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1.
Luminescent 50-nm silicon dioxide nanoparticles containing both types of rhodamine 6G (R; particles denoted R-SiO2) were synthesized by the sol–gel method. In the presence of Pb(Ac)2 as a heavy atom perturber the particle can emit the intense and stable room-temperature phosphorescence (RTP) signal of R on a polyamide membrane, with exmax/emmax=470/635 nm for R. Our research indicates that the specific immune reaction between goat-anti-human IgG antibody labeled with R-SiO2 and human IgG can be carried out quantitatively on a polyamide membrane, and the phosphorescence intensity was enhanced after the immunoreaction. Thus a new method for solid-substrate room-temperature phosphorescence immunoassay (SS-RTP-IA) for determination of human IgG was established on the basis of antibody labeled with the nanoparticles containing binary luminescent molecules. The linear range of this method is 0.0624–20.0 pg spot–1 of human IgG (corresponding to a concentration range of 0.156–50.0 ng mL–1, sample volume 0.40 L spot–1). The regression equations of the working curves are Ip=71.27+7.208mIgG (pg spot–1) (r=0.9996). Detection limits calculated as 3Sb/k are 0.022 pg spot–1. Compared with the same IA using fluorescein isothiocyanate (FITC) as the marker the new method was more sensitive and had a wider linear range. After elevenfold replicate measurement RSD are 4.5 and 3.6% for samples containing 0.156 and 50.0 ng mL–1 IgG, respectively. This method is sensitive, accurate, and of high precision.  相似文献   

2.
Liu JM  Wu AH  Xu HH  Wang QH  Li LD  Zhu GH 《Talanta》2005,65(2):501-504
Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2), which contains salicyl fluorones (THBF), Pb(CMC)2-THBF, were synthesized by sol-gel method. Pb(CMC)2-THBF can emit intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. EDTA can chelate the Pb2+ in Pb(CMC)2-THBF, causing it decompose into aqueous soluble components PbY2−, CMC and THBF, and these components can react with Hg2+ to form (CMC)2Hg-THBF, causing decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace mercury by SS-RTP quenching method was established. The linear range of this method is 2.0-40.0 fg spot−1 (5.0-100.0 pg ml−1) of Hg2+, with a detection limit (LD) of 0.26 fg spot−1, and the regression equation of working curve is (fg spot−1, 0.4 μl spot−1), r = 0.9994. This method has been applied to the determination of trace mercury in water sample with satisfactory results. The mechanism of SS-RTP emission is also discussed.  相似文献   

3.
Summary Reaction of CrCl3(DMF)3 with [15]aneN4 (L; L = 1,4,8,12-tetra-azacyclopentadecane) gives the green trans-{Cr([15]-aneN 4)Cl2}Cl in high yield. The base hydrolysis kinetics of the cations [CrLCl2]+ and [CrLCl(OH)] + have been investigated over a temperature range. For the dichloro complex, k OH = 1.03 dm3 mol–1 s–1] at 25° C with H =30.4 kJmol–1 and S inf298 sup = -143 JK–1 mol–1. The substantial negative entropy of activation implies more association of water in the loss of Cl from the conjugate base in a DCB mechanism. The kinetic parameters for the chlorohydroxo complex are k OH = 1.9 × 10–2dm3mol–1 s–1 at 25°C with H = 78.3kJmol–1 and H inf298 sup = -15 J K–1 mol –1. The chlorohydroxo complex probably has the trans VI configuration with the chloride ligand on the same side of the equatorial plane as the four chiral sec-NH groups. The visible spectra of a variety of complexes trans-[Cr(L)XY] n+ (X = Y = Cl, OH, OH2; X = Cl, Y = OH) have been determined.  相似文献   

4.
A new method of SS-RTP for the determination of trace silver has been established. This method is based on the fact that Ag+, when activated by ,-bipyridyl (bipy) in a media of HAc–NaAc (pH=4.9), can catalyze the reaction of Rhodamine B (RhoB) oxidized by K2S2O8, thus causing the Solid Substrate Room-Temperature Phosphorescence (SS-RTP) of RhoB to be quenched. The activating efficiency of bipy is 6.7 times higher than that of o-phenanthroline (phen). The reduction of the phosphorescence intensity (Ip) of RhoB is directly proportional to the concentration of Ag+ ions in the range of 1.6016.0agspot–1 (0.40µLspot–1). The regression equation of the working curve can be expressed as Ip=18.78+5.100mAg+ (agspot–1) (r=0.9994, n=6), the detection limit is 0.28agspot–1. This rapid, accurate and sensitive method has been successfully applied to the determination of trace silver in tea and human hair samples, and the results agree well with the Atomic Absorption Spectroscopy (AAS) method. The mechanism of the catalyzing reaction is also discussed.  相似文献   

5.
An indirect method of arsenic determination in the submicrogram range via the determination of molybdenum is presented here. High sensitivity is achieved by combination of the chemical amplification during formation of dodecamolybdoarsenic acid (arsenic: molybdenum ratio 1 12) with multiplication due to the formation of ion-association complexes during flotation-spectrophotometric molybdenum determination with crystal violet (molar ratio 1 2). Thus, the amplification factor relating to arsenic is 24.Dodecamolybdoarsenic acid is formed in a weakly acidic medium and is quantitatively extracted byn-butanol. Back extraction of the heteropoly acid to the aqueous phase and its simultaneous destruction provides the basis for the reaction of released molybdate ions with thiocyanate ions. The molybdenum-thiocyanate complex forms a sparingly soluble ion-association complex with crystal violet which can be floated with toluene on the phase boundary (film flotation). After separation of the aqueous phase the floated molybdenum compound is dissolved in acetone and the resulting free crystal violet ions are subjected to photometric determination at 590 nm as equivalent of the concentration of arsenic. The molar absorptivity of crystal violet is 3.2 · 1051 · mol–1 · cm–1. Beer's law is obeyed in a concentration range from 0.01 to 1 g Mo · ml–1 (0.001–0.1 g As · ml–1). The resulting detection limit for arsenic is 1 ng · ml–1.  相似文献   

6.
A high-performance thin layer chromatographic method coupled with densitometric analysis has been developed for measurement of benazepril and cilazapril, both pure and in their commercial dosage forms. The active substances were extracted from tablets with methanol (mean recovery 102%) and chromatographed on silica gel 60 F254 HPTLC plates in horizontal chambers with ethyl acetate–acetone–acetic acid–water, 8:2:0.5:0.5 (v/v), as mobile phase. Chromatographic separation of these ACE inhibitors was followed by UV densitometric quantitation at 215 nm. Calibration plots were constructed in the range 0.4 to 2.0 g L–1 for benazepril (2.0–10.0 g spot–1) and from 0.5 to 1.5 g L–1 for cilazapril (4.0–12.0 g spot–1) with good correlation coefficients (r 0.990). The method was used to determine benazepril and cilazapril in pharmaceutical preparations with satisfactory precision (1.4% < RSD < 5.6%) and accuracy (1.7 < RE < 5.1).  相似文献   

7.
The promotion of the branched-chain decomposition of nitrogen trichloride by molecular hydrogen additives at room temperature and 20 torr manifests itself in a decrease in the induction period and the acceleration of reactant consumption with an increase in the hydrogen concentration in the NCl3+ H2+ He mixtures. The emission spectrum of the H2+ NCl3flame contains the intense bands of NCl (b 1+X 3, = 1 – 0, = 0 – 1, and = 0 – 0, where is the vibrational quantum number) and the bands of a hydrogen-free compound. The latter bands can be assigned to electronically excited NCl 2radicals formed in the H + NCl3reaction. The calculations restrict the number of elementary reactions favoring promotion. The promotion effect in the system studied should be due to the side reaction of linear branching. The occurrence of the H + NCl3reaction via two pathways (NHCl + 2Cl and NCl 2+ HCl) ensures the qualitative agreement between the experimental data and calculation.  相似文献   

8.
A simple and sensitive extraction-spectrophotometric method for the determination of total dissolved ammonia and ammonium ion content is reported. The ternary complex DC18C6-ammonium-Orange II, (DC18C6–NH4–OR II), was quantitatively extracted into dichloromethane and its absorbances is measured at 483 nm. Linear calibration graph is obtained over the concentration ranges of 0.05–3.00 g mL–1 for ammonium. The relative standard deviations for 1.0 g mL–1 of ammonium was 1.10%. The method was applied to real samples such as sewage, agricultural soil and Persian golf shrimp. The results showed high potential of the recommended method for the determination of total dissolved NH3 and NH4+ content in different samples.  相似文献   

9.
A new catalytic solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace arsenic(V) has been established. It is based on the fact that fullerenol (F-ol) emitted strong and stable room temperature phosphorescence (RTP) on nitric acid cellulose membrane (NCM) substrate. H2O2 could oxidise F-ol to cause the quenching of RTP. As(V) could catalyse H2O2 to oxidise F-ol and decrease the RTP signal of F-ol sharply. After adding tween-80 in the system, its ΔI p enhanced 7.7 times compared with the without-tween-80 levels. Under the optimum conditions, the linear dynamic range of this method was 0.016?11.2 ag spot?1 with a detection limit (LD) of 9.3 zg spot?1 (corresponding concentration: 2.3 × 10?17 g mL?1). This sensitive, simple and selective method has been successfully applied to the determination of trace As(V) in human hair and tea samples. The reaction mechanism for SS-RTP is also discussed.  相似文献   

10.
Raman spectra of aqueous Zn(II)–perchlorate solutions were measured over broad concentration (0.50–3.54 mol-L–1) and temperature (25–120°C) ranges. The weak polarized band at 390 cm–1 and two depolarized modes at 270 and 214 cm–1 have been assigned to 1(a 1g), 2(e g), and 5(f 2g) of the zinc–hexaaqua ion. The infrared-active mode at 365 cm–1 has been assigned to 3(f 1u). The vibrational analysis of the species [Zn(OH2) 2 + ] was done on the basis of O h symmetry (OH2 as point mass). The polarized mode 1(a 1g)-ZnO6 has been followed over the full temperature range and band parameters (band maximum, full width at half height, and intensity) have been examined. The position of the 1(a 1g)-ZnO6 mode shifts only about 4 cm–1 to lower frequencies and broadens by about 32 cm–1 for a 95°C temperature increase. The Raman spectroscopic data suggest that the hexaaqua–Zn(II) ion is thermodynamically stable in perchlorate solution over the temperature and concentration range measured. These findings are in contrast to ZnSO4 solutions, recently measured by one of us, where sulfate replaces a water molecule of the first hydration sphere. Ab initio geometry optimizations and frequency calculations of [Zn(OH2) 2 + ] were carried out at the Hartree–Fock and second-order Møller–Plesset levels of theory, using various basis sets up to 6-31 + G*. The global minimum structure of the hexaaqua–Zn(II) species corresponds with symmetry T h. The unscaled vibrational frequencies of the [Zn(OH2) 2 + ] are reported. The unscaled vibrational frequencies of the ZnO6, unit are lower than the experimental frequencies (ca. 15%), but scaling the frequencies reproduces the measured frequencies. The theoretical binding enthalpy for [Zn(OH2) 2 + ] was calculated and accounts for ca. 66% of the experimental single-ion hydration enthalpy for Zn(II).Ab initio geometry optimizations and frequency calculations are also reported for a [Zn(OH2) 2 18 ] (Zn[6 + 12]) cluster with 6 water molecules in the first sphere and 12 in the second sphere. The global minimum corresponds with T symmetry. Calculated frequencies of the zinc [6 + 12] cluster correspond well with the observed frequencies in solution. The 1-ZnO6 (unscaled) mode occurs at 388 cm–1 almost in perfect correspondence to the experimental value. The theoretical binding enthalpy for [Zn(OH2) 2 18 ] was calculated and is very close to the experimental single ion-hydration enthalpy for Zn(II). The water molecules of the first sphere form strong hydrogen bonds with water molecules in the second hydration shell because of the strong polarizing effect of the Zn(II) ion. The importance of the second hydration sphere is discussed.  相似文献   

11.
Summary This work is concerned with the application of a one-channel model to obtaining predissociation lifetimes and transition rates in a system of crossing diabatic states. The calculation focuses on the first shape resonance of the 1 g 2 2 g diabatic state of He 2 + , which is relatively stable with respect to tunneling. This resonance predissociates as a result of the 1 g 2 2 g state being crossed by the 1 g 1 u 2 dissociative diabatic state near the resonance level. We have estimated its predissociation lifetime to be of the order of 10–11 s.  相似文献   

12.
Summary Simultaneous Determination of Chromium(VI) and Chromium(III) by Flame Atomic Absorption Spectrometry with a Chelating Ion-Exchange Flow Injection System A simple method is described for the simultaneous determination of chromium(VI) and chromium(III) in a flow injection system comprising chelating ion-exchange and flame atomic absorption spectrometry. Sampling rates for 2001 and 1 ml sample volumes were 120 and 60 h–1 (240 and 120 speciations per hour), respectively. Typical relative standard deviations were 0.52% for Cr(VI) (0.50g ml–1 and 0.67% for Cr(III) (0.10,g ml–1) and the corresponding limits of detection were 85 ng ml–1, and 16 ng ml–1, respectively.On leave from University of Belgrade.  相似文献   

13.
Summary New complexes of 2,2-dipyridyl and 4,4-dipyridyl with thulium salts TmX 3 (whereX=Cl, Br, NO 3 , NCS, and ClO 4 ) have been prepared and their solubilities in water at 21 °C were determined. The IR spectra of these compounds are discussed. The conditions of thermal decomposition of the complexes were also studied.
Synthese und Eigenschaften von 2,2-Dipyridyl- und 4,4-Dipyridylkomplexen mit Thuliumsalzen
Zusammenfassung Es wurden neue 2,2-Dipyridyl- und 4,4-Dipyridyl-Komplexen mit Thuliumsalzen TmX 3 (X=Cl, Br No 3 , NCS, ClO 4 ) dargestellt und ihre Wasserlöslihkeit bei 21 °C bestimmt. Die IR-Spektren werden diskutiert. Das thermische Verhalten der erhaltenen Komplexe wurde untersucht.
  相似文献   

14.
Summary The kinetics of the reaction betweencis-dichlorobisbipyridineruthenium(II) and nitric acid have been investigated spectrophotometrically in the 25°–40° range in the presence of 0.03 to 0.2 mol dm–3 HNO3. The reaction proceeds with the stepwise formation of monoaqua and diaqua products. Only the formation of the monoaqua intermediate was followed as this species could not be obtained in a pure state. Aquation proceeds through a dissociative process. The second order rate constants are 11.8 (25°), 17.5 (30°); 30.0 (35°) l mol–1 s–1. Activation parameters are H 52±3 kJ mol–1; S–108±8 JK–1 mol–1.  相似文献   

15.
Zusammenfassung Zinn gibt in essigsaurer Lösung mit Brompyrogallolrot einen 11-Komplex mit einem Absorptionsmaximum bei 515 nm und dem Extinktions-koeffizienten = 18000 l/Mol · cm. Die Farbbildung ist unabhängig von der Wertigkeitsstufe und eignet sich zur photometrischen Bestimmung des Zinns. Günstigster Meßbereich: 6–90 g Sn in 25 ml. Störungen durch andere Elemente — außer der durch SbIII und Ag — können durch vorherige Extraktion des Sn als SnJ4 vermieden werden.
Summary Tin forms a 11-chelate with bromopyrogallol red in acetic acid solution. The maximum absorptivity coefficient is = 18000l/Mol · cm at 510nm. The colour production is independent of the valence state of the tin and can be used for photometric determination. Optimum range for measurement: 6–90 g tin in 25 ml. Interferences caused by other cations — except those of SbIII and Ag — are prevented by extraction of tin as SnI4.


Wir danken der Deutschen Forschungsgemeinschaft und dem Verband der Chemischen Industrie (Fonds der Chemie) für Sachbeihilfen. Besonders sei auch Frl. Strehlau, Frl. Wortberg, Frl. Zuber, Herrn Höhn und Herrn Jackisch für die interessierte Mitarbeit bei der Überprüfung der Methode gedankt.  相似文献   

16.
Electrochemistry of a mixture of hydrofullerenes C70H36—46 composed of C70H36, C70H38, C70H44, and C70H46 (50, 20, 14, and 15%, respectively) was studied by cyclic voltammetry in THF and CH2Cl2 in the –43—–13 °C temperature range. Two cathodic peaks, namely, one-electron reversible (E° = –3.16 V (Fc0/+), Fc is ferrocene) and irreversible (E p = –3.37 V (Fc0/+)) were observed for this mixture in THF. The irreversible broad oxidation peak (E p = 1.22 V (Fc0/+)) was observed in CH2Cl2. The reversible reduction peak (E° = –3.16 V) and irreversible oxidation peak (E p = 1.22 V) were attributed to the most stable hydrofullerene C70H36. The irreversible reduction (E p = –3.37 V) and oxidation (E p = 1.22 V) peaks were attributed to hydrofullerenes C70H44—46 with a higher degree of hydrogenation. The values of an electrochemical gap, which is an analog of the energy gap (HOMO—LUMO), are 4.38 and 4.59 V for C70H36 and C70H44—46, respectively, and indicate that these hydrofullerenes are sufficiently hard molecules with low reactivity in redox reactions.  相似文献   

17.
A method has been developed for photometric detection of cyclodextrins (CD) in liquid chromatography using iodine (I2) generated electrochemically in-situ. Iodide ion in the mobile phase was electrochemically oxidized to I2 which was subsequently reacted with I, in an electrochemical flow cell, forming I3. The absorbance of I3 was found to be greatly enhanced when CD were present in the mobile phase. The absorbance enhancement was caused by the change in the mole fraction of I3, because of the inclusion reaction of I3 with CD. On the basis of this phenomenon, CD were detected by means of a photodiode-array UV–visible detector positioned downstream of the electrochemical flow cell. The signals were found to be linearly dependent on CD concentration. Because the formation constants of I3 with CD decrease in the order -CD>-CD>-CD, -CD was most detectable by the method. Detection limits were 1.0 mol L–1 for -CD, 65 mol L–1 for monoG1--CD, 100 mol L–1 for -CD, and 200 mol L–1 for -CD.  相似文献   

18.
The reaction cellulase (EC 3.2.1.4)—sodium carboxymethylcellulose (Na-CMC) with different degrees of polymerization (n=140, 640 and 900) was investigated by the use of a modifiedMichaelis-Menten equation, valid for enzymatic hydrolysis of linear homopolymers. TheMichaelis-Menten constant [Km (M)=6.31·10–2mol/dm3] and the reaction rate constant (k +2=4.07·10–6s–1), which correspond to the enzymatic hydrolysis of a single bond in the homopolymer substrates are determined. The free energy ( =101 kJ/mol), which corresponds to the degradation and formation of a single bond in the enzyme—polymer substrate is also estimated. This energy expressed in electronvolt units is =1.39 eV. The ratio between the effective cross section of the reactive substrate bond and the active enzyme center is =1.22.
Kinetik der enzymkatalysierten Hydrolyse von Natriumcarboxymethylcellulose mit verschiedenem Polymerisationsgrad durch Cellulase
Zusammenfassung Die modifizierte Gleichung nachMichaelis-Menten wird bei der durch Cellulase (EC 3.2.1.4) katalysierten hydrolytischen Spaltung von Natriumcarboxy-methylcellulose (Na-CMC) verschiedenen Polymerisationsgrades (n=140, 640 und 900) angewandt. Es wurde dieMichaelis-Menten-Konstante [Km (M)=6.31·10–2mol/dm3] und die Reaktionsgeschwindigkeitskonstante (k +2=4.07·10–6s–1), die der enzymatischen Hydrolyse einer Einfachbindung im homopolymeren Substrat entspricht, berechnet. Die freie Energie ( =101 kJ/mol), die dem Abbau und der Bildung einer Einfachbindung im Enzym—Polymer-Substrat entspricht, wurde bestimmt. Diese Energie — ausgedrückt in Elektronvolt-Einheiten — beträgt =1.39 eV. Das Verhältnis zwischen den effektiven Querschnitten der reaktiven Substratbindung ( S ) und des aktiven Enzym-Zentrums ( E ) beträgt =1.22.
  相似文献   

19.
The stability of metal aquo ions with respect to redox reactions is determined by the ionization energies of the atoms and the Gibbs energies of hydration for the ions(–hG0). We present critically selected values of –hG0 for 55 metal ions, determined from electrochemical, thermochemical, and spectra data. We consider the factors determining the values of –hG0 (charges, ionic radii, electronic structure, and relativistic effects). For isoelectronic ions, we observe correlations between the ratios of the Gibbs energies of hydration for these ions with different charges and the ratios of their ionic radii. Based on the use of these correlations, we find –hG0 for a number of aquo ions not observed experimentally and we estimate the unknown oxidation-reduction potentials for the pairs of ions M3+/M2+. We formulate the principles for stabilization of unstable oxidation states of the metals by including the corresponding ions in complexes with certain classes of ligands.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 1, pp. 1–11, January–February, 1994.  相似文献   

20.
The ionic strength and temperature dependencies of the molal acid association quotients of 2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol (also abbreviated as bis-tris) were determined potentiometrically in a concentration cell fitted with hydrogen electrodes. The emf was recorded for equimolal bis-tris/bis- trisHCl buffer solutions from 5 to 125°C at approximately 25°C intervals, and at nine ionic strengths from 0.05 to 5.0m (NaCl). The molal association quotients, combined with infinite dilution values from the literature, are described precisely by a seven parameter equation which yielded the following thermodynamic quantities at infinite dilution and 25°C: logK=6.481±0.003, H o =–28.5±0.2 kJ-mol –1 , S o =28.5±0.8 J-K –1 -mol –1 , and C P o =–22±5 J-K –1 -mol –1 . The equation incorporates a simple three term expression for logK, but requires four terms to describe the rather complex ionic strength dependence despite the reaction being isocoulombic. The molal association quotients from this study and the literature were also subjected to the Pitzer ion interaction treatment.  相似文献   

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