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1.
With exposure to trace amounts of air and moisture, the Cr2(II, II) complex Cr2(μ-3,5Cl2-form)4, where 3,5Cl2-form is [(3,5-Cl2C6H3)NC(H)N(3,5-Cl2C6H3)], undergoes an oxidative addition reaction. Structural information from the X-ray crystal structure of the edge-sharing bioctahedral (ESBO) Cr2(III, III) product Cr2(μ-OH)2(μ-3,5Cl2-form)22-3,5Cl2-form)2 (1) indicates 1 has a significantly longer Cr–Cr distance [2.732(2) Å] than Cr2(μ-3,5Cl2-form)4 [1.9162(10) Å], but the shortest Cr–Cr distance in an ESBO Cr2(III, III) complex recorded to date.  相似文献   

2.
Cobalt(III) complexes with a thiolate or thioether ligand, t-[Co(mp)(tren)]+ (2), t-[Co(mtp)(tren)]2+ (1Me) and t-[Co(mta)(tren)]2+ (2Me), (mp = 3-mercaptopropionate, MA = 3-(methylthio)propionate and MTA = 2-(methylthio)acetate) have been prepared in aqueous solutions. The crystal structures of 1, 2, 1Me and 2Me were determined by X-ray diffraction methods. The crystal data are as follows, t-[Co(mp)(tren)]ClO4 (1CIO4): monoclinic, P21/n, A = 10.877(8), B = 11.570(4), c = 12.173(7) Å, β = 92.20(5)°, V = 1531(1) Å3, Z = 4 and R = 0.060; t-[Co(ma)(tren)]Cl·3H2O (2Cl·3H2O): monoclinic, P21/n, a = 7.7688(8), B = 27.128(2), C = 7.858(1) Å, β = 100.63(1)°, V = 1627.7(3) Å3, Z = 4 and R = 0.066; (+)465CD-t-[Co(mtp)(tren)](ClO4)2 ((+)465CD-1Me(ClO4)2): orthorhombic, P212121, A = 10.6610(7), B = 11.746(1), C = 15.555(1) Å, V = 1947.9(3) Å3, Z = 4 and R = 0.068; (+)465CD-t-[Co(mta)(tren)](ClO4)2 ((+)465CD-2Me(ClO4)2): orthorhombic, P212121, a = 10.564(1), B = 11.375(1), C = 15.434(2) Å, V = 1854.7(4) Å3, Z = 4 and R = 0.047. All central Co(III) atoms have approximately octahedral geometry, coordinated by four N, one O, and one S atoms. All of the complexes are only isomer, of which the sulfur atom in the didentate-O,S ligands are located at the trans position to the tertiary amine nitrogen atom of tren. 1 and 1Me contain six-membered chelate ring, and 2 and 2Me do five-membered chelate ring in the didentate ligand. The chirality of the asymmetric sulfur donor atom in (+)465CD-1Me is the S configuration and that in (+)465CD-2Me is the R one. The 1H NMR, 13C NMR and electronic absorption spectral behaviors and electrochemical properties of the present complexes are discussed in relation to their stereochemistries.  相似文献   

3.
We report here the synthesis, characterization and in vitro antiamoebic activity of 5-nitrothiophene-2-carboxaldehyde thiosemicarbazones (TSC), 1–5, and their bidentate complexes [Ru(η4-C8H12)(TSC)Cl2] 1a–5a. The biological studies of these compounds were investigated against HK-9 strain of Entamoeba histolytica and the concentration causing 50% cell growth inhibition (IC50) was calculated in the micromolar range. The ligands exhibited antiamoebic activity in the range (2.05–5.29 μM). Screening results indicated that the potencies of the compounds increased by the incorporation of ruthenium(II) in the thiosemicarbazones. The complexes 1a–5a showed antiamoebic activity with an IC50 of 0.61–1.43 μM and were better inhibitors of growth of E. histolytica, based on IC50 values. The most promising among them is Ru(II) complex 2a having 1,2,3,4-tetrahydroquinoline as N4 substitution.  相似文献   

4.
The methanothermal reactions of M(CO)6 (M = Mo, W) with Na2S2 gave a series of homonuclear clusters [{M(CO)4}n(MS4)]2− (M=Mo, W; N=1, 2), i.e. (Ph4P)2[(CO)4Mo(MoS4)] (I), (Ph4P)2[(CO)4W(WS4)] (II), (Ph4P)2[(CO)4Mo(MoS4)Mo(CO)4] (III) and (Ph4P)2[(CO)4W(WS4)W(CO)4] (IV). The two dimers, I and II, as well as the two trimers, III and IV, are isostructural to each other, respectively. All compounds crystallize in the triclinic space group with Z=2. The cell dimensions are: a=12.393(8), b=19.303(9), c=11.909(6) Å, =102.39(5), β=111.54(5), γ=73.61(5)°, V=2522(3) Å3 at T=23 °C for I; a=12.390(3), b=19.314(4), c=11.866(2) Å, =102.66(2), β=111.49(1), γ=73.40(2)°, V=2511(1) Å3 at T=23 °C for II; a=11.416(3), b=22.524(4), c=10.815(4) Å, =91.03(2), β=100.57(3), γ=88.96(2)°, V=2733(1) Å3 at T=−100 °C for III, a=11.498(1), b=22.600(4), c=10.864(3) Å, =90.92(2), β=100.85(1), γ=88.58(1)°, V=2771(2) Å3 at T=23 °C for IV. The dimers are each formed by the coordination of the tetrathiometalate as a bidentate chelating ligand to an M(CO)4 fragment while addition of another M(CO)4 fragment to the dimers results in the trimers. All compounds contain both tetrahedral and octahedral metal centers with the formal 6+ and 0 oxidation states, respectively.  相似文献   

5.
The crystal structures of Li[Fe(trtda)]·3H2O and Na[Fe(eddda)]·5H2O (trtda = trimethylenediaminetetraacetate and eddda = ethylenediamine-N,N′-diacetate-N,N′-di-3-propionate) have been determined by single crystal X-ray diffraction techniques. The former crystal was monoclinic with the space group P21/n,a = 17.775(3),b = 10.261(1),c = 8.883(2)Å, β = 95.86(4)° and Z = 4. The latter was also monoclinic with the space group P21/n,a = 6.894(2),b = 20.710(6),c = 13.966(3)Å, β = 101.44(2)° and Z = 4. Both complex anions were found to adopt an octahedral six-coordinated structure with all of six ligand atoms of trdta4− or eddda4− coordinated to the Fe(III) ion, unlike the corresponding edta4− complex which is usually seven-coordinate with the seventh coordination site occupied by H2O. Of the three geometrical isomers possible for the eddda complex, the trans(O5) isomer was actually found in the latter crystal. Factors determining the structural types of metal–edta complexes are discussed in detail.  相似文献   

6.
7.
Compounds of formula [Al(CH3CN)6][MCl6]3(CH3CN)3 (M=Ta (1); Nb (2); Sb (3)) have been synthesized from the reactions of MCl5 and AlCl3 in acetonitrile and characterized by X-ray crystallography. Complex 1 crystallizes in the tetragonal space group P4/mbm with a = B = 10.408(2), C = 7.670(3) Å, V = 830.9(4) Å3 and Z = 2/3. Complex 2 crystallizes in the tetragonal space group P4/mnc with a = B = 330(a), C = 15.320(3) Å3 V = 1634.8(4) Å3 and Z = 4/3. Complex 3 also crystallizes in the tetragonal space group P4/mnc with a = B = 10.313(1), C = 15.238(2) Å, V = 1621.0(1) Å3 and Z = 4/3. The non-integer Z values for complexes 1–3 result unusual problems of disorder and/or twinning in these crystal structures due to their high symmetry. The M---Cl distances range from 2.329(3) Å in the Ta complex to 2.355(1) Å in the Sb complex, while the Al---N distances are similar in all three complexes, ranging from 1.92(1) to 1.97(1) Å, respectively. Complexes 1–3 are the first structurally characterized complexes that contain a (hexaacetonitrile)aluminum(III) cation.  相似文献   

8.
9.
Complexes of type A4[VO(tart)]2·nH2O, where A = Rb or Cs and tart =d,l-tartrate(4−) (n = 2) or d,d-tartrate(4−) (n = 2 for Rb and n = 3 for Cs), were prepared from an aqueous mixture of V2O5, AOH and H4tart. These complexes were studied by single-crystal X-ray diffraction methods: Rb4[VO(d,l-tart)]2·2H2O, space group P1 with a = 8.156(1),b = 8.246(1),c = 8.719(1)Å, = 66.09(1)°, β = 65.07(1)°, γ = 82.40(1)°,Z = 2, 1917 observed reflections, and final Rw = 0.035; Cs4[VO(d,l-tart)]2·2H2O, space group P21/c with a = 9.350(1),b = 13.728(2),c = 8.479(1)Å, β = 106.77(1)°,Z = 4, 2235 observed reflections, and final Rw = 0.054; Rb4[VO(d,d-tart)]2·2H2O, space group P4122 with a = 8.072(1),c = 32.006(3)Å,Z = 8, 1014 observed reflections and final Rw = 0.038; Cs4[VO(d,d-tart)]2·3H2O, space group P122 with a = 8.184(1),c = 33.680(5)Å,Z = 8, 1310 observed reflections, and final Rw = 0.063. Bulk magnetic susceptibility data (1.5–300 K) for these compounds and A4[VOl,l-tart)]2·nH2O (A = Rb, Cs) were obtained on polycrystalline samples. These data were analyzed in terms of a Van Vleck exchange coupled S = 1/2 model which was modified to include an interdimer exchange parameters Θ. Analysis of the low-temperature (1.5–20 K) susceptibility data gave 2J = +1.30 cm−1 and Θ = −1.86 K for Rb4[VO(d,l-tart)]2·2H2O, 2J = +1.16 cm−1 and Θ = −1.69 K for Cs4[VO(d,l-tart)]2·2H2O, 2J = +1.90 cm−1 and Θ = −0.82 K for Rb4[VO(d,d-tart)]2·2H2O, 2J = +2.04 cm−1 and Θ = −0.80 K for Rb4[VO(l,l-tart)]2·2H2O, 2J = +1.52 cm−1 and Θ = −0.25 K for Cs4[VO(d,d-tart)]2·3H2O, and 2J = +1.64 cm−1 and Θ = −0.31 K for Cs4[VO(l,l-tart)]2·3H2O. These results suggest the magnitudes of intradimer (ferromagnetic and interdimer (antiferromagnetic) exchange interactions are similar in these complexes, as observed for the analogous Na salts.  相似文献   

10.
UV mutagenesis in E. coli is believed to occur in two discrete steps. The second step involves continued DNA synthesis beyond a blocking lesion in the template strand. This bypass step requires induced levels of umuD and umuC gene products and activated recA protein. DNA polymerase III may be involved since a dnaE mutator strain (believed to have defective base selection) is associated with enhanced UV mutagenesis in conjunction with a genetic background permitting the bypass step. In non-UV-mutable umu and lexA strains, UV mutagenesis can be demonstrated if delayed photorevesal is given. This is interpreted as indicating that an earlier misincorporation step can occur in such strains but the resulting mutations do not survive because the bypass step is blocked. The misincorporation step does not require any induced SOS gene products and can occur either at the replication fork or during repair replication following excision of a DNA lesion. Neither a dnaE mutator gene (leading to a defective subunit of DNA polymerase III holoenzyme) nor a mutD5 mutator gene (leading to a defective ε proofreading subunit) had any effect on he misincorporation step. Although this is consistent with DNA polymerase III holoenzyme not being involved in the misincorporation step, other interpretations involving the inhibition of ε proofreading activity by recA protein are possible.

In vitro studies are reported in which sites of termination of synthesis by DNA polymerase III holoenzyme on UV-irradiated M13 mp8 DNA were examined in the presence of inhibitors of the 3′–5′ proofreading exonuclease (including recA protein). No evidence was found for incorporation of bases opposite photoproducts suggesting that either inhibition is more complete in the cell and/or that other factors are involved in the misincorporation step.  相似文献   


11.
The interaction of β1 integrin receptors and different extracellular matrix molecules during neuronal development was investigated by comparing both migration and morphological differentiation of D3 wild-type embryonic stem (ES) cell line-derived neural precursor cells with those of the β1 integrin knockout ES cell line G201. Analysing neurosphere explants on laminin and fibronectin as major β1 integrin ligands, the maximal spreading of outward migrating neuronal cells was determined. Compared with gelatine as a standard substrate, migration was found to be significantly increased for D3-derived neurospheres on fibronectin and laminin-1. These matrix effects were found to be even enhanced for G201 preparations. In addition, also the differentiation of wild-type and β1 integrin −/− neurones – as determined by MAP-2- and HNK-1-immunoreactive processes – was found to be increased on fibronectin and laminin when compared to gelatine standards. In the respective knockout preparations on these matrices, again perturbation effects were less pronounced than on gelatine. Our observations indicate that laminin and fibronectin are involved both in β1 integrin-dependent and -independent signalling mechanisms during neurogenesis. Upregulation of compensatory mechanisms such as β1 integrin-independent receptors for laminin and fibronectin might be responsible for the much less pronounced perturbations of G201 neural precursor migration and differentiation on these two substrates than on gelatine.  相似文献   

12.
13.
The aim of the experiment was to study the oestrous behaviour and the peripheral blood plasma profiles of luteinizing hormone (LH), progesterone and the prostaglandin metabolite, 15-keto-13,14-dihydro-PGF2, during oestrus and metoestrus in repeat breeder (RBH) and virgin heifers (VH). Ten animals of each category were utilized. The RBH had a history of at least three inseminations without conception, and the VH were sexually mature animals not previously inseminated or mated. Oestrous symptoms were recorded and blood collected from the onset of prooestrus to 7 days after oestrus. The animals were inseminated during oestrus and their embryos were collected by a nonsurgical technique 7 days after insemination. The morphology of the embryos was evaluated.

The duration of oestrus was longer (P < 0.05) in the RBH (31.5 ± 3.6 h) than in the VH (23.8 ± 2.0 h). No differences in duration of prooestrus or in the interval from the end of oestrus to postoestrous bleeding were found between the heifer categories. The interval from the onset of oestrus to the preovulatory LH peak was longer (P < 0.05) in the RBH (12.2 ± 2.8 h) than in the VH (4.8 ± 1.5 h). There was a lower LH release in the RBH than in the VH, measured as the magnitude of the preovulatory LH peak (P < 0.05; 28.0 ± 4.0 vs. 40.7 ± 3.6 μg/l) or as the area under the curve of the LH peak (P < 0.01; 1141 ± 164 vs. 1765 ± 144 mm2). The progesterone levels were higher (P < 0.05) in the RBH than in the VH during the interval 5–48 h and lower (P < 0.05) during the interval 121–168 h after the LH peak. Peaks of the prostaglandin metabolite were seen during oestrus in both heifer groups. There were more prostaglandin metabolite peaks in the RBH than in the VH during the interval 13–24 h after the LH peak. Fewer normal embryos (P < 0.05) and more degenerated embryos (P < 0.01) were found in the RBH than in the VH group 7 days after insemination. No apparent relation was found between the morphology of the embryos and the hormonal changes.

The result of the study indicates a hormonal imbalance in the RBH. The hormonal asynchronism starts before or early in oestrus, which presumably leads to a sequence of improper hormonal changes responsible for the elevated embryonic loss in repeat breeder animals.  相似文献   


14.
Wu LT  Chu CC  Chung JG  Chen CH  Hsu LS  Liu JK  Chen SC 《Mutation research》2004,556(1-2):75-82
The effect of tannic acid (TA), gallic acid (GA), propyl gallate (PA) and ellagic acid (EA) on DNA damage in human lymphocytes induced by food mutagens [3-amino-1-methyl-5H-pyrido (4,3-b) indole (Trp-P-2) and 2-amino-1-methyl-6-phenylimadazo (4,5-b) pyridine (PhIP) or H2O2 was evaluated by using single-cell electrophoresis (comet assay). The toxicity of these tested compounds (0.1–100 μg/ml) on lymphocytes was not found. These compounds did not cause DNA strand breaks at lower concentrations of 0.1–10 μg/ml. At a concentration of 100 μg/ml, TA and GA exhibited slight DNA damage, whereas PA and EA showed no DNA strand breaks. TA and its related compounds decreased the DNA strand breaks induced by Trp-P-2, PhIP or H2O2 at concentrations of 0.1–10 μg/ml. DNA repair enzymes endonuclease III (Endo III) and formamidopyrimidine-DNA glycoslase (FPG)] were used to examine the levels of oxidised pyrimidines and purines in human lymphocytes induced by H2O2. All the compounds at 10 μg/ml can reduce the level of FPG sensitive sites. However, only EA inhibited the formation of EndoIII sensitive sites. The results indicated that these compounds can enhance lymphocytes resistance towards DNA strand breaks induced by food mutagens or H2O2 in vitro.  相似文献   

15.
Fibronectin matrix assembly involves interactions among various regions of the molecule, which contribute to elongation and stabilization of the fibrils. In this study, we examined the possible role of the heparin III domain of fibronectin (repeats III4-5) in fibronectin fibrillogenesis. We show that a recombinant fragment comprising these repeats (FNIII4-5 fragment) blocked fibronectin fibril formation and the incorporation of 125I-fibronectin into cell layers. Binding assays using a biosensor revealed that FNIII4-5 bound fibronectin and the amino-terminal 70 kDa and 29 kDa fragments. It also bound to itself, indicating a previously unidentified self-association site in repeats III4-5. These interactions were specific since FNIII4-5 did not bind to the FNIII7-10 fragment, representing a central region in fibronectin. The fibronectin-binding property of the III4-5 domain, but not its matrix assembly inhibitory function, was apparently cryptic in larger fragments. By mutating the arginine residues in the WTPPRAQITGYRLTVGLTRR proteoglycan-binding sequence (HBP/III5 site) of FNIII4-5 [Moyano, J.V., Carnemolla, B., Albar, J.P., Leprini, A., Gaggero, B., Zardi, L., Garcia-Pardo, A., 1999. Cooperative role for activated alpha4beta1 integrin and chondroitin sulfate proteoglycans in cell adhesion to the heparin III domain of fibronectin. Identification of a novel heparin and cell binding sequence in repeat III5. J. Biol. Chem. 274, 135-142.], we found that the first two arginine residues in HBP/III5 were involved in the fibronectin-binding property of FNIII4-5, while the last two arginine residues in HBP/III5 were required for inhibition of matrix assembly and the binding of 125I-fibronectin to cell layers. Both properties appear to function independently from each other, depending on the conformation of the fibronectin dimer.  相似文献   

16.
The synthesis of the 3-heptyl, and the eleven isomeric 3-methylheptyl-Δ8-tetrahydrocannabinols (3–7, R and S methyl epimers, and 8) has been carried out. The synthetic approach entailed the synthesis of substituted resorcinols, which were subjected to acid catalyzed condensation with trans-para-menthadienol to provide the Δ8-THC analogue. The 1′-, 2′- and 3′-methylheptyl analogues (3–5) are considerably more potent than Δ8-THC. The 4′-, 5′- and 6′-methylheptyl isomers (6–8) are approximately equal in potency to Δ8-THC.  相似文献   

17.
The nucleotide (nt) sequences of the Sc3 and Sc4 genes of the filamentous fungus Schizophyllum commune, and the deduced amino acid (aa) sequences, were determined; moreover, the previously published sequence for the ScI gene [Dons et al., EMBO J. 3 (1984) 2101–2106] was corrected. All three independently isolated genes were found to have similar structures and nt sequences of their coding regions. At the aa level the homology is 43–62% (63–69% in the C-terminal parts of the proteins), the hydrophobic aa predominate and the hydrophobicity patterns are similar. All three proteins contain leader sequences and eight cysteines among about 110 aa, conserved at the same positions. Yet these genes are differentially regulated: Sc1 and Sc4 are only expressed at high levels in fruiting dikaryons, whereas Sc3 is highly expressed in both monokaryons and dikaryons, independent from fruiting.  相似文献   

18.
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   

19.
Myofibrillar proteins titin and myomesin stimulated myoblast proliferation as determined by MTT-test and labelled thymidine incorporation in the DNA. Specific Fn type III and Ig-like domains of these proteins were able to exert mitogenic effects as well. Proliferative effect of Fn type III domains was highly sensitive to inhibition of Ca2+/calmodulin dependent protein kinase, whereas the effect of Ig-like domains showed greater sensitivity to the inhibition of adenylyl cyclase – cAMP – PKA pathway. IGF-1 autocrine signalling inhibition partially suppressed mitogenic effects revealed by both domain types.  相似文献   

20.
Five heterometallic compounds with formulae [Ba(H2O)4Cr2(μ-OH)2(nta)2] · 3H2O (I), [M(bpy)2(H2O)2] [Cr2(OH)2(nta)2] · 7H2O, where M2+ = Zn, (II); Ni, (III); Co, (IV) and [Mn(H2O)3(bpy)Cr2(OH)2(nta)2] · (bpy) · 5H2O (V); bpy = 2,2′-bipyridine, (nta = nitrilotriacetate ion) have been prepared by reaction of I with the corresponding MII-sulfates in the presence of 2,2′-bipyridine. Substances I–V have been characterized by magnetic susceptibility measurements, EPR and X-ray determinations. I represents a 2D coordination polymer formed by coordination of centrosymmetrical dimeric chromium(III) units and Barium cations. The 10-coordinate Ba polyhedron is completed by four water molecules. Compounds II–IV are isostructural and consist of non-centrosymmetric dimeric anions [Cr2(μ-OH)2(nta)2]2−, complex cations [MII(bpy)2(H2O)2]2+ and solvate water molecules. The octahedral coordination of chromium atoms implies four donor atoms of the nta3− ligands and two bridging OH groups. Multiple hydrogen bonds of coordinated and solvate water molecules link anions and cations in a 3D network. A similar [Cr2(μ-OH)2(nta)2]2− unit is found in V. The bridging function is performed by a carboxylate oxygen atom of the nta ligand that leads to the formation of a trinuclear complex [Mn(bpy)(H2O)2Cr2(μ-OH)2(nta)2]. Experimental and calculated frequency and temperature dependences of EPR spectra of these compounds are presented. The fine structure appearing on the EPR spectra of compound V is analyzed in detail at different temperatures. It is established that the main part of the EPR signals is due to the transitions in the spin states of a spin multiplet with S = 2. Analyses of experimental and calculated spectra confirm the absence of interaction between metal ions (MII) and Cr-dimers in complexes III and IV and the presence of weak Mn–Cr interactions in V. The temperature dependence of magnetic susceptibilities for I–V was fitted on the basis of the expression derived from isotropic Hamiltonian including a bi-quadratic exchange term.  相似文献   

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