1 C, while delivers 80 mA h g?1 at 24 C. These results suggest a practical strategy to develop new cathode materials for high power lithium-ion batteries. 相似文献
964.
Formation of the SEI layer on Si–Cu film electrode in the ionic liquid electrolyte of 1 M lithium bis(trifluoromethylsulfonyl)imide/1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide (LiTFSI/MPP-TFSI) was investigated using ex-situ ATR FTIR and X-ray photoelectron spectroscopy. The SEI layer is found to be composed of organic and inorganic compounds that are the decomposition products of MPP cation and TFSI anion, and effectively passivate the electrode surface during initial cycling. Formation of a stable SEI layer leads to an excellent capacity retention 98% of the maximum discharge capacity, delivering discharge capacities of > 1620 mAhg? 1 over 200 cycles. The data contribute to a basic understanding of SEI formation and composition responsible for the cycling performance of Si-based alloy anodes in ionic liquid electrolyte-based rechargeable lithium batteries. 相似文献
965.
Phenyltriazolinones are one of the most important classes of herbicides targeting the protoporphyrinogen oxidase enzyme. A series of triazolinone derivatives containing a strobilurin pharmacophore were designed and synthesized with the aim of discovering new phenyltriazolinone analogues with high activity. The herbicidal activity of the synthesized compounds was assayed and some of the test compounds displayed moderate herbicidal activity at 150 g ai/ha. 相似文献
966.
It is shown that in LC of polymers, the interaction parameter in ternary mobile phases can be described by a plane, which is determined by the dependencies in binary mobile phases. Instead of a critical adsorption point, critical conditions are observed along a straight line of composition between the two critical points in binary mobile phases. Consequently, a separation of block copolymers under critical conditions for one block by an adsorption mechanism for the other block can be achieved in ternary mobile phases of different compositions, which allows an adjustment of the retention of the adsorbing block. 相似文献
967.
McGlone T Vilà-Nadal L Miras HN Long DL Poblet JM Cronin L 《Dalton transactions (Cambridge, England : 2003)》2010,39(48):11599-11604
Two titanium embedded polyoxometalates with unprecedented structural features are presented: a monotitanium containing tungstoantimonate Na(13)H(3)[TiO(SbW(9)O(33))(2)]·33 H(2)O featuring a {Ti=O}(2+) moiety (1) and a hexatitanium containing tungstoarsenate K(6)[Ti(4)(H(2)O)(10)(AsTiW(8)O(33))(2)]·30 H(2)O containing a {Ti(4)(H(2)O)(10)}(16+) moiety (2). Both compounds have been fully characterised by single crystal X-ray diffraction, elemental analysis, IR and TGA. 1 is constructed from two α-B-{Sb(III)W(9)O(33)} fragments linked by five sodium cations and an unprecedented square pyramidal Ti(O)O(4) group with a terminal Ti=O bond, and 2 exhibits a Krebs-type structure composed of two {AsTiW(8)O(33)} fragments, where one W(VI) centre has been substituted for a Ti(IV) centre in each, fused together via a belt of four additional Ti(IV) centres. This system represents the tungsten Ti-incorporated polyoxoanion with one of the highest Ti:W ratios so far reported. Additionally, 2 could also be isolated as an n-tetrabutylammonium salt and has been further characterised by electrochemistry and electrospray ionisation (ESI) MS studies. Due to the unique nature of these systems, both have been fully investigated using DFT calculations yielding highly interesting results. Structure 1 has been optimised with five sodium atoms in the belt position, which in addition to reducing the high charge of the cluster influence a stabilisation of the antimony lone pairs. Electrostatic potential calculations highlight the high electronegativity of the terminal oxygen on the titanium centre, enhancing real potentiality as a reactive site for catalysis. 相似文献
968.
Xiang H Lan Y Li HY Jiang L Lu TB Anson CE Powell AK 《Dalton transactions (Cambridge, England : 2003)》2010,39(20):4737-4739
Isostructural Co(II)?Co(III)?Ln(III)? (Ln = Y (1), Gd (2) and Dy (3)) coordination clusters formed using the ligand Tris are the first examples of 3d-4f complexes involving this ligand and show weak ferromagnetic coupling between the Co(II) ions and slow relaxation (SMM) behaviour for 3. 相似文献
969.
Ni C Fettinger JC Long GJ Power PP 《Dalton transactions (Cambridge, England : 2003)》2010,39(44):10664-10670
Reaction of {Li(THF)Ar'MnI(2)}(2) (Ar' = C(6)H(3)-2,6-(C(6)H(2)-2,6-(i)Pr(3))(2)) with LiAr', LiC≡CR (R = (t)Bu or Ph), or (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) afforded the diaryl MnAr'(2) (1), the alkynyl salts Ar'Mn(C≡C(t)Bu)(4){Li(THF)}(3) (2) and Ar'Mn(C≡CPh)(3)Li(3)(THF)(Et(2)O)(2)(μ(3)-I) (3), and the manganate salt {Li(THF)}Ar'Mn(μ-I)(C(6)H(2)-2,4,6-(i)Pr(3)) (4), respectively. Complex 4 reacted with one equivalent of (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) to afford the homoleptic dimer {Mn(C(6)H(2)-2,4,6-(i)Pr(3))(μ-C(6)H(2)-2,4,6-(i)Pr(3))}(2) (5), which resulted from the displacement of the bulkier Ar' ligand in preference to the halogen. The reaction of the more crowded {Li(THF)Ar*MnI(2)}(2) (Ar* = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)) with Li(t)Bu gave complex Ar*Mn(t)Bu (6). Complex 1 is a rare monomeric homoleptic two-coordinate diaryl Mn(II) complex; while 6 displays no tendency to eliminate β-hydrogens from the (t)Bu group because of the stabilization supplied by Ar*. Compounds 2 and 3 have cubane frameworks, which are constructed from a manganese, three carbons from three acetylide ligands, three lithiums, each coordinated by a donor, plus either a carbon from a further acetylide ligand (2) or an iodide (3). The Mn(II) atom in 4 has an unusual distorted T-shaped geometry while the dimeric 5 features trigonal planar manganese coordination. The chloride substituted complex Li(2)(THF)(3){Ar'MnCl(2)}(2) (7), which has a structure very similar to that of {Li(THF)Ar'MnI(2)}(2), was also prepared for use as a possible starting material. However, its generally lower solubility rendered it less useful than the iodo salt. Complexes 1-7 were characterized by X-ray crystallography and UV-vis spectroscopy. Magnetic studies of 2-4 and 6 showed that they have 3d(5) high-spin configurations. 相似文献
970.
Extraction and isolation of catechins from tea 总被引:1,自引:0,他引:1
Tea is a major source of catechins, which have become well known for their antioxidant potential. Numerous human, animal, and in vitro studies have linked tea catechins with prevention of certain types of cancers, reduction of the risks for obesity, diabetes, and cardiovascular disease, and improvement of the immune system. Tea catechins are widely used in various neutraceuticals, pharmaceuticals, and cosmetics for either enhancing product shelf-life or for enhancing human health. Thus, the demand for catechins has increased considerably. Catechins have been extracted and isolated from tea leaves by numerous methods through several steps including: treatment of the tea leaves, extraction of catechins from teas into solvents, isolation of catechins from other extracted components, and drying the preparations to obtain catechin extracts in a powder form. This paper outlines the physical and chemical properties of the tea catechins and reviews the extraction steps of the various extraction methods, as a basis to improve and further develop the extraction and isolation of the tea catechins. 相似文献