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71.
Dreos R Nardin G Randaccio L Siega P Tauzher G Vrdoljak V 《Inorganic chemistry》2003,42(21):6805-6811
The reduction of [Co(III)(tmsalen)py(2)](+)ClO(4)(-), where tmsalen = 4,4',7,7'-tetramethylsalen, with NaBH(4)/PdCl(2) in alkaline methanolic solution, followed by the oxidative addition of CH(2)ClI, leads to the expected trans organometallic dimeric species 1, [CH(2)ClCo(tmsalen)](2), provided that the product is recovered from the reaction mixture immediately after the completion of the reaction. If 1 is left for longer time in contact with the reaction mixture, the intramolecular reaction of the axial chloromethyl group with the equatorial chelate leads to the formation of the monocationic complex 2, containing a seven-membered ring. In this complex the novel tetradentate ligand coordinates Co in a cis fashion, the other two positions being occupied by one py and one water molecule. The resulting complex is chiral, even if the reaction product is a racemic compound. The unidentate ligands of 2 have been exchanged quantitatively for N-MeIm, and the resulting complex 3 still maintains the beta cis geometry. Therefore, 2 may be considered the precursor of a new class of organocobalt derivatives with a folded tetradentate ligand and two adjacent exchangeable sites. On the basis of the geometry of the tetradentate Schiff bases in complexes, where they adopt a planar geometry, it was suggested that there is a significant electron density delocalization involving the metal center over the two chemically equivalent moieties of Co(chel). Comparison of the geometry of the planar salicylaldiminate (sal) moiety with that of the cyclized methoxy-iminate one (imi) in 2 and 3 strongly supports that the delocalization, still present in sal, is essentially either lost or strongly reduced in imi. 相似文献
72.
Sauaia MG de Lima RG Tedesco AC da Silva RS 《Journal of the American Chemical Society》2003,125(48):14718-14719
The binuclear complex [RuII(NH3)5(pz)RuII(bpy)2(NO)](PF6)5 was prepared and characterized by elemental analysis, UV-vis, and IR spectroscopy. The complex UV-vis spectrum has presented bands at 242, 286, and 530 nm in acetate buffer solution at pH 4.5. The photochemical study by laser flash-photolysis at 532 nm showed the NO release account from the NO measured by a NO sensor. The quantum yield for NO release (0.025 +/- 0.004 mol einsten-1) was determined with a laser flash-photolysis apparatus (Continuum Q-switched Nd:YAG laser). The major irradiation product of the [RuII(NH3)5(pz)RuII(bpy)2(NO)]5+ complex besides nitric oxide is [RuIII(NH3)5(pz)RuII(bpy)2(H2O)]5+. 相似文献
73.
Damjana Miheli
Renata Jake Jurij Svete Branko Stanovnik Simona Goli Grdadolnik 《Journal of heterocyclic chemistry》2001,38(6):1307-1312
(S)‐5‐Benzoyloxymethyl‐3‐[(E)‐(dimethylamino)methylidene]tetrahydrofuran‐2‐one (6), prepared in 5 steps from L‐glutamic acid (1), was used as precursor in a one step ‘ring switching’ synthesis of (S)‐2‐hydroxy‐3‐heteroaryl‐l‐propyl benzoates 13‐18, 23, 24. In the reaction of 6 with 2‐aminopyridine (21) and 2‐amino‐4,6‐dimethylpyrimidine (22) the corresponding dimethylamine substitution products (25, 26) were obtained. 相似文献
74.
A study of the energy transfer process between thulium and erbium is presented. From our measurements of fluorescence emissions and decay times the energy transfer efficiencies and probabilities were calculated. In this work the energy transfer which occurs between the upper levels in the UV and VIS regions of the two ions was especially studied. In the Tm-Er system, a mutual migration of energy occurs. The energy transfer from thulium to erbium is a multichannel process in which the energy is transferred from all the metastable levels of thulium to the matching energy levels of erbium. In addition, backtransfer of energy from erbium to thulium occurs by crossrelaxation of respective erbium transitions. The efficiency of energy transfer from thulium to erbium is independent of the levels between which the transfer occurs, but is dependent on the matrix. It is concluded that the energy is transferred via the phonons of the host glass. 相似文献
75.
In this paper,the synthesis and characterization of a triarylpyrazoline modified four-H-bonded molecular duplex are described. Its molecular structure has been confirmed by ~1H NMR and ESI-MS.The duplex emits strong pure blue light peaking at 448 and 452 nm under UV photoexcitation in solution and solid state,respectively,and its relative photoluminescence quantum efficiency in solution is determined as 0.778 using quinine sulfate as reference.In concentration of>40 mmol/L,the duplex can gelate DMSO, and... 相似文献
76.
Alex Virgilio Renata Stabile Amais Daniela Schiavo José Anchieta Gomes Neto Joaquim de Araújo Nóbrega 《Analytical letters》2017,50(5):842-852
A procedure for the determination of As, Cd, Cr, Ni, Pb, and V in phytotherapy medicines by inductively coupled plasma–tandem mass spectrometry is reported. The use of tandem mass spectrometry with oxygen into an octopole reaction system at various gas flow rates and the combination of on-mass and mass-shift modes was evaluated. Cadmium, Cr, Ni, and Pb were determined as free atomic ions while As and V were determined as the oxides AsO+ and VO+ in the same run. Samples were prepared by microwave-assisted digestion with dilute nitric acid and hydrogen peroxide. Two plant-certified reference materials (apple leaves and tomato leaves) were used to check the accuracy. For tandem mass spectrometry with 0.5?mL min?1 O2, recoveries in the 85–113% were typically obtained and no statistical differences were observed at the 95% confidence level (t-test) in comparison with the certified values. Using these conditions, the limits of detection for the method were 0.01, 0.0002, 0.008, 0.008, 0.003, and 0.002?µg g?1 for As, Cd, Cr, Ni, Pb, and V, respectively. The procedure was used for the analysis of four phytotherapic drugs and the determined concentrations were up to 0.168?µg g?1 As, 0.03?µg g?1 Cd, 0.82?µg g?1 Cr, 1.18?µg g?1 Ni, 0.52?µg g?1 Pb, and 2.4?µg g?1 V with average precision values of 8% as the relative standard deviation. The found concentrations were compared with limits proposed in official guidelines and, in most cases, the values were below the maximum limits allowed. 相似文献
77.
Facile synthesis of a melt-spinnable polyborazine from asymmetric alkylaminoborazine 总被引:1,自引:0,他引:1
Yong Peng Lei Ying De Wang Yong Cai Song Yi He Li Hao Wang Cheng Deng Zheng Fang Xie 《中国化学快报》2010,21(9):1079-1082
<正>A novel asymmetric alkylaminoborazine monomer,2-propylamino-4,6-bis(methylamino)borazine,was synthesized for the first time,and directly polymerized to give a melt-spinnable polyborazine(PBN).This asymmetric alkylaminoborazine was synthesized by an aminolysis reaction of 2,4,6-trichloroborazine(TCB) with different amines under mild conditions.This route turns out to be much cheaper and simpler than the conventional routes.The chemical composition,structure,molecular weights and ceramic yield were investigated by EA,FTIR,NMR,GPC and TG analysis.The PBN exhibits suitable rheological property for melt-spinning, which suggests that it is a potential precursor for BN fibers. 相似文献
78.
An analytical procedure for direct introduction of biodiesel samples into an inductively coupled plasma mass spectrometer (ICP-MS) by using microemulsion for sample preparation was developed here. Cadmium, Co, Cu, Mn, Ni, Pb, Ti, and Zn were determined in biodiesel microemulsified samples prepared from different oleaginous sources (African palm, castor beans, palm, soybeans and an unknown oleaginous). Microemulsions were prepared using 0.25 mL Triton X-100, 0.25 mL 20% v v− 1 HNO3, 0.50 mL biodiesel sample and 4.0 mL n-propanol. Argon-oxygen mixture was added to the plasma as auxiliary gas for correcting matrix effects caused by the high carbon load due to biodiesel microemulsions. The oxygen gas flow rate was set in 37.5 mL min− 1. The accuracy of the developed procedure was evaluated by applying addition-recovery experiments for biodiesel samples from different sources. Recoveries varied from 76.5 to 116.2% for all analytes but Zn in castor beans biodiesel sample (65.0 to 76.2%). Recoveries lower than 86.6% were obtained for palm biodiesel sample, probably due to matrix effects. Detection limits calculated by using oxygen in the composition of the auxiliary gas added to the plasma were higher than those calculated without using it, probably due to the highest formation of oxides. Despite oxides formation, best analytical performance was reached by using oxygen as auxiliary gas and by proper correction of transport interferences. The developed procedure based on microemulsion formation was suitable for direct introduction of biodiesel samples in ICP-MS. 相似文献
79.
Karina B. Hueso Domínguez Ildikó V. Tóth M. Renata S. Souto Filipa Mendes Cándido García De María Isabel Vasconcelos António O. S. S. Rangel 《Applied biochemistry and biotechnology》2010,160(6):1664-1673
A sequential injection system to monitor glycerol in a Saccharomyces cerevisiae fermentation process was developed. The method relies on the rate of formation of nicotinamide adenine dinucleotide in its
reduced form (NADH, measured spectrophotometrically at 340 nm) from the reaction of glycerol with NAD+ cofactor, catalysed by the enzyme glycerol dehydrogenase present in solution. This procedure enables the determination of
glycerol between 0.046 and 0.46 g/l, (corresponding to yeast fermentation samples with concentrations up to 50 g/l) with good
repeatability (relative standard deviation for n = 10 lower than 2.2% for three different samples) at a sampling frequency of 25/h. The detection and quantification limits
using a miniaturised spectrophotometer were 0.13 and 0.44 mM, respectively. Reagent consumption was of 0.45 μmol NAD+ and 1.8 μg enzyme per assay, and the waste production was 2.8 ml per determination. Results obtained for samples were in
agreement with those obtained with a high-performance liquid chromatography method. 相似文献
80.
Puebla P Oshima-Franco Y Franco LM Santos MG Silva RV Rubem-Mauro L Feliciano AS 《Molecules (Basel, Switzerland)》2010,15(11):8193-8204
The effect of four sub-extracts prepared from the lyophilized hydroalcoholic bark of Dipteryx alata (Leguminosae-Papilionoideae) dissolved in a methanol-water (80:20) mixture through a liquid-liquid partition procedure has been investigated against the neuromuscular blockade of the venom of the snake Bothrops jararacussu. The active CH?Cl? sub-extract has been extensively analyzed for its chemical constituents, resulting in the isolation of four lupane-type triterpenoids: lupeol, lupenone, 28-hydroxylup-20(29)-en-3-one, betulin, nine isoflavonoids: 8-O-methylretusin, 7-hydroxy-5,6,4'-trimethoxyisoflavone, afrormosin, 7-hydroxy-8,3',4'-trimethoxyisoflavone, 7,3'-dihydroxy-8,4'-dimethoxyisoflavone, odoratin, 7,8,3'-trihydroxy-4'-methoxyisoflavone, 7,8,3'-trihydroxy-6,4'-dimethoxyisoflavone, dipteryxin, one chalcone: isoliquiritigenin, one aurone: sulfuretin and three phenolic compounds: vanillic acid, vanillin, and protocatechuic acid. Their chemical structures were elucidated on the basis of spectroscopic analysis, including HRMS, 1D- and 2D-NMR techniques. 相似文献