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61.
用硫酸铵分段盐析、超滤膜分级分离及DEAE-纤维素、Sephadex A-25和Sephadex G-50三种柱层析方法从双胸蚓组织的粗提取液中分离纯化出一种纤溶酶,分子量为29kD,由一条肽链组成。此晦具有强烈的溶解纤维蛋白的作用,对家兎实验性血凝块也具有明显的溶解作用。此酶的最适pH为8.0,在pH7.6~8.4之间活力相差不到2%;酶在PH4.7—11.0范围内稳定;酶作用的最适温度为57℃;此酶热稳定性较好,于25~50℃保温3小时,酶活力基本不变,60℃时,活力保留65%。金属离子Na~(+)、K~(+)、Mg~(2+)等可提高此酶的活力,而Hg~(2+)、Ca~(2+)等金属离子对此酶有不同程度的抑制作用。 相似文献
62.
B. Eva Villaroya Luis A. Oro Fernando J. Lahoz Andrew J. Edwards Miguel A. Ciriano Pablo J. Alonso Antonio Tiripicchio Marisa Titipicchio Camellini 《Inorganica chimica acta》1996,250(1-2):241-264
The multiple coordination possibilities of 1,8-naphthyridine-2-one (HOnapy) and 5,7-dimethyl-1,8-napthyridine-2-one (HOMe2napy) ligands allow the synthesis of a variety of tri- di- and mononuclear complexes, showing fluxional behaviour and frequent exchange of the coordinated ML2 fragments. Thus, reactions of [M2(μ-OMe)2(cod)2] (cod = 1,5-cyclooctadiene) with HOnapy and HOMe2napy yield the compounds of the general formula [M(μ-OR2napy) (cod)]n (M = Ir, R = Me (1a, 1b, H (2); M = Rh, R = Me (3a, 3b). They crystallise as inconvertible yellow (a) and purple/orange (b) forms and also show a puzzling behaviour in solution. X-ray diffraction studies on both forms (3a, 3b) and spectroscopic data reveal that the yellow forms are mononuclear complexes whilst the dark-coloured crystals contain dinuclear complexes. In solution, the nuclearity of the complexes depends on the solvent. In addition both types of complexes are fluxional. The mixed-ligand complexes [M2(μ-OMe2napy)2(CO)2(cod)] M = Ir (5), Rh (6) have been isolated and characterised; they are found to be intermediates in the synthesis of the trinuclear complexes [M3(μ3-OMe2napy)2(CO)2(cod)2]+ M = Rh (8), Ir (9). Reactions of [IrCl(CO)2(NH2-p-tolyl] with the complexes [Rh(μ-OR2napy)(diolefin)]n followed by addition of a poor donor anion is a general one-pot synthesis for the hetertrinuclear complexes [Rh2Ir(μ3-OR2napy)2(CO)2(diolefin)2]+ (R=Me, DIOLEFIN = cod (10), tetrafluorobenzo-barrelene (tfbb) (11), 2,5-norbornadiene (nbd) (12); R=H, DIOLEFIN=cod (13)). This synthesis follows a stepwise mechanism from the mononuclear to the trinuclear complexes in which mixed-ligand heterodinuclear complexes are involved as intermediates of the type [(diolefin)Rh(μ-OMe2napy)2Ir(CO)2]. Heteronuclear complexes which possess the core [RhIr2]3+, such as [RhIr2(μ3-OR2napy)2(CO)2(cod)2]BF4 (R=Me (14), H (15)), result from the reaction of 1 or 2 with [Rh(CO)2Sx]+ (S = solvent). The trinuclear complexes undergo two chemically reversible one-electron oxidation processes. The chemical oxidation of 10, 14 and 9 with silver salts gives the mixed-valence trinuclear radicals [Rh2Ir(μ3-OMe2napy)2(CO)2(cod)2]2+ (16), [RhIr2(μ3-OMe2napy)2(CO)2(cod)2]2+ (17) and [Ir3(μ3-OMe2napy)2(CO)2(cod)2]2+ (18), which have been isolated as the perchlorate and tetrafluoroborate salts. The EPR spectrum of 16 indicates that the unpaired electron is essentially in an orbital delocalised on the metals. The molecular structures of the complexes 3a, 3b, 6, 10b and 16a are described. Crystals of 3a are triclinic, P-1, with a = 9.7393(2), b = 14.0148(4), c = 16.0607(4) Å, α = 88.122(3), β = 83.924(3), γ = 87.038(3)°, Z = 4; 3b crystallises in the Pna2i orthorhhombic space group, with a = 16.7541(3), B = 11.7500(8), c = 17.7508(7) Å, Z = 4; complex 6 is packed in the monoclinic space group P2i/c, a = 9.6371(1), b = 11.8054(4), c = 27.2010(9) Å, β = 90.556(4)°, Z = 4; crystals of 10b are monoclinic, P21/n, with a = 17.546(7), b = 13.232(6), c = 17.437(8) Å, β = 106.18(1)°, Z = 4; crystals of 16a are triclinic, P-1, with a = 10.318(4), b = 12.562(6), C = 19.308(8) Å, α = 92.12(8), β = 97.65(9), γ = 90.68(5)°, Z = 2. The five different structures show the coordination versatility of the OMe2napy molecule as ligand, which behaves as a N,N′-chelating (3a), bidentate N,O-donor (3b, 6), or as a tridentate N,N′,O-donor bridging ligand (10b, 16a). 相似文献
63.
The reactions of cadmium halides with the 15-membered macrocyclic crown ethers, 15-crown-5 and benzo-15-crown-5, have been carried out and six new complexes have been isolated and structurally characterized. Metal to ligand stoichiometries of 1:1, 2:1, 3:1 and 3:2 have been observed with a variety of different formulations. Examples of charge separated ion pairs ([(NH4)(benzo-15-crown-5)2]2[Cd2I6]), halogen bridged monomers, dimers or polymers ([Cd(15-crown-5)(OHMe)(μ-Br)CdBr3], [Cd(15-crown-5)(μ-Br)2CdBr(μ-Br)]2(isolated from the same reaction mixture) and [(CdCl2)2CdCl2(15-crown-5)]n), and hydrogen bonded finite chains or polymers ([(Cd(OH2)2(15-crown-5)][CdI3(OH2)]2·2(15-crown-5)·2CH3CN and [CdI2(OH2)2(THF)]·benzo-15-crown-5) have been isolated. Three different types of 15-crown-5 coordination modes have been observed in these complexes. In-cavity coordination resulting in pentagonal bipyramidal geometries about Cd2+ was observed in [(CdCl2)2CdCl2(15-crown-5)]n, [Cd(15-crown-5)(OHMe)(μ-Br)CdBr3], and [Cd(OH2)2(15-crown-5)][CdI3(OH2)]2·2(15-crown-5)·2CH3CN, [Cd(15-crown-5)(μ-Br)2CdBr(μ-Br)]2 displays out-of-cavity coordination with one etheric donor distorted into an axial position of a distorted pentagonal bipyramid. The third coordination mode is secondary sphere coordination via hydrogen bonding which is observed for [Cd(OH2)2(15-crown-5)][CdI3(OH2)]2·2(15-crown-5)·2CH3CN. The good fit of Cd2+ within the cavity of 15-crown-5 results in shorter bonding contacts and a more narrow distribution in Cd---O values (2.273(7)-2.344(6) Å) than observed for cadmium halide complexes of 18-crown-6 (Cd---O = 2.69(1)–2.81(1) Å). 相似文献
64.
Harry Adams Neil A. Bailey Philippe Bertrand Simon R. Collinson David E. Fenton Simon J. Kitchen 《Inorganica chimica acta》1996,250(1-2):139-148
The cyclocondensation of 2,5-diformylthiophene and the amines N,N-bis-(2-aminoethyl)-2-phenylethylamine, N,N-bis-(2aminoethyl)-t-butyl-amine and N,N-bis-(2-aminoethyl)-t-butyl-amine in the presence of silver(I) salts yields homodinuclear bibracchial tetraimine Schiff base macrocyclic complexes. The structures of two such complexes are also reported. The complex Ag2L4(NO3)(PF6) (2) crystallises in the triclinic space group
, No. 2) and has unit-cell dimensions a = 12.834(6), B = 13.183(6), C = 14.588(7) Å, = 64.86(4), β = 79.77(4), γ = 69.44(3)° with Z = 2; there is a monodentate and singly bridging nitrate anion present and the Ag---Ag separation is 4.161 Å. The complex Ag2L4(CH3CN)2(BF4)2·CH3CN (9) crystallises in the triclinic space group
, No. 2) and has unit-cell dimensions a = 9.297(4), B = 12.985(3), C = 21.770(5) Å, = 91.570(10), β = 92.33(3), γ = 97.92(3) ° with Z = 2; there is a strongly bonded acetonitrile molecule coordinated to each silver atom and the Ag---Ag separation is 4.920 Å. 相似文献
65.
N. Kositzyna M. Antipin K. Lyssenko P. S. Pregosin G. Trabesinger 《Inorganica chimica acta》1996,250(1-2):365-373
A series of cationic allyl complexes of Pd(II) derived from the diterpene carvone
have been synthesised and characterised using the chelating ligands, bipyridine, 1,8-phenanthroline, neocuproin, S,S (-)-Chiraphos and R (+)-Binap as co-ligands. These complexes can be readily converted to new organic products in which one C---H bond of the allyl methyl has been substituted. The structure of a bipyridyl complex as its tetraphenyl borate salt has been determined via X-ray diffraction. 2-D NOESY studies on the Chiraphos and Binap complexes are reported. The Binap, but not the Chiraphos, complex reveals η3-η3η3 isomerisation at ambient temperature. 相似文献
66.
Lisa M. Vogler Sumner W. Jones Glen E. Jensen R. Gary Brewer Karen J. Brewer 《Inorganica chimica acta》1996,250(1-2):155-162
A number of osmium and ruthenium complexes of the tridentate ligands 2,2′:6′,2″-terpyridine (tpy) and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tpp) have been prepared and characterized by our laboratory. All these complexes possess metal based oxidations and ligand based reductions localized on each polyazine ligand. Polymetallic complexes bridged by the tpp ligand exhibit two sequential tpp based reductions prior to the reduction of other polyazine ligands in these complexes. The spectroscopy of these complexes is dominated by ligand based π-π* transitions in the ultraviolet and MLCT (metal-to-ligand charge transfer) bands terminating on each polyzine ligand in the visible. For the complexes reported herein the lowest lying optical transitionis a M → BL CT band. For most of the complexes reported, occupation of this excited state gives rise to an observable emission at room temperature. For ruthenium complexes of these tridentate ligands, the presence of a low-lying LF state shortens the excited state lifetimes of these chromophores. This gives rise to ruthenium complexes that display shorter excited state lifetimes than the analogous osmium based systems. Incorporation of tpp based chromophores into polymetallic frameworks leads to the production of bimetallic species with long-lived excited states, 100 ns at room temperature. This makes these chromophores good candidates for the development of stereochemically defined supramolecular complexes. It is possible to measure an electrochemical HOMO-LUMO energy gap and a correlation between this electrochemically measured energy gap and the spectroscopic energy associated with this HOMO→LUMO transition are reported herein (HOMO== highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital). 相似文献
67.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4. 相似文献
68.
Luísa M. D. R. S. Martins Armando J. L. Pombeiro Richard A. Henderson 《Inorganica chimica acta》1996,250(1-2):311-315
The kinetics of the displacement reactions of the bromide ligands of trans-[FeBr2(depe)2] (depe = Et2PCH2CH2PEt2) by the organonitrile NCCH2C6H4OMe-4, in tetrahydrofuran (either in the absence or in the presence of added Br−), to give the corresponding mono- and dinitrile complexes trans-[FeBr(NCCH2C6H4OMe-4)(depe)2]+ and trans-[Fe(NCCH2C6H4OMe-4)2(depe)2]2+, have been investigated by stopped-flow spectrophotometry. The substitution reaction occurs by a mechanism involving rate-limiting dissociation of bromo ligands to form the unsaturated intermediates [FeBr(depe)2]+ (k1 = 1.52 ± 0.02 s−1) and [Fe(NCR)(depe)2]2+ (k3 = 0.063 ± 0.008 s−1) which add the nitrile ligand to form those nitrile complexes. The competition between the nitrile and Br− for such metal centres has also been investigated and a stronger inhibiting effect of added Br− is observed for the substitution of the second bromo ligand relative to the first one. The kinetic data are rationalized in terms of π-electronic effects of these unsaturated metal centres and of the bromide and nitrile ligands. 相似文献
69.
James M. Chen Spero Manolatos Paul W. Brandt-Rauf Randall B. Murphy Regina Monaco Matthew R. Pincus 《Journal of Protein Chemistry》1996,15(6):511-518
The three-dimensional structures of theras-p21 protein and its protein inhibitor, rap-1A, have been computed bound to theras-binding domain, RBD (residues 55–131), of theraf-p74 protein, a critical target protein ofras-p21 in theras-induced mitogenic signal transduction pathway. The coordinates of RBD have been reconstructed from the stereoview of an X-ray crystal structure of this domain bound to rap-1A and have been subjected to energy minimization. The energy-minimized structures of bothras- p21 and rap-1A, obtained in previous studies, have been docked against RBD, using the stereo figure of the RBD-rap-1A complex, based on a six-step procedure. The final energy-minimized structure of rap-1A-RBD is identical to the X-ray crystal structure. Comparison of theras-p21- and rap-1A-RBD complexes reveals differences in the structures of effector domains ofras-p21 and rap-1a, including residues 32–47, a domain that directly interacts with RBD, 60–66, 96–110, involved in the interaction ofras-p21 withjun kinase (JNK) andjun protein, and 115–126, involved in the interaction of p21 with JNK. The structure of the RBD remained the same in both complexes with the exception of small deviations in its-2 binding loop (residues 63–71) and residues 89–91, also involved in binding to rap-1A. The results suggest that the binding of these two proteins to RBD may allow them to interact with other cellular target proteins such as JNK andjun. 相似文献
70.
To clarify the mechanism of aluminum (Al) toxicity and Al tolerance, we isolated a new clone (pAL201) from a tobacco cDNA library. Northern blot hybridization analysis indicated that the expression of pAL201 is induced by Al treatment and phosphate (P1 ) starvation. The complete cDNA sequence suggested that this clone encodes a moderately anionic peroxidase (EC 1.11.1.7). Analysis by isoelectric focussing indicated that a moderately anionic peroxidase (approximately pI 6.7) and two cationic peroxidases (pI 9.2 and 9.7) in the soluble fraction are activated by Al treatment and P1 starvation, while two moderately anionic isozymes are repressed by these stresses. We suppose that Al ion stress can control the activity of some peroxidase isozymes, one of which is probably induced by enhanced gene expression of pAL201. There is a possibility that some of these isozymes have some functions in Al ion stress. 相似文献