Effects of light and cGMP on membrane fluidity of frog rod outer segments.

Abstract—We have used a spin-labeled fatty acid to detect changes induced by light and by cGMP in isolated rod outer segment membranes. We chose a spin probe (5-doxylstearic acid) which has the nitroxide group placed on the hydrocarbon chain, so the probe should reside somewhat inside the hydrophobic region of the membrane. We found that light exposures which bleached the rhodopsin also produced a small change in the EPR spectra. The spectral changes are consistent with a small increase in membrane fluidity. Light exposures which bleach rhodopsin are known to activate a phosphodiesterase that markedly decreases the cGMP level in rod outer segment. Therefore, we attempted to vary cGMP levels directly by adding Bu₂-cGMP, or indirectly, by adding IBMX, CDTA or ATP to try to inhibit the phosphodiesterase. In each case where the cGMP level is expected to increase, we observed spectral changes in the dark which suggested a small decrease in membrane fluidity. Thus, all of our results with this probe are consistent with the idea that changing the level of cGMP produces changes in membrane fluidity. The light-induced spectral changes we observed required the presence of ATP, and were inhibited by 2mM Ca²⁺, or by the chelator of divalent cations, CDTA.     

Separation of Cr ions from Co and mn ions by poly (bis(phenoxy) phosphazene) membranes

Poly(bis (phenoxy)phosphazene) was synthesized and cast by knife techniques into membranes supported on porous Inconel plates for separation testing. A solution of Cr³⁺, Co²⁺ and Mn^2/t+ nitrates was used as the feed solution in diffusion experiments conducted from 25 to 180°C. It was discovered that Co²⁺ and Mn²⁺ ions had much higher diffusion coefficients than Cr³⁺ ions through the membrane, with a maximum difference occurring near 100°C. The lower diffusion associated with Cr³⁺ ions is believed to be due to formation of polymerized hydrated Cr³⁺ ions that are too large to penetrate the membranes. Diffusion activation energies are reported.     

Differences in permeability of dioleoylphosphatidylcholine model membranes containing saturated or unsaturated phosphatidic acids

At low millimolar Ca²⁺ concentrations, large unilamellar dioleoylphosphatidylcholine vesicles containing dimyristoylphosphatidate (20 mol%) release enclosed solutes like sulphate, but influx of Ca²⁺ is not demonstrable. Coincident with the permeability change, vesicle aggregation and membrane fusion are observed. These results contrast with those for dioleoylphosphatidate-containing vesicles under the same conditions, which show Ca²⁺ influx and Ca²⁺ chelator efflux, but no sulphate efflux, vesicle aggregation or membrane fusion. The observed differences in permeability behaviour of membranes containing these two phosphatidate molecular species are discussed with respect to the differences in their phase behaviour.     

Membrane binding of the neuronal calcium sensor recoverin – modulatory role of the charged carboxy-terminus

Background  

The Ca²⁺-binding protein recoverin operates as a Ca²⁺-sensor in vertebrate photoreceptor cells. It undergoes a so-called Ca²⁺-myristoyl switch when cytoplasmic Ca²⁺-concentrations fluctuate in the cell. Its covalently attached myristoyl-group is exposed at high Ca²⁺-concentrations and enables recoverin to associate with lipid bilayers and to inhibit its target rhodopsin kinase. At low Ca²⁺-concentrations the myristoyl group is inserted into a hydrophobic pocket of recoverin thereby relieving inhibitory constraint on rhodopsin kinase. Hydrophobic and electrostatic interactions of recoverin with membranes have not been clearly determined, in particular the function of the positively charged carboxy-terminus in recoverin ¹⁹¹QKVKEKLKEKKL²⁰² in this context is poorly understood.     

Effects of Divalent Metal Ions on Electrochemiluminescence Sensor with Ru(bpy)32+ Immobilized in Eastman‐AQ Membrane

Different effects of divalent metal ions on electrochemiluminescence (ECL) sensor with Ru(bpy)₃²⁺ immobilized in Eastman‐AQ membrane were investigated. Mg²⁺, Ca²⁺ and Fe²⁺ can elevate the ECL of Ru(bpy)₃²⁺/proline; while metal ions that underwent redox reactions on the electrode such as Mn²⁺ and Co²⁺ presented intensive quenching effects on Ru(bpy)₃²⁺ ECL. Also, the quenching effect of Mn²⁺ on the ECL sensor with Ru(bpy)₃²⁺ immobilized in Eastman‐AQ membrane enhanced to about 30‐folds compared with the case that Ru(bpy)₃²⁺ was dissolved in phosphate buffer, and the enhanced quenching effects of Mn²⁺ were studied.     

LIGHT-INDUCED CHANGE IN RHODOPSIN EMISSION: PHOSPHORESCENCE and FLUORESCENCE

Abstract— Phosphorescence measurements of rhodopsin in bovine rod disk membranes were made to study changes in protein conformation on bleaching by probing the environment of tryptophan and tyrosine residues of the protein. Bleaching decreased the tyrosine phosphorescence by about 25% and significantly affected the amplitude of triplet decay when rhodopsin was excited at 280 nm, where both tyrosine and tryptophan absorb. Computer analysis using one or two exponential model functions showed the presence of two components in the decay curve at 410 nm—one with a lifetime of 2.2 s, the other with a lifetime of 4.8 s>—which are typical of tyrosine and tryptophan respectively. When the rod outer segment sample was bleached, there was a significant decrease in the amplitude of the tyrosine component. However, the lifetime values of the two components did not change. Analyses of the fluorescence spectra of dark and bleached membranes at different excitation wavelengths and the phosphorescence change on bleaching suggest energy transfer between tyrosine and tryptophan singlet states, which may result from a conformational change of the opsin moiety on bleaching.     

Study on the PSL mechanism in BaFCl:Eu<Superscript>2+</Superscript> phosphors

In this paper, the ESR and photoluminescence (PL) of BaFCl and BaFCl:Eu²⁺ radiated or un-radiated by X-ray were observed. The single electron in the color center could be produced in BaFCl without Eu²⁺. A series of traps of different energy level in BaFCl lattice were formed, and some shallow traps of them could be bleached by Vis-light, and the other deep traps could not. The bleaching effects on ESR and photostimulated luminescence (PSL) were investigated. An F-H-Eu²⁺ complex (F color center, H color center and Eu²⁺ complex) in the lattice of BaFCl:Eu²⁺ was suggested when the phosphor was X-ray irradiated. The Eu²⁺ located in the complex has only contribution to the ESR signal, but has no contribution to PL spectrum. The excitation of both F-center and located Eu²⁺ could decompose the complex to induce bleaching. The 440 nm light could excite the F-centers and the 220 nm and 270 nm could excite the located Eu²⁺, and the excitation disturbed the F-H-Eu²⁺ complex and caused a decrease of the PSL.     

Die gravimetrische Halbmikro-Bestimmung des Palladiums mit Violursäure

Zusammenfassung Die Fällung des Palladiums als Violurat eignet sich zur Bestimmung des als Chlorid vorliegenden Metalls neben Pt⁴⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Zn²⁺, Ca²⁺, den Alkalien und neben größeren Mengen von Pb²⁺-Ionen.

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Summary The precipitation of palladium as violurate is suitable for the determination of the metal present as chloride even in the presence of: Pt⁴⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Zn²⁺, Ca²⁺, the alkalis and also considerable amounts of Pb²⁺ ions.

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Résumé Le précipité de violurate de palladium convient pour le dosage de cet élément préexistant sous forme de chlorure, en présence de Pt⁴⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Zn²⁺, Ca²⁺, des métaux alcalins et de grandes quantités d'ions Pb²⁺.

     

Interaction of first row transition metals with α1-3, α1-6 mannotriose and conserved trimannosyl core oligosaccharides: A comparative electrospray ionization study of doubly and singly charged complexes

Electrospray ionization and tandem mass spectrometry were used in the analysis of metalcoordinated oligosaccharides. Four transition metal ions, Cu²⁺, Mn²⁺, Co²⁺, and Zn²⁺, and the alkaline earth metal ion Ca²⁺, were each coordinated to the trimer α1–3, α1–6 mannotriose and the pentamer conserved trimannosyl core (mannotriosyl-chitobiose). Instrumental and concentration ratio optimization studies were carried out to determine the best conditions for producing the [M + Met]²⁺, [M + MetCl]⁺, and [M + Met ? H]⁺ ions (Met = metal dication). These precursors were then subjected to tandem mass spectrometry (MS/MS) analysis and compared. Both the ionic radii and efficacy of ligand coordination were observed as important criteria for producing the precursor ions. Tandem mass spectra for the Cu²⁺- and Zn²⁺-coordinated species did not produce significant structural information about either the trimer or the pentamer. Although tandem mass spectra for the Ca²⁺-, Co²⁺-, and Mn²⁺-coordinated trimer were very similar, those of the pentamer were not. MS/MS of the Co²⁺-coordinated pentamer was the most unique and exhibited very different dissociation pathways.     

Enhancement of the hydrolysis of geranyl pyrophosphate by bivalent metal ions. A model for enzymic biosynthesis of cyclic monoterpenes

Hydrolysis of geranyl pyrophosphate is catalyzed by salts of Mn²⁺ and involves C-O bond cleavage. The first order rate constants reach limiting values with [Mn²⁺] > 10^?2 M, and the most reactive species is GPP(Mn²⁺)₂ at the optimum pH of 6.5–7. The products are similar to those from acid hydrolysis except that more cyclic hydrocarbons are formed in the presence of metal ions. Hydrolysis of geranyl phosphate is inhibited, and that of citronnellyl pyrophosphate is weakly catalyzed by Mn²⁺. Other divalent metal cations catalyze the hydrolysis of geranyl pyrophosphate and the sequence of effectiveness is Cu²⁺ > Mn²⁺ > Zn²⁺ > Co²⁺ < Mg²⁺ ~ Ca²⁺.     

Fluorescent chemosensor based-on naphthol-quinoline for selective detection of aluminum ions

In this study, an assay to quantify the presence of aluminum ions with a receptor containing naphthol and quinoline moieties was developed using a turn-on fluorescence enhancement approach. Upon treatment with aluminum ions, the fluorescence of the receptor was enhanced at 510 nm due to the formation of a complex between the ligand and aluminum ions at room temperature. As the concentration of Al³⁺ was increased, the fluorescence gradually increased. Other metal ions, such as K⁺, Ag⁺, Ca²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Cr³⁺, Fe³⁺, In³⁺, had no significant effect on the fluorescence.     

Configuration mixing in the s-hole states of metal ions

Configuration interaction calculation have been carried out on the s-hole states of Mn²⁺ Fe²⁺ (both high- and low-spin configurations). Co²⁺, Ca²⁺, K⁺ and Na⁺ including configurations involving virtual orbitals. The results show good agreement with the multiplet structures found in X-ray photoelectron spectra of these ions.     

Chromatography of Alkaline Earths and Transition Metals on TIN(IV) Arsenosilicate and Arsenophosphate thin Layers in Buffered EDTA Solutions

Abstract

The complex forming ability of ethylene diamine tetraacetic acid at various pH values and the ion exchange behavior of tin(IV) arsenosilicate and arsenophosphate cation exchangers have been combined in a chromatographic study of some metal ions. As a result some interesting observations have been made, which have led to certain analyti-cally difficult separations such as Ca²⁺?Sr²⁺ Ca²⁺?Ba²⁺ and Hg²⁺ from Cu²⁺, Ni²⁺, Zn²⁺, Co²⁺ and Mn²⁺.     

Anthracene-tethered aminomethyl oxadiazole chemosensor: a probe offering selective chromo- and fluorogenic signalings for targeting Cu(II)

A new optical chemosensor featuring anthracene as a fluorophore and an aminomethyl oxadiazole moiety as a bidentate chelate has been synthesized. From photophysical studies, we find the probe to offer remarkably selective chromo- and fluorogenic signaling responses towards biologically and environmentally significant Cu²⁺. In the presence of Cu²⁺, fluorescence is quenched to the extent of 95%, while the absorbance due to the anthracene chromophore is nearly completely bleached out. On the other hand, Li⁺, Na⁺, K⁺, Ba²⁺, Ca²⁺, Zn²⁺, Mg²⁺, Cd²⁺, Co²⁺, Ni²⁺, Ag⁺, Pb²⁺ and Hg²⁺ even at 10 times higher concentration than Cu²⁺ do not cause detectable photophysical perturbations. The stability constants, logK for Cu²⁺ were calculated to be 4.36 and 4.76 on the basis of spectrophotometric and fluorimetric titrations, respectively. However, logKs for other metal ions are too low (<0.1) to pose any interferences in the optical detection of Cu²⁺. Though, not fully defined, the uncommon phenomenon of the absorbance bleaching by Cu²⁺ is tentatively explained by invoking the involvement of non-covalent anthracene-Cu²⁺ complex.     

Binding Interaction of Captopril with Metal Ions: A Fluorescence Quenching Study

The binding interaction of captopril (CPL) with biologically active metal ions Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ was investigated in an aqueous acidic medium by fluorescence spectroscopy. The experimental results showed that the metal ions quenched the intrinsic fluorescence of CPL by forming CPL‐metal complexes. It was found that static quenching was the main reason for the fluorescence quenching. The quenching constant in the case of Cu²⁺ was highest among all quenchers, perhaps due to its high nuclear charge and small size. Quenching of CPL by metal ions follows the order Cu²⁺>Ni²⁺>Co²⁺>Ca²⁺>Zn²⁺>Mn²⁺>Mg²⁺. The quenching constant K_sv, bimolecular quenching constant K_q, binding constant K and the binding sites "n" were determined together with their thermodynamic parameters at 27 and 37°C. The positive entropy change indicated the gain in configurational entropy as a result of chelation. The process of interaction was spontaneous and mainly ΔS‐driven.     

Metal Ions as Activators of Hypoxia Inducible Factor

Activation of antihypoxic program under the action of a number of transition and heavy metals has been studied using cell-based HIF1 ODD-luc and HRE-luc reporters. It has been demonstrated that Au³⁺, Pb²⁺, Sn²⁺, Hg²⁺ are weak HIF1 ODD-luc activators, likely reflecting their weak competition for the ironbinding site in the active center of HIF prolyl hydroxylase. Metals capable of replacing iron–Mn²⁺, Zn²⁺, Cu²⁺ и Ni²⁺–activate at high submillimolar concentrations, which indicates low permeability of the cell membrane for transition metals. The highest activation is observed for Co²⁺ and Cd²⁺, however, Cd²⁺ is highly toxic even at 10 μM, in contrast to Co²⁺, which activates both reporters without toxicity signs up to 25 μM for 24 h. A significant activation by Co²⁺ is observed already in low micromolar range of concentrations, which can be recommended for use in hypoxia mimicking.     

Magnetic interactions in ternary cobalt oxides with cubic perovskite structure

Magnetic properties were measured on the cubic perovskite systems SrCoO_3?δ, (La_1?xSr_x)CoO₃ (0.5 ≦ x ≦ 1.0), and Sr(Co_1?xMn_x)O₃ (0 ≦ x ≦ 1.0). It is found that S²⁺ and La³⁺ ions strongly affect the spin state of the Co²⁺ ion and that the Mn⁴⁺ ion located at the octahedral site affects the spin state of Co⁴⁺ ion. The magnetic properties (T_c, T_θ, and σ) are explained by the magnetic interaction Co³⁺OCo³⁺, Co³⁺OCo⁴⁺, Co⁴⁺OCo⁴⁺, Mn⁴⁺OMn⁴⁺, and Mn⁴⁺OCo⁴⁺ in these systems.     

Role of Calcium in Photodynamically Induced Cell Damage of Human Fibroblasts

Photodynamically induced changes in the cytoplasmic free calcium concentration ([Ca²⁺]_i) and its role in cell damage were investigated in human skin fibroblasts using confocal laser microscopy. Fluorescence and absorbance spectrophotometry measurements indicate that the photosensitizer aluminum phthalocyanine tetrasulfonate (AlPcS₄) binds to the plasma membrane and only after irradiation is able to enter the cells, causing massive morphologic alterations. Upon irradiation of sensitizer-treated cells, the increase in [Ca²⁺]_i is related to the amount of light and extracellular [Ca²⁺]_e. The increase in [Ca²⁺]_i was substantially reduced in the absence of [Ca²⁺]_e. Cell damage or death after photodynamic treatment was prevented and shifted toward higher fluence by increasing [Ca²⁺]_i at high [Ca²⁺]_e and was greater at low [Ca²⁺]_e. Application of Ca²⁺ channel blockers, such as Co²⁺, Cd²⁺ or verapamil, could not prevent the increase of [Ca²⁺]_i. Our results indicate that activation of the photosensitizer, AlPcS₄, causes an influx of Ca²⁺, which protects cells from photodamage. At low [Ca²⁺]_e and high fluence values, release of Ca²⁺ from internal stores probably as a protective measure occurs in order to increase the [Ca²⁺]_i.     

Application of microcalorimetry and principal component analysis

Thermogravimetric analysis was used in order to study the reduction in air of submicronic powders of Co_3−x Mn _x O₄ spinels, with 0 ≤ x ≤ 1. For x = 0 (i.e. Co₃O₄), cation reduction occurred in a single step. It involved the Co^III ions at the octahedral sites, which were reduced to Co²⁺ on producing CoO. For 0 < x ≤ 1, the reduction occurred in two stages at increasing temperature with increasing amounts of manganese. The first step corresponded to the reduction of octahedral Co^III ions and the second was attributed to the reduction of octahedral Mn⁴⁺ ions to Mn³⁺. From the individual weight losses and the electrical neutrality of the lattice, the Co^III and Mn⁴⁺ ion concentrations were calculated. The distribution of cobalt and manganese ions present on each crystallographic site of the spinel was determined. In contrast to most previous studies that took into account either Co^III and Mn³⁺ or Co²⁺, Co^III and Mn⁴⁺ only, our thermal analysis study showed that Co²⁺/Co^III and Mn³⁺/Mn⁴⁺ pairs occupy the octahedral sites. These results were used to explain the resistivity measurements carried out on dense ceramics prepared from our powders sintered at low temperature (700–750 °C) in a Spark Plasma Sintering apparatus.     

1,8-萘酰亚胺为发色团的Zn2+荧光探针的合成及性能研究

合成了以1,8-萘酰亚胺为发色团,以联吡啶为离子受体的Zn²⁺荧光探针,并进行了表征及离子识别性能的研究。研究表明该化合物对Zn²⁺具有良好的识别性能,同时相对于Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Ni²⁺, Pb²⁺等金属离子具有良好的选择性。