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1.
A series of 4‐alkoxyethoxy‐N‐octadecyl‐1,8‐naphthalimides with intense blue fluorescence were designed and synthesized as polarity and spectrofluorimetric probes for the determination of proteins. In solvents of different polarities, the Stokes shifts of two dyes increased with increasing solvent polarity and fluorescence quantum yields decreased significantly, suggesting that electronic transiting from ground to excited states was π–π* in character. Dipole moment changes were estimated from solvent‐dependent Stokes shift data using a solvatochromic method based on bulk solvent polarity functions and the microscopic solvent polarity parameter (). These results were generally consistent with semi‐empirical molecular orbital calculations and were found to be quite reliable based on the fact that the correlation of the solvatochromic Stokes shifts with was superior to that obtained using bulk solvent polarity functions. Fluorescence data revealed that the fluorescence quenching of human serum albumin (HSA) by dyes was the result of the formation of a Dye–HSA complex. The method was applied to the determination of total proteins (HSA + immunoglobulins) in human serum samples and results were in good agreement with those reported by the research institute. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

2.
The UV/Vis absorption and fluorescence characteristics of 3‐cyano‐7‐hydroxycoumarin [ CHC ] and 7‐amino‐4‐methyl‐3‐coumarinylacetic acid [ AMCA‐H ] were studied at room temperature in several neat solvents and binary solvent mixtures of 1,4‐dioxane/acetonitrile. The effects of solvent on the spectral properties are analyzed using single and multi‐parameter solvent polarity scales. Both general solute/solvent interactions and hydrogen bond interactions are operative in these systems. The solvation of CHC and AMCA‐H dyes in 1,4‐dioxane/acetonitrile solvent mixtures has been studied. The solutes CHC and AMCA‐H are preferentially solvated by acetonitrile and a synergistic effect is observed for both molecules in dioxane/acetonitrile solvent mixtures. In addition, using the solvatochromic method the ground‐ and the excited‐state dipole moments of both the dyes were calculated. The ground‐ and excited‐state dipole moments, absorption and emission maxima and HOMO–LUMO gap were also estimated theoretically using B3LYP/6–311+ G (d,p) level of theory in the gaseous phase, dioxane and acetonitrile solvents. Furthermore, changes in dipole moment values were also calculated using the variation of Stokes shift with the molecular–microscopic empirical solvent polarity parameter ( ). The observed excited‐state dipole moments are larger than their ground‐state counterparts, indicating a substantial redistribution of the electron densities in a more dipolar excited state for both coumarins investigated.  相似文献   

3.
The effect of solvents of varying polarity and hydrogen bonding ability, solvent mixture and silver nanoparticles on the photophysical properties of a ketocyanine dye, 2,5‐di[(E)‐1‐(4‐diethylaminophenyl) methylidine]‐1‐cyclopentanone (2,5‐DEAPMC), is investigated at room temperature. Solvent effect is analyzed using Lippert–Mataga bulk polarity function, Reichardt's microscopic solvent polarity parameter, and Kamlet's and Catalan's multiple linear regression approaches. The spectral properties better follow Reichardt's microscopic solvent polarity parameter than the Lippert–Mataga bulk polarity function. This indicates that both general and specific solute–solvent interactions are operative. Kamlet's and Catalan's multiple linear regression approaches indicate that polarizability/dipolarity solvent influences are greater than hydrogen bond donor and hydrogen bond acceptor solvent influences. The solvatochromic correlations are used to estimate excited state dipole moment using the experimentally determined ground state dipole moment. The excited state dipole moment of the dye is found to be larger than its corresponding ground state dipole moment and ground and excited state dipole moments are not parallel, but subtend an angle of 77°. The absorption and emission spectra are modulated in the presence silver nanoparticles. The fluorescence of 2,5‐DEAPMC is quenched by silver nanoparticles. The possible fluorescence quenching mechanisms are discussed. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

4.
A new A–π–D–π–A phenothiazine derivative, 2,2′‐((10‐octyl‐10H‐phenothiazine‐3,7‐diyl)bis (ethene‐2,1‐diyl))bis(1‐ethyl‐3,3‐dimethyl‐3H‐indol‐1‐ium)iodide (PTZ‐BEI) was prepared and fully characterized using infra‐red (IR), 1H nuclear magnetic resonance (NMR), 13C NMR, ultraviolet–visible light and mass spectra. Electronic spectra of PTZ‐BEI solutions in solvents with different polarities displayed absorption bands (λmax) related to intramolecular charge transfer. In addition, the emission spectra of PTZ‐BEI solutions were strongly solvent dependent for both wavelength and intensity. Stokes’ shift ( increased with increasing solvent polarity up to 4105 cm?1 in the most polar solvent, dimethylformamide. The linear solvation‐energy relationship was utilized to investigate solvent dependency of the Stokes’ shifts. Relative quantum yield (φ ) of PTZ‐BEI was calculated. Finally, density functional theory was employed at the B3LYP level for geometrical optimization and simulation of electron spectra for the PTZ derivative in gaseous and solvated states to explore the solvent effect.  相似文献   

5.
A series of flavonyl‐2,4‐thiazolidinedione, imidazolidinedione and rhodanine derivatives were tested for their antioxidant activity as scavengers of oxygen free radicals. Free radical scavenging activities, including superoxide anion radical , hydroxyl radical (HO?) and 2,2′‐diphenyl‐1‐picrylhydrazyl free radical have been evaluated using chemiluminescence, electron paramagnetic resonance and spin trapping with 5,5‐dimethyl‐1‐pyrroline‐1‐oxide as a spin trap. Potassium superoxide in dimethylsulfoxide and 18‐crown‐6 ether were used for the production of . Hydroxyl radical was generated using the Fenton reaction. Ten of the eleven examined compounds exhibited decrease in chemiluminescence, but there were large differences in the decrease, ranging from 16% to 89%; also, two of these compounds increased light emission by about 200%. On the contrary, all compounds tested exhibited 30–68% scavenging HO? and 25–96% scavenging the DPPH? radical respectively. Possible mechanisms are proposed to explain the results. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

6.
The direct effect of the four catecholamines (adrenaline, noradrenaline, dopamine and isoproterenol) on superoxide anion radicals () was investigated. The reaction between 18‐crown‐6‐ether and potassium superoxide in dimethylsulfoxide was used as a source of . The reactivity of catecholamines with was examined using chemiluminescence, reduction of nitroblue tetrazolium and electron paramagnetic resonance spin‐trapping techniques. 5,5‐Dimethyl‐1‐pyrroline‐N‐oxide was included as the spin trap. The results showed that the four catecholamines were effective and efficient in inhibiting chemiluminescence accompanying the potassium superoxide/18‐crown‐6‐ether system in a dose‐dependent manner over the range 0.05–2 mm in the following order: adrenaline > noradrenaline > dopamine > isoproterenol, with, IC50 = 0.15 ± 0.02 mm 0.21 ± 0.03 mm , 0.27 ± 0.03 mm and 0.50 ± 0.04 mm , respectively. The catecholamines examined also exhibited a strong scavenging effect towards when evaluated this property by the inhibition of nitroblue tetrazolium reduction (56–73% at 1 m concentration). A very similar capacity of scavenging was monitored in the 5,5‐dimethyl‐1‐pyrroline‐N‐oxide spin‐trapping assay. The results suggest that catecholamines tested may involve a direct effect on scavenging radicals. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

7.
The tetracycline family antibiotics are widely used as human and veterinary treatments. The drugs are effective as antibiotics and also show antimicrobial and non‐microbial action. However, the antioxidant properties of tetracyclines have not been characterized in aprotic media. To better understand their biological functions, the in vitro superoxide anion radical () scavenging activities of tetracycline, chlortetracycline, oxytetracycline, doxycycline and methacycline were characterized, along with a very efficient scavenger, tiron, in dimethyl sulphoxide (DMSO), using ultra‐weak chemiluminescence (CL). We found that tetracycline, chlortetracycline and doxycycline efficiently inhibited CL from the ‐generating system at concentration levels of 0.02–1.0 mmol/L. Methacycline and oxytetracycline were the scavengers at concentration levels of 0.01–0.1 mmol/L, whereas when their concentration was lowered the drugs were capable of generating , leading to CL enhancement. For all the data obtained in this study, the scavenging activity for the compounds tested decreased in the following order: tetracycline > doxycycline > chlortetracycline > tiron methacycline > oxytetracycline. These results indicate that the tetracycline drugs directly alter redox chemistry in aprotic media. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

8.
A series of controllable emissions SrWO4:Eu3+ and charge‐compensated SrWO4: (m = 0.01 or 0.20) phosphors was successfully prepared via a simple co‐precipitation method. The energy transfer mechanism was studied based on the Huang's theory. A low magnitude of Huang‐Rhys factor (10?2) was calculated using phonon sideband spectra. The Judd–Ofelt parameters Ωλ (λ = 2, 4 and 6) of Eu3+‐activated SrWO4 doped with charge compensation were obtained. The calculated Commission Internationale de l'Eclairage chromaticity coordinates were found to be about (0.67, 0.33) for SrWO4: and charge‐compensated SrWO4: phosphors, which coincided with the National Television Standard Committee system standard values for red. A white light emission was obtained under 362 nm excitation. The correlated color temperature was computed by a simple equation to characterize light sources. Thus, warm white light‐emitting diodes with higher Ra can be constructed by combining as‐prepared high efficiency, low correlated color temperature and high color purity phosphor.  相似文献   

9.
This article reports on the optical properties of Er3+ ions doped CdO–Bi2O3–B2O3 (CdBiB) glasses. The materials were characterized by optical absorption and emission spectra. By using Judd–Ofelt theory, the intensity parameters Ωλ (λ = 2, 4, 6) and also oscillatory strengths were calculated from the absorption spectra. The results were used to compute the radiative properties of Er3+:CdBiB glasses. The concentration quenching and energy transfer from Yb3+–Er3+ were explained. The stimulated emission cross‐section, full width at half maximum (FWHM) and FWHM × values are also calculated for all the Er3+:CdBiB glasses. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

10.
Rapid, simple and highly sensitive flow‐injection (FI) chemiluminescence (CL) and flow‐injection electrogenerated chemiluminescence (ECL) methods were developed for the determination of escitalopram oxalate (ESC), a selective serotonin reuptake inhibitor used as an antidepressant drug. The CL method was based on the CL reaction of ESC with acidic cerium(IV) and tris(2,2'‐bipyridyl)ruthenium(II) (Ru). Various experimental parameters affecting CL intensity were carefully studied and optimised. The method enabled the determination of 0.001‐50 µg/mL of ESC in bulk form with a correlation coefficient r = 0.9999. The limit of detection (LOD) was 0.01 ng/mL (S/N = 3). The ECL method was based on the ECL reaction of Ru with the drug in an acidic medium, permitting the determination of ESC in the range of 0.00001‐70 µg/mL with r = 0.9999 and LOD of 1 x 10‐4 ng/mL. The proposed methods were applied to the determination of ESC in commercial tablets. The results were compared statistically with those obtained from a published method using t‐ and F‐tests. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

11.
Free radical activity towards superoxide anion radical (), hydroxyl radical (HO?) and 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH?) of a series of novel thiazolidine‐2,4‐dione derivatives (TSs) was examined using chemiluminescence, electron paramagnetic resonance (EPR) and EPR spin trapping techniques. 5,5‐Dimethyl‐1‐pyrroline‐N‐oxide (DMPO) was applied as the spin trap. Superoxide radical was produced in the potassium superoxide/18‐crown‐6 ether dissolved in dimethyl sulfoxide. Hydroxyl radical was generated in the Fenton reaction (Fe(II) + H2O2. It was found that TSs showed a slight scavenging effect (15–38% reduction at 2.5 mmol/L concentration) of the DPPH radical and a high scavenging effect of (41–88%). The tested compounds showed inhibition of HO? ‐dependent DMPO‐OH spin adduct formation (the amplitude of EPR signal decrease ranged from 20 to 76% at 2.5 mmol/L concentration. Our findings present new group compounds of relatively high reactivity towards free radicals. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

12.
Recent reviews evidence that the naturally occurring compounds containing the chromone skeleton exhibit antiradical activities, providing protection against oxidative stress. The antioxidant activities of 13 new synthesized chromonyl‐2,4‐thiazolidinediones, chromonyl‐2,4‐imidazolidinediones and chromonyl‐2‐thioxoimidzolidine‐4‐ones were evaluated using in vitro antioxidant assays, including superoxide anion radical (), hydroxyl radical (), 2,2‐diphenyl‐1‐picryl‐hydrazyl free radical (DPPH?) scavenging capacity and total antioxidant capacity ferric ion reducing activity. Superoxide anion radical was produced using potassium superoxide/18‐crown‐6‐ether dissolved in dimethylsulfoxide, and the Fenton‐like reaction (Fe(II) + H2O2) was a generator of hydroxyl radicals. Chemiluminescence, spectrophotometry, electron paramagnetic resonance (EPR) and 5,5‐dimethyl‐1‐pyrroline‐N‐oxide (DMPO) as the spin trap were the measurement techniques. The results showed that the majority of the chromone derivatives tested showed a strong scavenging effect towards free radicals, similar to the chemiluminescence reaction with superoxide anion radical with a high activity, inhibition of the DMPO‐OOH radical EPR signal (24–58%), the DMPO‐OH radical EPR signal (4–75%) and DPPH radical EPR signal (6–100%) at 1 mmol/L. Several of the examined compounds exhibited the high reduction potentials. The results obtained show that the new synthesized chromone derivatives may directly scavenger reactive oxygen species and thus may play a protective role against oxidative damage. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

13.
The change in photophysical properties of the organic molecule due to solvatochromic effect caused by different solvent environments at room temperature gives information about the dipole moments of 3‐N‐(N′‐methylacetamidino)benzanthrone (3‐MAB). The quantum yield, fluorescence lifetime of 3‐MAB was measured in different solvents to calculate radiative and non‐radiative rate constants. The results revealed that the excited state dipole moment (μe) is relatively larger compared to the ground state dipole moment (μg), indicating the excited state of the dye under study is more polar than the ground state and the same trend is noticed with theoretical calculations performed using the CAM‐B3LYP/6‐311+G(d,p) method. Further, the study on preferential solvation was carried out for 3‐MAB dye in ethyl acetate–methanol solvent mixture. The fluorescence quenching method has been employed for the detection of dopamine using 3‐MAB as fluorescent probe, using steady‐state and time resolved methods at room temperature. The method enables dopamine in the micro molar range to be detected. Also, an attempt to verify the quenching process by employing different models has been tried. Various rate parameters are measured using these models, our results indicates the quenching process is diffusion limited.  相似文献   

14.
Itaconic acid (IA) has a high potential to be used as a bio‐based platform chemical and its biocatalytic production via fermentation has significantly improved within the last decade. Additionally downstream processing using reactive extraction (RE) was described, potentially enabling a more efficient sustainable bioprocess producing IA. The bottleneck to overcome is the connection of up‐ and downstream processing, caused by lack of biocompatibility of the RE systems and direct application to fermentation broth. Within this study, a biocompatible RE system for IA is defined (pH dependency, extraction mechanism) and used for direct application to a fermentation broth. By optimizing the biocatalyst, the production medium, and the extraction system in an integrated approach, it was possible to define critical parameters that enabled a tuning of the overall bioprocess. With an extraction yield of YIA = 0.80 ± 0.03, IA could be produced as sole carboxylic acid ( = 0.490 mol/kgaq) using a RE system consisting of ethyl oleate as organic solvent and tri‐n‐octylamine as extractant ( = 0.6 mol/kgorg). This work is a proof of concept and demonstrates that by joint consideration of up‐ and downstream processing, optimized bioprocesses can be developed.  相似文献   

15.
In this work several molecular properties of symmetrically disubstituted formaldehyde and thioformaldehyde have been studied using a quantum chemistry approach based on density functional theory. Five-membered heteroaromatic rings containing a single group 16 heteroatom were taken into account as the substituents (i.e., furan-2-yl, thiophen-2-yl, selenophen-2-yl, tellurophen-2-yl, and the experimentally as yet unknown polonophen-2-yl). For the resulting ten formaldehyde and thioformaldehyde derivatives, the geometry, energetics, frontier molecular orbitals, dipole moment and polarizability of their molecules were examined in order to establish the effect of ring heteroatom on these properties. Furthermore, these properties were also determined for the molecules in three solvents of low polarity (benzene, chloroform, and dichloromethane) in order to expand our study to include solvent effects. The dipole moment and polarizability of the investigated molecules show regular variations when the ring heteroatom descends through group 16 and the solvent polarity grows. The heteroatom and/or solvent effects on the part of the studied properties are, however, more complex. An attempt is made to rationalize the observed variations in the molecular properties. The conformational behavior of the investigated molecules was also explored and the conformationally weighted values of dipole moment and polarizability are presented.
Graphical abstract Some molecular properties of symmetrically disubstituted formaldehyde and thioformaldehyde
  相似文献   

16.
《Proteins》2018,86(5):581-591
We compare side chain prediction and packing of core and non‐core regions of soluble proteins, protein‐protein interfaces, and transmembrane proteins. We first identified or created comparable databases of high‐resolution crystal structures of these 3 protein classes. We show that the solvent‐inaccessible cores of the 3 classes of proteins are equally densely packed. As a result, the side chains of core residues at protein‐protein interfaces and in the membrane‐exposed regions of transmembrane proteins can be predicted by the hard‐sphere plus stereochemical constraint model with the same high prediction accuracies (>90%) as core residues in soluble proteins. We also find that for all 3 classes of proteins, as one moves away from the solvent‐inaccessible core, the packing fraction decreases as the solvent accessibility increases. However, the side chain predictability remains high (80% within ) up to a relative solvent accessibility, , for all 3 protein classes. Our results show that % of the interface regions in protein complexes are “core”, that is, densely packed with side chain conformations that can be accurately predicted using the hard‐sphere model. We propose packing fraction as a metric that can be used to distinguish real protein‐protein interactions from designed, non‐binding, decoys. Our results also show that cores of membrane proteins are the same as cores of soluble proteins. Thus, the computational methods we are developing for the analysis of the effect of hydrophobic core mutations in soluble proteins will be equally applicable to analyses of mutations in membrane proteins.  相似文献   

17.
The effects of solvent polarity on absorption and fluorescence spectra of biologically active compounds (chlorogenic acid (CGA) and caffeic acids (CA)) have been investigated. In both spectra pronounced solvatochromic effects were observed with shift of emission peaks larger than the corresponding UV‐vis electronic absorption spectra. From solvatochromic theory the ground and excited‐state dipole moments were determined experimentally and theoretically. The differences between the excited and ground state dipole moment determined by Bakhshiev, Kawski–Chamma–Viallet and Reichardt equations are quite similar. The ground and excited‐state dipole moments were determined by theoretical quantum chemical calculation using density function theory (DFT) method (Gaussian 09) and were also similar to the experimental results. The HOMO‐LUMO energy band gaps for CGA and CFA were calculated and found to be 4.1119 and 1.8732 eV respectively. The results also indicated the CGA molecule is more stable than that of CFA. It was also observed that in both compounds the excited state possesses a higher dipole moment than that of the ground state. This confirms that the excited state of the hydroxycinnamic compounds is more polarized than that of the ground state and therefore is more sensitive to the solvent. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

18.
The effect of solvents of varying polarity on the absorption and fluorescence emission of the Schiff base, 2‐{[3‐(1H‐benzimidazole‐2‐yl) phenyl]carbonoimidoyl}phenol, was studied using Lippert‐Mataga bulk polarity function, Reichardt's microscopic solvent polarity parameter and Kamlet's multiple linear regression approach. The spectral properties follow Reichardt's microscopic solvent polarity parameter better than Lippert‐Mataga bulk polarity parameter, indicating the presence of both general solute–solvent interactions and specific interactions. Catalan's multiple linear regression approach indicates the major role of solvent polarizability/dipolarity influence compared with solvent acidity or basicity. The solvatochromic effect was utilized to calculate the dipole moments of ground and excited states of the Schiff base using different methods. Bathochromic shift in the emission spectrum and the increase in dipole moment in the excited state signifies the intramolecular charge transfer character in the emitting singlet state. Fluorescence quenching by aniline was also studied in 1,4‐dioxane and n‐butanol, and the results were analyzed using sphere of action static quenching and finite sink approximation models. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

19.
Polarization‐dependent second‐harmonic generation (P‐SHG) microscopy is used to characterize molecular nonlinear optical properties of collagen and determine a three‐dimensional (3D) orientation map of collagen fibers within a pig tendon. C6 symmetry is used to determine the nonlinear susceptibility tensor components ratios in the molecular frame of reference and , where the latter is a newly extracted parameter from the P‐SHG images and is related to the chiral structure of collagen. The is observed for collagen fibers tilted out of the image plane, and can have positive or negative values, revealing the relative polarity of collagen fibers within the tissue. The P‐SHG imaging was performed using a linear polarization‐in polarization‐out (PIPO) method on thin sections of pig tendon cut at different angles. The nonlinear chiral properties of collagen can be used to construct the 3D organization of collagen in the tissue and determine the orientation‐independent molecular susceptibility ratios of collagen fibers in the molecular frame of reference.   相似文献   

20.
The weathering of volcanic rocks contributes significantly to the global silicate weathering budget, effecting carbon dioxide drawdown and long‐term climate control. The rate of chemical weathering is influenced by the composition of the rock. Rock‐dwelling micro‐organisms are known to play a role in changing the rate of weathering reactions; however, the influence of rock composition on bio‐weathering is unknown. Cyanobacteria are known to be a ubiquitous surface taxon in volcanic rocks. In this study, we used a selection of fast and slow growing cyanobacterial species to compare microbial‐mediated weathering of bulk crystalline rocks of basaltic and rhyolitic composition, under batch conditions. Cyanobacterial growth caused an increase in the pH of the medium and an acceleration of rock dissolution compared to the abiotic controls. For example, Anabaena cylindrica increased the linear release rate () of Ca, Mg, Si and K from the basalt by more than fivefold (5.21–12.48) and increased the pH of the medium by 1.9 units. Although A. cylindrica enhanced rhyolite weathering, the increase in was less than threefold (2.04–2.97) and the pH increase was only 0.83 units. The values obtained with A. cylindrica were at least ninefold greater with the basalt than the rhyolite, whereas in the abiotic controls, the difference was less than fivefold. Factors accounting for the slower rate of rhyolite weathering and lower biomass achieved are likely to include the higher content of quartz, which has a low rate of weathering and lower concentrations of bio‐essential elements, such as, Ca, Fe and Mg, which are known to be important in controlling cyanobacterial growth. We show that at conditions where weathering is favoured, biota can enhance the difference between low and high Si‐rock weathering. Our data show that cyanobacteria can play a significant role in enhancing rock weathering and likely have done since they evolved on the early Earth.  相似文献   

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