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1.
Astronomical constraints on a possible cosmologicalvariation of the proton-to-electron mass ratio μ=mp/me are discussed. The analysis of H2 lines observed in thespectra of distant quasars Q 0405-443 (zem=3.02) andQ 0347-383 (zem=3.22) is performed [1] using, partly, very precise values of H2 frequencies from new laboratorymeasurements [2] and sensitivity coefficients from newaccurate calculations [2,3]. A possibleμ-variation of Δμ/ μ= (2.0±0.6)×10-5over 12 Gyr is not excluded. However, the discussion of systematicerrors show that some may well be underestimated. Thus, the abovevalue should be treated as the most stringent limit the cosmologicalvariation of μ at z≈2.6 - 3.0 (12 Gyr ago).  相似文献   

2.
We present the results of an experimental study of the ablation spectral energy thresholds for a number of polymer materials ((C2F4) n , (CH2O) n ) exposed to femtosecond (τ0.5 ~ 45–70 fs) laser pulses (λ ~ 266, 400, 800 nm) under atmospheric conditions and under vacuum (p ~ 10–2 Pa). We have analyzed the energy thresholds and the efficiency of optical, thermophysical, and gasdynamic processes in laser ablation vs. the laser pulse duration and photon energy.  相似文献   

3.
Luteolin and apigenin, extracted from Reseda luteola L., were spectrophotometrically and fluorimetrically studied. The spectra were investigated as a function of pH in methanol/water solutions (1/2, v/v) in the 2–12 pH range. The absorption spectra markedly shifted to the red by increasing the pH. Three acid–base dissociation steps were detected for luteolin (pK a = 6.9; 8.6; 10.3) and two for apigenin (pK a = 6.6; 9.3). Fluorescence emission was very weak or undetectable (Φ F < 10−4) in acidic solution, but increased in intensity with increasing the pH. Both molecules exhibited a great propensity towards complex formation with metal ions, with association constants on the order of 105–107 for the first complexation step; in the presence of excess Al3+ ions, multiple equilibria were detected. A marked fluorescence enhancement was observed upon complexation with Al3+ ions (Φ F ∼ 1 for luteolin and ∼10−2 for apigenin).  相似文献   

4.
Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H2F20TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H2F20TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H2F20TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H2F20TPP. The fluorescence quenching rate constants ranged from 1 × 109 to 4 × 109 s−1, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H2F20TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G0) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.  相似文献   

5.
The structural and solvent effects on the electronic absorption and fluorescence spectra, and fluorescence quantum yields, of four new fused benzothiophene derivatives, including benzothieno[3,2b]-thiophene (BTT), benzothieno[3,2-b]benzothiophene (BTBT), 6-methoxy[1]benzothieno[3,2b]-thiophene (MeOBTT), and benzothieno[3,2-b]indole (BTI) were investigated at 295 K. The luminescence properties of the corresponding conductive oligomers, poly(BTT) and poly (MeOBTT), electrosynthesized in acetonitrile, were also studied. Satisfactory McRae, Suppan, and Kawski-Chamma-Viallet solvatochromic correlations were established for the four monomers in most solvents. A weak negative solvatochromic behavior was found for these compounds, indicating that their dipole moments are slightly lower in the excited singlet state than in the ground state. Kamlet-Abboud-Taft multiparametric correlations were also obtained for absorption and fluorescence wave numbers and quantum yields, demonstrating the existence of specific solute-solvent interactions. In the case of the oligomers, important red-shifts of the fluorescence emission maxima ( 90–110 nm) relative to the corresponding monomers were observed, which shows the extent of conjugated segments in the oligomer chains.  相似文献   

6.
在B3LPY/6-31G(d, p)基组水平上,利用密度泛函理论(DFT)优化了吲哚并咔唑五种同分异构体的几何和电子结构.基于这五种同分异构体的几何结构下,其吸收和发射光谱的研究使用相同的基组水平并采用极化连续介质模型(PCM)下用含时密度泛函理论(TD-DFT)计算.由于三种近似线性分子(吲哚并[2,3-a]咔唑、吲哚并[2,3-b]咔唑和吲哚并[3,2-b]咔唑)的电荷转移跃迁的振荡强度较大,这些异构体的发射光谱存在明显差异;基于吲哚并[2,3-c]咔唑和吲哚并[3,2-a]咔唑的构型特征,这两种同分异构体的发射谱具有高能量.比较计算结果表明,吲哚并[2,3-b]咔唑在这些分子中的振荡强度最大.这是因为当吲哚并咔唑的五种同分异构体的结构从基态变为激发态时,这些分子的分子轨道(MO)能级不同.由计算结果还得出,这五个分子适用于P型传输材料,并且每个分子的三个苯环均具有共轭效应.  相似文献   

7.
BaMoO4:Eu (BEMO) powders were synthesized by the polymeric precursor method (PPM), heat treated at 800 °C for 2 h in a heating rate of 5 °C/min and characterized by powder X-ray diffraction patterns (XRD), Fourier Transform Infra-Red (FTIR) and Raman spectroscopy, besides room temperature Photoluminescence (PL) measurements. The emission spectra of BEMO samples under excitation of 394 nm present the characteristic Eu3+ transitions. The relative intensities of the Eu3+ emissions increase as the concentration of this ion increases from 0.01 to 0.075 mol, but the luminescence is drastically quenched for the Ba0.855Eu0.145MoO4 sample. The one exponential decay curves of the Eu3+ 5D07F2 transition, λ exc = 394 nm and λ em = 614 nm, provided the decay times of around 0.54 ms for all samples. It was observed a broadening of the Bragg reflections and Raman bands when the Eu+3 concentration increases as a consequence of a more disordered material. The presence of MoO3 and Eu2Mo2O7 as additional phases in the BEMO samples where observed when the Eu3+ concentration was 14.5 mol%.  相似文献   

8.
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   

9.
SrMoO4 doped with rare earth are still scarce nowadays and have attracted great attention due to their applications as scintillating materials in electro-optical like solid-state lasers and optical fibers, for instance. In this work Sr1−xEuxMoO4 powders, where x = 0.01; 0.03 and 0.05, were synthesized by Complex Polymerization (CP) Method. The structural and optical properties of the SrMoO4:Eu3+ were analyzed by powder X-ray diffraction patterns, Fourier Transform Infra-Red (FTIR), Raman Spectroscopy, and through Photoluminescent Measurements (PL). Only a crystalline scheelite-type phase was obtained when the powders were heat-treated at 800 °C for 2 h, 2θ = 27.8° (100% peak). The excitation spectra of the SrMoO4:Eu3+Em. = 614 nm) presented the characteristic band of the Eu3 + 5L6 transition at 394 nm and a broad band at around 288 nm ascribed to the charge-transfer from the O (2p) state to the Mo (4d) one in the SrMoO4 matrix. The emission spectra of the SrMoO4:Eu3+ powders (λExc. = 394 and 288 nm) show the group of sharp emission bands among 523–554 nm and 578–699 nm, assigned to the 5D17F0,1and 2 and 5D07F0,1,2,3 and 4, respectively. The band related to the 5D07F0 transition indicates the presence of Eu3+ site without inversion center. This hypothesis is strengthened by the fact that the band referent to the 5D07F2 transition is the most intense in the emission spectra.  相似文献   

10.
An efficient synthesis of 2-hydroxy-3-[2-oxo-2-phenylethylidene]-2-phenyl-2, 3-dihydro-4 H-furo[3, 2-c]chromene-4(2H)-one is described. This involves the reaction between dibenzoylacetylene and 4-hydroxycoumarine in the presence of NaH (10 mol %) in nearly quantitative yield. Treatment of this heterocyclic system with trimethyl chlorosilane in CHCl3 leads quantitatively to 4-oxo-3-[2-oxo-2-phenylethylidene]-2-phenyl-3H, 4H-furo[3,2-c]chromene-1-ium chloride. Direct addition of nucleophiles, such as alcohols, amines or trialkyl phosphites to this salt in water as the solvent produces functionalized 2-phenyl-4H-furo[3,2-c] chromen derivatives in excellent yields.  相似文献   

11.
The metal-ligand complex, [Ru(2,2′-bipyridine)2(4,4′-dicarboxy-2,2′-bipyridine)]2+ (RuBDc), was used as a spectroscopic probe for studying macromolecular dynamics. RuBDc is a very photostable probe that possesses favorable photophysical properties including long lifetime, high quantum yield, large Stokes’ shift, and highly polarized emission. To further show the usefulness of this luminophore for probing macromolecular dynamics, we examined the intensity and anisotropy decays of RuBDc when conjugated to R17 bacteriophage using frequency-domain fluorometry with a blue light-emitting diode (LED) as the modulated light source. The intensity decays were best fit by a sum of two exponentials, and we obtained a longer mean lifetime at 4 °C (<τ> = 491.8 ns) as compared to that at 25 °C (<τ> = 435.1 ns). The anisotropy decay data showed a single rotational correlation time, which is typical for a spherical molecule, and the results showed a longer rotational correlation time at 4 °C (2,574.9 ns) than at 25 °C (2,070.1 ns). The use of RuBDc enabled us to measure the rotational correlation time up to several microseconds. These results indicate that RuBDc has significant potential for studying hydrodynamics of biological macromolecules.  相似文献   

12.
A sensitive time- resolved luminescence method for the determination of meloxicam (MX) in methanol and in aqueous solution is described. The method is based on the luminescence sensitization of europium (Eu3+) by formation of ternary complex with MX in the presence of 1,10- phenanthroline as coligand, Tween-80 as surfactant and gadolinium ion as a co-luminescence reagent. The signal for Eu- MX-1, 10- phenanthroline is monitored at λex = 360 nm and λem = 620 nm. Optimum conditions for the formation of the complex in aqueous system were 0.01 M TRIS buffer, pH 8.0, 1,10- phenanthroline (6.0 × 10−6 M) , Gd3+ (7.0 × 10−6 M), Tween-80 (0.28%) and 1.75 mM of Eu3+ which allows the determination of 20–800 ppb of MX with limit of detection (LOD) of 7 ppb. The relative standard deviations of the method range between 0.1 and 1.1% indicating excellent reproducibility of the method. The proposed method was successfully applied for the assay of MX in pharmaceutical formulations, plasma and in urine samples. Average recoveries of 99.8 ± 1.1%, 100.2 ± 0.9% and 100.9 ± 1.1% were obtained for MX in tablet, plasma and urine sample respectively.  相似文献   

13.
In this work, a new simple and sensitive flow injection method is developed for the determination of homocysteine with spectrofluorimetric detection technique. This method is based on the oxidation of homocysteine with Tl (III) in acidic media, producing fluorescence reagent, TlCl32-ex = 237 nm, λem = 419 nm). The effects of chemical parameters (including pH of the solutions, the buffer, Tl (III) and potassium chloride concentrations), instrumental parameters (such as flow rate of the solutions, reaction coil length, and sample loop volume) and temperature on the fluorescence intensity as an analytical signal are studied and optimized. In the optimum conditions of the above variables, homocysteine can be determined in the range 4.0 × 10-7–40.0 × 10-6 M with the LDR from 4.0 × 10-7 to 25.0 × 10-6 M. The detection limit (with S/N = 3) is 6.0 × 10-8 M of homocysteine and precision for the injection of 5.0, 10.0 and 15.0 μM of homocysteine are 0.8%, 1.5% and 2.5% (n = 10) respectively. The rate of analysis is 90 samples per hour. The influence of potential interfering substances, including amino acids and carbohydrates is also studied. The proposed method has been successfully used for the determination of homocysteine in the real sample (blood serum and tap water) matrix.  相似文献   

14.
We used fluorescence spectroscopy and nanosecond flash photolysis to study the photophysical properties of the laser dye 4-dicyanomethylene-2-methyl-6-(p-dimethylamino)styryl-4H-pyran (DCM) and its two fluoro derivatives: (E)-2-〈2-[2-(4-dimethylaminophenyl)ethenyl]-6-trifluoromethyl-4H-4-pyranylidene〉malononitrile (DCMF3) and (E)-2-〈2-[2-(4-dimethylaminophenyl)ethenyl]-6-n-heptafluoro-propyl-4H-4-pyranylidene〉 malononitrile (DCMF7), in nonpolar n-hexane, mixtures of low-polarity toluene and polar dimethylsulfoxide (DMSO), n-propanol at room temperature and at 77 K. The fluorescence quantum yield Φfl of the laser dye DCM increases linearly as the polarity of the binary solvent mixture (toluene+DMSO) increases, from 0.08 in toluene to 0.80 in DMSO. The dependence of Φfl on the polarity of the mixture toluene+DMSO for DCMF3 and DCMF7 reaches a maximum for a small amount (∼2 vol.%) of added polar DMSO; and with further increase in the DMSO concentration (≥50 vol.%), the fluorescence of the fluoro derivatives of DCM is practically completely quenched. The quantum yield for intersystem crossing ΦST for DCM, DCMF3, and DCMF7 is no greater than 0.01 in solutions of different polarities. We discuss the mechanisms for nonradiative deactivation of the electronic excitation energy for the fluoro derivatives compared with DCM. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 606–612, September–October, 2006.  相似文献   

15.
For trigonal siderite-type antiferromagnetic materials with allowance for the crystal symmetry considered in the thermodynamic potential, it is demonstrated that an amplitude dependence of the internal friction is observed in the absence of accompanying magnetic field along the [001] easy axis, whereas in the presence of the field, the amplitude-independent internal friction component is observed. In this case, it is expedient to use the ratio of energy dissipated for the period to oscillation energy as a measure of the internal friction for frequencies ω < τ−1 (τ is the relaxation time), whereas for frequencies comparable with the Larmor frequency, the magnetic resonance phenomenon must be taken into account.  相似文献   

16.
Three symmetric ligands 7-methyl dipyrido-[3,2-a;2′,3′-c]phenazine (dppz-CH3), 7-nitro dipyrido-[3,2-a;2′,3′-c]phenazine (dppz-NO2) and benzo[i]dipyrido-[3,2-a;2′,3′-c]phenazine (dppn) and their ruthenium(II) complexes [Ru(en)2(L)][ClO4]2 (en= ethylenediamine), L= dppz-CH3, dppz-NO2 and dppn have been synthesized and characterized by IR, 1H, 13C NMR and Mass spectra. The interactions of these complexes with calf thymus DNA have been investigated by spectrophotometric, spectrofluorimetric, circular dichroism, viscosity and thermal denaturation studies. As the planar extension of the intercalative ligand increases, the interaction of the complex with DNA increases, indicating that the size and shape of the intercalalative ligand has a marked effect on the strength of interaction. The plot of log K versus log [Na+] yield a slope of -1.26, -1.53, -1.60 for the complexes 1, 2 and 3 respectively. These three complexes have been found to promote the cleavage of plasmid pBR 322 DNA upon irradiation.  相似文献   

17.
Alternating donor-acceptor type copolymers, poly[{5,11-di(9′-heptadecanyl)indolo[3,2-b]carbazole}-alt-{2,5-di(thiophen-2-yl)thiazolo[5,4-d]thiazole-5,5′-diyl}] (PIC-TZ) and poly[{6,6′,12,12′-tetraoctylindeno[1,2-b]fluorene}-alt-{2,5-di(thiophen-2-yl)thiazolo[5,4-d]thiazole-5,5′-diyl}] (PIF-TZ), were synthesized and examined for applications in polymeric photovoltaic cells. The polymers have a fused coplanar main backbone with good planarity for intermolecular packing and high charge mobility. The indolocarbazole and indenofluorene units contain two or four binding sites for alkyl substituents that have pronounced solution processiblity compared to the carbazole and fluorene moieties. The number-average molecular weights (Mn) of the synthesized polymers were determined to be 11,000 g/mol (PDI = 2.27) for PIC-TZ, and 17,000 g/mol (PDI = 1.77) for PIF-TZ. The optical band gap of PIC-TZ and PIF-TZ in film was determined to be 2.14 eV and 2.21 eV, respectively, and an electrochemical study confirmed the desirable HOMO/LUMO levels of the copolymers, which enabled efficient electron transfer and a high open circuit voltage (VOC) when blending them with fullerene derivatives. The space charge limited current mobility measurements showed a hole mobility of 10−3 cm2 V−1 s−1 for the copolymers. When the polymers were blended with [6,6]phenyl-C61-butyric acid methyl ester (PCBM), PIC-TZ showed the best performance with VOC, short-circuit current and power conversion efficiency of 0.86 V, 4.16 mA/cm2 and 1.64%, respectively, under AM 1.5G illumination conditions (100 mW cm−2).  相似文献   

18.
Variable temperature two-dimensional nuclear Overhauser enhancement experiment (2-D NOESY) is used to extract the rate constants and cross-relaxation rates that contribute to the same cross-peaks in NOESY spectra. Rate constants (k AB) and cross-relaxation rates (R AB) for two-site spin systems are related to the ratio between the cross-peak and diagonal peak integrals (F) by the expression:R AB -k AB = (1/2τ m)ln[(1 -F)/(1 +F)], where τm is the mixing time. As a model, we investigated the exchange processes in a system of dimer calix[4]arenes of C4v symmetrical configuration with guest inclusion (benzene or benzene-d6), where the measurement of exchange processes is hindered by the presence of strong nuclear Overhauser enhancement between protons in adjacent aromatic rings in the cone conformation of the calix[4]arene.  相似文献   

19.
The spectral-luminescent characteristics of newly synthesized styrylcyanine dyes on the base of dyes Sbo ((E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide) and Sil ((E)-2-(4-(dimethylamino)styryl)-1,3,3-trimethyl-3H-indolium perchlorate) in aqueous solutions without and in the presence of bovine serum albumin (BSA) were studied. It was established that the absorption spectra of dyes Tol-6, Dbo-10 and Dil-10 with increasing amount of BSA appear new bands with λmax = 505 nm, λmax = 512 nm and λmax = 566 nm, respectively, whose intensity increases in proportion to the amount of albumin. The intensity of the glow of the main band of fluorescence in the presence of BSA sharply increases. The binding constant (K) and the number of binding sites (N) of studied dyes with BSA were determined. The dependence of binding constants with BSA on the dipole moment of dye molecules was determined, which indicates that besides electrostatic forces of attraction between molecules styrylcyanine dyes with BSA, hydrophobic interactions are essential.  相似文献   

20.
Wang X  Li Y  Du X  Lin Z  Huang C 《Journal of fluorescence》2011,21(4):1643-1648
Previous reports have seldom concerned about the RTILs (Room temperature ionic liquids), and their effects on derivatization reaction or derivatives. In this study, we reported that the effects of four different RTILs, i.e., [EMIM]PF6, [BMIM]PF6, [HMIM]PF6 and [OMIM]PF6, on fluorescence spectra of 17 β-estradiol (E2), and its derivatization solvent dansyl chloride (DNSCl) and the derivative. [BMIM]PF6 had a significant quenching effect on the fluorescence intensity of E2, suggesting the formation of [BMIM]PF6/E2 complexes and possible buried E2 molecular in a more hydrophobic microenvironment. The estimated Stern-Volmer quenching constant (Ksv = 0.3519) proved that E2 quenching caused by [BMIM]PF6 was a dynamic quenching process. Four RTILs, with different alkyl chain-length in imidazolium cation, resulted in different quenching intensities to E2 as follows: [EMIM]PF6 > [BMIM]PF6 > [HMIM]PF6 > [OMIM]PF6. At 5 mg L−1 of DNSCl, [BMIM]PF6, [HMIM]PF6 and [OMIM]PF6 increased the fluorescence intensities of E2 in water by 8.5, 7.6 and 6.1 times, respectively, and a 37-nm hypsochromic shift occurred. The fluorescence intensity for [BMIM]PF6-extracted derivative of E2 increased more than two times compared with that for the control. In conclusion, this study demonstrated that above four hexafluorophosphate salt ionic liquids could be used in derivatization reaction to enhance fluorescent sensitivity in E2 trace residual analysis.  相似文献   

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