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1.
Short-term (10 min) effects of 100 nM 12-O-tetradecanoylphorbol-13-acetate (TPA), the protein kinase C (PKC) activator, on cardiac macroscopic (gj) and single channel (γj) gap junctional conductances were studied in pairs of neonatal rat cardiomyocytes. Under dual whole-cell (WC) or perforated patch (PP) voltageclamp, gj increased by 15.5 ± 7.2% (mean ± SD, n = 9) and by 46.3 ± 17.0% (n = 5), respectively. The latter difference is not related to intracellular calcium concentration, because raising the Ca2+ concentration in the electrode solution did not change the TPA-induced increase in gj observed under WC conditions. The inactive phorbol ester, 4α-phorbol 12,13-didecanoate (αPDD), did not affect gj. Single cardiac gap junction channel events, resolved in the presence of heptanol, indicated two γj sizes of 20 and 40-45 pS. Under control conditions, the larger events were most frequently observed. Whereas αPDD did not change this distribution, TPA shifted the γj distribution to the lower sizes. Diffusion of Lucifer Yellow (LY) and 6-carboxyfluorescein (6-CF), gap junction permeant tracers, was studied on small clusters of cardiomyocytes. Under control conditions, LY labeled 19.4 ± 7.2 cells (mean ± SD, n = 18) and 6-CF labeled 8.4 ± 2.2 cells (n = 20). Whereas αPDD did not change the extent of dye transfer, TPA restricted the diffusion of LY to 2.8 ± 1.3 cells (n = 11) and of 6-CF to 2.4 ± 1.4 cells (n = 20). This suggests that permeability and single channel conductance of connexin 43 channels are parallely related. Altogether, these results point to the opposite modulation of electrical and metabolic coupling of cardiac cells evoked by TPA.  相似文献   

2.
Complexes of formula M(2,5-DHB)24H2O (M = Mn, Co, Ni, Zn, Cu and Cd; 2,5-DHB = 2,5-dihydroxybenzoate) were prepared and characterized by means of infrared and electronic spectroscopy, and by electron spin resonance. For the Zn complex the crystal and molecular structure was also determined by single-crystal X-ray diffraction analysis. The crystal is orthorhombic, space group Pbca (No. 61), with a = 18.503(4), b = 13.536(3), c = 6.900(2) Å, and Z = 4. The final refinement used 877 reflections and gave a residual R value of 0.041. The complex has slightly compressed octahedral coordination, with the zinc atom bound to two monodentate carboxylate groups lying in trans positions and four water molecules. X-ray data and infrared spectra show the Mn, Co, Ni, Zn and Cd complexes to be isostructural with the Zn compound. The electronic, infrared and ESR spectra of the copper(II) complex are consistent with a CuO4? based chromophore involving two water molecules and two monodentate carboxylate groups in the metal plane, and long axial contacts.  相似文献   

3.
《Inorganica chimica acta》2009,362(14):5085-524
New, heteroleptic zinc and cobalt complexes with tri-tert-butoxysilanethiolate and imidazole co-ligands are characterized by crystal structure studies. The ligands exhibit different coordination modes to Co(II) ions: NOS2 (with methanol as O-donor ligand) in 2, NO2S2 in 2′′, N2S2 in 1, and to Zn(II) ions: N2S2 in 3 and N3S in 4. Complex 2′ is a structural analog of cobalt-substituted active site of alcohol dehydrogenase. All four-coordinate Co(II) and Zn(II) complexes have tetrahedral geometry. Solution and solid state electronic spectra of cobalt(II) complexes are discussed and compared to literature data available for the cobalt-substituted liver alcohol dehydrogenase and sorbitol dehydrogenase. The EPR spectra of all cobalt complexes exhibit at 77 K a characteristic broad signal with g ∼3.6 and 5.6, strongly indicating a high-spin state, S = 3/2, of Co(II) complexes.  相似文献   

4.
Herein, a two‐species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) incorporated in cobalt hexacyanoferrate (CoFe(CN)6) is proposed as a breakthrough to achieve jointly high‐capacity and high‐voltage aqueous Zn‐ion battery. The Zn/CoFe(CN)6 battery provides a highly operational voltage plateau of 1.75 V (vs metallic Zn) and a high capacity of 173.4 mAh g?1 at current density of 0.3 A g?1, taking advantage of the two‐species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) couples. Even under extremely fast charge/discharge rate of 6 A g?1, the battery delivers a sufficiently high discharge capacity of 109.5 mAh g?1 with its 3D opened structure framework. This is the highest capacity delivered among all the batteries using Prussian blue analogs (PBAs) cathode up to now. Furthermore, Zn/CoFe(CN)6 battery achieves an excellent cycling performance of 2200 cycles without any capacity decay at coulombic efficiency of nearly 100%. One further step, a sol–gel transition strategy for hydrogel electrolyte is developed to construct high‐performance flexible cable‐type battery. With the strategy, the active materials can adequately contact with electrolyte, resulting in improved electrochemical performance (≈18.73% capacity increase) and mechanical robustness of the solid‐state device. It is believed that this study optimizes electrodes by incorporating multi redox reaction species for high‐voltage and high‐capacity batteries.  相似文献   

5.
The IR spectra of a number of dithiocarbamate (dtc) complexes (M(R2dtc)2, n = 2, M = Ni, Cu, Zn, Cd, Pb, Hg, Se, Te; n = 3, M = Cr, Fe, Co, As, Sb, Bi, R = Et, Prn, Pri, Bun, Bri, as well as the laser Raman spectra of a few colourless compounds (M(Et2dtc)2 M = Zn, Cd, Pb, Hg), have been recorded and discussed as to the validity of the Bonati-Ugo (BU) criterion for discerning the dtc bonding type from its νas(CS) band (ca. 1000 cm?1), By comparing these bands for dtc complexes containing different N-substituted ligands, their splittings can be proved to be due to interligand coupling of the CS ligand modes. Further comparison with X-ray diffraction data shows that the dtc ligands, irrespective of the host complex or the ligand bonding type, are at sites of C1 symmetry, thus ruling out the possibility to detect the ligand bonding type from the solid state vibrational spectra. New evidence is presented that the RN modes are present in the 1000 cm?1 region, thus making it unsuitable for the determination of the ligand bonding type.  相似文献   

6.
Complexes of Mn(II), Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Pt(II) with 3- and 5-substituted salicylaldehyde o-hydroxybenzoylhydrazones (XSBH, X = H, 3-NO2, 3-CH3O, 5-Cl, 5-Br, 5-CH3 or 5-NO2) have been prepared and characterized by elemental analysis, conductance measurements, magnetic susceptibilities (from room temperature down to liquid nitrogen temperature) and spectral studies. These studies indicate the following structures: monomeric, high-spin, distorted octahedral for Mn(XSBH)2; monomeric, high-spin, five-coordinate for Fe(XSBH)SO4·H2O; dimeric, high-spin phenoxide bridged, five-coordinate for Fe(XSBH)Cl; dimeric, high-spin five-coordinate for Co(XSBH)Cl·2H2O; dimeric low-spin, five-coordinate for Ni(XSBH)Cl·2H2O; dimeric, four-coordinate for Zn(XSBH); and a square-planar structure for M(XSBH)Cl·H2O (M = Cu(II) or Pt(II).Intermolecular antiferromagnetic exchange interactions are present in Fe(III) complexes, where the exchange parameter (J) is ca. −8.0 cm−1 for these complexes. The Fe(III) complexes exhibit asymmetric quadrupole split doublets in their 57Fe Mössbauer spectra. The asymmetry is found to be temperature dependent with relatively symmetrical doublets seen at low temperature. The polycrystalline ESR spectra of Cu(II) complexes are isotropic and indicate a dx2−y2 ground state in square-planar stereo-chemistry. All these metal complexes have been screened for their antitumor activity against the P 388 lymphocytic leukaemia test system in mice and enhanced antitumor activity relative to the free ligand was found but no significant activity at the dosages used.  相似文献   

7.
Four new Co(III) complexes, namely [Co(cq)3](PF6)3, [Co(phen)2(cq)](PF6)3, [Co(bnp)3] (PF6)3, and [Co(phen)2(bnp)](PF6)3 (where cq = chromeno[2,3-b]quinoline, phen = 1,10-phenanthroline and bnp = dibenzo[b,g][1,8]naphthyridine), were synthesized and structurally characterized. Spectroscopic data suggested an octahedral geometry for all the complexes. Binding studies of these complexes with double-stranded (ds)DNA were analyzed by absorption spectra, viscosity, and thermal denaturation studies. The results revealed that the metal complex intercalates into the DNA base stack as intercalator. The oxidative cleavage activities of the complexes were studied with supercoiled pUC19 DNA using gel electrophoresis and the results show that the complexes have potent nuclease activity.  相似文献   

8.
The interactions between N-tosylamino acids and cobalt(II), nickel(II) and zinc(II) ions in aqueous solution and in the solid state have been investigated. From concentrated aqueous solutions, compounds of general formula [M(II)(N-tosylaminoacidato)2(H2O)4](M = Co(II), Ni(II) and N-tosylaminoacidato = N-tosylglycinate (Tsgly?), N-tosyl-α- and -β-alaninate (Ts-α- and Ts-β-ala?); M = Zn(II) and N-tosylaminoacidate = Tsgly?, Ts-β-ala?) and [Zn(II)(N- tosylaminoacidato)2(H2O)2] were isolated and characterized by means of thermogravimetric, electronic and infrared spectra. For two of them: [Co(Tsgly)2(H2O)4](I) and [Zn(Ts-β-ala)2(H2O)4](II) the crystal and molecular structures were also determined. Both compounds crystallize in the monoclinic space group P21/c, with two formula units in a cell of dimensions: a = 13.007(6), b = 5.036(2), c = 18.925(7) Å, β = 102.33(3)° for (I) and a = 14.173(6), b = 5.469(2), c = 17.701(7) Å, β = 106.63(3)° for (II). The structures were solved by the heavy-atom method and refined by least-squares calculations to R = 0.031 and 0.064 for (I) and (II) respectively. The cobalt and zinc atoms lie in the centers of symmetry, each bonded to two amino- acid molecules through a carboxylic oxygen atom and four water molecules in a slightly tetragonally distorted octahedral geometry. The second carboxylic oxygen atom is not involved in metal coordination. Electronic and X ray-powder spectra suggest that the tetrahydrate complexes of Co2+, Ni2+ and Zn2+ ions of the same amino acids are isomorphous and isostructural. No coordinative interactions between ligand and metal ions were found in aqueous solution on varying the pH values before hydroxide precipitation.  相似文献   

9.
A facile two‐step strategy is developed to design the large‐scale synthesis of hierarchical, unique porous architecture of ternary metal hydroxide nanowires grown on porous 3D Ni foam and subsequent effective sulfurization. The hierarchical Zn–Co–S nanowires (NWs) arrays are directly employed as an electrode for supercapacitors application. The as‐synthesized Zn–Co–S NWs deliver an ultrahigh areal capacity of 0.9 mA h cm?2 (specific capacity of 366.7 mA h g?1) at a current density of 3 mA cm?2, with an exceptional rate capability (≈227.6 mA h g?1 at a very high current density of 40 mA cm?2) and outstanding cycling stability (≈93.2% of capacity retention after 10 000 cycles). Most significantly, the assembled Zn–Co–S NWs//Fe2O3@reduced graphene oxide asymmetric supercapacitors with a wide operating potential window of ≈1.6 V yield an ultrahigh volumetric capacity of ≈1.98 mA h cm?3 at a current density of 3 mA cm?2, excellent energy density of ≈81.6 W h kg?1 at a power density of ≈559.2 W kg?1, and exceptional cycling performance (≈92.1% of capacity retention after 10 000 cycles). This general strategy provides an alternative to design the other ternary metal sulfides, making it facile, free‐standing, binder‐free, and cost‐effective ternary metal sulfide‐based electrodes for large‐scale applications in modern electronics.  相似文献   

10.
We have replaced labile sulfur atoms of adrenodoxin with Se80, or Se77 in the presence and absence of the labile sulfur source (Na2S). When the labile sulfur source was absent but the selenium source was present in the reaction mixture for the reconstitution from apoadrenodoxin, the electron paramagnetic resonance spectra of the Se80Se80 and Se77Se77 derivatives had g = 2.051 and g⊥ = 1.975, and a distinct triplet of the g -signal, respectively. When both labile sulfur and selenium sources were present, new spectral species were observed. In the case of the Se80S32 derivative, the signal had g = 2.038, g2 = 1.973, and g3 = 1.934, and in the case of Se77S32 derivative, the g -signal was split into a doublet.From these results, it is concluded that the compound with one sulfur and one selenium atom in the replacement of the two labile sulfur atoms of native adrenodoxin has a g-value of 2.038, and its paramagnetic center is more rhombohedral than those of native adrenodoxin and the SeSe derivative.  相似文献   

11.
Theoretical studies on the coordination stabilities, spectra and DNA-binding trend for the series of metal-varied complexes, M(IDB)Cl2 (M = Mn, Fe, Co, Ni, Cu and Zn; IDB = N, N -bis(2-benzimidazolylmethyl) amine), have been carried out by using the DFT/B3LYP method and PCM model. The calculated coordination stabilities (S) for these complexes present a trend of S(Ni) > S(Co) > S(Fe) > S(Cu) > S(Zn) > S(Mn). It has been estimated from the molecular orbital energies of the complexes that the DNA-binding affinities (A) of the complexes are in the order of A(Zn) < A(Mn) < A(Fe) ≈ A(Co) < A(Ni) < A(Cu). The studied results indicate that the Cu, Ni and Co complexes with large coordination stabilities present the low virtual orbitals, consequently yielding to the favorable DNA-binding affinities. The spectral properties of excitation energies and oscillator strengths for M(IDB)Cl2 in the ultraviolet region were calculated by TD-DFT/B3LYP method.  相似文献   

12.
Novel cobalt(III) complexes containing three kinds of assembled ligands, L1L2=dapymt-tbba(2-), tbba-dapymt(1-) and apymt-tbba(1-) (H3tbba=thiobarbituric acid; Hdapymt=4,6-diamino-2-thiouracil; Hapymt=4-amino-2-thiouracil), were prepared from the mixed ligand systems, where L2 indicates the coordinated ligand to the Co(III) ion and L1 is a pendant ligand bonded to L2. These complexes were characterized by UV-Vis absorption spectra and NMR spectroscopy. The crystal structures of [Co(Htbba)(en)2]ClO4·2H2O (2) (en=ethane-1,2-diamine), [Co{dapymt-tbba(2-)}(en)2]ClO4·3H2O (3) and [Co{apymt-tbba(1-)}(en)2](ClO4)Cl·3H2O (5′) revealed that coordination occurs through the S(1) and N(1) donors of tbba and the latter complexes 3 and 5′ have an assembled ligand; a new bond is formed between the C(5) atom of tbba and the S(2) atom of dapymt or apymt. An intramolecular hydrogen bond between O(1) of tbba and NH of en was found in all crystals. An interesting intermolecular π-π stacking interaction was found in 5′.  相似文献   

13.
《BBA》2001,1503(1-2):112-122
The parallel polarization electron paramagnetic resonance (EPR) method has been applied to investigate manganese EPR signals of native S1 and S3 states of the water oxidizing complex (WOC) in photosystem (PS) II. The EPR signals in both states were assigned to thermally excited states with S=1, from which zero-field interaction parameters D and E were derived. Three kinds of signals, the doublet signal, the singlet-like signal and g=11–15 signal, were detected in Ca2+-depleted PS II. The g=11–15 signal was observed by parallel and perpendicular modes and assigned to a higher oxidation state beyond S2 in Ca2+-depleted PS II. The singlet-like signal was associated with the g=11–15 signal but not with the YZ (the tyrosine residue 161 of the D1 polypeptide in PS II) radical. The doublet signal was associated with the YZ radical as proved by pulsed electron nuclear double resonance (ENDOR) and ENDOR-induced EPR. The electron transfer mechanism relevant to the role of YZ radical was discussed.  相似文献   

14.
Methionine enkephalin (ME = YGGFM) was measured in five individual human post-mortem pituitaries using four different analytical methods, with the objective of comparing the molecular specificities of the methods. Radioreceptor assay (RRA) used a receptor-rich preparation from brain and [3H]etorphine as radioligand to determine ME-like receptoractivity (ME-LR). Radioimmunoassay (RIA) measured ME-like immunoreactivity (ME-LI). Pituitary samples analyzed by RRA and RIA were purified first with a high-performance liquid chromatography (HPLC) gradient on a polymer analytical column. Fast atom bombardment mass spectrometry (FAB-MS) in two different detection modes quantified ME using the protonated molecular ion MH+ of ME at 574 a.m.u. and B/E linked-field selected reaction monitoring (SRM) to monitor the specific unimolecular metastable transition that produced the unique amino acid sequence-determining tetrapeptide fragment ion YGGF+ from the MH+ precursor ion. Both FAB-MS methods used the deuterated internal standard YGG[2H5-F]M. Samples analyzed with FAB-MS were purified first with multi-dimensional reversed-phase HPLC. The first dimension was an ODS gradient, and the second dimension was a polymer isocratic elution. The following ME amounts were measured (mean ± standard error of the mean): ME-LR, 7.0 ± 1.9 μg g−1 tissue; ME-LI, 1.8 ± 0.7 μg g−1 tissue; MH+, 2.7 ± 0.6 μg g−1 tissue; SRM, 3.0 ± 0.8 μg g−1 tissue. The FAB SRM method provided the highest level of molecular specificity amount these four analytical methods used to measure picomole amounts of endogenous ME in a human pituitary.  相似文献   

15.
Phytoaccumulation of zinc by the aquatic plant, Lemna gibba L.   总被引:2,自引:0,他引:2  
The uptake of zinc (Zn) by the duckweed Lemna gibba L., native to the north-east region of Algeria, was investigated in quarter Coïc solutions enriched with 6.0, 10.0, 14.0 and 18.0 mg l−1 of Zn supplied as zinc sulphate (ZnSO4). Zinc concentrations were measured in the water daily and in duckweed biomass at the end of the experiments. These results showed that under experimental conditions (pH = 6.0 ± 0.1, T = 21 ± 1 °C, photoperiod = 12 h/j), L. gibba was able to accumulate in its biomass 4.23; 15.62; 23.88 and 25.81 mg g−1 DM, respectively for the four initial concentrations selected. At these concentrations, the metal removed percentages were 61–71%. The mass balance performed on the system showed that about 49–68% of Zn (depending on the initial concentration in water) was removed by precipitation as zinc phosphate. The results showed that this aquatic plant can be successfully used for Zn removal.  相似文献   

16.
Zn‐based batteries are safe, low cost, and environmentally friendly, as well as delivering the highest energy density of all aqueous battery systems. However, the application of Zn‐based batteries is being seriously hindered by the uneven electrostripping/electroplating of Zn on the anodes, which always leads to enlarged polarization (capacity fading) or even cell shorting (low cycling stability). How a porous nano‐CaCO3 coating can guide uniform and position‐selected Zn stripping/plating on the nano‐CaCO3‐layer/Zn foil interfaces is reported here. This Zn‐deposition‐guiding ability is mainly ascribed to the porous nature of the nano‐CaCO3‐layer, since similar functionality (even though relatively inferior) is also found in Zn foils coated with porous acetylene black or nano‐SiO2 layers. Furthermore, the potential application of this strategy is demonstrated in Zn|ZnSO4+MnSO4|CNT/MnO2 rechargeable aqueous batteries. Compared with the ones with bare Zn anodes, the battery with a nano‐CaCO3‐coated Zn anode delivers a 42.7% higher discharge capacity (177 vs 124 mAh g?1 at 1 A g?1) after 1000 cycles.  相似文献   

17.
A light-driven reaction model for the Ca2+-depleted Photosystem (PS) II is proposed to explain the split signal observed in electron paramagnetic resonance (EPR) spectra based on a comparison of EPR assignments with recent x-ray structural data. The split signal has a splitting linewidth of 160 G at around g = 2 and is seen upon illumination of the Ca2+-depleted PS II in the S2 state associated with complete or partial disappearance of the S2 state multiline signal. Another g=2 broad ESR signal with a 110 G linewidth was produced by 245 K illumination for a short period in the Ca2+-depleted PS II in S1 state. At the same time a normal YZ· radical signal was also efficiently trapped. The g=2 broad signal is attributed to an intermediate S1X· state in equilibrium with the trapped YZ· radical. Comparison with x-ray structural data suggests that one of the split signals (doublet signal) is attributable to interaction between His 190 and the YZ· radical, and other signals is attributable to interaction between His 337 and the manganese cluster, providing further clues as to the mechanism of water oxidation in photosynthetic oxygen evolution.  相似文献   

18.
19.
《Inorganica chimica acta》1988,146(2):161-165
The compound [Cr(en)3][ZnCl4]Cl has been synthesized by reaction of CrCl3·6H2O, Zn and [Cr(en)3]2(SO4)3 in HCl. Its molecular and crystalline structure was determined by X-ray diffraction methods, being monoclinic, P21/c, a=21.215(3), b=12.532(2), c=13.707(2) Å, β=95.21°, V= 3629(2) Å3, Dx=1.738g cm−3, MW=474.9, Z= 8, F(000)=1928, λ(Mo Kα)=0.71069 Å, μ(Mo Kα)= 27.04 cm−1, 288 K. No significant exchange interactions between Cr(III) cations in the crystalline lattice were found. Curie-Weiss behavior was found in the three directions tested (g1=2.06±0.02,g2= 2.08±0.02,g3=2.09±0.01), T=1.2-1.4 K.  相似文献   

20.
The role of prostanoids in regulation of the renal circulation during hypercapnia was examined in unanesthetized rabbits. Renal blood flow (RBF) was determined with 15 μm radioactive microspheres during normocapnia (PaCO2 30 mmHg) and hypercapnia (PaCO2 60 mmHg), before and after intravenous administration of indomethacin (10 mg/kg) or vehicle (n=6 for each group). Arterial blood pressure was not different among the 4 conditions in each group. RBF was 438±61 and 326 ± 69 (P<0.05) ml/min per 100 g during normocapnia and hypercapnia, respectively, before indomethacin, and following administration of indomethacin, RBF was 426 ± 59 ml/min per 100 g during normocapnia and 295 ± 60 ml/min per 100 g during hypercapnia (P<0.05). In the vehicle group, RBF was 409±74 and 226±45(P<0.05) ml/min per 100 g during normocapnia and hypercapnia, respectively, before vehicle; and following administration of vehicle, RBF was 371±46 ml/min per 100 g during normocapnia and 219 ± 50 (P<0.05) per 100 g during hypercapnia. RBF during normocapnia was not affected by administration of indomethacin or vehicle. The successive responses to hypercapnia were not different within the indomethacin and vehicle groups, and the second responses to hypercapnia were not different between the two groups. These findings suggest that prostanoids do not contribute significantly to regulation of the renal circulation during normocapnia and hypercapnia in unanesthetized rabbits.  相似文献   

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