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101.
Neves EA  de Oliveira E  Santos ZL 《Talanta》1980,27(7):609-612
The reaction between copper (II) and azide has been studied spectrophotometrically at four wavelengths, at 25 degrees , and ionic strength 4.00M (sodium perchlorate). The formation constants beta(2) and beta(3) found are 2.90 +/- 0.08 x 10(4) and 3.02 +/- 0.07 x 10(6) respectively. The results obtained from potentiometric measurements with a solid-state electrode disagree with those calculated from the spectrophotometric data. Causes of the discrepancy are discussed.  相似文献   
102.
Monterine 1 as well as granjine 3, 1R,1'S configured biphenylic bisbenzylisoquinoline alkaloids, generate two highly populated conformers. The interconversion of two forms was detected by saturation tranfer in (1)H NMR NOEs experiments. Tridimensional structure of the conformers was determined on the basis of (1)H NMR analysis of anisotropic shielding protons, by NOEs measurements and vicinal proton coupling constants of CH1-CH(2)alpha and CH1'-CH(2)alpha'. The structures established from NMR data were further refined to observe the mobility of 3D conformations by molecular dynamics simulation in vacuo. The highly populated conformers, monterine 1a and 1b, as well as granjine 3a and 3b, are interconvertible by rotation about the C1'-Calpha', Calpha'-C9', and C11'-C11 bonds and inversion of the benzyl D ring by reference to CH(2)alpha'. The slow exchange system was investigated by dynamic NMR spectroscopy: DeltaG()(c) 77.9 KJ/mol and k(c) 200 s(-)(1) for monterine 1; DeltaG()(c) 77.7 KJ/mol and k(c) 211 s(-)(1) for granjine 3. Natural and synthetic biphenylic bisbenzylisoquinolines displayed, in vitro, cytotoxic activities against human prostate and breast cancer cell lines.  相似文献   
103.
104.
The cutinase from Fusarium solani pisi is an enzyme with a single L-tryptophan (Trp) involved in a hydrogen bond with an alanine (Ala) residue and located close to a cystine formed by a disulfide bridge between two cysteine (Cys) residues. The Cys strongly quenches the fluorescence of Trp by both static and dynamic quenching mechanisms. The Trp fluorescence intensity increases by about fourfold on protein melting because of the disruption of the Ala-Trp hydrogen bond that releases the Trp from the vicinity of the cystine residue. The Trp forms charge-transfer complexes with the disulfide bridge, which is disrupted by UV light irradiation of the protein. This results in a 10-fold increase of the Trp fluorescence quantum yield because of the suppression of the static quenching by the cystine residue. The Trp fluorescence anisotropy decays are similar to those in other proteins and were interpreted in terms of the wobbling-in-cone model. The long relaxation time is attributed to the Brownian rotational correlation time of the protein as a whole below the protein-melting temperature and to protein-backbone dynamics above it. The short relaxation time is related to the local motion of the Trp, whose mobility increases on protein denaturation.  相似文献   
105.
The bis(phosphatediester)-bridged complexes [[Ni([12]aneN(3))(mu-O(2)P(OR)(2))](2)](PF(6))(2) [[12]aneN(3)=Me(3)[12]aneN(3), 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene; R=Me (1), Bu (2), Ph (3), Ph-4-NO(2) (4); [12]aneN(3)=Me(4)[12]aneN(3), 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene; R=Me (5), Bu (6), Ph (7), Ph-4-NO(2) (8)] were prepared by hydrolysis of the phosphate triester with the hydroxo complex [[Ni([12]aneN(3))(mu-OH)](2)](PF(6))(2) or by acid-base reaction of the dialkyl or diaryl phosphoric acid and the above hydroxo complex. The acid-base reaction was also used to synthesise the phosphinate-bridged complexes [[Ni([12]aneN(3))(mu-O(2)PR(2))](2)](PF(6))(2) [[12]aneN(3)=Me(3)[12]aneN(3), R=Me (9), Ph (10); [12]aneN(3)=Me(4)[12]aneN(3), R=Me (11), Ph (12)]. The molecular structures of complexes 2, 3 and 12 were established by single crystal X-ray diffraction studies. The eight-membered rings defined by the nickel atoms and the bridging ligands show distorted twist-boat, chair and boat-boat conformations in 2, 3 and 12, respectively. The experimental susceptibility data for compounds 2, 3 and 12 were fitted by least-squares methods to the analytical expression given by Ginsberg. The best fit was obtained with values of J=-0.11 cm(-1), D=-9.5 cm(-1) and g=2.20 for 2; J=-0.97 cm(-1), D=-9.3 cm(-1) and g=2.21 for 3; and J=-0.14 cm(-1), D=-11.9 cm(-1) and g=2.195 for 12. The magnetic-exchange pathways must involve the phosphate/phosphinate bridges, because these favour antiferromagnetic interactions. The observation of a higher exchange parameter for compound 3 is a consequence of a favourable disposition of the O-P-O bridges. The kinetics for the hydrolysis of TNP (tris(4-nitrophenyl)phosphate) with the dinuclear nickel(II) hydroxo complex [[Ni(Me(3)[12]aneN(3))(mu-OH)](2)](PF(6))(2) was studied by UV-visible spectroscopy. The proposed mechanism for TNP-promoted hydrolysis can be described as one-substrate/two-product, and can be fitted to a Michaelis-Menten equation.  相似文献   
106.
The reactions of the zerovalent carbonyl complexes Mo(CO)6 and Mo(CO)4(bipy) with a series of uninegative bidentate (X,Y)-donor ligands (X,Y = xanthates, dithiocarbamates, o-aminophenoxide, o-aminothiophenoxide, 2-picolinate and thioacetate) lead to new anionic tetracarbonyl complex anions [Mo0(X,Y)(CO)4]?. These anions, which can be isolated as their tetraphenylphosphonium salts, contain the (X,Y)-ligand as a bidentate group. In the case of (X,Y) = monothioacetate the decarbonylated species [PPh4][MoII(TA)3] is formed. The reacions of the new complexes with allyl bromide and methyl iodide are described.  相似文献   
107.
Chitosan is alternated with sulfonated polystyrene (PSS) to build layer‐by‐layer (LBL) films that are used as sensing units in an electronic tongue. Using impedance spectroscopy as the principle method of detection, an array using chitosan/PSS LBL film and a bare gold electrode as the sensing units was capable of distinguishing the basic tastes – salty, sweet, bitter, and sour – to a concentration below the human threshold. The suitability of chitosan as a sensing material was confirmed by using this sensor to distinguish red wines according to their vintage, vineyard, and brands.

PCA Plot for red wine samples obtained from impedance measurements at 1 kHz for the sensor array comprising a 3‐bilayer chitosan/PSS film and a bare gold electrode.  相似文献   

108.
In the present work, a slurry sampling flame atomic absorption spectrometric method to determine directly manganese and zinc in powdered chocolate samples is proposed. The optimization step was performed using univariate methodology involving the following factors: nature and concentration of the acid solution, sonication time, and particle size. The established conditions led to the use of a sample mass of 150 mg, 2.0 mol L− 1 nitric acid solution, sonication time of 15 min, and a slurry volume of 50 mL. This method allows the determination of manganese and zinc with detection limit of 52 and 61 ng g− 1, respectively, and a precision expressed as relative standard deviation (RSD) of 2.6% and 3.2% (both, n = 10) for contents of manganese and zinc of 52.4 and 100.0 μg g− 1, respectively. The proposed method was applied for determination of manganese and zinc in five powdered chocolate samples. In these, the manganese content varied from 42.8 to 52.7 and from 88.6 to 102.4 μg g− 1 of zinc. The analytical results were compared with the results obtained by analysis of these samples after digestion using open vessel and acid bomb digestion procedures and determination using FS-FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.  相似文献   
109.
A new chelating sorbent has been developed using Amberlite XAD-2 resin anchored with pyrocatechol through –N=C– group. This sorbent, characterised by elemental analysis and infrared (IR) spectra, was used as packing for the minicolumn in an on-line system preconcentration system for cadmium, cobalt, copper and nickel determination. Metal ions were sorbed in the minicolumn, from which it could be eluted directly to the nebulizer–burner system of the flame atomic absorption spectrometer (FAAS). Elution of all metals from minicolumn can be made with 0.50 mol L 1 HCl or HNO3. The enrichment factors obtained were 16 (Cd), 24 (Co), 15 (Cu) and 19 (Ni), for 60 s preconcentration time, and 39 (Cd), 69 (Co), 36 (Cu) and 41 (Ni), if used 180 s preconcentration time. Under the optimum conditions, the proposed procedure allowed the determination of cadmium, cobalt, copper and nickel with detection limits of 0.31, 0.32, 0.39 and 1.64 μg L 1, respectively, when used preconcentration periods of 180 s. The accuracy of the developed procedure was sufficient and evaluated by the analysis of the certified reference materials NIST 1515 apple leaves and NIST 1570a spinach leaves. The method was applied to the analysis of food samples (spinach, black tea and rice flour).  相似文献   
110.
Singlet oxygen generation ability of squarylium cyanine dyes   总被引:1,自引:0,他引:1  
The quantum yields for singlet oxygen generation of several squarylium cyanine dyes derived from benzothiazole, benzoselenazole and quinoline, displaying absorption within the so-called “phototherapeutic window” (600–1000 nm), were determined, envisioning their potential usefulness for photodynamic therapy (PDT). The determination was performed by a direct method measuring the luminescence decay of the dyes in the near infrared. Considering the absorption and the quantum yields displayed by some of the dyes, these seemed to be potential candidates as sensitizers for PDT.  相似文献   
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