928 resultados para Ni^2
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///////(m)(e)1.5(e')2.5(e'')/Ni~(2+)Cd~(2+)Co~(2+)Cd~(2+)/
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Magnetic nanoparticles of Ni-doped cobalt ferrite [Co1-xNixFe2O4(0 <= x <= 1)] synthesized by coprecipitation route have been studied as a function of doping concentration (x) and particle size. The size of the particles as determined by X-ray diffractometer (XRD) and transmission electron microscope (TEM) analyses was found in the range 12-48 nm. The coercivity (H-C) and saturation magnetization (M-S) showed a decreasing behavior with increasing Ni concentration. M-S of all the samples annealed at 600 degrees C lies in the range 65.8-13.7 emu/gm. Field-cooled (FC) studies of the samples showed horizontal shift (exchange bias) and vertical shift in the magnetization loop. Strong decrease in exchange bias (H-b) and vertical shift (delta M) was found for low Ni concentrations while negligible decrease was found at higher concentrations. The presence of exchange bias in the low Ni-concentration region has been explained with reference to the interface spins interaction between a surface region (with structural and spin disorder) and a ferrimagnetic core region. M(T) graphs of the samples showed a decreasing trend of blocking temperature (T-b) with increasing Ni concentration. The decrease of T-b with increasing Ni concentration has been attributed to the lower anisotropy energy of Ni+2 ions as compared to Co+2 that increases the probability of the jump across the anisotropy barrier which in turn decreases the blocking temperature of the system.
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By introducing the flexible 1,1'-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the polyoxovanadate system, five novel polyoxoanion-templated architectures based on [As8V14O42](4-) and [V16O38Cl](6-) building blocks were obtained: [M(bbi)(2)](2)[As8V14O42(H2O)] [M = Co (1), Ni (2), and Zn (3)], [Cu(bbi)](4)[As8V14O42(H2O)] (4), and [Cu(bbi)](6)[V16O38Cl] (5). Compounds 1-3 are isostructural, and they exhibit a binodal (4,6)-connected 2D structure with Schlafli symbol (3(4)center dot 4(2))(3(4)center dot 4(4)center dot 5(4)center dot 6(3))(2), in which the polyoxoanion induces a closed four-membered circuit of M-4(bbi)(4). Compound 4 exhibits an interesting 3D framework constructed from tetradentate [As8V14O42](4-) cluster anions and cationic ladderlike double chains. There exists a bigger M-8(bbi)(6)O-2 circuit in 4. The 3D extended structure of 5 is composed of heptadentate [V16O38Cl](6-) anions and flexural cationic chains; the latter consists of six Cu(bbi) segments arranged alternately. It presents the largest 24-membered circuit of M-24(bbi)(24) so far observed made of bbi molecules and transition-metal cations. Investigation of their structural relations shows the important template role of the polyoxoanions and the synergetic interactions among the polyoxoanions, transition-metal ions, and flexible ligand in the assembly process.
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Nafion117(),K~+Ni~(2+)Fe~(3+)Nafion 117,H~+K~+Pb~(2+)Ni~(2+)Co~(2+)Fe~(3+)Nemst..
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KegginZW_(11)O_(39)M(H_2O)~(n-)(Z=Si,Ge,P;M=Ni~(2+),C~(2+),Cr~(3+),Co~(2+);n=46)DawsonP_2W_(17)O_(61)M(H_2O)~(n-)(M=Ni~(2+),Cu~(2+),Cr~(3+),Co~(2+);n=7,8)(),,.Lewis,,,,ESR.,,,,ZW_(11)O_(39)M(L)~(n-)+PyZW_(11)O_(39)M(Py)~(n-)+L(L=).,,.
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(=1-kh),N,f_cd_L,h:h=(f_c_LN)~(1/2),hCr~(3+),Co~(2+),Ni~(2+),Mn~(2+),Ti~(2),V~(2+),Cr~(2+),Fe~(2+)k
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,,10~(-1)810~(-5)mol/L,-25.50.4 mV/pC_((Ni)~(2+))(20).:8.11~(-5)8.610~(-5)8.210~(-5)4.110~(-3)7.510~(-4)3.210~(-2)8.010~(-2)4.410~(-1).,,,
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Acetylcholine released from parasympathetic excitatory nerves activates contraction in detrusor smooth muscle. Immunohistochemical labeling of guinea pig detrusor with anti-c-Kit and anti-VAChT demonstrated a close structural relationship between interstitial cells of Cajal (ICC) and cholinergic nerves. The ability of guinea pig bladder detrusor ICC to respond to the acetylcholine analog, carbachol, was investigated in enzymatically dissociated cells, loaded with the Ca(2+) indicator fluo 4AM. ICC fired Ca(2+) transients in response to stimulation by carbachol (1/10 microM). Their pharmacology was consistent with carbachol-induced contractions in strips of detrusor which were inhibited by 4-DAMP (1 microM), an M(3) receptor antagonist, but not by the M(2) receptor antagonist methoctramine (1 microM). The source of Ca(2+) underlying the carbachol transients in isolated ICC was investigated using agents to interfere with influx or release from intracellular stores. Nifedipine (1 microM) or Ni(2+) (30-100 microM) to block Ca(2+) channels or the removal of external Ca(2+) reduced the amplitude of the carbachol transients. Application of ryanodine (30 microM) or tetracaine (100 microM) abolished the transients. The phospholipase C inhibitor, U-73122 (2.5 microM), significantly reduced the responses. 2-Aminoethoxydiethylborate (30 microM) caused a significant reduction and Xestospongin C (1 microM) was more effective, almost abolishing the responses. Intact in situ preparations of guinea pig bladder loaded with a Ca(2+) indicator showed distinctively different patterns of spontaneous Ca(2+) events in smooth muscle cells and ICC. Both cell types responded to carbachol by an increase in frequency of these events. In conclusion, guinea pig bladder detrusor ICC, both as isolated cells and within whole tissue preparations, respond to cholinergic stimulation by firing Ca(2+) transients. PMID: 18171995 [PubMed - indexed for MEDLINE]
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Rabbit urethral smooth muscle cells were studied at 37 degrees C by using the amphotericin B perforated-patch configuration of the patch-clamp technique, using Cs(+)-rich pipette solutions. Two components of current, with electrophysiological and pharmacological properties typical of T- and L-type Ca(2+) currents, were recorded. Fitting steady-state inactivation curves for the L current with a Boltzmann equation yielded a V(1/2) of -41 +/- 3 mV. In contrast, the T current inactivated with a V(1/2) of -76 +/- 2 mV. The L currents were reduced by nifedipine (IC(50) = 225 +/- 84 nM), Ni(2+) (IC(50) = 324 +/- 74 microM), and mibefradil (IC(50) = 2.6 +/- 1.1 microM) but were enhanced when external Ca(2+) was substituted with Ba(2+). The T current was little affected by nifedipine at concentrations
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Nitric oxide generates slow electrical oscillations (SEOs) in cells near the myenteric edge of the circular muscle layer, which resemble slow waves generated by interstitial cells of Cajal (ICCs) at the submucosal edge of this muscle. The properties of SEOs were studied to determine whether these events are similar to slow waves. Rapid frequency membrane potential oscillations (MPOs; 16 +/- 1 cycles/min and 9.6 +/- 0.2 mV) were recorded from control muscles near the myenteric edge. Sodium nitroprusside (0.3 microM) reduced MPOs and initiated SEOs (1.3 +/- 0.3 cycles/min and 13.4 +/- 1.4 mV amplitude). SEOs were abolished by the guanylate cyclase inhibitor 1H-[1,2,4]-oxadiazolo-[4,3-a]-quinoxaline-1-one (10 microM). MPOs were abolished by nifedipine (1 microM), whereas SEO frequency increased and the amount of depolarization decreased. BAY K 8644 (1 microM) prolonged SEOs and reduced their frequency. SEOs were abolished by Ni(2+) (0.5 mM), low Ca(2+) solution (0.1 mM Ca(2+)), cyclopiazonic acid (10 microM), and the mitochondrial uncouplers antimycin (10 microM) and carbonyl cyanide p-trifluoromethoxyphenylhydrazone (1 microM). Oligomycin (10 microM) was without effect. These effects are similar to those described for colonic slow waves. Our results suggest that nitric oxide-induced SEOs are similar in mechanism to slow waves, an activity not previously thought to be generated by myenteric pacemakers.
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1. Measurements of artery contraction, cytosolic [Ca(2+)], and Ca(2+) permeability were made to examine contractile and cytosolic [Ca(2+)] responses of canine pulmonary arteries and isolated cells to 5-hydroxytryptamine (5-HT), and to determine the roles of intracellular Ca(2+) release and extracellular Ca(2+) entry in 5-HT responses. 2. The EC(50) for 5-HT-mediated contractions and cytosolic [Ca(2+)] increases was approximately 10(-7) M and responses were inhibited by ketanserin, a 5-HT(2A)-receptor antagonist. 3. 5-HT induced cytosolic [Ca(2+)] increases were blocked by 20 microM Xestospongin-C and by 2-APB (IC(50)=32 microM inhibitors of InsP(3) receptor activation. 4. 5-HT-mediated contractions were reliant on release of InsP(3) but not ryanodine-sensitive Ca(2+) stores. 5. 5-HT-mediated contractions and cytosolic [Ca(2+)] increases were partially inhibited by 10 microM nisoldipine, a voltage-dependent Ca(2+) channel blocker. 6. Extracellular Ca(2+) removal reduced 5-HT-mediated contractions further than nisoldipine and ablated cytosolic [Ca(2+)] increases and [Ca(2+)] oscillations. Similar to Ca(2+) removal, Ni(2+) reduced cytosolic [Ca(2+)] and [Ca(2+)] oscillations. 7. Mn(2+) quench of fura-2 and voltage-clamp experiments showed that 5-HT failed to activate any significant voltage-independent Ca(2+) entry pathways, including store-operated and receptor-activated nonselective cation channels. Ni(2+) but not nisoldipine or Gd(3+) blocked basal Mn(2+) entry. 8. Voltage-clamp experiments showed that simultaneous depletion of both InsP(3) and ryanodine-sensitive intracellular Ca(2+) stores activates a current with linear voltage dependence and a reversal potential consistent with it being a nonselective cation channel. 5-HT did not activate this current. 9. Basal Ca(2+) entry, rather than CCE, is important to maintain 5-HT-induced cytosolic [Ca(2+)] responses and contraction in canine pulmonary artery.
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Experiments were performed to determine whether capacitative Ca(2+) entry (CCE) can be activated in canine pulmonary and renal arterial smooth muscle cells (ASMCs) and whether activation of CCE parallels the different functional structure of the sarcoplasmic reticulum (SR) in these two cell types. The cytosolic [Ca(2+)] was measured by imaging fura-2-loaded individual cells. Increases in the cytosolic [Ca(2+)] due to store depletion in pulmonary ASMCs required simultaneous depletion of both the inositol 1,4,5-trisphosphate (InsP(3))- and ryanodine (RY)-sensitive SR Ca(2+) stores. In contrast, the cytosolic [Ca(2+)] rises in renal ASMCs occurred when the SR stores were depleted through either the InsP(3) or RY pathways. The increase in the cytosolic [Ca(2+)] due to store depletion in both pulmonary and renal ASMCs was present in cells that were voltage clamped and was abolished when cells were perfused with a Ca(2+)-free bathing solution. Rapid quenching of the fura-2 signal by 100 microM Mn(2+) following SR store depletion indicated that extracellular Ca(2+) entry increased in both cell types and also verified that activation of CCE in pulmonary ASMCs required the simultaneous depletion of the InsP(3)- and RY-sensitive SR Ca(2+) stores, while CCE could be activated in renal ASMCs by the depletion of either of the InsP(3)- or RY-sensitive SR stores. Store depletion Ca(2+) entry in both pulmonary and renal ASMCs was strongly inhibited by Ni(2+) (0.1-10 mM), slightly inhibited by Cd(2+) (200-500 microM), but was not significantly affected by the voltage-gated Ca(2+) channel (VGCC) blocker nisoldipine (10 microM). The non-selective cation channel blocker Gd(3+) (100 microM) inhibited a portion of the Ca(2+) entry in 6 of 18 renal but not pulmonary ASMCs. These results provide evidence that SR Ca(2+) store depletion activates CCE in parallel with the organization of intracellular Ca(2+) stores in canine pulmonary and renal ASMCs.
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The Arabidopsis NPRI protein regulates systemic acquired resistance dependent on salicylic acid. Analyses by plant two-hybrid analysis in vivo and pull-down assays in vitro showed that the BTB/POZ domain of NPRI at the N-terminus serves as an autoinhibitory domain to negate the function of the transactivation domain at the C-terminus through direct binding of these two domains. I t was also shown that the binding of the BTB/POZ domain to the C-terminus of NPRI was abolished by SA treatment, suggesting that SA could interfere directly with this binding. By gel filtration, it was demonstrated that SA affects the conformation of full-length NPRl , confirming the role of NPRI as an SA receptor. Gel filtration analysis also indicated that NPRI could be converted from an oligomer to a dimer with SA treatment. Furthermore, one N-terminal deletion ~513 has been shown to act as a metal-binding protein and its two Cys-521 and Cys-529 are important for binding to Ni 2 + by pull-down assays.
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Cette thse dcrit la synthse, la caractrisation, les ractivits, et les proprits physiques de complexes divalents et trivalents de Ni forms partir de nouveaux ligands pincer de type POCN. Les ligands POCN de type amine sont prpars dune faon simple et efficace via lamination rductrice de 3-hydroxybenzaldhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de lamino alcool rsultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est prpar de faon similaire en faisant usage de PhCH2NH2 en labsence de NaBH4. La raction de ces ligands pincer de type POCN avec NiBr2(CH3CN)x en prsence dune base rsulte en un bon rendement de la cyclomtalation du lien C-H situ en ortho aux fonctions amine et phosphinite. Il fut dcouvert que la base est essentielle pour la propret et le haut rendement de la formation des complexes pincer dsirs. Nous avons prpar des complexes pincer plan- carrs de type POCN, (POCNRR)NiBr, possdant des fonctions amines secondaires et tertiaires qui dmontrent des ractivits diffrentes selon les substituants R et R. Par exemple, les complexes possdant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) dmontrent des proprits rdox intressantes et pourraient tre convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque ragis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagntiques 17 lectrons adoptent une gomtrie de type plan-carr dforme, les atomes de Br occupant les positions axiale et quatoriale. Les analyses DSC et TGA des ces composs ont dmontr quils sont thermiquement stables jusqu ~170 C; tandis que la spectroscopie dabsorption en solution a dmontr quils se dcomposent thermiquement beaucoup plus basse temprature pour regnrer les complexes divalents ne possdant quun seul Br; lencombrement strique des substitutants amines acclre cette route de dcomposition de faon significative. Les analogues NMe2 et N(morpholinyl) de ces espces de NiIII sont actifs pour catalyser la raction daddition de Kharasch, de CX4 des olfines telles que le styrne, tandis quil fut dcouvert que lanalogue le moins thermiquement stable (POCNEt2)Ni est compltement inerte pour catalyser cette raction. Les complexes (POCNRH)NiBr possdant des fonctions amines secondaires permettent laccs des fonctions amines substitues de faon non symtrique via leur raction avec des halognures dalkyle. Un autre avantage important de ces complexes rside dans la possibilit de dprotonation pour prparer des complexes POCN de type amide. De telles tentatives pour dprotoner les fonctions NRH nous ont permis de prparer des espces dimriques possdant des ligands amides pontants. La nature dimrique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut tablie par des tudes de diffraction des rayons-X qui ont dmontr diffrentes gomtries pour les curs Ni2N2 selon le substituant N: lanalogue (PhCH2)N possde une orientation syn des substitutants benzyles et un arrangement ressemblant celui du cyclobutane du Ni et des atomes dazote, tandis que lanalogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes dazote et une orientation anti des substituants phnyles. Les espces dimriques ne se dissocient pas en prsence dalcools, mais elles promouvoient lalcoolyse catalytique de lacrylonitrile. De faon intressante, les rendements de ces ractions sont plus levs avec les alcools possdant des fonctions O-H plus acides, avec un nombre de turnover catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces ractions dalcoolyse procdent par activation htrolytique de lalcool par lespce dimrique via des liaisons hydrognes avec une ou deux des fonctions amides du dimre. Les espces dimriques de Ni (II) soxydent facilement lectrochimiquement et par reaction avec NBS ou Br2. De faon surprenante, loxydation chimique mne lisolation de nouveaux produits monomriques dans lesquels le centre mtallique et le ligand sont oxyds. Le mcanisme doxydation fut aussi investigu par RMN, UV-vis-NIR, DFT et spectrolectrochimie.
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Two 28-membered octaazamacrocycles, [28]py(2)N(6) and Me-2[28]py(2)N(6), have been synthesized. The protonation constants of the N-methyl. derivative and the stability constants of its complexes with Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ were determined at 25degreesC in 0.10 mol dm(-3) KNO3. The high overall basicity of Me-2[28]py(2)N(6) is ascribed to the weaker repulsion between protonated contiguous charged ammonium sites separated by propyl chains. These studies together with NMR, UV-vis and EPR spectroscopies indicated the presence of mono- and di-nuclear species, The single crystal structure of the complex [Ni-2([28]py(2)N(6))(H2O)(4)]Cl-4.3H(2)O was determined, and showed each nickel centre in a distorted octahedral co-ordination environment. The nickel centres are held within the macrocycle at a large distance of 6.991(g) Angstrom from each other. The formation of mononuclear complexes was evaluated theoretically via molecular mechanics (MM) and molecular dynamics (MD) calculations and showed that these large macrocycles have sufficient flexibility to encapsulate metal ions with different stereo-electronic sizes. Structures for small and large metal ions are proposed.
