Gene/Protein Disease Symptom Drug Enzyme Compound
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Query: UNIPROT:Q86TM3 (cage)
29,987 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

The role of the endogenous corticotropin-releasing hormone (CRH) system in the regulation of heart rate, PQ interval (a measure of vagal activity), gross activity and release of adrenocorticotropic hormone (ACTH), noradrenaline and adrenaline into the blood during conditioned fear was studied in freely moving rats. Intracerebroventricular (i.c.v.) infusion of alpha-helical CRH-(9-41) (10 microgram/3 microliter), a non-selective CRH receptor antagonist, under resting conditions had no significant effect on gross activity, heart rate and PQ interval, indicating that alpha-helical CRH at this dose was devoid of agonist effects. Conditioned fear was induced by 10 min forced exposure to a cage in which the rat had experienced footshocks (5x0.5 mAx3 s) 1 day before. Conditioned-fear rats showed freezing behaviour, associated with an increase in heart rate, PQ interval, noradrenaline and adrenaline, indicating that the conditioned-fear-induced cardiac effects were the result of coactivation of the sympathetic and parasympathetic nervous system. The i.c.v. pre-treatment of rats with alpha-helical CRH significantly reduced the conditioned-fear-induced tachycardiac and ACTH response, and enhanced the increase in PQ interval, without affecting the noradrenaline and adrenaline response. These results suggest that endogenous CRH reduces the vagal response to conditioned-fear stress in rats. To test this, rats were pre-treated with atropine methyl nitrate (0.3 mg/kg, subcutaneously; s.c.), a peripherally acting cholinergic receptor antagonist. This resulted in a complete blockade of the alpha-helical CRH-induced decrease in heart rate response and increase in PQ interval. From these findings, it is concluded that endogenous CRH in the brain inhibits vagal outflow induced by emotional stress.
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PMID:Endogenous corticotropin-releasing hormone inhibits conditioned-fear-induced vagal activation in the rat. 1068

Chronically instrumented, conscious rats were used to examine whether mild exteroceptive stress produces differential neurochemical changes in the hypothalamic paraventricular nucleus (PVN) region. We constructed systems for stress experiment of air jet and swing rotation that were conducted on freely moving conscious rats in a computer-controlled home cage. Concentration of extracellular norepinephrine (NE) and nitric oxide metabolites (NO(X)(-)), nitrite (NO(2)(-)) and nitrate (NO(3)(-)), in the PVN region was then measured by high-performance liquid chromatography with the respective detector; blood pressure (BP) and heart rate (HR) were also measured. Both stressors increased NE concentration in the PVN region as well as BP and HR. Neither stressor altered NO(X)(-) in the PVN region. Cardiovascular and NE changes showed reproducibility in intensity-dependent manner in response to repeated stressors. This finding demonstrated that exteroceptive stress produced different effects on the neurochemical mediators, NE and NO, in the PVN region.
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PMID:Increase in norepinephrine but not nitric oxide metabolite levels in the hypothalamic paraventricular nucleus region in response to air jet and swing rotation in freely moving conscious rats. 1097 11

A centered icosahedral 12-coordinate samarium cluster formed by six bis(L-prolinato)nickel(II) ([Ni(pro)2]) ligands, [Sm(Ni(pro)2)6]3+, was prepared. The reaction of Sm with [Ni(pro)2] in a small excess (a 2-fold excess) and also in a large excess (even a 10-fold excess) of the latter produced the cluster. Therefore, this system is a self-assembly. In the cluster, each nickel atom is surrounded by six atoms: two amino nitrogens, two carboxylate oxygens which form chelate rings with the nitrogen atoms, and two carboxylate oxygen atoms which link the neighboring nickel atoms. The samarium atom is coordinated by six [Ni(pro)2] ligands, and the metal is in an icosahedral environment formed by 12 oxygen atoms. The icosahedral geometry is almost ideal. Crystals of [Sm(Ni(pro)2)6](ClO4)3.6MeOH, which were prepared from a methanol solution, immediately decompose after filtration because of loosely trapped MeOH molecules in the crystal lattice. Therefore, crystals without MeOH molecules, which must be stable, were prepared by recrystallization from acetonitrile with tetramethylammonium perchlorate (TMAP). According to the X-ray crystal analysis, the cluster is TMA[Sm(Ni(pro)2)6](ClO4)4, cubic of space group F23, with a = 21.273(9) A, V = 9626(1) A3, and Z = 4; R = 0.053 (Rw = 0.049) for 1296 reflections. In addition, several crystals of cluster salts that have different counteranions, i.e., tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), iodide (I-), and nitrate (NO3-), were prepared. The order of increasing ease of crystallization of the cluster salts was I- > PF6- approximately ClO4- > BF4- >> NO3-. The cluster structure is retained in alcohol and acetonitrile solutions; the UV-vis spectra of the solutions are perfectly consistent with the powder diffuse reflection spectrum. Cyclic voltammograms of [Sm(Ni(pro)2)6]3+ in acetonitrile proved that the structure of [Sm(Ni(pro)2)6]3+ is retained in the redox process and that the nickel atoms electrochemically interact with one another. Thermal analysis of the cluster salts with different counteranions was investigated. The results imply that the cluster is very stable until bis(L-prolinato)nickel(II) ligands, which form the cage structure, disintegrate and that the thermal decomposition processes of the cluster salts depend on their counteranions.
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PMID:Synthesis of stable crystals of a self-assembled centered icosahedral samarium cluster formed by bis(L-prolinato)nickel(II) ligands. 1119 3

Activation volumes (delta V++) have been determined for several reactions of peroxynitrite using the stopped-flow technique. Spontaneous decomposition of ONOOH to NO3- in 0.15 M phosphate, pH 4.5, gave delta V++ = 6.0 +/- 0.7 and 14 +/- 1.0 cm3 mol-1 in the presence of 53 microM and 5 mM nitrite ion, respectively. One-electron oxidations of Mo(CN)8(4-) and Fe(CN)6(4-), which are first order in peroxynitrite and zero order in metal complex, gave delta V++ = 10 +/- 1 and 11 +/- 1 cm3 mol-1, respectively, at pH 7.2. The limiting yields of oxidized metal complex were found to decrease from 61 to 30% of the initially added peroxynitrite for Mo(CN)8(3-) and from 78 to 47% for Fe(CN)6(3-) when the pressure was increased from 0.1 to 140 MPa. The bimolecular reaction between CO2 and ONOO- was determined by monitoring the oxidation of Fe(CN)6(4-) by peroxynitrite in bicarbonate-containing 0.15 M phosphate, pH 7.2, for which delta V++ = -22 +/- 4 cm3 mol-1. The Fe(CN)6(3-) yield decreased by approximately 20% upon increasing the pressure from atmospheric to 80 MPa. Oxidation of Ni(cyclam)2+ by peroxynitrite, which is first order in each reactant, was characterized by delta V++ = -7.1 +/- 2 cm3 mol-1, and the thermal activation parameters delta H++ = 4.2 +/- 0.1 kcal mol-1 and delta S++ = -24 +/- 1 cal mol-1 K-1 in 0.15 M phosphate, pH 7.2. These results are discussed within the context of the radical cage hypothesis for peroxynitrite reactivity.
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PMID:Pressure dependence of peroxynitrite reactions. Support for a radical mechanism. 1120 11

High-temperature 33Na MAS NMR experiments up to 873 K for a number of different sodalites (Na8[AlSiO4]6(NO3)2, Na8[AlSiO4]6(NO2)2, Na8[AlSiO4]6I2, Na7.9[AlSiO4]6(SCN)7.9 x 0.5H2O, Na8[AlGeO4]6(NO3)2, and Na7[AlSiO4]6(H3O2) x 4H2O) were carried out. The spectra of the first five sodalites consist of a quadrupolar MAS pattern with different quadrupolar coupling constants. The quadrupolar interaction for the thiocyanate sodalite, the nitrate aluminosilicate, and germanate sodalite decreases strongly passing a coalescence state on heating, while the quadrupolar interaction of the iodide and nitrite sample shows nearly no change. The basic hydrosodalite shows an asymmetric lineshape at room temperature and, between 350 and 370 K, a second line due to the evaporation of cage-water emerges. The linewidth increases with rising temperature. The temperature dependence of the quadrupolar interaction seems to be a function of the sodalite beta-cage expansion. Two conceivable jump mechanisms are proposed for a tetrahedral two-site jump between occupied and unoccupied tetrahedral sites.
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PMID:Influence of sodium ion dynamics on the 23Na quadrupolar interaction in sodalite: a high-temperature 23Na MAS NMR study. 1127 Jul 43

Reactions of MnX2.nH2O with tris(N-(D-mannosyl)-2-aminoethyl)amine ((D-Man)3-tren), which was formed from D-mannose and tris(2-aminoethyl)amine (tren) in situ, afforded colorless crystals of [Mn((D-Man)3-tren)]X2 (3a, X = Cl; 3b, X = Br; 3c, X = NO3; 3d, X = 1/2SO4). The similar reaction of MnSO4.5H2O with tris(N-(L-rhamnosyl)-2-aminoethyl)amine ((L-Rha)3-tren) gave [Mn((L-Rha)3-tren)]SO4 (4d), where L-rhamnose is 6-deoxy-L-mannose. The structures of 3b and 4d were determined by X-ray crystallography to have a seven-coordinate Mn(II) center ligated by the N-glycoside ligand, (aldose)3-tren, with a C3 helical structure. Three D-mannosyl residues of 3b are arranged in a delta(ob3) configuration around the metal, leading to formation of a cage-type sugar domain in which a water molecule is trapped. In 4d, three L-rhamnosyl moieties are in a delta(lel3) configuration to form a facially opened sugar domain on which a sulfate anion is capping through hydrogen bonding. These structures demonstrated that a configurational switch around the seven-coordinate manganese(II) center occurs depending on its counteranion. Reactions of 3a, 3b, and 4d with 0.5 equiv of Mn(II) salt in the presence of triethylamine yielded reddish orange crystals formulated as [[Mn((aldose)3-tren)]2Mn(H2O)X3.nH2O (5a, aldose = D-Man, X = Cl; 5b, aldose = D-Man, X = Br; 6d, aldose = L-Rha, X = 1/2SO4). The analogous trinuclear complexes 6a (aldose = L-Rha, X = Cl), 6b (aldose = L-Rha, X = Br), and 6c (aldose = L-Rha, X = NO3) were prepared by the one-pot reaction of Mn(II) salts with (L-Rha)3-tren without isolation of the intermediate Mn(II) complexes. X-ray crystallographic studies revealed that 5a, 5b, 6c, and 6d have a linearly ordered trimanganese core, Mn(II)Mn(III)Mn(II), bridged by two carbohydrate residues with Mn-Mn separations of 3.845(2)-3.919(4) A and Mn-Mn-Mn angles of 170.7(1)-173.81(7) degrees. The terminal Mn(II) atoms are seven-coordinate with a distorted mono-face-capped octahedral geometry ligated by the (aldose)3-tren ligand through three oxygen atoms of C-2 hydroxyl groups, three N-glycosidic nitrogen atoms, and a tertiary amino group. The central Mn(III) atoms are five-coordinate ligated by four oxygen atoms of carbohydrate residues in the (aldose)3-tren ligands and one water molecule, resulting in a square-pyramidal geometry. In the bridging part, a beta-aldopyranosyl unit with a chair conformation bridges the two Mn(II)Mn(III) ions with the C-2 mu-alkoxo group and with the C-1 N-glycosidic amino and the C-3 alkoxo groups coordinating to each metal center. These structures could be very useful information in relation to xylose isomerases which promote aldose-ketose isomerization by using divalent dimetal centers such as Mn2+, Mg2+, and Co2+.
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PMID:Novel Mn(II)Mn(III)Mn(II) trinuclear complexes with carbohydrate bridges derived from seven-coordinate manganese(II) complexes with N-glycoside. 1127 63

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.
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PMID:Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3]infinity coordination polymers. 1146 55

A family of nanoscale-sized supramolecular cage compounds with a trigonal prismatic framework was prepared by means of spontaneous self-assembly from the combination of a predesigned molecular "clip" with tritopic pyridyl subunits. As confirmed by x-ray crystallography, the smallest structure of the reported series is approximately 1 x 2 nm and possesses a nitrate anion incarcerated inside its molecular cavity. The largest structure has dimensions of approximately 1 x 4 nm.
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PMID:Self-assembly of nanoscopic coordination cages of D(3h) symmetry. 1188 May 99

Ion exchange of the sodium hydro sodalites [Na3(H2O)4]2-[Al3Si3O12]2 [Na4(H3O2)]2[Al3Si3O12]2 and [Na4(OH)]2[Al3Si3O12]2 with aqueous Pb(NO3)2 solutions yielded, whichever reactant sodalite phase was used, the same lead hydro sodalite, [Pb2(OH)-(H2O)3]2[Al3Si3O12]2. Thus, in the case of the non-basic reactant [Na3(H2O)4]2-[Al3Si3O12]2 an overexchange occurs with respect to the number of nonframework cationic charges. Rietveld structure refinement of the lead hydro sodalite based on powder X-ray diffraction data (cubic, a = 9.070 A, room temperature, space group P43n) revealed that the two lead cations within each polyhedral sodalite cage form an orientationally disordered dinuclear [Pb2(micro-OH)(micro-H2O)(H2O)2]3+ complex. Due to additional lead framework oxygen bonds the coordination environment of each metal cation (CN 3+3) is approximately spherical, and clearly the lead 6s electron lone pair is stereochemically inactive. This is also suggested by the absence of a small peak at 13.025 keV, attributed in other Pb2+-O compounds to an electronic 2p-6s transition, in the PbL3 edge XANES spectrum. 1H MAS NMR and FTIR spectra show that the hydrogen atoms of the aqua hydroxo complex (which could not be determined in the Rietveld analysis) are involved in hydrogen bonds of various strengths.
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PMID:Lead hydro sodalite [Pb2(OH)(H2O)3]2[Al3Si3O12]2: synthesis and structure determination by combining X-ray rietveld refinement, 1H MAS NMR FTIR and XANES spectroscopy. 1193 Nov 9

A crystalline salt has been synthesized that contains H(+) and Na(-) rather than the usual hydride oxidation states of H(-) and Na(+). The key is irreversible encapsulation of H(+) within the cage of 3(6)adamanzane (Adz). The internal proton is kinetically inert to reduction by Na(-) in solution in NH(3)-MeNH(2) mixtures. Synthesis of the sodide is accomplished by a metathesis reaction between Na and AdzH(+)X(-) in which X(-) is a sacrificial anion such as glycolate, isethionate, or nitrate. Reduction or deprotonation of the sacrificial anion forms insoluble byproducts and AdzH(+)Na(-) in solution. After solvent removal, the sodide is dissolved in dimethyl ether and transferred through a frit into a separate chamber for crystallization. The compound was characterized as the sodide by analysis, NMR spectra, and optical absorption spectroscopy.
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PMID:"Inverse sodium hydride": a crystalline salt that contains H(+) and Na(-). 1202 11


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