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1.
The fluorescence quenching of 2,2″-dimethyl-p-terphenyl (DMT) by carbon tetrachloride (CCl4) was investigated in different solvent mixtures of benzene and acetonitrile at room temperature (300 K). A positive deviation from linearity was observed in the Stern-Volmer plots for all the solvent mixtures. This could be explained satisfactorily by static and dynamic quenching models. The nonlinearities in the S-V plots are interpreted in terms of ground state complex model and the sphere of action static quenching model. The results suggest that positive deviations in the S-V plot are due to the presence of both static and dynamic quenching processes. To explain that bimolecular reactions are diffusion limited, we have used finite sink approximation model. Various rate parameters for the quenching process have been determined by static and dynamic quenching models. The dynamic quenching constant depends on the solvent polarity and indicates that quenching reaction is diffusion limited.  相似文献   

2.
The fluorescence quenching of 1, 4-bis[2-(2-methylphenyl)ethenyl]-benzene (Bis-MSB) in toluene has been studied with carbon tetrachloride (CCl4) and aniline by steady-state and transient methods. A positive deviation was observed in the Stern-Volmer (S-V) plot for both the quenchers. This indicates the presence of either static or transient quenching component in the overall dynamic quenching. The experimental data are analysed by sphere of action static quenching model. The value of radius of sphere of action determined from this model is greater than the sum of the radii of the Bis-MSB and respective quenchers. From the studies of temperature dependence of rate parameters and lifetime measurements, it could be explained that the positive deviation is due to the presence of a small static quenching component in the overall dynamic quenching. This fact suggests the simultaneous presence of static and dynamic component in the fluorescence quenching Bis-MSB by CCl4 and aniline.  相似文献   

3.
The fluorescence quenching of newly synthesized coumarin (chromen-2-one) derivative, 4-(5-methyl-3-furan-2-yl-benzofuran-2-yl)-7-methyl-chromen-2-one (MFBMC) by aniline in different solvent mixtures of benzene and acetonitrile was determined at room temperature (296 K) by steady-state fluorescence measurements. The quenching is found to be appreciable and positive deviation from linearity was observed in the Stern-Volmer (S-V) plots in all the solvent mixtures. This could be explained by static and dynamic quenching models. The positive deviation in the S-V plot is interpreted in terms of ground-state complex formation model and sphere of action static quenching model. Various rate parameters for the fluorescence quenching process have been determined by using the modified Stern-Volmer equation. The sphere of action static quenching model agrees very well with experimental results. The dependence of Stern-Volmer constant KSV, on dielectric constant ε of the solvent mixture suggests that the fluorescence quenching is diffusion-limited. Further with the use of finite sink approximation model, it is concluded that these bimolecular quenching reactions are diffusion-limited. Using lifetime (τo) data, the distance parameter R′ and mutual diffusion coefficient D are estimated independently.  相似文献   

4.
Abstract

In the two stable conformations of the diazabicyclanol 3, 7-dimethyl-3, 7-diazabicyclo[3. 3. 1]nonan-9-ol, chair-chair (Va) and chair-boat (Vb), the infrared spectra (200–4000 cm?1) were recorded, compared and their vibrations analysed. Using the AMI senlempirical method, the geometry was fully optimized in both forms, and the theoretical Infrared spectra were calculated and compared. In the (Vb) conformation, the IR spectra were recorded in CCl3D, CCl4 and S2C solvents. Some correlations were established.  相似文献   

5.

A new ligand FIPB?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl-2-boronic acid, having three cobalt(III) polypyridyl complexes [Co(phen)2(FIPB)]3+(1) {FIPB?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl-2-boronic acid}, (phen?=?1,10-Phenanthroline), [Co(bpy)2(FIPB)]3+(2) (bpy?=?2,2’bipyridyl), [Co(dmb)2(FIPB)]3+(3) (dmb?=?4, 4′-dimethyl 2, 2′-bipyridine) have been synthesized and characterized by elemental analysis, ES-MS,1H-NMR, 13C-NMR, UV-Vis and FTIR. Their DNA binding behavior has been explored by various spectroscopic titrations and viscosity measurements, which indicated that all the complexes bind to calf thymus DNA by means of intercalation with different binding strengths. The binding properties of these all three complexes towards calf-thymus DNA (CT-DNA) have been investigated by UV-visible, emission spectroscopy and viscosity measurements.The experimental results suggested that three Co(III) complexes can intercalate into DNA base pairs,but with different binding affinities. Photo induced DNA cleavage studies have been performed and results indicate that three complexes efficiently cleave the pBR322-DNA in different forms. The three synthesized compounds were tested for antimicrobial activity by using Staphylococcus aureus and Bacillus subtilis organisms, these results indicated that complex 1 was more activity compared to other two complexes against both tested microbial strains. The in vitro cytotoxicity of these complexes was evaluatedby MTT assay, and complex 1 shows higher cytotoxicity than complex 2 and 3 on HeLa cells.

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6.
The fluorescence quenching of 5, 6-benzo-4-azidomethyl coumarin (5BAMC) by aniline have been carried in different solvent mixtures of benzene (BN) and acetonitrile (AN) at room temperature by steady state fluorescence measurements. The quenching is found to be appreciable and a positive deviation from linearity was observed in the Stern-Volmer plot for the fluorophore in all the solvent mixtures. Various parameters for the quenching process have been determined using the extended S-V equation and have been found to be dependent on the solvent polarity. Further, with the use of finite sink approximation model, it is concluded that the bimolecular reactions quenching reactions are diffusion limited, and the distance parameter R′ and mutual diffusion coefficient D are estimated independently.  相似文献   

7.
Abstract

An N-methylated compound of S-145, (±)-(5Z)-7-[3-endo-[N-methyl)phenylsulphonyl)amino]bicyclo [2.2.1]hept-2-exo-yl]heptenoic acid 1, its chain analogue 12-[N-methyl(phenylsulphonyl)amino]dodecanoic acid 3, (±)-(5Z)-7-[3-endo-(benzoylamino)bicyclo[2.2.1]hept-2-exo-yl] heptenoic acid 5 and related compounds were synthesized in order to study the formation of a new class of intramolecular hydrogen bond IX (cis-CO2H…O = Y). Their FTIR spectra were measured in dilute CCl4 solution and subjected to curve analysis in order to separate overlapping absorption bands. For compounds 1,3 and 5, the intramolecular hydrogen bonds of the IX type involving 14-, 17- and 14-membered rings were found between a carboxyl group, which takes a cis-structure IV, and an oxygen atom of a sulphonyl or benzoylamino group, respectively. The C[dbnd]O stretching vibration bands of these carboxyl groups shifted to lower wavenumbers (ca. 19 cm?1). The direction of these shifts was contrary to that found for α-keto and α-alkoxycarboxylic acids in which carboxyl groups take a trans-structure III due to the formation of intramolecular hydrogen bonds I and II, respectively.  相似文献   

8.
A C 3-symmetric triphenylbenzene based photoluminescent compound, 1,3,5-tris(4′-(N-methylamino)phenyl) benzene ([NHMe]3TAPB), has been synthesized by mono-N-methylation of 1,3,5-tris(4′-aminophenyl) benzene (TAPB) and structurally characterized. [NHMe]3TAPB acts as a selective fluorescent sensor for picric acid (PA) with a detection limit as low as 2.25 ppm at a signal to noise ratio of 3. Other related analytes (i.e. TNT, DNT and DNB) show very little effect on the fluorescence intensity of [NHMe]3TAPB. The selectivity is triggered by proton transfer from picric acid to the fluorophore and ground-state complex formation between the protonated fluorophore and picrate anion through hydrogen bonding interactions. The fluorescence lifetime measurements reveal static nature of fluorescence quenching.  相似文献   

9.
The interactions between room temperature ionic liquids (RTILs) and weak fluorescent chemicals still remain unclear, which hinders the complete and efficient utilization of these “green” solvents in fluorescent analyses of organic chemicals. Herein, we reported the effects of four RTILs, [C8MIM]BF4, [C14MIM]BF4, [C8MIM]PF6 and [C14MIM]PF6, on fluorescence behavior of 4-tert-octylphenol (4-t-OP). In the fortified concentration range of 0.2–1.0 mM, the quenching effects were increased with increasing concentrations of RTILs. However, no obvious variation of peak shape of 4-t-OP was observed in the quenching process, suggesting no formation of ground-state complex between fluorophores in 4-t-OP and quencher (ionic liquids). As for anion effect, the fluorescence quenching efficiency of 4-t-OP by BF4 - was greater than PF6 -, but the carbon chain length on the imidazolium ring had no significant relationship with fluorescence intensity of 4-t-OP. Both Ksv values (>1.0?×?103?L/mol.s) and the different temperature effects demonstrated that the quenching of 4-t-OP by four RTILs was the presence of dynamic and static quenching mechanism. The FI of dansyl chloride within [C8MIM]BF4 increased nearly 5-fold as compared to the control, showing a sensitizing effect on the strong fluorescent chemicals, while a quenching effect on 4-t-OP belonging to weak fluorescent chemicals. The fluorescence-enhanced amplitude of dansyl chloride in [C8MIM]PF6 was greater than [C8MIM]BF4. The fluorescence quenching of 4-t-OP by [C8MIM]PF6 did not belong to FRET phenomenon because of no overlap of emission spectrum of 4-t-OP and absorption spectrum of [C8MIM]PF6. When 0.6 mM [C8MIM]PF6 in acetonitrile was used as the solvent, the detection limit of 4-t-OP was 3.7 μg/L, and the linearity range was 0.01–0.8 mg/L (R2?=?0.9990). In summary, these results provide a theoretical foundation for the application of RTILs in weak fluorescent chemicals.  相似文献   

10.
DFT/TDDFT calculations were carried out to investigate the electronic structures, absorption and phosphorescence properties of a series of heteroleptic Ir(III) complexes consisting of two N-heterocyclic carbene ligands and a conjugated bicyclic N,N′-heteroaromatic (N?N) ligand. On the basis of the results reported herein, we attempt to explain the experimental observations according to which complex (mpmi)2Ir(pybi) (1) [Hmpmi = 1-(4-tolyl)-3-methyl-imidazole; Hpybi = 2-(pyridin-2-yl)-1H-benzo[d]imidazole] emits green light with an extremely high-quantum phosphorescence efficiency (Φ PL ) of 79.3%, while a relatively lower Φ PL (only 11%) was measured for (fpmi)2Ir(tfpypz) (2) [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C, C2′; tfpypz = 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridinato] emitting blue light by tuning the N?N ligands. Besides, we also designed (fpmi)2Ir(pyN3) (3) [pyN3H = 2-(5-(trifluoromethyl)-2H-1,2,4-triazol-3-yl)pyridine] and (fpmi)2Ir(pyN4) (4) [pyN4H = 2-(1H-tetrazol-5-yl)pyridine] to explore the influence of electron-withdrawing substituents on N?N ligands on the electronic and optical properties of these Ir(III) complexes. The results revealed that electron-withdrawing substituents can stabilise both HOMOs and LUMOs and induce HOMO–LUMO energy gap change. Moreover, the emission properties can be significantly tuned by introducing different N?N ligands. While new insights were gained on structural and electronic properties, the extremely high Φ PL of 1 was found to be not inherent to spin-orbital coupling effects, but determined by its large transition dipole moment (μS 1) upon S 0S 1 transition compared with that of 2. On the basis of these results, the designed complexes 3 and 4 are considered to be the promising candidates for blue-emitting phosphorescence materials with higher Φ PL than the complex 2.  相似文献   

11.
The luminescence kinetics of the Cd II ion at a wavelength of 441.6 nm has been studied experi-mentally in a high-pressure He-Cd mixture in the presence of Ar, Ne, Xe, and CCl4 impurities. Cadmium ions were excited through the bombardment of a cadmium foil heated up to 240°C by a pulsed electron beam with an electron energy of 150 keV, a pulse duration of 3 ns, and a current of 500 A. The constants of collisional quenching of the Cd II 5s 2 2 D 5/2 level by Ar, Ne, and Xe atoms and CCl4 molecules and the integral luminescence quenching constants of this level in the helium medium by these impurity gases have been determined. The constants of collisional quenching appeared to be 8.1 × 10−12 (Ar), 1.2 × 10−12 (Xe), 1.5 × 10−13 (Ne), and 1.8 × 10−10 cm3/s (CCl4, for λ = 325 nm), while the integral constants were found to be, respectively, 4.1 × 10−11, 3.4 × 10−11, 9.5 × 10−12, 1.4 × 10−9 cm3/s for Ar, Ne, Xe, and CCl4 at a buffer gas pressure of 1 atm. Original Russian Text ? A.I. Miskevich, Liu Tao, 2009, published in Optika i Spektroskopiya, 2009, Vol. 107, No. 1, pp. 45–49.  相似文献   

12.
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   

13.
The fluorescence quenching of coumarin derivative, 4-(5-chloro-3-furan-2-yl-benzofuran-2-yl)-6-methyl-2H-chromen-2-one (ClFBMC), in the presence of aniline in different proportion of benzene-acetonitrile mixture was studied by means of steady-state measurement (296 K). The quenching process was characterized by Stern-Volmer (S-V) plots, which display positive (upward) deviation. The positive deviation from linearity suggests that the quenching is due to the simultaneous presence of dynamic and static quenching, which is interpreted in terms of the ground-state complex formation and the sphere of action static quenching model. The sphere of action static quenching model agrees very well with experimental results. Further with the use of finite sink approximation model, it is concluded that the bimolecular quenching reactions are diffusion-limited. Various rate parameters for the fluorescence quenching process have been determined. The value of quenching constant kq increases with increase in dielectric constant of the mixed solvent, suggesting the charge transfer character of the excited complex.  相似文献   

14.
In the present work, we have carried out energy transfer studies using newly synthesised derivatives of thiophene substituted 1,3,4-oxadiazoles namely, 2-(-4-(thiophene-3-yl)phenyl)-5-(5-(thiophene-3-yl)thiophene-2-yl)-1,3,4-oxadiazole [TTO], 2-(-4-(benzo[b]thiophene-2-yl)phenyl)-5-(5-(benzo[b]thiophene-2-yl)-1,3,4-oxadiozole [TBO] and 2-(4-(4-(trifluoromethyl)phenyl)phenyl)-5-(5-(4-(trifluoromethyl)phenyl)thiophen-2-yl)-1,3,4-oxadiazole [TMO] as donors and laser dye coumarin-334 as acceptor in ethanol and dye-doped polymer (poly(methyl methacrylate) (PMMA)) media following steady-state and time-resolved fluorescence methods. Bimolecular quenching constant (k q), translation diffusion rate parameter (k d), diffusion length (D l), critical transfer distance (R 0), donor- acceptor distance (r) and energy transfer efficiency (E T) are calculated. It is observed that, critical transfer distance is more than the diffusion length for all the pairs. Further, bimolecular quenching constant is also more than the translation diffusion rate parameter. Hence, our experimental findings suggest that overall energy transfer is due to Förster resonance energy transfer (FRET) between donor and acceptor in both the media and for all the pairs. In addition, considerable increase in fluorescence intensity and energy transfer efficiency is observed in dye-doped polymer matrix systems as compared to liquid media. This suggests that, these donor-acceptor pairs doped in PMMA matrix may be used for applications such as energy transfer dye lasers (ETDL) to improve the efficiency and photostability, to enhance tunability and for plastic scintillation detectors.  相似文献   

15.
ABSTRACT

Microscale crystals of a 2D layered Mn-MOF [Mn2(TylP)4]n (TylP=5-(1,2,4-triazol-1-yl)isophthalic) with a thiolate-bridged binuclear Mn(II) node similar to the active site of the [MnAu]-hydrogenase were prepared. This material shows high catalytic activity for visible-light-driven hydrogen production under the illumination of white LED or direct sunlight. The turn-over frequency of the catalyst can reach up to 6?h?1. In this study, the heterogeneous nature and recyclability of the catalyst, as well as the factors that affect the catalytic activity have been investigated and described. Moreover, the photocatalytic mechanism for the hydrogen generation of [Mn2(TylP)4]n has also been proposed, based on fluorescence spectra and cyclic voltammetry.  相似文献   

16.
Intermolecular photoinduced electron transfer (PET) in a gas phase was studied using carbazole vapor fluorescence quenching by halomethanes (CHCl3, CH2Br2, CCl4, CHBr3). The fluorescence quenching rate constants k q changing from 2.3·105 sec–1·torr–1 in mixtures with CHCl3 to 4.6·106 sec–1·torr–1 in mixtures with CHBr3 at a constant temperature of 403 K were estimated. The dependence of the carbazole fluorescence decay rates in the presence of halomethanes on the free energy change G during transfer of the electron from carbazole to halomethanes is considered. It is suggested to take into account the influence of the vibrational energy of the carbazole molecule E vib and its temperature changes in estimation of the G values. The differences between PET in the gas and liquid phases were analyzed. It is found that for mixtures with CCl4 and CHBr3 the negative temperature dependence of k q is observed, when the decay rates and efficiencies of the intermolecular PET decreased with temperature increase in the range 403–573 K, i.e. these mixtures the electron transfer is not a barrier-restricted process.  相似文献   

17.
The laser-induced fluorescence excitation spectrum of jet-cooled CoF molecules has been studied in the range of 18 800–22 000 cm−1. Ten observed vibronic bands have been classified into three transitions with the 0–0 band at 18 909, 19 236, and 20 654 cm−1, assigned as the [18.8]3Φ4X3Φ4, [19.2]3Φ4X3Φ4, and [20.6]3Γ5X3Φ4 transition, respectively, the two 3Φ states, [18.8]3Φ and [19.2]3Φ, are consistent with Adam’s results (10). The previously unanalyzed [20.6] state is identified in the current work. A rotational analysis of [20.6]3Γ5X3Φ4 transition has been performed and effective equilibrium molecular constants have been determined for the first time. In addition, lifetime measurements of the three electronic transitions were carried out under the collision-free condition. From the lifetime analysis, we consider that the V=1, 2, and 3 vibrational levels of [18.8]3Φ state are perturbed by another state.  相似文献   

18.
Vibrational bands belonging to the [15.0] 2Δ5/2-A2Δ5/2, [15.0] 2Δ5/2-X2Π3/2, and [15.0] 2Π3/2-X2Π3/2 electronic transitions of NiCl have been observed in the 14 000-16 000 cm−1 region. The [15.0] 2Δ5/2 and [15.0] 2Π3/2 states are identified for the first time. The observed bands have been recorded at high spectral resolution using several techniques, which include intracavity laser spectroscopy (ILS), Fourier transform emission spectroscopy (FTS), and laser induced fluorescence (LIF) spectroscopy. For the ILS absorption spectra, NiCl molecules were produced in a nickel hollow cathode operated with a small amount of CCl4. For the FTS emission spectra, excited NiCl molecules were produced in a King-type carbon tube furnace loaded with NiCl2 and heated to 1600 °C. In the LIF work, NiCl molecules were produced by reacting laser-ablated nickel with PCl3 seeded in argon. Detailed analysis of rotational transition lines indicates that the observed [15.0] 2Δ5/2 and [15.0] 2Π3/2 states are only separated by 10 cm−1 and are interacting with each other. Molecular constants for these newly observed electronic states are reported.  相似文献   

19.
Three Ruthenium(II) polypyridine complexes, [Ru(phen)2(mipc)]2+(1), [Ru(bpy)2(mipc)]2+ (2) and [Ru(dmb)2(mipc)]2+(3) [mipc?=?2-(6-methyl-3-(1H-imidazo[4, 5-f][1,10]-phenanthroline-2-yl)-4H-chromene-4-one, phen?=?1,10-phenanthroline,bpy?=?2, 2′bipyridine,dmb?=?4, 4′-dimethyl-2, 2′-bipyridine] have been synthesized and characterized by elemental analysis, IR, UV–Vis, 1H& 13C NMR and mass spectra. The DNA-binding properties of the Ruthenium(II) complexes were investigated by spectrophotometric methods, viscosity measurements and light switch studies. These three complexes have been focused on photo activated cleavage studies with pBR-322 and antimicrobial studies. Experimental results indicate that the three complexes intercalate into DNA base pairs and follows the order of 1?>?2?>?3 respectively. Molecular docking studies also support the DNA interactions with complexes through hydrogen bonding and vander Waal’s interactions. Cytotoxicity studies with Hela cell lines has been revealing about anti tumor activity of these complexes.  相似文献   

20.
Eosin Y belongs to a xanthene group. It is an anionic fluorescent dye. The absorbance and fluorescence of Eosin Y have been investigated in a series of alkanols (methanol to propanol). When the solvents are added to the aqueous solution of Eosin Y (EY) the absorbance and fluorescence intensity are enhanced. The alkanols are found to affect the absorption and fluorescence spectra of the dye. On the basis of solvent adsorption model the binding constants of the dye with alkanols have been estimated. The interaction of solvent molecule with dye in aqueous solution is specific in nature. The fluorescence quenching of Eosin Y by the inorganic ions [Fe(CN)6]−3, [Fe(CN)6]−4 and Cl was also observed. The ions influenced the quenching process to different extents. The rate constants of quenching were calculated using the Stern-Volmer equation. The equilibrium constant of dye in presence of inorganic ions are determined by Scott equation.  相似文献   

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