Photochemically catalyzed reaction of ochratoxin A with D- and L-cysteine

The photolysis (>300 nm) of ochratoxin A (OTA, N-[[(3R)-5-chloro-8-hydroxy-3-methyl-1-oxo-7-isochromanyl]carbonyl]-3-phenyl-L-alanine, 1) in the presence of excess (2 and 12 molar equiv) cysteine (CySH) has been investigated and found to yield sulfur adducts 5 and 6 that are characterized by liquid chromatography-mass spectrometry and 1H-NMR spectroscopy. The adduct 5 was ascribed to the Michael addition conjugate resulting from covalent attachment of CySH to the ochratoxin quinone (4) generated by photooxidation of OTA. This species was also formed by photolysis of a synthetic sample of the hydroquinone of OTA (ochratoxin hydroquinone, 3) in the presence of 12 equiv L-CySH. The conjugate 5 derived from photolysis of 3 with L-CySH was used for 1H-NMR analysis. The sulfur adduct 6 was the major species detected from covalent attachment of CySH to photoactivated OTA, and it resulted from direct displacement of the OTA Cl atom by CySH. The implications of the cysteinyl adducts to the in vivo toxicity of OTA are discussed, with particular emphasis given to conjugate 5, as products from the photooxidative pathway may be of relevance to the nephrotoxic properties of OTA.     

Electron impact and chemical ionization mass spectra of alkyldiphenylphosphine oxides

In the 70 e V electron impact mass spectra of a series of alkyldiphenylphosphine oxides (R?₂PO, R = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu, neopentyl, n-decyl), molecular ions of low abundance are observed and [M + H]⁺ ions are formed to a small extent at high sample pressures. The major ions include [?₂PO]⁺, [?₂POH]⁺; [?₂CH₂PO]⁺ and [?₂CH₂POH]⁺ which are formed by rearrangement and cleavage processes. The chemical ionization mass spectra obtained with methane and isobutane reagents consist of [M + H]⁺ ions. The proton affinity of R?₂PO was found to be 219 ± 2.5 kcal mol^?1.     

Single particle versus ensemble average: from power-law intermittency of a single quantum dot to quasistretched exponential fluorescence decay of an ensemble

Light-induced diffusion-controlled electron transfer is proposed as an underlying mechanism for the intermittency (power law and breakdown) of a single quantum dot and ensemble-averaged fluorescence decay. The intensity decay can be approximated to a stretched exponential expression. The physical links to the free energy gap, reorganization energy, electronic coupling, and diffusion correlation times are discussed. A procedure is described for extracting these molecular-based parameters from experiments and is demonstrated with examples using existing data.     

Neutral and ionic aluminum,gallium, and indium compounds carrying two or three terminal ethynyl groups

The syntheses of the ionic compounds [Li(+).2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe(3))Al(C triplebond CSiMe(3))(3))(-)].0.75 dioxane (1), [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))Ga(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (2), and [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))In(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiC triplebond CSiMe(3) are reported. The neutral ethynyl compounds Br-Al(C triplebond CtBu)(2).2 THF (4), Cl-Ga(C triplebond CtBu)(2).THF (5), Cl-In(C triplebond CtBu)(2).2 THF (6), Al(C triplebond CtBu)(3).C[N(Me)CMe](2) (7), Ga(C triplebond CtBu)(3).dioxane (8), and In(C triplebond CtBu)(3).NEt(3) (9) have been obtained in good yields from the reaction of AlBr(3), GaCl(3), and InCl(3) with LiC triplebond CtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(C triplebond CPh)(3).NMe(3) (10) and Ga(C triplebond CPh)(3).NMe(3) (11) have been prepared by the reaction of AlH(3).NMe(3) or GaH(3).NMe(3) with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.     

Fluorescent properties of oligonucleotide-conjugated thiazole orange probes

The fluorescence properties of thiazole orange, linked via a (1) hydrophobic alkyl or a (2) hydrophilic ethylene glycol chain to the central internucleotidic phosphate group of a pentadeca-2'-deoxyriboadenylate (dA15), are evaluated. Linkage at the phosphate group yields two stereoisomers, S-isomer of the phosphorus chiral center (Sp) and R-isomer of the phosphorus chiral center (Rp); these are studied separately. The character of the linkage chain and the chirality of the internucleotidic phosphate linkage site influence the fluorescent properties of these thiazole orange-oligonucleotide conjugates (TO-probes). Quantum yields of fluorescence (phifl) of between 0.04 and 0.07 were determined for the single-stranded conjugates. The fluorescence yield increased by up to five times upon hybridization with the complementary sequence (d5'[CACT15CAC3']); (phifl values of between 0.06-0.35 were determined for the double-stranded conjugates. The phifl value (0.17) of thiazole orange, 1-(N,N'-trimethylaminopropyl)-4-[3-methyl-2,3-dihydro-(benzo-1,3-thiazole)-2-methylidene]-quinolinium iodide (TO-Pro 1) in the presence of the oligonucleotide duplex (TO-Pro 1: dA15.d5'[CACT15CAC3'] (1:1)) is much less than that for some of the hybrids of the conjugates. Our studies, using steady-state and time-resolved fluorescence experiments, show that a number of discrete fluorescent association species between the thiazole orange and the helix are formed. Time-resolved studies on the four double-stranded TO-probes revealed that the fluorescent oligonucleotide-thiazole orange complexes are common, only the distribution of the species varies with the character of the chain and the chirality at the internucleotidic phosphate site. Those TO-probes in which the isomeric structure of the phosphate-chain linkage is Rp, and therefore such that the fluorophore is directed toward the minor groove, have higher phifl values than the Sp isomer. Of the systems studied, thiazole orange linked by an alkyl chain to the internucleotidic phosphate (Rp isomer) has the highest phifl and the greatest fraction of the longest-lived fluorescent thiazole orange species (in the hybrid form).     

Untersuchungen zur Physisorption und Chemisorption von Wasser auf Zinkoxid-Oberflächen

The investigation of different zinc oxide samples by means of thermogravimetry and infrared spectroscopy has shown that the surface of the samples is covered by an approximately monoatomic layer of hydroxide groups. Furthermore, varying amounts of carbonate groups are found which are due to the presence of zinc hydroxide carbonate II [Zn₅(OH)₆(CO₃)₂]. Below relative water vapour pressures of p/p₀ = 0.2 (25°C), two hydrogen bridges connect one physisorbed water molecule with two chemisorbed surface hydroxide groups. In addition, about the same amount of water is physically adsorbed between vapour pressures of p/p₀ 0.2 and 0.8. At still higher relative humidity, a multimolecular layer is built up which reaches a thickness of about 200 water molecules at p/p₀ = 1.0. All samples show in the v-OH region of the IR. spectrum a broad absorption with four bands, A, B, C, and D. The position of the bands and the change of their intensities when rising the temperature of the samples up to 600°C indicate that both bands of longer wave lengths, C and D, arise from physically adsorbed water molecules, while the bands A and B are due to hydroxide groups located on the crystallographic faces (0001) and (0001 ), respectively.     

Non-Template-Centered, Closed Tetravanadium Phosphate and Phosphonate Clusters

Tetranuclear V(III) complexes, [HB(pz)(3)](4)V(4)(&mgr;-C(6)H(5)OPO(3))(4) (I), its acetonitrile solvate (I.4CH(3)CN), and [HB(pz)(3)](4)V(4)(&mgr;-O(2)NC(6)H(4)OPO(3))(4).4C(7)H(8).H(2)O (II), and tetranuclear vanadyl complexes, (t-Bupz)(4)V(4)O(4)(&mgr;-C(6)H(5)PO(3))(4).2H(2)O (III) and (t-Bupz)(5)V(4)O(4)(&mgr;-C(6)H(5)PO(3))(4).4CH(3)CN.0.6 H(2)O (IV), have been prepared and characterized by spectroscopic, magnetic, and electrochemical methods (pz = pyrazole, t-Bupz = tert-butylpyrazole). The use of organic solvents and bulky organic groups as ancillary ligands leads to formation of neutral species instead of the anionic clusters commonly found in the hydrothermal synthesis of vanadium organophosphate/phosphonate systems. Complexes I.4CH(3)CN and IV have also been characterized by single-crystal X-ray diffraction. Crystal data: I.4CH(3)CN, triclinic, P&onemacr;, a = 15.495(3) ?, b = 17.000(3) ?, c = 17.949(4) ?, alpha = 89.17(3) degrees, beta = 86.00(3) degrees, gamma = 78.60(3) degrees, Z = 2; IV, triclinic, P&onemacr;, a = 15.541(3) ?, b = 16.340(2) ?, c = 19.069(5) ?, alpha = 83.58(2) degrees, beta = 79.67(2) degrees, gamma = 63.68(1) degrees, Z = 2. Both are closed clusters, the core structure of the first consisting of a cubane-like arrangement of metal octahedra and phosphate tetrahedra and the core structure of the second consisting of a distorted, collapsed variant of the first. Unlike other vanadium phosphate clusters, these compounds form in the absence of a central, templating agent. As such they represent the simplest form of a closed cluster in which steric forces and cluster connectivity requirements play the primary role in organizing the cluster framework.     

Transition metal complexes in organic synthesis. Part 68: Iron-mediated total synthesis of mukonine and mukonidine by oxidative cyclization with air as the oxidizing agent

The oxidative cyclization of 5-(2-amino-5-methoxycarbonylphenyl)-substituted tricarbonyl[η⁴-cyclohexa-1,3-diene]iron complexes by air in protic medium provides the corresponding tricarbonyl[η⁴-4a,9a-dihydro-9H-carbazole]iron complexes. This procedure is applied to the total synthesis of the 3-methoxycarbonylcarbazole alkaloids mukonine and mukonidine.