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1.
H A Hill D R Turner G Pellizer 《Biochemical and biophysical research communications》1974,56(3):739-744
The reaction of superoxide ion with one equivalent of iron(III)protoporphyrin IX dimethyl ester perchlorate in NN-dimethylformamide at ?50°C yields a complex with an absorption spectrum comparable to that of oxymyoglobin. The complex decomposes at ?10° to iron(II)protoporphyrin IX dimethyl ester which does not react with oxygen. 相似文献
2.
Porphyromonas gingivalis, an obligate anerobe with a growth requirement for iron protoporphyrin IX (FePPIX), is exposed to increased temperatures
in the inflamed periodontal pocket. In this study, P. gingivalis was grown in a chemostat at 37°C (control), 39°C, and 41°C, and examined for hemagglutinating (HA) activity, hemoglobin binding
and degrading activity, and iron protoporphyrin IX binding. HA activity decreased in cells as the growth temperature increased.
Binding of μ-oxo bishaem (dimeric haem), and Fe(II)- and Fe(III)-monomeric forms was increased in 39°C-grown cells but decreased
in 41°C-grown cells compared with controls. Cellular hemoglobin binding and degradation decreased with increased growth temperature.
The decrease in cellular hemagglutination and hemoglobin degradation occurring with increased growth temperature would limit
the potential overproduction of toxic monomeric haem molecules. The increased binding of μ-oxo bishaem and monomeric forms
of FePPIX at 39°C may reflect a defense strategy against reactive oxidants and a mechanism of dampening down the inflammatory
response to maintain an ecological balance.
Received: 24 April 2000 / Accepted: 30 May 2000 相似文献
3.
Etsuo Hasegawa Yoh-ichi Matsushita Manabu Kaneda Kiyoshi Ejima Eishun Tsuchida 《Biochemical and biophysical research communications》1982,104(2):793-798
The enzyme system consisting of glucose-6-phosphate, glucose-6-phosphate dehydrogenase, ferredoxin, ferredoxin-NADP-reductase, and NADP was used to reduce various synthetic iron(III) porphyrins to iron(II) in aqueous buffer (pH7.0) at 25°C. The oxygenation reactions of the thus prepared iron(II) porphyrin complexes were examined and it was found that only the iron(II) picket fence porphyrin-mono(1-lauryl-2-methylimidazole) complex incorporated in liposomes of phosphatidylcholine can form a stable oxygen adduct at 25°C in neutral aqueous medium. 相似文献
4.
The polymeric cobalt(II) porphyrin complexes were prepared from cobalt(II) protoporphyrin IX dimethyl ester(Co(II)P) and copolymers of 4-vinylpyridine and styrene(PSP), and their binding ability of molecular oxygen was studied in toluene solution. The five- and six-coordinate structure of CoP-PSP complexes were confirmed by esr spectra. The esr parameters for the CoP-PSP complexes were not affected by the molecular weight and the vinylpyridine-unit content of PSP-ligand. The 1:1 dioxygen-Co complex was reversibly formed when the solution of CoP-PSP was exposed to oxygen atmosphere at low temperature. While the visible spectra and esr parameters for the dioxygen complexes of CoP-PSP were the same as those of the CoP-pyridine complex, the equilibrium constant for the oxygen binding increased with the vinylpyridine-unit content of the PSP-ligand. The larger entropy change was observed for the oxygenation in the CoP-PSP system especially, of which the vinylpyridine-unit content was large. 相似文献
5.
H Hori M Ikeda-Saito W Froncisz T Yonetani 《The Journal of biological chemistry》1983,258(20):12368-12372
Artificial myoglobins (Mbs) substituted for protoheme with Co(II) proto-and mesoporphyrins IX (proto-and meso-CoMbs, respectively) were prepared. The principal values and eigenvectors of g tensors and the hyperfine coupling tensors of the paramagnetic Co(II) centers of their deoxy forms have been determined by single crystal EPR spectroscopy at 77 K in order to elucidate orientation and electronic structure of the prosthetic group in myoglobin. The orientation of the porphyrin plane of deoxy meso-CoMb were found to be identical to that of deoxy proto-CoMb. However, the in-plane hyperfine coupling constants of deoxy meso-CoMb were more anisotropic and larger than those of deoxy proto-CoMb, suggesting an increase in the electron spin density on the Co(II) ion upon the exchange of protoporphyrin IX with mesoprophyrin IX. Powder EPR spectra of these CoMbs, which were measured at S- and L-band microwave frequencies, exhibited well resolved 59Co hyperfine splittings and can be clearly interpreted by the use of the EPR parameters obtained from single crystal EPR measurements. 相似文献
6.
Acclimation of chlorophyll biosynthetic reactions to temperature stress in cucumber (Cucumis sativus L.) 总被引:1,自引:0,他引:1
The adaptive responses of the greening process of plants to temperature stress were studied in cucumber (Cucumis sativus L. cv. Poinsette) seedlings grown at ambient (25 °C), low (7 °C) and high (42 °C) temperatures. Plastids isolated from these
seedlings were incubated at different temperatures and the net syntheses of various tetrapyrroles were monitored. In plastids
isolated from control seedlings grown at 25 °C, the optimum temperature for synthesis of Mg-protoporphyrin IX monoester or
protochlorophyllide was 35 °C. Temperature maxima for Mg-protoporphyrin IX monoester and protochlorophyllide syntheses were
shifted to 30 °C in chill-stressed seedlings. The net synthesis of total tetrapyrroles was severely reduced in heat-stressed
seedlings and the optimum temperature for Mg-protoporphyrin IX monoester or protochlorophyllide synthesis shifted slightly
towards higher temperatures, i.e. a broader peak was observed. To further study the temperature acclimation of seedlings with
respect to the greening process, tetrapyrrole biosynthesis was monitored at 25 °C after pre-heating the plastids (28–70 °C)
isolated from control, chill- and heat-stressed seedlings. In comparison to 28 °C-pre-heated plastids the percent inhibition
of protochlorophyllide synthesis in 40 °C-pre-heated plastids was higher than for the control (25 °C-grown) in chill-stressed
seedlings and lower than for the control in heat-stressed seedlings. Maximum synthesis of total tetrapyrroles and protoporphyrin
IX was observed when chloroplasts were heated at 50 °C, which was probably due to heat-induced activation of the enzymes involved
in protoporphyrin IX synthesis. Prominent shoulders towards lower or higher temperatures were seen in chill-stressed or heat-stressed
seedlings, respectively. The shift in optimum temperature for tetrapyrrole biosynthesis in chill- and heat-stressed seedlings
was probably due to acclimation of membranes possibly undergoing desaturation or saturation of membrane lipids. Proteins synthesized
in response to temperature-stress may also play an important role in conferring stress-tolerance in plants.
Received: 8 October 1998 / Accepted: 19 November 1998 相似文献
7.
Electron spin resonance spectra of the first Cu(II) complexes of human serum albumin, dog serum albumin, l-aspartyl-l-histidine N-methylamide and glycyl-glycyl-l-histidine N-methylamide have been studied using isotopically pure 65Cu in its chloride form. At 77° K, the esr spectra of Cu(II) complex of human serum albumin exhibited only one form of esr signal between pH 6.5 and 11. No intermediate forms were detected. The presence of an equally spaced nine-line superhyperfine structure with spacing ~15 G indicated considerable covalent bonding between Cu(II) and four nitrogen atoms derived from the protein. The esr spectrum form of Cu(II) bound to human serum albumin detected at neutral pH would be consistent with the participation of four nitrogens from the α-NH2 group, two peptide groups, and the imidazole group of a histidine residue. In contrast, the esr spectra of Cu(II)-dog serum albumin complex showed a transition from a low pH form to a high pH form as the pH was increased to 9.5. These spectral changes were found to be reversible upon lowering the pH. Ligand superhyperfine splittings in the low pH form of the esr signal of Cu(II)-dog albumin were not resolved. The distinct pH dependence of the esr signals observed in human and dog serum albumin complexes could be correlated to their respective optical spectra changes as a function of pH. At room temperature and in the pH range between 6 and 11, the esr spectra of Cu(II) complexes of l-aspartyl-l-alanyl-l-histidine N-methylamide and glycyl-glycyl-l-histidine N-methylamide exhibited a well-resolved nine-line superhyperfine structure indicating metal coordination with four equivalent nitrogen atoms of peptide. 相似文献
8.
《Inorganica chimica acta》1986,125(1):55-62
The binuclear copper in the active site of Carcinus maenas hemocyanin has been substituted with one EDTA-resistant Co(II) per 75 000 Mr by reconstitution of the apo protein. Specific cobalt substitution at the copper binding site is demonstrated from the optical spectral changes directly correlated with the amount of Co(II) bound to the protein, the ellipticity in CD spectra in the near UVVis region, and the efficiency of tryptophan fluorescence quenching. The optical absorption spectrum of the cobalt-substituted protein is characterized by a band pattern attributable to d-d transitions of the metal ion. Both the position of the wavelength maximum (568 nm) and the molar extinction coefficient (≅300 M-1 cm-1) are typical of a four-coordinate, pseudo-tetrahedral Co(II) center.Optical titrations indicate that Cl-, Br-, N3-, SCN-, and CN- bind to Co(II)Hc, each with a stoichiometry of 1:1 per metal center. The apparent stability constants determined from Hill plots of titration data decrease in the order CN- » N3- ≅ SCN- >Cl->Br-. Low temperature EPR studies demonstrate that at pH 7, the cobalt is high spin both in the presence and absence of anionic ligands. A low spin species is formed at pH 9 in the presence of cyanide. The spectrum of this latter complex exhibits superhyperfine structure indicative of metal ligation to 14N supplied by the protein. Direct ligation of cyanide to cobalt is demonstrated by additional spectral splitting observed when this complex is formed using 13C-labelled CN-. 相似文献
9.
Regulation of soluble guanylate cyclase activity by porphyrins and metalloporphyrins 总被引:14,自引:0,他引:14
Alterations of the chemical structure of protoporphyrin IX markedly altered the activation of soluble guanylate cyclase purified from bovine lung. Hydrophobic side chains at positions 2 and 4 and vicinal propionic acid residues at positions 6 and 7 of the porphyrin ring (protoporphyrin IX, mesoporphyrin IX) were essential for maximal enzyme activation (Ka = 7-8 nM; Vmax = 6-8 mumol of cGMP/min/mg). Substitution of hydrophobic with polar groups (hematoporphyrin IX, coproporphyrin III), or with hydrogen atoms ( deuteroporphyrin IX), and methylation of propionate residues resulted in decreased enzyme stimulation. Stimulatory porphyrins increased the Vmax and the apparent affinities of enzyme for MgGTP and uncomplexed Mg2+. An open central core in the porphyrin ring was essential for enzyme activation. The pyrrolic nitrogen adduct, N-phenylprotoporphyrin IX, was inhibitory and competitive with protoporphyrin IX (KI = 73 nM). Similarly, metalloporphyrins inhibited enzymatic activity and ferro-protoporphyrin IX (KI = 350 nM), zinc-protoporphyrin IX (KI = 50 nM) and manganese-protoporphyrin IX (KI = 9 nM) were competitive with protoporphyrin IX. Inhibitory porphyrins and metalloporphyrins also prevented enzyme activation by S-nitroso-N- acetylpenicillamine and NO. Guanylate cyclase reconstituted with such porphyrins required higher concentrations of protoporphyrin IX for further activation and were not activated by NO. Thus, porphyrins, metalloporphyrins, and NO appeared to interact at a common binding site on guanylate cyclase. This common site is likely that which normally binds heme and, therefore, NO-heme when the heme-containing enzyme is exposed to NO. Thus, NO and nitroso compounds may react with enzyme-bound heme to generate a modified porphyrin which structurally resembles protoporphyrin IX in its interaction with guanylate cyclase. 相似文献
10.
Freely diffusable lipid spin labels in bovine rod outer segment disc membranes display an apparent two-component ESR spectrum. One component is markedly more immobilized than that found in fluid lipid bilayers, and is attributed to lipid interacting directly with rhodopsin. For the 14-doxyl stearic acid spin label this more immobilized component has an outer splitting of 59 G at 0°C, with a considerable temperature dependence, the effective outer splitting decreasing to 54 G at 24°C. Spin label lipid chains covalently attached to rhodopsin can also display a two-component spectrum in rod outer segment membranes. In unbleached, non-delipidated membranes the 16-doxyl stearoyl maleimide label shows an immobilized component which has an outer splitting of 59 G at 0°C and a considerable temperature dependence. This component which is not resolved at high temperatures (24–35°C), is attributed to the lipid chains interacting directly with the monomeric protein, as with the diffusable labels. In contrast, in rod outer segment membranes which have been either delipidated or extensively bleached, a strongly immobilized component is observed with the 16-doxyl maleimide label at all temperatures. This immobilized component has an outer splitting of 62–64 G at 0°C, with very little temperature dependence (61–62 G at 35°C), and is attributed to protein aggregation. 相似文献
11.
《Inorganica chimica acta》1988,153(4):201-204
The reactions of the superoxide ion (O2−) with tetra-p-tolyporphyrinatocobalt(II) [Co(II)TTP] in dimethyl sulfoxide(DMSO) have been investigated by use of electron spin resonance (ESR) spectroscopy. In the absence of oxygen, Co(II)TTP in DMSO gives the DMSO adduct, Co(II)(TPP)(DMSO). When this DMSO adduct is exposed to air, an oxygen complex, Co(II)(TTP)(DMSO)(O2), is formed in which the binding state between Co(II) and O2 has been considered formally as Co(III)O2−. When the superoxide ion (O2− is added to this oxygen complex, a new superoxide complex, Co(II)(TTP)(O2−)2, is formed. The same superoxide adduct is formed by the reaction of O2− with Co(II)TTP in the absence of oxygen. 相似文献
12.
《Inorganica chimica acta》1989,161(2):247-251
An X-ray structure determination is reported for the N-oxide-bridged dimeric complex [Co(poph)- (NCS)2]2 with 2-pyridinecarboxaldehyde 1-oxide 2′-pyridinylhydrazone (poph). The complex is monoclinic, P21/c, with a = 12.460(7), b = 9.884(3), c = 16.562(8) Å, β= 127.60(2)° and Z = 4. The ligand coordinates as a planar ONN tridentate via the N-oxide oxygen and the hydrazone and pyridyl nitrogens. A second out-of-ligand-plane bond from the N-oxide oxygen to another cobalt produces a centrosymmetric N-oxide-bridged structure. The in-ligand and out-of-ligand-plane CoO distances are 2.028(5) and 2.460(5) Å, respectively. Each cobalt(II) is octahedrally coordinated by two cisN- bonded thiocyanates, by an ONN-bonded poph molecule, and by a bridging N-oxide oxygen. This is the first structure report of a pyridine N-oxide. bridged cobalt(II) complex. 相似文献
13.
Maurizio Leone Antonio Cupane Valeria Militello Lorenzo Cordone 《European biophysics journal : EBJ》1994,23(5):349-352
We report the thermal broadening of the Soret band in heme-CO, heme-OH and protoporphyrin IX in the temperature range 300–20 K. For protoporphyrin IX the temperature dependent Gaussian line broadening follows the behavior predicted by the harmonic approximation in the entire temperature range investigated. In contrast, for heme-CO and heme-OH the harmonic behavior is obeyed only up to about 180 K and an anomalous line broadening increase is observed at higher temperatures. This effect is attributed to the onset of anharmonic motions of the iron atom with respect to the porphyrin plane. Comparison with previously reported analogous data for heme proteins enables us to suggest that the onset of substate interconversions in these latter systems can be reflected in motions of the iron atom with respect to the porphyrin plane.
Correspondence to: L. Cordone 相似文献
14.
Etsuo Hasegawa Yoh-ichi Matsushita Manabu Kaneda Kiyoshi Ejima Eishun Tsuchida 《Biochemical and biophysical research communications》1982,105(4):1416-1419
To prepare a potent synthetic oxygen carrier in aqueous media, the iron(II) picket fence porphyrin complex with one hydrophobic imidazole was incorporated into a lipid bilayer of phosphatidylcholine. The incorporation was confirmed by gel permeation chromatography and ultracentrifugation, which indicates the complex being trapped in the multilayer liposome. The liposomal iron(II) porphyrin complex could bind molecular oxygen reversibly in neutral aqueous media and in the serum of a rat blood at 25°C. 相似文献
15.
Feng R Zhai WL Yang HY Jin H Zhang QX 《Biochemical and biophysical research communications》2011,411(2):299-304
Porphyromonas gingivalis acquires heme through an outer-membrane heme transporter HmuR and heme-binding hemophore-like lipoprotein HmuY. Here, we compare binding of iron(III) mesoporphyrin IX (mesoheme) and iron(III) deuteroporphyrin IX (deuteroheme) to HmuY with that of iron(III) protoporphyrin IX (protoheme) and protoporphyrin IX (PPIX) using spectroscopic methods. In contrast to PPIX, mesoheme and deuteroheme enter the HmuY heme cavity and are coordinated by His134 and His166 residues in a fully analogous way to protoheme binding. However, in the case of deuteroheme two forms of HmuY–iron porphyrin complex were observed differing by a 180° rotation of porphyrin about the α-γ-meso-carbon axis. Since the use of porphyrins either as active photosensitizers or in combination with antibiotics may have therapeutic value for controlling bacterial growth in vivo, it is important to compare the binding of heme derivatives to HmuY. 相似文献
16.
《Inorganica chimica acta》1988,151(1):77-83
Mössbauer (78 K) and electronic absorption spectra (298 K) of tetra(p-carboxyphenyl)porphyrin iron(II) solutions are reported and discussed. Evidence for only two iron(II) complexes, the first an intermediate spin and the second a high spin complex, is found in the Mössbauer spectra. Electronic absorption spectra show a low spin complex is present at very low concentrations. It is observed from these results that the carboxy groups on the phenyl rings of this porphyrin greatly influence the chemistry. From the difference in the quadrupole splitting for the intermediate spin complex compared to that found in the tetra(p-sulphophenyl)porphyrin iron(II) system, the substituent on the phenyl ring clearly changes the electron density on the pyrrole nitrogen atoms. 相似文献
17.
Dariusz Man Rudolf Słota Małgorzata A. Broda Giuseppe Mele Jun Li 《Journal of biological inorganic chemistry》2011,16(1):173-181
Liposomes characterized by membranes featuring diverse fluidity (liquid-crystalline and/or gel phase), prepared from egg yolk
lecithin (EYL) and dipalmitoylphosphatidylcholine (DPPC), were doped with selected metalloporphyrins and the time-related
structural and dynamic changes within the lipid double layer were investigated. Porphyrin complexes of Mg(II), Mn(III), Fe(III),
Co(II), Ni(II), Cu(II), Zn(II), and the metal-free base were embedded into the particular liposome systems and tested for
350 h at 24°C using the electron spin resonance (ESR) spin probe technique. 5-DOXYL, 12-DOXYL, and 16-DOXYL stearic acid methyl
ester spin labels were applied to explore the interior of the lipid bilayer. Only the 16-DOXYL spin probe detected evident
structural changes inside the lipid system due to porphyrin intercalation. Fluidity of the lipid system and the type of the
porphyrin complex introduced significantly affected the intermolecular interactions, which in certain cases may result in
self-assembly of metalloporphyrin molecules within the liposome membrane, reflected in the presence of new lines in the relevant
ESR spectra. The most pronounced time-related effects were demonstrated by the EYL liposomes (liquid-crystalline phase) when
doped with Mg and Co porphyrins, whereas practically no spectral changes were revealed for the metal-free base and both the
Ni and Zn dopants. ESR spectra of the porphyrin-doped gel phase of DPPC liposomes did not show any extra lines; however, they
indicated the formation of a more rigid lipid medium. Electronic configuration of the porphyrin’s metal center appeared crucial
to the degree of molecular reorganization within the phospholipid bilayer system. 相似文献
18.
Lorentzen MS Moe E Jouve HM Willassen NP 《Extremophiles : life under extreme conditions》2006,10(5):427-440
The gene encoding catalase from the psychrophilic marine bacterium Vibrio salmonicida LFI1238 was identified, cloned and expressed in the catalase-deficient Escherichia coli UM2. Recombinant catalase from V. salmonicida (VSC) was purified to apparent homogeneity as a tetramer with a molecular mass of 235 kDa. VSC contained 67% heme b and 25% protoporphyrin IX. VSC was able to bind NADPH, react with cyanide and form compounds I and II as other monofunctional small subunit heme catalases. Amino acid sequence alignment of VSC and catalase from the mesophilic Proteus mirabilis (PMC) revealed 71% identity. As for cold adapted enzymes in general, VSC possessed a lower temperature optimum and higher catalytic efficiency (k
cat/K
m) compared to PMC. VSC have higher affinity for hydrogen peroxide (apparent K
m) at all temperatures. For VSC the turnover rate (k
cat) is slightly lower while the catalytic efficiency is slightly higher compared to PMC over the temperature range measured, except at 4°C. Moreover, the catalytic efficiency of VSC and PMC is almost temperature independent, except at 4°C where PMC has a twofold lower efficiency compared to VSC. This may indicate that VSC has evolved to maintain a high efficiency at low temperatures. 相似文献
19.
Madhusudan K. Vasudevamurthy Laurence R. Weatherley Michael Lever 《Biocatalysis and Biotransformation》2013,31(3-4):285-291
The protective effect of the synthetic compensatory solutes, dimethylthetin (CAS 4727-41-7) and homodeanol betaine (N,?N-dimethyl-N-(2-hydroxyethyl)-N-(2 carboxyethyl) ammonium inner salt, CAS 6249-53-2), on two enzymes: lactate dehydrogenase (LDH from rabbit muscle) and a microbial lipase, was compared with that of glycine betaine, trehalose and sorbitol. When the enzyme plus 1?M solute were heated for 10?min at temperatures between 35–75°C, the temperature at which 50% of enzyme activity was lost increased most in the presence of trehalose (7.9° for LDH, 11.6° for lipase) and homodeanol betaine (10.7° for LDH, 11.0° for lipase). With both enzymes, more activity was retained at extreme temperatures in the presence of homodeanol betaine than with trehalose. Glycine betaine, dimethylthetin and sorbitol were less effective. Enzyme plus 1?M stabilizer solutions were frozen at ?30°C and freeze-dried for 24?h. Trehalose was the most effective stabilizer of lactate dehydrogenase, and homodeanol betaine of lipase, during freeze-drying. 相似文献
20.
T R Tephly B L Coffman G Ingall M S Ziet-Har H M Goff H D Tabba K M Smith 《Archives of biochemistry and biophysics》1981,212(1):120-126
Administration of the porphyrogenic agent, 3,5-diethoxycarbonyl-1,4-dihydrocollidine (DDC) to mice, leads to the accumulation of N-methylprotoporphyrin IX in liver. This porphyrin is a potent inhibitor of ferrochelatase activity and accounts for the porphyria produced after DDC administration. The N-methylprotoporphyrin IX extracted from DDC-treated mice is primarily of one isomeric form, as shown by nuclear magnetic resonance spectroscopy. The methyl group of N-methylprotoporphyrin IX isolated from DDC-treated mice is derived mostly from the 4-methyl group of DDC. The transfer of this methyl group and its subsequent covalent attachment to protoporphyrin IX may be mediated by a form of hepatic microsomal cytochrome P-450. N-Methylprotoporphyrin IX is also found in livers of untreated mice at levels that are low but significant. 相似文献