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1.
The flow injection technique is applied to study the binding to DNA of new platinum complexes—E1: ethylenediaminechlorocholylglycinateplatinum(II): [PtCl(CG)(en)], C54H92O12Pt and E2: ethylenediaminebischolylglycinateplatinum(II): [Pt(CG)2(en)], C28H50ClN3O6Pt—derived from cisplatin in which the exchangeable ligands were replaced by bile acids, such that these anticancer drugs have less toxicity and less resistance is developed towards them. Both compounds are fluorescent and their fluorescence is enhanced when they form adducts with DNA, a property that is extremely useful for monitoring the cytotoxic activity and their mechanisms of action. The binding parameters to DNA of E1 [apparent intrinsic binding constant KE1: (11.2 ± 0.4) × 103 M−1 and maximum number of binding sites per nucleotide, n E1: 0.121 ± 2 × 10−3) and E2 (KE2: 9.2 ± 0.7) × 103 M−1 and n E2 0.098 ± 2 × 10−3] were determined following the Scatchard method and the type of binding was studied experimentally through the modifications introduced by each of the compounds into the ethidium bromide–DNA bond.  相似文献   

2.
It is found that silver nanoparticles (AgNPs) can further enhance the fluorescence intensity of curcumin (CU) - cetyltrimethylammonium bromide (CTAB) – nucleic acids and improve its anti-photobleaching activity. Under optimum conditions, the enhanced fluorescence intensity is proportion to the concentration of nucleic acids in the range of 2.0 × 10−8–1.0 × 10−6 g mL−1 for fish sperm DNA (fsDNA), 2.0 × 10−8–1.0 × 10−6 g mL−1 for calf thymus DNA (ctDNA), 1.0 × 10−8–1.0 × 10−6 g mL−1 for yeast RNA (yRNA), and their detection limits (S/N = 3) are 8.0 ng mL−1, 10.5 ng mL−1 and 5.8 ng mL−1, respectively. This method is used for determining the concentration of DNA in actual sample with satisfactory results. The interaction mechanism is also studied.  相似文献   

3.
We have used UV and visible spectrophotometry to study self-association of aromatic riboflavin molecules (RFN, vitamin B2, 7,8-dimethyl-10-N-(1′-D-ribityl)isoalloxazine) in aqueous solution (pH 6.86) at T = 298 K, using a dimer model. We have determined the equilibrium dimerization constant for riboflavin, KdB = 125 ± 40 M−1. We have studied heteroassociation in the system of molecules of 7,8-dimethyl-10-ribitylisoalloxazine with 1,3,7-trimethylxanthine (caffeine) and sodium salicylate (NAS) in aqueous solution (pH 6.86; T = 298 K). We have determined the heteroassociation constants for RFN-NAS and RFN-caffeine molecules in the absence and in the presence of urea in solutions using a modified Benesi-Hildebrand equation: 25 ± 4, 17 ± 3, and 74 ± 11, 53 ± 7 M−1 respectively. We have determined the dimerization constants for NAS (2.7 ± 0.5 M−1) and caffeine (17.0 ± 1.5 M−1). We conclude that heteroassociation of the aromatic molecules leads to a lower effective riboflavin concentration in solution, and the presence of urea in mixed solutions leads to an decrease in the complexation constants for the RFN-NAS and RFN-caffeine systems. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 188–194, March–April, 2007.  相似文献   

4.
The formation of a complex between ketoconazole and β-cyclodextrin was followed by spectrofluorimety. The inclusion of ketoconazole in β-cyclodextrin cavity enhanced the native fluorescence of the drug. The stoichiometry of the complex was 1:1 β-cyclodextrin to ketoconazole and the stability constant of the complex (log K f) was determined to be 4.3 ± 0.01 at pH = 7.9 and 3.7 ± 0.04 at pH = 2.6. A sensitive spectrofluorimetric method for the detection of ketoconazole is presented. At optimized experimental conditions, a linear relationship between the fluorescence intensity of the solution and concentration of ketoconazole is observed in the range of 0.01–10 μg ml−1 (5 × 10−8 M–1.88 × 10−5 M). The method was applied to the detection of ketoconazole in pharmaceutical products and the results were satisfactory in comparison to the official method (relative error = 2.8% and standard deviation = 0.06 for tablets of ketoconazole). The recovery of ketoconazole from a blood serum sample, determined by the proposed method, was 97.1 ± 2.4%.  相似文献   

5.
When 1.00 mol l−1 I is used as ion perturber, rhodamine 6G (Rh 6G) can emit strong and stable room temperature phosphorescence (RTP) on filter paper substrate in KHC8H4O4–HCl buffer solution (pH = 3.50), heated at 70 °C for 10 min. NaIO4 can oxidize Rh 6G, which makes the RTP signal quench. Terbutaline sulfate (TBS) can inhibit NaIO4 from oxidizing Rh 6G, which makes the RTP signal of Rh 6G enhance sharply. The content of TBS is linear correlation to ΔIp of the system. Based on the facts above, a new inhibition solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace TBS has been established. The linear range of this method is 0.0104–2.08 pg spot−1 (corresponding concentration: 0.026–5.2 ng ml−1, with a sample volume of 0.4 μl) with a detection limit (L.D.) of 2.6 fg spot−1 (corresponding concentration: 6.5 × 10−12 g ml−1), and the regression equation of working curve is ΔIp = 2.040 + 54.54 mTBS (pg spot−1), n = 6, correlation coefficient is 0.9994. For the samples containing 0.0104 pg spot−1 and 2.08 pg spot−1 TBS, the relative standard deviation (RSD) are 3.8% and 2.3% (n = 8), respectively, indicating good precision. This method has been applied to determination of trace TBS in the practical samples with satisfactory results. The reaction mechanism of NaIO4 oxidizing Rh 6G to inhibit SS-RTP for the determination of trace TBS is also discussed.  相似文献   

6.
The synthesis and functionalization of carbon nanoparticles with PEG200 and mercaptosuccinic acid, rendering fluorescent carbon dots, is described. Fluorescent carbon dots (maximum excitation and emission at 320 and 430 nm, respectively) with average dimension 267 nm were obtained. The lifetime decay of the functionalized carbon dots is complex and a three component decay time model originated a good fit with the following lifetimes: τ 1 = 2.71 ns; τ 2 = 7.36 ns; τ 3 = 0.38 ns. The fluorescence intensity of the carbon dots is affected by the solvent, pH (apparent pK a of 7.4 ± 0.2) and iodide (Stern-Volmer constant of 78 ± 2 M−1).  相似文献   

7.
In this paper we reported a metal complex 1-Zn (2,5-di-[2-(3,5-bis(2-pyridylmethyl)amine-4-hydroxy-phenyl)-ethylene]-pyrazine-Zn) as a fluorescent probe sensing DNA. The result of the competitive experiment of the probe with ethidium bromide (EB) to bind DNA, absorption spectral change and polarization change in the presence and absence of DNA revealed that interaction between the probe and DNA was via intercalation. Ionic strength experiment showed the existence of electrostatic interaction as well. Scatchard plots also confirmed the combined binding modes. The fluorescence enhancement of the probe was ascribed to highly hydrophobic environment when it bound the macromolecules such as DNA, RNA or denatured DNA. The binding constant between the probe and DNA was estimated as 3.13 × 107 mol−1 L. The emission intensity increase was proportional to the concentration of DNA. Based on this, the probe was used to determine the concentration of calf thymus DNA (ct-DNA). The corresponding linear response ranged from 2.50 × 10−7 to 4.75 × 10−6 mol L−1, and detection limit was 1.93 × 10−8 mol L−1 for ct-DNA.  相似文献   

8.
The specific heats of liquid Ti–20at.%Al and Ti–51at.%Al alloys are determined to be 33.01±2.75 and 31.27±2.91 J mol−1 K−1 in the stable superheated and metastable undercooled states by using an electromagnetic levitation drop calorimeter. The experimental temperature ranges are 1733–2133 K and 1511–1948 K, and maximum undercoolings of 230 (0.12 T L) and 242 K (0.14 T L) are achieved, respectively. On the basis of the experimental results, the specific heat dependence on the composition is obtained for binary Ti–Al alloys.  相似文献   

9.
R. Donat 《Ionics》2010,16(8):741-749
The adsorption of U(VI) from aqueous solutions onto composite adsorbent (algistar) has been studied using a batch adsorber. The parameters that affect the U(VI) sorption, such as contact time, solution pH, initial U(VI) concentration, and temperature, have been investigated and optimized conditions determined. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of composite adsorbent, and experimental results showed this to be 43.10 mg/g. The adsorption patterns of metal ions on composite adsorbent followed the Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherms. The Freundlich, Langmuir, and D–R models have been applied, and the data correlate well with Langmuir model, and that the sorption is physical in nature (the sorption energy E ads = 12.90 kJ/mol). Thermodynamic parameters (∆H adso = −41.08 kJ/mol, ∆S adso = −68.00 J/mol K, ∆G ads (298.15 K) = −20.81 kJ/mol) showed the exothermic heat of adsorption and the feasibility of the process. The results suggested that the composite adsorbent is suitable as a sorbent material for recovery and biosorption/adsorption of uranium ions from aqueous solutions.  相似文献   

10.
The interaction between thyroxine hormone and 7 hydroxycoumarin (7HC) was investigated using fluorescence quenching method. The experimental results showed that thyroxine could quench the fluorescence of 7HC by forming the 7HC–thyroxine complex with static quenching. The apparent binding constants (K) between 7HC and thyroxine were determined to be 1.51 × 104 (297 K) and 9.06 × 103 (310 K). The binding sites (n) 0.98 ± 0.1. The thermodynamic parameters showed that the interaction between 7HC and thyroxine was driven mainly by hydrogen bonding interactions and van der Waals force. Calibration for thyroxine, based on quenching titration data, was linear in the concentration range 2.0 × 10−8 to 3.0 × 10−7 mol/l. The relative standard deviation was 2.58% for 2.0 × 10−7 mol/l thyroxine (n = 4) and the 3σ limit of detection was 3.42 × 10−8 mol/l in cationic surfactant CTAB medium.  相似文献   

11.
We report an experimental investigation of the non-steady-state photoelectromotive force in nanostructured GaN within porous glass and polypyrrole within chrysotile asbestos. The samples are illuminated by an oscillating interference pattern created by two coherent light beams and the alternating current is detected as a response of the material. Dependences of the signal amplitude versus temporal and spatial frequencies, light intensity, and temperature are studied for two wavelengths λ=442 and 532 nm. The conductivity of the GaN composite is measured: σ=(1.1–1.6)×10−10 Ω−1 cm−1 (λ=442 nm, I 0=0.045–0.19 W/cm2, T=293 K) and σ=(3.5–4.6)×10−10 Ω−1 cm−1 (λ=532 nm, I 0=2.3 W/cm2, T=249–388 K). The diffusion length of photocarriers in polypyrrole nanowires is also estimated: L D=0.18 μm.  相似文献   

12.
We have studied self-association of aromatic molecules of the thiazine dye methylene blue in aqueous solution, using a dimer model. We have determined the dimerization equilibrium constant for the dye molecules KD = 3900 ± 800 M−1 at T = 293 K. We have decomposed the experimental spectrum into dimer and monomer components. Using the ratio of the molar absorption coefficients for two absorption bands of the dimer spectrum, we obtained the “average” value of the angle between the electronic transition moments of the molecules in the dimers, α = 48°. We have studied heteroassociation of methylene blue (MB) and 1,3,7-trimethylxanthine (caffeine) molecules in aqueous solution. We have calculated the heteroassociation constant as 200 ± 34 M−1. We conclude that heteroassociation of methylene blue and caffeine molecules leads to a lower effective dye concentration in solution, which hypothetically may affect its biological activity. We have determined the values of the Gibbs free energy, the enthalpy, and the entropy for dimerization of methylene blue molecules: ΔG293 = −(20 ± 3) kJ/mol, ΔH = −(25 ± 9) kJ/mol, Δ S293 = −(17 ± 6) J/mol·K; and for methylene blue-caffeine heteroassociation: ΔG293 = −(13 ± 3) kJ/mol, ΔH = −(14 ± 10) kJ/mol, ΔS293 = −(2.4 ± 0.2) J/mol·K, respectively. We have shown that the methylene blue aggregates and the heteroassociates with caffeine are predominantly stabilized by dispersion interactions between the chromophore molecules in the associates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 158–163, March–April, 2006.  相似文献   

13.
This paper explores an ultra-sensitive luminescence method for the determination of Ketoprofen (KP) in pharmaceutical formulations. The technique is indirect and exploits the luminescence enhancement of terbium (Tb3+) by complexation with KP (Tb3+–KP), which was monitored at respective excitation and emission wavelengths of λ ex = 258 nm and λ em = 549 nm. The effect of varying the Tb3+ concentration and using multiple solvents was examined to determine optimal experimental conditions. Maximum sensitization was accomplished in the presence of methanol where the most favourable condition for the formation of the complex was recorded at a level of 1.0 × 10−5 M of Tb3+. Under these optimum experimental conditions, linear calibration curve was obtained in the range of 2.8 × 10−7–3.1 × 10−6 M with a detection limit of 8.7 × 10−8 M. The technique was validated with ‘working’ reference standards and produced relative standard deviations < 2% indicating that the reproducibility was highly acceptable. The proposed method was successfully applied to assays of KP in pharmaceutical formulations with average recoveries of 92–98%. The results were found to be in good agreement with those obtained by HPLC. The method is highly suited for general applications of this nature.  相似文献   

14.
Infrared (IR) and UV spectra of ternary Li2O–CuO–P2O5 glasses in two series Li2O(65−X)%–CuO(X%)–P2O5(35%), X = 20, 30, 40 and Li2O(55−X)%–CuO(X%)–P2O5(45%), X = (10, 20, 30) were studied. Infrared (IR) investigations showed the metaphosphate and pyrophosphate structures and with increase of CuO content in metaphosphate glass, the skeleton of metaphosphate chains is gradually broken into short phosphate groups such as pyrophosphate. IR spectra showed one band at about 1,220 and 1,260 cm−1 for P2O5(35%) and P2O5(45%) series, respectively, assigned to P=O bonds. For CuO additions ≤20 mol%, the glasses exhibit two bands in the frequency range 780–720 cm−1 which are attributed to the presence of two P–O–P bridges in metaphosphate chain. But for CuO addition ≥30 mol%, the glasses exhibit only a single band at 760 cm−1 which is assigned to the P–O–P linkage in pyrophosphate group. In optical investigations, absorption coefficient versus photon energy showed three regions: low energy side, Urbach absorption, and high energy side. In Urbach’s region, absorption coefficient depends exponentially on the photon energy. At high energy region, optical gap was calculated and investigations showed indirect transition in compounds and decreases in optical gap with increases of copper oxides contents that is because of electronic transitions and increasing of nonbridging oxygen content.  相似文献   

15.
Four novel copper(II) complexes of the composition [CuLX] where L = 2,6-bis(benzimidazole-2yl)pyridine, X = dipyridophenazine (L1), 1,10-phenanthroline (L2), hydroxyproline (L3) and 2,6-pyridine dicarboxylic acid (L4) were synthesized and characterized by using elemental analysis, FT-IR, UV–vis, ESI-MS, molar conductance and magnetic susceptibility measurements. The complexes [CuLL1](NO3)2 [1], [CuLL2](NO3)2 [2], [CuLL3](NO3) [3] and [CuLL4] (NO3) [4] are stable at room temperature. In DMSO the complexes [1] and [2] are 1:2 electrolytes, [3] and [4] are 1:1 electrolytes. Based on elemental and spectral studies five coordinated geometry is assigned to all the four complexes. The interaction of four copper ion complexes with calf thymus DNA were carried out by UV–vis titrations, fluorescence spectroscopy, thermal melting and viscosity measurements .The binding constant (Kb) of the above four metal complexes were determined as 5.43 × 104 M,−1 2.56 × 104 M−1, 1.21 × 104 M−1 and 1.57 × 104 M−1 respectively. Quenching studies of the four complexes indicates that these complexes strongly bind to DNA, out of all complex 1 is binding more strongly. Viscosity measurements indicate the binding mode of complexes with CT DNA by intercalation through groove. Thermal melting studies also support intercalative binding. The nuclease activity of the above metal complexes shows that 1, 2 and 3 complexes cleave DNA through redox chemistry.  相似文献   

16.
6-Hydroxy chromone-3-carbaldehyde-(4′-hydroxy) benzoyl hydrazone (L) and its Ln (III) complexes, [Ln = La, Nd, Eu and Tb] have been prepared and characterized on the basis of elemental analyses, molar conductivities, mass spectra, 1H NMR, thermogravimety/differential thermal analysis (TG-DTA), UV-vis spectra, fluorescence spectra and IR spectra. The formula of the complex is [Ln L·(NO3)2]·NO3. Spectrometric titration, ethidium bromide displacement experiments and viscosity measurements indicate that Eu (III) complex bind with calf-thymus DNA, presumably via an intercalation mechanism. The intrinsic binding constant of Eu (III) with DNA was 2.48 × 105 M−1 through fluorescence titration data.  相似文献   

17.
A nanoparticle TiO2 solid-state photoelectrochemical cell utilizing as a solid electrolyte of poly(acrylonitrile)–propylene–carbonate–lithium perchlorate (PAN–PC–LiClO4) has been fabricated. The performance of the device has been tested in the dark and under illumination of 100-mW cm−2 light. A nanoparticle TiO2 film was deposited onto indium tin oxide-covered glass substrate by controlled hydrolysis technique assisted with spin-coating technique. The average grain size for the TiO2 film is 76 nm. LiClO4 salt was used as a redox couple. The room temperature conductivity of the electrolyte is 4.2 × 10−4 S cm−1. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows the rectification property in the dark and shows the photovoltaic effect under illumination. The best J sc and V oc of the device were 2.82 μA cm−2 and V oc of 0.58 V, respectively, obtained at the conductivity of 4.2 × 10−4 S cm−1 and intensity of 100 mW cm−2. The J sc was improved by about three times by introducing nanoparticle TiO2 and by using a solid electrolyte of PAN–PC–LiClO4 replacing PVC–PC–LiClO4 in the device. The current transport mechanism of the cell is also presented in this paper.  相似文献   

18.
LiAl x Mn2 − x O4 and LiAl0.05Mn1.95O4 − y F y spinel have been successfully synthesized by citric acid-assisted sol–gel method. The structure and physicochemical properties of this as-prepared powder were investigated by electronic conductivity test, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge test in detail. The electronic conductivity decreases with increasing of the content of doped Al. XRD patterns show that the diffraction of LiAl0.05Mn1.95O4 − y F y samples is similar, with all the peaks indexable in the Fd3m space group, and a little impurity appears in the LiAl0.05Mn1.95O3.8F0.2 sample. SEM reveals that all LiAl0.05Mn1.95O4 − y F y powders have the uniform, nearly cubic structure morphology with narrow size distribution which is less than 500 nm. Galvanostatic charge–discharge test indicates that LiAl0.05Mn1.95O4 has the highest discharge capacity and electrochemical performance among all LiAl x Mn2 − x O4 samples after 50 cycles, and the initial discharge capacity of LiAl0.05Mn1.95O4 − y F y (y = 0, 0.02, 0.05, 0.1) is 123.9, 124.6, 124.9, and 125.0 mAh g−1, respectively, and their capacity retention ratios are 94.2%, 94.9%, 91.7%, and 89.9% after 50 cycles, respectively. EIS indicates that LiAl0.05Mn1.95O3.98F0.02 have smaller charge transfer resistance than that of LiAl0.05Mn1.95O4 corresponding to the extraction of Li+ ions.  相似文献   

19.
In the paper, a chemiluminescence (CL) system was developed based on the catalytical effect of diperiodatocuprate (III) (DPC) on the 1,10-phenanthroline (phen)/hydrogen peroxide (H2O2) in the presence of cetyltrimethylammonium bromide (CTAB). The effects of experimental conditions were investigated. Meanwhile the increase of CL intensity of the DPC/phen/H2O2/CTAB system is proportional to the concentration of phen in the range of low concentration. The linear range of the calibration curve is 5.0 × 10−9–1.0 × 10−6 mol L−1, and the corresponding detection limit is 1.9 × 10−9 mol L−1. The effects of phenolic compounds (PCs) on the system were investigated. Hydroquinone was used as an example to investigate the application of the CL system to the determination of PCs. The quenched CL intensity is linearly related to the logarithm of concentration of hydroquinone. The linear range of the calibration curve is 2.5 × 10−9–1.0 × 10−5 g mL−1, and the corresponding detection limit is 1.8 × 10−9 g mL−1. This phen and hydroquinone can be synchronously determined. The method was applied to the determination of hydroquinone in water samples and the recoveries were from 92% to 106%.  相似文献   

20.
A new, simple, sensitive and selective spectrofluorimetric method for the determination of Hydrochlorothiazide was developed in acetonitrile at pH 6.2. The Hydrochlorothiazide can remarkably enhance the luminescence intensity of the Tb3+ ion doped in sol–gel matrix at λex = 370 nm. The intensity of the emission band of Tb3+ ion doped in sol–gel matrix was increased due to the energy transfer from the triplet excited state of Hydrochlorothiazide to (5D4) excited energy state of Tb3 ion. The enhancement of the emission band of Tb3+ ion doped in sol–gel matrix at (5D47 F5) 545 nm was directly proportion to the concentration of Hydrochlorothiazide with a dynamic ranges of 5.0 × 10−10—5.0 × 10−6 mol L−1 and detection limit of 2.2 × 10−11 mol L−1.  相似文献   

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