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1.
Interaction between the sodium salt of a DNA extracted from salmon sperm (41% GC) with [Pt(NH3)4]Cl2, [Pt(NH2? (CH2)2? NH? (CH2)2? NH2Cl]Cl, cis-Pt(NH2? (CH2)2? NH2)Cl2, cis-Pt(NH3)2Cl2, trans-Pt(NH3)2Cl2, K[Pt(C2H4)Cl3], and K2[PtCl4) indicates at least three types of complexation. A correlation is found between the change of pH and the number of platinum atoms fixed per (AT + GC) unit. The first binding site is located on the G-C pairs (guanine–cytosine), most likely the N-7(G) site, as it was shown in a previous study of the guanosine-platinum salts. The fixation of the second platinum atom by the pair (AT + GC) takes place with liberation of protons. In the case of the complexes cis-Pt(NH2? (CH2)2? NH2)Cl2, cis-Pt(NH3)2Cl2, and trans-Pt(NH3)2Cl2 the second interaction seems to involve simultaneously the N-7(A) and the N-1(G) and N-3(C) sites. This latter intercrosslink between guanine and cytosine obviously liberates protons and the decrease of pH is related in this case to the trans effect of the platinum compounds. The first two platinum atoms in the reaction of K2PtCl4] or the Zeise salt, K[Pt(C2H4)Cl3] with DNA are fixed on the G-C pairs. A maximum of six platinum atoms per (AT + GC) unit were fixed in this case. Preliminary experiments with a DNA extracted from bacteria Micrococcus lysodeikticus (72% GC) give similar results.  相似文献   

2.
3.
《Inorganica chimica acta》1986,113(2):131-135
Treatment of Al2iBu4 with THF and Et2O results in partial decomposition to afford Al metal while reaction with γ-picoline products a bis-adduct of limited stability. Reactions with AlMe3 and BCl3, separately, involves ligand exchange with accompanying disproportionation to yield Al metal. Dimethylamine induces disproportionation to afford AliBu3·HNMe2 and an intemediate trialuminum species. The latter undergoes AlAl bond cleavage with formation of H2, iBu2AlNMe2, and [Me2N- (iBu)AlAliBu2]2· Al2iBu4 eliminates Me2CCH2 in solution at 80 °C, and the catenated AlH intermediate reacts with ethylene to afford AlEt and AlCH2CH2CH2CH3 moieties.  相似文献   

4.
A new dithiolene ligand with 3,5-dibromo substituted phenyl groups was designed and synthesized. The protected form of the ligand was reacted with a nickel salt providing neutral Ni(S2C2(3,5-C6H3Br2)2)2 and anionic [Ni(S2C2(3,5-C6H3Br2)2)2] isolated as a Bu4N+ salt. Both were characterized by UV-Vis and IR spectroscopy and compared with the similar known molecular systems. They exhibit intense low energy transitions that are characteristic of such systems. The electrochemical behavior of these molecules was investigated by cyclic voltammetry.  相似文献   

5.
Experiments were conducted to determine why 10,10-difluoro, 13-dehydroprostacyclin (DF2-PGI2) has a long vascular relexant activity but like PGI2 hads a short duration of effect . DF2-PGI2 produced depressor responses in anesthetized dogs which were not affected by nephrectomy suggesting that the kidney was not responsible for the termination of action. DF2-PGI2 given intravenously or into the ascending oarta produced depressor responses of a similar magnitude but injection of the same doses into the hepatic portal circulation resulted in a large attenuation of responses. The data suggest hepatitic, but not pulmonary, metabolism of DF2-PGI2. Injection or infusion of PGI2 and DF2-PGI2 into the hindlimb circulation caused vasodilation of a similar duration suggesting diffusion from tissue sites as another mechanims of termination of action.  相似文献   

6.
Synopsis Oxygen uptake (Vo 2) was measured in carp of approximately 40 cm length swimming at controlled variable oxygen tensions (Po 2). At Po 2> 120 mm Hg Vo 2 increased with an increase in swimming speed from 5.6 to 11.3 cm · sec–1. Extrapolation of Vo 2 to zero activity at Po 2 = 140 mm Hg revealed a standard O2 uptake of 36.7 ml O2 · kg–1 · h–1 at 20° C. At the lowest swimming speed (5.6 cm · s–1) the oxygen uptake increased when the water Po 2 was reduced. A near doubling in Vo 2 was seen at Po 2 = 70 mm Hg compared to 140 mm Hg. At higher swimming speeds in hypoxic water Vo 2 decreased relative to the values at low swimming speeds. As a result the slope of the lines expressing log Vo 2 as a function of swimming speed decreased from positive to negative values with decreasing Po 2 of the water. pH of blood from the caudal vein drawn before and at termination of swimming at Po 2 = 70 mm Hg and 100 mm Hg did not show any decrease in relation to rest values at Po 2 = 140 mm Hg. Blood lactate concentration did not increase during swimming at these tensions.  相似文献   

7.
The effects of several metals on microbial methane, carbon dioxide, and sulfide production and microbial ATP were examined in sediments from Spartina alterniflora communities. Anaerobically homogenized sediments were amended with 1,000 ppm (ratio of weight of metal to dry weight of sediment) of various metals. Time courses in controls were similar for CH4, H2S, and CO2, with short initial lags (0 to 4 h) followed by periods of constant gas production (1 to 2 days) and declining rates thereafter. Comparisons were made between control and experimental assays with respect to initial rates of production (after lag) and overall production. Methane evolution was inhibited both initially and overall by CH3HgCl, HgS, and NaAsO2. A period of initial inhibition was followed by a period of overall stimulation with Hg, Pb, Ni, Cd, and Cu, all as chlorides, and with ZnSO4, K2CrO4, and K2Cr2O7. Production of CO2 was generally less affected by the addition of metals. Inhibition was noted with NaAsO2, CH3HgCl, and Na2MoO4. Minor stimulation of CO2 production occurred over the long term with chlorides of Hg, Pb, and Fe. Sulfate reduction was inhibited in the short term by all metals tested and over the long term by all but FeCl2 and NiCl2. Microbial biomass was decreased by FeCl2, K2Cr2O7, ZnSO4, CdCl2, and CuCl2 but remained generally unaffected by PbCl2, HgCl2, and NiCl2. Although the majority of metals produced an immediate inhibition of methanogenesis, for several metals this was only a transient phenomenon followed by an overall stimulation. The initial suppression of methanogenesis may be relieved by precipitation, complexation, or transformation of the metal (possibly by methylation), with the subsequent stimulation resulting from a sustained inhibition of competing organisms (e.g., sulfate-reducing bacteria). For several environmentally significant metals, severe metal pollution may substantially alter the flow of carbon in sediments.  相似文献   

8.
Clostridium acetobutylicum, an obligate anaerobe, grows normally under continuous-O2-flow culture conditions, where the cells consume O2 proficiently. An O2-responsive NADH:rubredoxin oxidoreductase operon composed of three genes (nror, fprA2, and dsr), encoding NROR, functionally uncharacterized flavoprotein A2 (FprA2), and the predicted superoxide reductase desulfoferrodoxin (Dsr), has been proposed to participate in defense against O2 stress. To functionally characterize these proteins, native NROR from C. acetobutylicum, recombinant NROR (rNROR), FprA2, Dsr, and rubredoxin (Rd) expressed in Escherichia coli were purified. Purified native NROR and rNROR both exhibited weak H2O2-forming NADH oxidase activity that was slightly activated by Rd. A mixture of NROR, Rd, and FprA2 functions as an efficient H2O-forming NADH oxidase with a high affinity for O2 (the Km for O2 is 2.9 ± 0.4 μM). A mixture of NROR, Rd, and Dsr functions as an NADH-dependent O2 reductase. A mixture of NROR, Rd, and rubperoxin (Rpr, a rubrerythrin homologue) functions as an inefficient H2O-forming NADH oxidase but an efficient NADH peroxidase with a low affinity for O2 and a high affinity for H2O2 (the Kms for O2 and H2O2 are 303 ± 39 μM and ≤1 μM, respectively). A gene encoding Rd is dicistronically transcribed with a gene encoding a glutaredoxin (Gd) homologue, and the expression levels of the genes encoding Gd and Rd were highly upregulated upon exposure to O2. Therefore, nror operon enzymes, together with Rpr, efficiently function to scavenge O2, O2, and H2O2 by using an O2-responsive rubredoxin as a common electron carrier protein.  相似文献   

9.
The ability of 17 inorganic compounds (POCl3, PSC13, PC13, P2O5, P2S5, P4S3, P4S7, PC15, Sb2O5, As2O5, BiOC12, SeOC12, SO2C12, Sb2S5, VOC12, SiC14 and CrO2Cl2) dissolved in pyridine or 2,2,4-trimethyl pentane, to enhance subsequent staining of tissue components with toluidine blue, phosphotungstic acid-hematoxylin (PTAH), leukofuchsin, and dihydroxydinaphthyl-disulfide (DDD) was studied. Eight of these compounds were also tested for ability to enhance staining with Alcian blue 8GN and Luxol fast blue MBS. Nine of the 17 compounds produced increased staining of certain tissue components with leukofuchsin, 13 with toluidine blue, 16 with PTAH, and 16 with DDD. The results suggest additional approaches to identification of tissue entities by induced metachromatic basophilia and leukofuchsin positivity as well as by the other stains studied, and also suggest a number of hitherto unstudied modes of reaction between the dyes used and reactive groups of tissue components. Many reactions of the compounds tested, with reactive groups known to be present in tissue components, are basecatalyzed, so that choice of solvent can influence the results obtained.  相似文献   

10.
Imino ligands have proven to be able to activate the trans geometry of platinum(II) complexes towards antitumor activity. These ligands, like aromatic N-donor heterocycles, have a planar shape but, different from the latter, have still an H atom on the coordinating nitrogen which can be involved in H-bond formation. Three classes of imino ligands have been extensively investigated: iminoethers (HN=C(R)OR′), ketimines (HN=CRR′), and amidines (HN=C(R)NR′R″). The promising efficacy of the platinum compounds with amidines (activity comparable to that of cisplatin for cis complexes and much greater than that of transplatin for trans complexes) prompted us to extend the investigation to amidine complexes with a bulkier organic residue (R = t-Bu). The tert-butyl group can confer greater affinity for lipophilic environments, thus potentiating the cellular uptake of the compound. In the present study we describe the synthesis and characterization of pivaloamidine complexes of platinum(II), (cis and trans-[PtCl2(NH3){Z-HN=C(t-Bu)NH2}] and cis and trans-[PtCl2{Z-HN=C(t-Bu)NH2}2]), platinum(III) ([Pt2Cl4{HN=C(t-Bu)NH}2(NH3)2]), and platinum(IV) (trans-[PtCl4(NH3){Z-HN=C(t-Bu)NH2}] and trans-[PtCl4{Z-HN=C(t-Bu)NH2}2]). The cytotoxicity of all new Pt complexes was tested toward a panel of cultured cancer cell lines, including cisplatin and multidrug resistant variants. In addition, cellular uptake and DNA binding, perturbations of cell cycle progression, induction of apoptosis, and p53 activation were investigated for the most promising compound trans-[PtCl2(NH3){Z-HN=C(t-Bu)NH2}]. Remarkably, the latter complex was able to overcome both acquired and intrinsic cisplatin resistance.  相似文献   

11.
The hydride ligands of ReH7(PPh3)2 undergo fast hydrogen exchange with water at room temperature while exchanging with the hydrogen atoms of aromatic solvent molecules at a slower rate. The amount of time required for isotopomer peaks to appear in the 1H NMR hydride resonance of ReH7(PPh3)2 was used to distinguish fast hydrogen exchange from slow hydrogen exchange. The room temperature 1H NMR T1 values of adventitious water resonances were used to distinguish two rhenium heptahydride compounds that participate in fast hydrogen exchange with water, ReH7(PPh3)2 and ReH7(AsPh3)2, from one compound that does not participate, ReH7(PCy3)2. Fast hydrogen exchange between ReH7(PPh3)2 and water is greatly slowed or stopped when the compound is dissolved in a solution that contains DMSO. The compound ReH6D(PPh3)2, an isotopomer of ReH7(PPh3)2 that was prepared in situ, exhibited an isotopomer shift in its 31P-{1H} NMR spectrum as well as D-P coupling when measured in the solvent anisole. In a solvent system containing deuteroaniline, nearly all of the hydride ligands were exchanged with deuterium, from aniline, in less than 2 h. Hydrogen exchange between the hydride ligands of ReH7(PPh3)2 and deuteroaniline was found to be reversible upon the addition of normal aniline. The distribution of hydrogen isotopes in the rhenium coordination spheres reflected the overall composition of the exchangeable hydrogen isotopes present in the bulk sample. In a deuteromethanol-containing solvent system, the exchange of hydride ligands between separate ReH7(PPh3)2 isotopomers was evident. The presumed hydrogen exchange intermediate, [ReH6(H2)(PPh3)2]+, may be responsible for the evident exchange of hydride ligands and may also be important to the thermal loss of dihydrogen from ReH7(PPh3)2.  相似文献   

12.
Lipoprotein-associated phospholipase A2 (Lp-PLA2) has been shown to play a crucial role in atherosclerosis, and has been proposed as a promising target for drug discovery. Here, we cloned the Lp-PLA 2 gene from differentiated THP-1 cells, and inserted a carboxy-terminal His6-tagged version of the gene into the pPIC9 Pichia expression vector. The Lp-PLA2 fusion protein was successfully expressed in Pichia pastoris expression system and could be rapidly purified to apparent homogeneity using a single-step purification method. The activity of our recombinant Lp-PLA2 was strong when [3H] PAF was used as a substrate, and the Lp-PLA2 inhibitor SB435495 exhibited an inhibitory curve against the recombinant Lp-PLA2 (IC50=15.93±1 μM). This novel recombinant Lp-PLA2 could prove useful as a screening model for Lp-PLA2 inhibitors, and may facilitate further investigation of this protein in atherosclerosis.  相似文献   

13.
All aerobic biological systems, including N2-fixing root nodules, are subject to O2 toxicity that results from the formation of reactive intermediates such as H2O2 and free radicals of O2. H2O2 may be removed from root nodules in a series of enzymic reactions involving ascorbate peroxidase, dehydroascorbate reductase, and glutathione reductase. We confirm here the presence of these enzymes in root nodules from nine species of legumes and from Alnus rubra. Ascorbate peroxidase from soybean nodules was purified to near homogeneity. This enzyme was found to be a hemeprotein with a molecular weight of 30,000 as determined by sodium dodecyl sulfate gel electrophoresis. KCN, NaN3, CO, and C2H2 were potent inhibitors of activity. Nonphysiological reductants such as guaiacol, o-dianisidine, and pyrogallol functioned as substrates for the enzyme. No activity was detected with NAD(P)H, reduced glutathione, or urate. Ascorbate peroxidation did not follow Michaelis-Menten kinetics. The substrate concentration which resulted in a reaction rate of ½ Vmax was 70 micromolar for ascorbate and 3 micromolar for H2O2. The high affinity of ascorbate peroxidase for H2O2 indicates that this enzyme, rather than catalase, is responsible for most H2O2 removal outside of peroxisomes in root nodules.  相似文献   

14.
Species differences in the response to dietary MoO42? as a metabolic antagonist of Cu are considered briefly. Suggestions that (i) the potency of MoO42? as a Cu antagonist is enhanced by normally innocuous dietary concentrations of S2? and (ii) that MoS42? may be a more effective antagonist than either MoO42? or S2? were investigated in a series of studies with rats. Diets including MoS42? but not of MoO42? or S2? alone promoted a decline in hepatic Cu and ceruloplasmin activity and induced clinical signs of Cu deficiency. Evidence of concurrent anomalies in the partition of Cu between tissues and in the distribution of Cu between proteins of plasma and kidney cytosol suggested that such effects were partly attributable to the development of systemic defects in Cu metabolism. The relationship of such findings to the suggested involvement of MoS42? or its derivatives in the etiology of Mo-induced Cu deficiency in ruminant animals is considered.  相似文献   

15.
We studied the distribution of dissolved O2, CO2, CH4, and N2O in a coastal swamp system in Thailand with the goal to characterize the dynamics of these gases within the system. The gas concentrations varied spatially and seasonally in both surface and ground waters. The entire system was a strong sourcefor CO2 and CH4, and a possible sink for atmospheric N2O. Seasonal variation in precipitation primarily regulated the redox conditions in the system. However, distributions of CO2, CH4, and N2O in the river that received swamp waters were not always in agreement with redox conditions indicated by dissolvedO2 concentrations. Sulfate production through pyriteoxidation occurred in the swamp with thin peat layerunder aerobic conditions and was reflected by elevatedSO 4 2– /Cl in the river water. When SO 4 2– /Cl was high, CO2 and CH4 concentrations decreased, whereas the N2O concentration increased. The excess SO 4 2– in the river water was thus identified as a potential indicator for gas dynamics in this coastal swamp system.  相似文献   

16.
The effect of 21% O2 and 3% O2 on the CO2 exchange of detached wheat leaves was measured in a closed system with an infrared carbon dioxide analyzer. Temperature was varied between 2° and 43°, CO2 concentration between 0.000% and 0.050% and light intensity between 40 ft-c and 1000 ft-c. In most conditions, the apparent rate of photosynthesis was inhibited in 21% O2 compared to 3% O2. The degree of inhibition increased with increasing temperature and decreasing CO2 concentration. Light intensity did not alter the effect of O2 except at light intensities or CO2 concentrations near the compensation point. At high CO2 concentrations and low temperature, O2 inhibition of apparent photosynthesis was absent. At 3% O2, wheat resembled tropical grasses in possessing a high rate of photosynthesis, a temperature optimum for photosynthesis above 30°, and a CO2 compensation point of less than 0.0005% CO2. The effect of O2 on apparent photosynthesis could be ascribed to a combination of stimulation of CO2 production during photosynthesis, and inhibition of photosynthesis itself.  相似文献   

17.
Treatment of Tp′Rh(PMe3)Cl2 and Tp′Rh(CNCH2CMe3)Cl2 with Cp2ZrH2 produces Tp′Rh(PMe3)H2 and Tp′Rh(CNCH2CMe3)H2, respectively, in excellent yield. Photolysis of benzene solutions of each dihydride complex generates hydrogen and the fragment [Tp′Rh(L)] which inserts into the solvent C-H bond. The phosphine dihydride has also been shown to be a catalyst for the hydrogenation of biphenylene, showing a capability to cleave C-C bonds. Reductive elimination of benzene from Tp′Rh(PMe3)PhH is nearly 250 times slower than from Cp*Rh(PMe3)PhH.  相似文献   

18.
The reaction of Ph2PCH2CH2PPh2 (dppe) with BrCH2C(O)C6H4NO2 (1:1.05 molar ratio) in acetone produces a mixture of the new monophosphonium salt [Ph2PCH2CH2PPh2CH2C(O)C6H4NO2]Br (1) and the diphosphonium salt [NO2C6H4C(O)CH2PPh2CH2CH2PPh2CH2C(O)C6H4NO2]Br2 (2). Compound 2 was insoluble in acetone and thus easily separated from the solution of 1. Further, by reacting both the mono- and diphosphonium salts with the appropriate bases the bidentate phosphorus ylides, [Ph2PCH2CH2PPh2CHC(O)C6H4NO2] (3) and [NO2C6H4C(O)CHPPh2CH2CH2PPh2CHC(O)C6H4NO2] (4) were obtained. The reaction of ligand 3 with mercury(II) halides in dry methanol leads to the formation of the P,P-coordinated monomeric complexes {HgX2(Ph2PCH2CH2PPh2CHC(O)C6H4NO2)2} [X = Cl (5), Br (6), I (7)]. The structure of complex 7 being unequivocally determined by single crystal X-ray diffraction techniques. Characterization of these species was also performed by elemental analysis, IR spectroscopy and 1H, 31P, and 13C NMR techniques. These analyses being consistent with a 2:1 stoichiometry ylide/Hg(II) for compounds 5 through 7. Results obtained from theoretical studies are also consistent with a product in which two ylides are coordinated to the Hg(II) center through their phosphine groups, being this product the most stable among all the possible products.  相似文献   

19.
Preparation and characterization of (triphenylphosphine)ruthenium complexes bearing N,O,N′-tridentate ligands, [(L1)RuCl(PPh3)2](BF4) (L1 = 2-[(2-pyridylmethoxy)methyl]pyridine), 1), [(L2)RuCl(PPh3)2](BF4) (L2 = 8-(2-pyridylmethoxy)quinoline, 2) and [(L3)RuCl2(PPh3)] (L3 = 2-[(2-pyridylmethoxy)methyl]quinoline, 3) are described. Complexes 1-3 have been characterized by NMR and elemental analyses. Molecular structures of 2 and 3 have been determined by X-ray crystallography. Both compounds exhibit the octahedral geometry. L2 adopts the facial configuration in 2 while L3 is in a mer-arrangement in 3. Complexes 1-3 have proven to be able to catalyze the transfer hydrogenation of several ketones to alcohols in the presence of KOH and 2-propanol at refluxing, among which complex 3 was found to be the most active.  相似文献   

20.
Treatment of a suspension of AgNO3 and AgCl in MeOH with a solution of N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda) in CHCl3 afforded a binuclear complex [Ag2(dppeda)Cl](NO3)·2MeOH (1). The analogous reactions using AgSCN and dppeda in EtOH/CH2Cl2 gave rise to a polymeric complex [Ag2(dppeda)(SCN)2]n (2). Both compounds were fully characterized by elemental analyses, IR spectra, 1H(31P) NMR, and single-crystal X-ray crystallography. The cation of 1 shows an interesting molecular basket framework in which dppeda adopts a side-by-side coordination mode. Compound 2 possesses an unique 2D (6,3) layer network with 34-membered metallomacrocycles in which dppeda takes a end-to-end coordination mode. The 2D topological framework of 2 is rare in the chemistry of tetraphosphines. The photoluminescent properties of 1 and 2 in solid state at ambient temperature were investigated.  相似文献   

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