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 reagent [arachno-4-CB8H14] reacts with [Fe3(CO)12] in tetrahydrofuran (THF) at reflux temperatures, followed by addition of [N(PPh3)2]Cl, to afford [N(PPh3)2][4,9-{Fe(CO)4}-9,9,9-(CO)3-arachno-9,6-FeCB8H11] (3). In the anion of 3, one iron atom is part of the open CBBFeBB face of a 10-vertex {arachno-9,6-FeCB8} cage, to which the second iron atom is attached via an Fe-Fe bond and an additional exo-polyhedral Fe-B sigma bond. Upon heating 3 in refluxing toluene, the closed 10-vertex species [N(PPh3)2][2,2,2-(CO)3-closo-2,1-FeCB8H9] (4) is obtained, whereas the isomeric compound [N(PPh3)2][6,6,6-(CO)3-closo-6,1-FeCB8H9] (5) is isolated upon heating [closo-4-CB8H9]- and [Fe3(CO)12] in refluxing THF with subsequent addition of [N(PPh3)2]Cl. Protonation of 3 using CF3SO3H in CH2Cl2 gives the charge-compensated compound [4,9-{Fe(CO)4}-4-(mu-H)-9,9,9-(CO)3-arachno-9,6-FeCB8H11] (6), in which the B-Fe sigma bond of the precursor has been converted to a B-H right harpoon-up Fe linkage. In contrast, 3 with {M(PPh3)}+ gives the trimetallic species [1,3,4,9-{MFe(CO)4(PPh3)}-1,3-(mu-H)2-9,9,9-(CO)3-arachno-9,6-FeCB8H9] (M = Cu (7), Ag 8) in which the three metal centers form a V-shaped M-Fe-Fe unit. Compound 6 reacts with PEt3 in the presence of Me(3)NO to yield [4,9-(PEt3)2-9,9-(CO)2-nido-9,6-FeCB8H10] (9). In the latter, the formerly exo-polyhedral {Fe(CO)4} fragment has been replaced by a PEt3 ligand, with a second PEt3 substituting one CO group at the remaining cluster iron vertex. The novel structural features of compounds 3-9 have been confirmed by single-crystal X-ray diffraction studies.
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PMID:Ten-vertex iron-monocarbollide complexes: synthesis and reactivity of the anion [4,9-{Fe(CO)4}-9,9,9-(CO)3-arachno-9,6-FeCB8H11]-. 1652 90

A sterically hindered aryl phosphonic acid ArP(O)(OH)2 (2) (Ar = 2,4,6-isopropylphenyl) was synthesized and structurally characterized. ArP(O)(OH)2 forms an interesting hydrogen-bonded corrugated sheet-type supramolecular structure in the solid-state. A three-component reaction involving ArP(O)(OH)2, 3,5-dimethylpyrazole(DMPZH), and Cu(CH3COO)2.H2O produces the tetranuclear Cu(II) compound [Cu4(mu3-OH)2{ArPO2(OH)}2(CH3CO2)2(DMPZH)4][CH3COO]2.CH2Cl2 (3). A similar three-component reaction involving ArP(O)(OH)2, 3,5-dimethylpyrazole, and Zn(CH3COO)2.2H2O yields the tetranuclear Zn(II) compound [Zn4{ArPO3}2{ArPO2(OH)}2{DMPZH}4(DMPZ)2].5MeOH (4). While 3 has been found to have an asymmetric cage structure where two dinuclear copper cores are bridged by bidentate [ArPO2(OH)]- ligands, 4 possesses an open-book tricyclic structure composed of three fused metallophosphonate rings. Magnetic studies on 3 revealed antiferromagnetic behavior.
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PMID:Assembly of lipophilic tetranuclear (Cu4 and Zn4) molecular metallophosphonates from 2,4,6-triisopropylphenylphosponic acid and pyrazole ligands. 1660 93

The complex [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9] has been synthesized by treatment of the complex salt [NHMe3][3,3-Cl2-3,3-(CO)2-closo-3,1,2-ReC2B9H11] with PPh3 in refluxing THF (tetrahydrofuran) and isolated as intensely colored orange-red microcrystals. Spectroscopic NMR and IR data have suggested that the product has a highly asymmetric structure with two inequivalent PPh3 ligands and a single CO ligand. Measurement of 11B NMR spectra in particular have indicated seven distinct boron vertexes, although the resulting cage degradation by removal of two BH vertexes was confirmed only following X-ray crystallographic analysis, which revealed the pentadecahedral isonido-7,8,9-ReC2B7 architecture. The 11B NMR resonances span an enormous chemical shift range (Deltadelta = 113), and this appears to be a direct consequence of the deshielding of the boron vertex directly opposite the quadrilateral |ReCCB| aperture. The new complex has been shown by electrochemical measurements to undergo a reversible one-electron oxidation. Digitally simulated cyclic voltammograms support a proposed square scheme (E(1/2) = 0.58, 0.69 V vs ferrocene) involving a reversible isonido-closo transition of the metallacarborane cage. Most unusually for a metallacarborane complex, ambient temperature solutions in CH2Cl2 and DMF have been shown to be intensely turquoise-blue fluorescent (lambda(em) = 442 nm, Phi = 0.012). Fluorescence spectroscopy measurements in MeTHF (2-methyltetrahydrofuran) glass at 77 K have indicated that the likely cause of such a broad emission is dual fluorescence (lambda(em) = 404, 505 nm), with both emissions displaying vibronic structure. Following excited-state lifetime decay analysis, the emissive behavior has been accredited to metal-perturbed 1IL states, with the lower energy emission arising from a slight geometric distortion of the initially excited complex.
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PMID:Dual fluorescence from an isonido ReIII rhenacarborane phosphine complex, [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9]. 1693 36

We report the first UV-vis spectroscopic study of bromine molecules confined in clathrate hydrate cages. Bromine in its natural hydrate occupies 51262 and 51263 lattice cavities. Bromine also can be encapsulated into the larger 51264 cages of a type II hydrate formed mainly from tetrahydrofuran or dichloromethane and water. The visible spectra of the enclathrated halogen molecule retain the spectral envelope of the gas-phase spectra while shifting to the blue. In contrast, spectra of bromine in liquid water or amorphous ice are broadened and significantly more blue-shifted. The absorption bands shift by about 360 cm-1 for bromine in large 51264 cages of type II clathrate, by about 900 cm-1 for bromine in a combination of 51262 and 51263 cages of pure bromine hydrate, and by more than 1700 cm-1 for bromine in liquid water or amorphous ice. The dramatic shift and broadening in water and ice is due to the strong interaction of the water lone-pair orbitals with the halogen sigma* orbital. In the clathrate hydrates, the oxygen lone-pair orbitals are all involved in the hydrogen-bonded water lattice and are thus unavailable to interact with the halogen guest molecule. The blue shifts observed in the clathrate hydrate cages are related to the spatial constraints on the halogen excited states by the cage walls.
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PMID:Spectroscopic signatures of halogens in clathrate hydrate cages. 1. Bromine. 1718 36

Treatment of [RhCl(eta4-diene)]2 (diene = nbd, cod) with the N-heterocyclic ligands 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), 1,10-phenanthroline (phen), and pyridine (py) followed by addition of Cs[arachno-6-SB9H12] affords the corresponding salts, [Rh(eta4-diene)(L2)][SB9H12] [diene = cod, L2 = bpy (1), Me2bpy (3), phen (5), (py)2 (7); diene = nbd, L2 = bpy (2), Me2bpy (4), phen (6), (py)2 (8)]. These compounds are characterized by NMR spectroscopy and mass spectrometry, and in addition, the cod-Rh species 1 and 3 are studied by X-ray diffraction analysis. These saltlike reagents are stable in the solid state, but in solution the rhodium(I) cations, [Rh(eta4-diene)(L2)]+, react with the polyhedral anion [SB9H12]- leading to a chemistry that is controlled by the d8 transition element chelates. The nbd-Rh(I) complexes react faster than the cod-Rh(I) counterparts, leading, depending on the conditions, to the synthesis of new rhodathiaboranes of general formulas [8,8-(L2)-nido-8,7-RhSB9H10] [L2 = bpy (9), Me2bpy (10), phen (11), (py)2 (12)] and [8,8-(L2)-8-(L')-nido-8,7-RhSB9H10] [L' = PPh3, L2 = bpy (13), Me2bpy (14), phen (15); L' = NCCH3, L2 = bpy (16), Me2bpy (17), phen (18)]. Compound 13 is characterized by X-ray diffraction analysis confirming the 11-vertex nido-structure of the rhodathiaborane analogues 14-18. In dichloromethane, 1 and 3 yield mixtures that contain the 11-vertex rhodathiaboranes 9 and 10 together with new species. In contrast, the cod-Rh(I) reagent 5 affords a single compound, which is proposed to be an organometallic rhodium complex bound exo-polyhedrally to the thiaborane cage. In the presence of H2(g) and stoichiometric amounts of PPh3, the cod-Rh(I) reagents, 1, 3, and 5, afford the salts [Rh(H)2(L2)(PPh3)2][SB9H12] [L2 = bpy (19), Me2bpy (20), phen (21)]. Similarly, in an atmosphere of CO(g) and in the presence of PPh3, compounds 1-6 afford [Rh(L2)(PPh3)2(CO)][SB9H12] (L2 = bpy (22), Me2bpy (23), phen (24)]. The structures of 19 and 24 are studied by X-ray diffraction analysis. The five-coordinate complexes [Rh(L2)(PPh3)2(CO)]+ undergo PPh3 exchange in a process that is characterized as dissociative. The observed differences in the reactivity of the nbd-Rh(I) salts versus the cod-Rh(I) analogues are rationalized on the basis of the higher kinetic lability of the nbd ligand and its faster hydrogenation relative to the cod diene.
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PMID:Square-planar rhodium(I) complexes partnered with [arachno-6-SB(9)H(12)]- : a route toward the synthesis of new rhodathiaboranes and organometallic/thiaborane salts. 1762 37

Density functional theory calculations indicate that the cage molecule 4 can trap F- in the gas phase (-80.5 kcal/mol) as well as in CH2Cl2 (-14.7 kcal/mol) via strong C-H...F- hydrogen bonds and pi...F- interaction.
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PMID:Oxa-bicyclocalixarenes: a new cage for anions via C-H...anion hydrogen bonds and anion...pi interactions. 1785 94

The high-yield syntheses of 6-X-B 10H 13 [X = Cl (88%), Br (96%), I (84%)] resulted from the cage-opening reactions of the (NH 4 (+)) 2B 10H 10 (2-) salt with ionic-liquid-based superacidic hydrogen halides, while both the previously unknown 6-F-B 10H 13 (77%) derivative and 6-Cl-B 10H 13 (90%) were synthesized in high yields via the reactions of (NH 4 (+)) 2B 10H 10 (2-) with triflic acid in the presence of 1-fluoropentane and dichloromethane, respectively. Structural characterizations of 1- 4 confirm the predicted structures and indicate strong halogen back-bonding interactions with the B6 boron. The reaction of 6-Br-B 10H 13 with Bu 3SnH produced the parent B 10H 14 in 70% yield, and thus, this reaction, in conjunction with the haloacid-induced closo-B 10H 10 (2-) cage-opening reactions, has the potential to provide an alternative to the traditional diborane pyrolysis route to decaborane.
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PMID:Crystallographic characterizations and new high-yield synthetic routes for the complete series of 6-X-B10H13 halodecaboranes (X = F, Cl, Br, I) via superacid-induced cage-opening reactions of closo-B10H10(2-). 1875 57

The reaction of the 16e half-sandwich complex [CpCo(S2C2B10H10)] (1S; Cp: cyclopentadienyl) with ethynylferrocene in CH2Cl2 at ambient temperature leads to [CpCo(S2C2B10H9)-(CH2CFc)] (2S; Fc: ferrocenyl) and 1,2,4-triferrocenylbenzene. In 2S, B substitution occurs at the carborane cage in the position B3/B6 with the formation of a C-B bond. In the presence of the protic solvent MeOH, 2S loses a CpCo fragment to generate [(CH2CFc)(S2C2B10H9)] (3S). On the other hand, 2S can take a free CpCo fragment to form [(CpCo)2(S2C2B9H8)-(CHCFc)] (4S) containing a nido-C2B9 unit. In sharp contrast, [CpCo-(Se2C2B10H10)] (1Se) does not react with the alkyne in CH2Cl2, but in MeOH [(CHCFc)(Se2C2B10H10)] (5Se) is generated without the presence of a CpCo unit. The reaction of 1 with dimethyl acetylenedicarboxylate at ambient temperature leads to insertion compounds [CpCo(E2C2B10H10){(MeO2C)-C=C(CO2Me)}] (6S, E=S; 6 Se, E=Se). Upon heating, 6S rearranges to two geometrical isomers [CpCo(S2C2B10H9){(MeO2C)C=CH(CO2Me)}] (7S) and [CpCo(S2C2B10H9){(MeO2C)-CHC(CO2Me)}] (8S). In both, B-H functionalization takes place at the carborane cage in the position B3/B6, but 7S is a 16e complex with an olefinic unit in a Z configuration, and 8S is an 18e complex containing an alkyl B-CH group. Further treatment of 7 S with dimethyl acetylenedicarboxylate at ambient temperature affords two B-disubstituted complexes at the carborane cage in the positions of the B3 and B6 sites, that is, [CpCo(S2C2-B10H8){(MeO2C)C=CH(CO2Me)}2] (9S) and [CpCo(S2C2B10H8){(MeO2C)-CHC(CO2Me)}{(MeO2C)C=CH-(CO2Me)}] (10S). Compound 9S is a 16e complex with two olefinic units in E/E configurations, whereas 10S is an 18e species containing both an olefinic substituent and an alkyl B--CH unit. The reaction of 7S with methyl acetylenemonocarboxylate at ambient temperature leads to the sole 16e compound [CpCo(S2C2B10H8){CH=CH(CO2Me)}-{(MeO2C)C=CH(CO2Me)}] (11S). In contrast, 6Se does not rearrange. All new complexes 2S-4S, 5Se, 6Se, and 7S-11S were characterized by NMR spectroscopy (1H, 11B, 13C) and X-ray structural analyses were performed for 2S-4S, 5Se, 6Se, and 7S-9S.
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PMID:Reactions of 16e CpCo half-sandwich complexes containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligand with ethynylferrocene and dimethyl acetylenedicarboxylate. 1876 76

We describe the thermodynamic characterization of the assembly process of a covalently connected trimeric Zn porphyrin induced by coordination to a bispyridyl functionalized perylene bisimide . The perylene bisimide ligands act as pillars via two axial coordination bonds with the porphyrinic Zn(ii) ions fixing the planes of the porphyrin units in a nearly co-facial orientation and inducing the formation of trigonal prism-like structures. The fully assembled (2).(3) aggregate and the partially assembled one, (2).(2), in which only two zinc porphyrin sites of trimeric are axially coordinated to , are present in solution in equilibrium with freely diffusing species and . The strong quenching observed in the mixture for the luminescence of the components and is ascribed to an efficient photoinduced electron transfer from the Zn porphyrin units of to coordinated occurring upon excitation of both components within the assemblies. In the formed assemblies, the Zn porphyrin units of the trimer behave independently. Thus, the porphyrin units that are not coordinated with in the partially assembled complex, (2).(2), display the same photophysical behaviour registered for freely diffusing . The rate of charge separation within the cage is nearly independent on the polarity of the solvent (ca. 10(10) s(-1)) whereas the charge recombination process, leading to the ground state, has a lifetime of 110 ps in dichloromethane and ca. 6 ns in toluene, in agreement with a Marcus inverted behaviour.
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PMID:Self-assembly of double-decker cages induced by coordination of perylene bisimide with a trimeric Zn porphyrin: study of the electron transfer dynamics between the two photoactive components. 1944 Jun 2

Deoxycorticosterone (DOC: a weak mineralocorticoid) is the precursor to corticosterone (B: the major glucocorticoid in rodents) and aldosterone (the major mineralocorticoid). The genes Cyp11b1 and Cyp11b2 that encode the enzymes responsible for DOC to B (11beta-hydroxylase) and DOC to aldosterone (aldosterone synthase) conversions are located on the same chromosome. The aim of this study was to develop sensitive and specific ELISA methods to quantify urinary DOC and B concentrations to assess the physiological and genetic control of the Cyp11b1/b2 locus. Antibodies raised in rabbits against DOC and B and horse radish peroxidase-goat anti-rabbit IgG enzyme tracer were used to develop the assays. Urine samples collected from mice held in metabolic cages were extracted with dichloromethane and reconstituted in assay buffer. The assays were validated for specificity, sensitivity, parallelism, accuracy and imprecision. Cross-reactivities with major interfering steroids were minimal: DOC assay (progesterone=0.735% and corticosterone=0.045%), and for B assay (aldosterone=0.14%, 11-dehydro-B=0.006%, cortisol=0.016% and DOC=0.04%) and minimum detection limit for DOC ELISA was 2.2 pg/mL (6.6 pmol/L), and for B ELISA was 6.2 pg/mL (17.9 pmol/L). The validity of urinary DOC and B ELISAs was confirmed by the excellent correlation between the results obtained before and after solvent extraction and HPLC (DOC ELISA: Y=1.092X-0.054, R(2)=0.988; B ELISA: Y=1.047X-0.226, R(2)=0.996). Accuracy studies, parallelism and imprecision data were determined and all found to be satisfactory. The methods were used in a series of metabolic cage studies which demonstrated that (i) females produce more DOC and corticosterone than males; (ii) DOC and corticosterone respond to ACTH treatment but not dietary sodium restriction; (iii) DOC:B ratios in Cyp11b1 null mice were >200-fold greater than wild type.
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PMID:Physiological and pathophysiological applications of sensitive ELISA methods for urinary deoxycorticosterone and corticosterone in rodents. 1957 84


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