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1.
A new automated spectrophotometric method for the determination of total sulfite in white and red wines is reported. The assay is based on the reaction of o-phthalaldehyde (OPA) and ammonium chloride with the analyte in basic medium under SI conditions. Upon on-line alkalization with NaOH, a blue product is formed having an absorption maximum at 630 nm. The parameters affecting the reaction - temperature, pH, ionic strength, amount concentration and volume of OPA, amount concentration of ammonium chloride, flow rate and reaction coil length - and the gas-diffusion process - sample and HCl volumes, length of mixing coil, donor flow rate - were studied. The proposed method was validated in terms of linearity (1-40 mg L−1, r = 0.9997), limit of detection (cL = 0.3 mg L−1) and quantitation (cQ = 1.0 mg L−1), precision (sr = 2.2% at 20 mg L−1 sulfite, n = 12) and selectivity. The applicability of the analytical procedure was evaluated by analyzing white and red wine samples, while the accuracy as expressed by recovery experiments ranged between 96% and 106%.  相似文献   

2.
The novel methacrylic monomer, 4-nitro-3-methylphenyl methacrylate (NMPM) was synthesized by reacting 4-nitro-3-methylphenol dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in the presence of triethylamine as a catalyst. The homopolymer and copolymers of NMPM with glycidyl methacrylate having different compositions were synthesized by free radical polymerization in EMK solution at 70 ± 1 °C using benzoyl peroxide as free radical initiator. The homopolymer and the copolymers were characterized by FT-IR, 1H NMR and 13C NMR spectroscopic techniques. The solubility tests were tested in various polar and non-polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in NMPM content. The thermogravimetric analysis of the polymers performed in air showed that the thermal stability of the copolymer increases with NMPM content. The copolymer composition was determined using 1H NMR spectra. The monomer reactivity ratios were determined by the application of conventional linearization methods such Fineman-Ross (r1 = 1.862, r2 = 0.881), Kelen-Tudos (r1 = 1.712, r2 = 0.893) and extended Kelen-Tudos methods (r1 = 1.889, r2 = 0.884).  相似文献   

3.
Theoretical investigations on the thermochemistry and the reaction mechanism of the formation of Lewis acid/base stabilised phosphanyltrielanes D · H2EPH2 · A (D = Lewis base, A = Lewis acid) were conducted. The reactions of EH3 · D with A · PH3 to form D · H2EPH2 · A and H2 (E = B, Al, Ga; D = NH3; A = BH3, Cr(CO)5) are all exothermic, regardless of whether donors and acceptors are present or absent. The lithium chloride elimination reactions between EH2Cl · D and A · PH2Li to give D · H2EPH2 · A and LiCl are endothermic for donor/acceptor stabilised compounds, if formation of gaseous LiCl is considered. If solid lithium chloride is considered all reactions are strongly exothermic. Studies of the transition state for H2-elimination reactions between EH3 · D and A · PH3 to yield D · H2EPH2 · A and H2 were only successful for E = Al, Ga. In these cases the reaction proceeds via a transition state featuring a five or six-coordinate group 13 element. Different donor molecules do not influence the activation energy of such H2-elimination reactions, but nevertheless they have an effect on the reaction energy. The synthesis of the Cr(CO)5 substituted phosphanyltrielanes [(CO)5Cr(H2PBH2 · NMe3)] (3a) and [(CO)5Cr(H2PAlH2 · NMe3)] (3b), as well as of the dinuclear complex [(CO)8Cr2(μ-HPBH2 · NMe3)2] (4) are described, the latter as a subsequent reaction product of the photolysis of 3a. All compounds were characterised spectroscopically and by X-ray structure analysis.  相似文献   

4.
The reaction of Ni(xbsms) (H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) with [Ru(CO)3Cl2(thf)] yields green crystals of [NiCl(xbsms)Ru(CO)3Cl]. The structure of this structural model of the active site of NiFe hydrogenase reveals a pentacoordinated nickel(II) center with bound chloride anion. It therefore adopts a paramagnetic (S = 1) electronic configuration as shown by magnetic susceptibility measurements. In DMF, this compound is converted into a red ionic-salt [NiL(xbsms)Ru(CO)3Cl]Cl (L = water or DMF) that catalyzes hydrogen electro-evolution from Et3NHCl at −1.52 V vs. Ag/AgCl (−2.05 V vs. Fc0/+).  相似文献   

5.
Transition metal mediated living radical polymerisation of butyl methacrylate has been demonstrated with a copper(I) halide N-alkyl-2-pyridylmethanimine ligands based catalyst. Optimum conditions were found to be with copper(I) chloride and N-octyl-2-pyridylmethanimine catalyst at 65 °C where conversions of 85% were achieved with polymers of Mn = 8900 g mol−1 (theoretical = 8400 g mol−1) and PDI = 1.23. Both non-ionic and ionic surfactants were employed which were also made by living radical polymerisation. The non-ionic surfactant was a block copolymer of PMMA from a polyethyleneglycol macroinitiator (total Mn = 7600 g mol−1, PDI = 1.20) and the ionic surfactant PDMEAMA-PMMA (total Mn = 8000 g mol−1, PDI = 1.21) with the PDMEAMA block quaternized with MeI (13.8%, 28.4%, 47.7% and 100%). A range of ligands were employed in the suspension polymerisation by varying the alkyl group on the ligand increasing the hydrophobicity (alkyl = propyl (PrMI), pentyl (PMI), octyl (OMI), dodecyl (DMI) and octadecyl (ODMI)). The more hydrophobic ligands were found to be more effective due to lower partitioning into the aqueous phase. Block copolymers of P(EMA)-P(BMA) and P(MMA)-P(BMA) were prepared by first preparing macroinitiators via living radical polymerisation (Mn = 1600 g mol−1 (PDI = 1.23) for P(EMA) and Mn = 1500 g mol−1 (PDI = 1.22) for P(MMA)) and using them for initiation of BMA in suspension polymerisation. Block copolymers had Mn between 12,800 and 13,700 g mol−1 with PDI between 1.33 and 1.54. Block copolymer growth showed excellent linear first order kinetics wrt monomer and demonstrated characteristics expected of a living radical polymerisation. Particle sizes were measured by SEM and DLS with good agreement (1.4-2.8 μm) and SEM showed spherical particles were formed.  相似文献   

6.
Addition of M2SCN(CH2R)2 to D(C6H4S)2SbCl in methylene chloride solution leaded to the formation of the stable compounds D(C6H4S)2SbS2CN(CH2R)2 (D = O, R = Me, 1; D = S, R = Me, 2; R = Ph, 3). The new dibenzostibocines derivatives containing two different types of dithioligands were characterized by elemental analysis and spectroscopic studies (IR, 1H and 13C NMR). Single crystal X-ray diffraction determinations of complexes 13 revealed that the antimony atom acts as an acceptor atom exhibiting an intramolecular transannular interaction with the donor D atom, expanding its coordination from three to five and displaying a skew trapezoidal local geometry.  相似文献   

7.
The reactions of palladium(II) chloride, PPh3 and heterocyclic-N/NS ligand in a mixture of CH3CN (5 ml) and CH3OH (5 ml) produced [PdCl2(PPh3)(L1)]·(CH3CN) (1) (L1 = ADMT = 3-amino-5,6-dimethyl-1,2,4-triazine), [PdCl2(PPh3)(L2)] (2) (L2 = 3-CNpy = 3-cyanopyridine), [PdCl(PPh3)(L3)]2·(CH3CN) (3), [PdCl(PPh3)2(HL3)]Cl (4) (HL3 = Hmbt = 2-mercaptobenzothiazole). The coordination geometry around the Pd atoms in these complexes is a distorted square plane. In 3, L3 acts as a bidentate ligand, bridging two metal centers, while in 4, HL3 appears as monodentate ligand with one nitrogen donor atom uncoordinated. Complexes 1-4 are characterized by IR, luminescence, NMR and single crystal X-ray diffraction analysis. All complexes exhibit luminescence in solid state at room temperature.  相似文献   

8.
The use of boric acid as a modifier for the determination of trace amount of rubidium in high purity cesium chloride matrix by electrothermal atomic absorption is described. It was found that the negative influence of the chloride matrix could not be eliminated using stabilized temperature platform (STPF) alone. Due to the high dissociation energy (D0 = 427 kJ mol−1) of rubidium chloride, it was difficult to dissociate in the gas phase and hence is lost. Elimination of interferences was achieved by the addition of boric acid as a chemical modifier. Diluted cesium chloride samples (5%, m/v) were analyzed applying the standard addition method. The characteristic mass of 24 pg was obtained. The detection limit of the proposed method is around 26 ng g−1. The developed method was applied to the determination of traces of rubidium in high purity cesium chloride samples. The data obtained by this method were in good agreement with those obtained by other independent method like FAAS.  相似文献   

9.
The flexible, multi dentate, heteroelemental, dipodal ligands; bis(2pyridylthio)methane, (PyS)2CH2 (Py = pyridyl = C5H4N), (PymS)2CH2, bis(2pyrimidylthio)methane, and bipyrimidyldisulfide, (PymS)2 (Pym = pyrimidine, C4H3N2), were reacted with a series of copper precursors to determine whether monomeric compounds, cubane clusters or polymeric chains would be obtained. Copper(II) chloride, copper(I) cyanide and copper(I) thiocyanate afforded infinite polymeric chains while copper(I) iodide afforded tetranuclear clusters supported by two ligand molecules. All products were characterized in the solid-state by X-ray crystallography.  相似文献   

10.
Dacres H  Narayanaswamy R 《Talanta》2006,69(3):631-636
A highly sensitive optical humidity probe based on reflectance measurements has been developed using Nafion®-crystal violet (CV) films. This sensor can be used to calibrate relative humidity (RH) in the range 0-0.25% with a detection limit (blank signal + 3σb, where σb = the standard deviation (S.D.) of the blank signal) of 0.018% RH (∼4.37 ppm) and exhibited low hysteresis. The sensor films were fully reversible in dry nitrogen and reversal times were shown to be dependent on exposure time and % RH. The response to 1% RH was highly reproducible (S.D. = 1.67%, number of samples (n) = 5). Hydrogen chloride gas did not interfere with the response of the sensor to RH but did reduce sensor reversal times. This sensor displayed sufficient sensitivity that it could be used to detect ppm levels of moisture in process gases such as nitrogen and HCl.  相似文献   

11.
The monocationic chloro complexes containing chelating 1,10-phenanthroline (phen) ligands [(arene)Ru(N∩N)Cl]+ (1: arene = C6H6, N∩N = phen; 2: arene = C6H6, N∩N = 5-NO2-phen; 3: arene = p-MeC6H4Pri, N∩N = phen; 4: arene = p-MeC6H4Pri, N∩N = 5-NO2-phen; 5: arene = C6Me6, N∩N = phen; 6: arene = C6Me6, N∩N = 5-NO2-phen; 7: arene = C6Me6, N∩N = 5-NH2-phen) have been prepared and characterised as the chloride salts. Hydrolysis of these chloro complexes in aqueous solution gave, upon precipitation of silver chloride, the corresponding dicationic aqua complexes [(arene)Ru(N∩N)(OH2)]2+ (8: arene = C6H6, N∩N = phen; 9: arene = C6H6, N∩N = 5-NO2-phen; 10: arene = p-MeC6H4Pri, N∩N = phen; 11: arene = p-MeC6H4Pri, N∩N = 5-NO2-phen; 12: arene = C6Me6, N∩N = phen; 13: arene = C6Me6, N∩N = 5-NO2-phen; 14: arene = C6Me6, N∩N = 5-NH2-phen), which have been isolated and characterised as the tetrafluoroborate salts. The catalytic potential of the aqua complexes 8-14 for transfer hydrogenation reactions in aqueous solution has been studied: complexes 12 and 14 catalyse the reaction of acetophenone with formic acid to give phenylethanol and carbon dioxide with turnover numbers around 200 (80 °C, 7 h). In the case of 12, it was possible to observe the postulated hydrido complex [(C6Me6)Ru(phen)H]+ (15) in the reaction with sodium borohydride; 15 has been characterised as the tetrafluoroborate salt, the isolated product [15]BF4, however, being impure. The molecular structures of [(C6Me6)Ru(phen)Cl]+ (1) and [(C6Me6)Ru(phen)(OH2)]2+ (12) have been determined by single-crystal X-ray structure analysis of [1]Cl and [12](BF4)2.  相似文献   

12.
Simple, easy to use and selective method of Al(III) sorption-spectroscopic (SS) determination was proposed. For this purpose, silica modified with tridecyloctadecylammonium chloride(SGII) using adsorption technique and glass slide modified with thin silica-poly(dimethyldiallyl-ammonium chloride) (SGI) composite film obtained by sol-gel technique were worked out. It was shown that lumogallion (LG) easily absorbs on SGI and SGII. Obtained sorbents SGIII and SGIV, respectively, were used for aluminum(III) determination by diffuse reflectance and spectrophotometric methods. The ranges of determination were (mg L−1): (0.08-0.54), sr ≤ 0.13, n = 4 for SGIII and (0.05-2.0), sr ≤ 0.11, n = 4 for SGIV. The detection limits (blank + 3σ) for aluminum were 70 and 30 μg L−1 using SGIII and SGIV, respectively, where σ is the standard deviation of blank estimation. The accuracy of the developed spectrophotometric method was examined by the determination of standard addition of aluminum in alcohol-free beverages. The relative error did not exceed 9%. SGIII can be regenerated by 0.05 M EDTANa2H2 solution and reused. SGIV was shown to be perspective for determination of aluminum in solution in the range of 0.01-0.13 mg L−1 by solid phase luminescent technique.  相似文献   

13.
A simple and sensitive liquid chromatographic method is described for the analysis of γ-amino-n-butyric acid (GABA) in human urine. GABA is increased in the urine of cancer patients and could be used as a biomarker in the diagnosis and treatment of related patients. The method is based on derivatizing GABA with a fluorescent reagent (naproxen acyl chloride) for transforming the non-chromophoric GABA to a derivative with chromophoric and fluorophoric properties. The resulting derivative is highly responsive to a fluorimetric detector (λex = 230 nm, λem = 350 nm). The lower quantitation of the method is attainable at 100 nM GABA with a detection limit about 10 nM (S/N = 3 with 20 μL injected). Application of the method to the analysis of GABA in the urine of patients with ovarian and uterine cancer was demonstrated.  相似文献   

14.
A series of triorganotin (IV) complexes with 2,3,4,5-tetrafluorobenzoic acid and mixed-ligands of the types: R3Sn(O2CC6HF4)m · L (m = 1, L = 0, R = Ph 1; m = 1, L = Ph3PO, R = Ph 4, Me 5), [R3Sn(O2CC6HF4)]m · L (m = 2, L = 4,4′-bipy, R = Ph 2, Me 3; m = n, L = 0, R = Me 6), and [R3Sn(O2CC6HF4) · (H2O)]m · L · C2H5OH (m = 2, L = Phen, R = Ph 7, Me 8), (4,4′-bipy = 4,4′-bipyridyl; Phen = 1,10-phenanthroline), have been synthesized by the reaction of triorganotin chloride and 2,3,4,5-tetrafluorobenzoic acid in the presence of mixed-ligands: 4,4′-bipy, triphenylphosphine oxide, or phen. All complexes were characterized by elemental analysis, IR, 1H, 13C, 119Sn NMR spectroscopy analysis. Except for 5 and 8, all the complexes were also characterized by X-ray crystallography.  相似文献   

15.
Overcrowded silanedichalcogenols Tbt(Mes)Si(EH)(E′H), such as silanedithiol (E = E′ = S), hydroxysilanethiol (E = O, E′ = S) and hydroxysilaneselenol (E = O, E′ = Se), bearing an efficient combination of steric protection groups, Tbt and Mes (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes = 2,4,6-trimethylphenyl), were synthesized and isolated as air- and moisture-stable crystals, and their structures were fully characterized by spectroscopic and elemental analyses together with X-ray crystallographic analyses. The results of IR spectroscopy and the X-ray structural analyses suggested that these compounds exist as monomers without any intra- and intermolecular interactions such as hydrogen bonds even in the solid state and in solution. Novel four-membered-ring compounds, such as Tbt(Mes)Si(μ-S)2PnBbt and [Tbt(Mes)Si(μ-E)(μ-E′)MLn] [E, E′ = O, S, Se; Pn = Sb, Bi; Bbt = 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl; MLn = Pd(PPh3)2, Pt(PPh3)2, Ru(η6-benzene)] were synthesized by utilizing the silanedichalcogenols as key building blocks. The molecular structures of these newly isolated compounds were determined by NMR spectroscopic data together with X-ray crystallographic analyses.  相似文献   

16.
The reactivity of M(η6-arene)2 derivatives of early transition metals (M = Ti, Cr, Mo, arene = MeC6H5; M = V, Nb, arene = 1,3,5-Me3C6H3) has been investigated and the syntheses of new and known compounds are described. The derivatives M(CH3COO)3, M = Ti, V, Nb, Cr; M(CF3COO)3, M = Ti, Nb, Cr; M(acac)3, M = Ti, V, Mo, acac = acetylacetonato, and M(F6acac)3, F6acac = hexafluoroacetylacetonato, M = V, Nb have been prepared by reaction of the metal bis(arene) derivatives with the appropriate Lewis acid. The crystal and molecular structure of V(F6acac)3 has been determined. Hydrogen halides or halogens react with M(η6-arene)2 with formation of metal halides, a highly reactive form of VCl3 being obtained from V(η6-1,3,5-Me3C6H3)2 and hydrogen chloride in heptane. TiCl4 oxidizes Ti(η6-arene)2 with complete loss of the arene ligands. An electron transfer process affording ionic derivatives of formula [M(η6-MeC6H5)2][TiCl4(THF)2], M = Cr (structurally characterized), Mo, has been observed between the THF-adduct of TiCl4 and the appropriate metal-arene derivative of Group 6.  相似文献   

17.
We found new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a 0-D molecular complex containing a Nb2S4 core from a 2-D ternary thiophosphate, Nb4P2S21. When Nb4P2S21 was reacted with alkali metal halides (ACl; A=Na, K, Rb, Cs) or TlCl at 500-700 °C, the -S-S-S- bridges in 2-D Nb2PS10-S-S10PNb2 were excised to form a 1-D chain, and cations were inserted between the chains to form ANb2PS10 (A=Na, K, Rb, Cs, Tl). We also found that thallium chloride (TlCl) is an excellent reagent for further excision, and it substitutes chloride ligands for the sulfur ligands of 2-D Nb4P2S21 to form the molecular complex Tl5[Nb2S4Cl8]Cl. Crystal data for TlNb2PS10: monoclinic, Pn, a=6.9452(11) Å, b=7.3761(12) Å, 12.873(2) Å, β=104.472(3)°, and Z=2. Crystal data for Tl5[Nb2S4Cl8]Cl: orthorhombic, Immm, a=7.001(5) Å, b=9.509(7) Å, c=15.546(11) Å, and Z=2.  相似文献   

18.
The yttrium chloride with the bridged bis(amidinate) L (L = Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3) LYCl(DME) (2) was synthesized and structurally characterized. Treatment of LLnCl(sol)x (Ln = Yb, sol = THF, x = 2 1; Ln = Y, sol = DME, x = 1 2) with the dilithium salt Li2L(THF)0.5 afforded the novel bimetallic lanthanide complexes supported by three ligands, Ln22-L)3 · DME (Ln = Yb 3, Y 4; DME = dimethylether), instead of the designed complex LLn(μ2-L)LnL via the ligand redistribution reaction. Complexes 3 and 4 were fully characterized including X-ray analysis and 1H NMR spectrum for 4. Reaction of LnCl3 (Ln = Yb, Y) with 2 equiv. of Li2L(THF)0.5 gave the anionic complexes [Li(DME)3][L2Ln] (Ln = Yb 5, Y 6), which were confirmed by a crystal structure determination. The further study indicated that complexes 3 and 4 can also be synthesized by reaction of LnCl3 (Ln = Yb, Y) with 1.5 equiv. of Li2L(THF)0.5 or reaction of 1 and 2 with anionic complexes 5 and 6. Complexes 3, 4, 5 and 6 were found to be high active catalysts for ring-opening polymerization of ε-caprolactone (CL).  相似文献   

19.
20.
The electrochemical behavior of terazosin at the hanging mercury drop electrode was studied in Britton-Robinson buffer (pH 2-11), acetate buffer (4.5-5.5), and in 0.1 M solution of each of sodium sulfate, sodium nitrate, sodium perchlorate and potassium chloride as supporting electrolytes. The square-wave adsorptive cathodic stripping voltammogram of terazosin exhibited a single well-defined two-electron irreversible cathodic peak which may be attributed to the reduction of CO double bond of the drug molecule. A fully validated, simple, high sensitive, precise and inexpensive square-wave adsorptive cathodic stripping voltammetric procedure was described for determination of terazosin in bulk form, tablets and human serum. A mean recovery for 1×10−8 M terazosin in bulk form, following preconcentration onto the hanging mercury drop electrode for 60 s at a −1.0 V (versus Ag/AgCl/KCls), of 99±0.7% (n=5) was obtained. Limits of detection (LOD) and quantitation (LOQ) of 1.5×10−11 and 5×10−11 M bulk terazosin were achieved, respectively. The proposed procedure was successfully applied to determination of the drug in its Itrin® tablets and human serum samples. The achieved LOD and LOQ of the drug in human serum samples were 5.3×10−11 and 1.8×10−10 M THD, respectively. The pharmacokinetic parameters of the drug in human plasma were estimated as: Cmax=77.5 ng ml−1, tmax=1.75 h, AUC0-t=602.3 ng h ml−1, Ke=0.088 h−1 and t1/2=11.32 h) which are favorably compared with those reported in literature.  相似文献   

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