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21.
Raffaello Romeo Giuseppe Arena Luigi Mons Scolaro Maria Rosario Plutino 《Inorganica chimica acta》1995,240(1-2):81-92
The rates of displacement of dimethyl sulfoxide from the cation [Pt(phen) (CH3) (Me2SO)]+ by a series of uncharged and negatively charged nucleophiles have been measured in a methanol/water (19:1 vol./vol.) mixture. The starting complex and the reaction products were characterized either as solids or in solution by their IR and 1H NMR spectra. The substitution reactions take place by way of a direct bimolecular attack of the ligand on the substrate. The sequence of reactivity observed is as expected on the basis of a nucleophilicity scale relevant for + 1 charged substrates ([Pt(en) (NH3)Cl]+ used as standard). The difference of reactivity between the first (t-BuNH2) and the last (SeCN−) members of the series spans five orders of magnitude. The value measured for the nucleophilic discrimination (1.55) is the highest found so far for cationic substrates. This is a result of the easy transfer of some of the electron density brought in by the incoming ligand into the ancillary ligands. When the reaction is carried out in a series of protic and dipolar aprotic solvents, using chloride ion as nucleophile, the rate of formation of [Pt (phen) (CH3)Cl] is dominated by the extent of solvation of Cl−, as measured by its values of the Gibbs molar energy of transfer ΔtG0. Conductivity measurements at 25°C in dichloromethane were fitted to the Fuoss equation and the values of the dissociation constants Kd for the ion pairs were calculated as follows: 2.27 × 10−5 M for Bu4NCl, 2.75 × 10−5 M for Bu4NSCN and 17.05 × 10−5 M for [Pt(phen) (CH3) (Me2SO)]PF6. The pseudo-first-order rate constants kobs for the reactions with Bu4NCl, Bu4NBr, Bu4NSCN and Bu4NI showed a curvilinear dependence on the concentration of the salt which levels off very soon (at concentrations higher than 0.005 M the kinetics are zero order in [Bu4NX]). On addition of the inert electrolyte Bu4NPF6 the rates slow down and the kinetics follow the rate law kobs = kKip[Bu4NX]/[Bu4NPF6] + Kip[Bu4NX]). These findings fit well with a reaction scheme which involves a pre-equilibrium Kip between ion pairs, followed by unimolecular substitution within the contact ion pair [Pt(phen) (CH3) (Me2SO)X]ip. Values of the equilibrium constants Kip for ion-pair exchange and of the internal substitution rates k were derived. The latter showed that the discrimination in reactivity between Cl−, Br−, SCN− and I− is greatly reduced with respect to aqueous solutions. The reason behind this may be desolvation of the ions coupled to the fact that a contact ion pair is already at a certain distance along the reaction coordinate in the direction of the transition state. Applications of the special salt effect and of ion pairing to synthesis are discussed. 相似文献
22.
Hints on the evolutionary design of a dimeric RNase with special bioactions. 总被引:2,自引:2,他引:0
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A. Di Donato V. Cafaro I. Romeo G. D'Alessio 《Protein science : a publication of the Protein Society》1995,4(8):1470-1477
Residues P19, L28, C31, and C32 have been implicated (Di Donato A, Cafaro V, D'Alessio G, 1994, J Biol Chem 269:17394-17396; Mazzarella L, Vitagliano L, Zagari A, 1995, Proc Natl Acad Sci USA: forthcoming) with key roles in determining the dimeric structure and the N-terminal domain swapping of seminal RNase. In an attempt to have a clearer understanding of the structural and functional significance of these residues in seminal RNase, a series of mutants of pancreatic RNase A was constructed in which one or more of the four residues were introduced into RNase A. The RNase mutants were examined for: (1) the ability to form dimers; (2) the capacity to exchange their N-terminal domains; (3) resistance to selective cleavage by subtilisin; and (4) antitumor activity. The experiments demonstrated that: (1) the presence of intersubunit disulfides is both necessary and sufficient for engendering a stably dimeric RNase; (2) all four residues play a role in determining the exchange of N-terminal domains; (3) the exchange is the molecular basis for the RNase antitumor action; and (4) this exchange is not a prerequisite in an evolutionary mechanism for the generation of dimeric RNases. 相似文献
23.
Mutant hemoglobin stability depends upon location and nature of single point mutation 总被引:1,自引:0,他引:1
The temperature dependence of the rates of heme release from the beta subunits of methemoglobin A and 5 beta mutant methemoglobins has been determined. The rates were largest for two hemoglobins with mutations distal to heme, previously known to be unstable. The other 3 mutants also released heme faster than A. These hemoglobins, with single point mutations at the alpha 1/beta 2 interface, were previously thought to be stable. The low reported yields of the 5 mutant proteins covaries with the relative rates of heme release from the met species. 相似文献
24.
Gianfranco Di Matteo Giovanni Romeo Guido Di Prisco 《Archives of biochemistry and biophysics》1980,200(1):55-60
A study on the response of the stability and activity of crystalline ox liver nuclear and mitochondrial glutamate dehydrogenases to temperature variations has been carried out. The thermodynamic properties of the heat inactivation process and of the reaction with the substrates glutamate and α-ketoglutarate have been investigated. The heat inactivation of nuclear glutamate dehydrogenase proceeds at a faster rate than that of the mitochondrial enzyme in the temperature range 40–51 °C; the enthalpy of activation of the inactivation process is higher and the entropy is almost double, compared to the values of mitochondrial glutamate dehydrogenase. The effect of temperature on the maximal velocity shows that, with both glutamate and α-ketoglutarate, the enthalpy of activation with nuclear glutamate dehydrogenase is double and the decrease in entropy almost half of the values of the mitochondrial enzyme. The variation of the apparent Km with temperature shows a decrease of the affinity of both enzymes for glutamate, with no major difference in the thermodynamic properties of the reaction. With α-ketoglutarate, on the other hand, the affinity of nuclear glutamate dehydrogenase decreased, whereas that of the mitochondrial enzyme increased with temperature. The process is therefore exothermic with the former enzyme, endothermic with the latter; furthermore, it occurs with a decrease in enthropy with nuclear glutamate dehydrogenase, but with a large increase with the mitochondrial enzyme. The studies on the effect of temperature on the activity were carried out in the range 20–44 °C. 相似文献
25.
A Oliva G Cacciapuoti G Romeo M Porcelli 《Bollettino della Società italiana di biologia sperimentale》1979,55(19):2019-2024
The paper reports the preparation and the chromatographic separation of new deaminated analogs of S-adenosyl(5')-3-methylthiopropylamine, i.e. S-adenosyl(5')-3-methylthiopropanol and S-inosyl(5')(-3-methylthiopropanol. These compounds can be used as specific inhibitors of polyamine biosynthesis. It is also reported the characterization of new sulfonium compounds by U.V. spectrophotometry, thin layer chromatography, high voltage electrophoresis, hydrolysis to known fragments. 相似文献
26.
Giovanni Romeo 《Human genetics》1977,39(3):261-276
Summary In four of the five autosomal dominant porphyrias four different partial enzymatic defects of the porphyrin biosynthetic pathway have been discovered in the last few years. With the exception of protoporphyria, the residual enzymatic activity in carriers of these defects is approximately equal to 50% of that found in controls. In each case the pattern of excretion of porphyrin and/or porphyrin precursors reflects the site of the partial metabolic block. There are indications, at least in intermittent acute porphyria, that the degree of penetrance of the disorder varies according to the level of phenotypic expression, being highest for the enzyme deficiency, lower for the excretion of precursors and lowest for the clinical symptoms. It is proposed that environmental factors, and probably also gene interaction, are the cause of the different degrees of penetrance.On leave from the University of Naples, Italy 相似文献
27.
Stimulus-induced maturation of probactenecins, precursors of neutrophil antimicrobial polypeptides 总被引:12,自引:0,他引:12
M Zanetti L Litteri G Griffiths R Gennaro D Romeo 《Journal of immunology (Baltimore, Md. : 1950)》1991,146(12):4295-4300
The antimicrobial polypeptides Bac7 and Bac5 (bactenecins) are stored in the large granules of bovine neutrophils as precursor forms, or probactenecins. Maturation of probactenecins has been investigated by studying the effects of stimulus-induced degranulation on this process. Stimulation of neutrophils with PMA, which is a secretagogue for specific and large granules but not for azurophils, induces a substantial discharge of uncleaved probactenecins in the extracellular medium, as revealed by Western blot analysis. When neutrophils are exposed to opsonized bacteria in the presence of cytochalasin B, resulting in exocytosis of the content of azurophils in addition to that of specific and large granules, probactenecins are secreted and rapidly converted into the corresponding mature antimicrobial peptides. Such a conversion is prevented if serine proteases, stored in the azurophils, are inhibited by pretreatment of neutrophils with PMSF. Phagocytosis, while causing a rapid discharge of the contents of azurophil and of the large granules into phagocytic vacuoles, as indicated by immunogold electron microscopy, also induces cleavage of probactenecins into mature peptides, as revealed by Western blot analysis. We conclude that the final processing of the storage forms of bactenecins arises from their interaction with the serine protease(s) of azurophils during bacteria-induced degranulation of neutrophils. 相似文献
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ATPase activity and phosphorylation by [γ-32P] ATP of isolated plasma membrane of alveolar macorphages are stimulated in a parallel fashion by physiologic concentrations of Ca2+, with half-maximal activating effect of this ion at (3–7) × 10?7 M. For various membrane preparations, a direct proportionality exists between Ca2+-dependent ATPase activity and amount of 32P incorporated. Labeling of membrane attains the steady-state level by 10 sec at 0°C, and is rapidly reversed by adenosine diphosphate (ADP). K+ decreases the amount of membrane-bound 32P, mainly by enhancing the rate of dephosphorylation of the 32P-intermediate. Hydroxylamine causes a release of about 90% of 32P bound to the membrane, thus indicating that the 32P-intermediate contains an acyl-phosphate bond. When the labeled plasma membrane is solubilized and electrophoresed on acrylamide gels in the presence of sodium dodecyl sulphate, the radioactivity appears to be largely associated with a single protein fraction of 132,500 ± 2,000 apparent molecular weight. These features of the macrophage Ca2+-ATPase suggest that the enzyme activity might be part of a surface-localized Ca2+-extrusion system, participating in the regulation of Ca2+-dependent activities of the macrophage. 相似文献