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1.
《Inorganica chimica acta》1988,153(2):115-118
Luminescence in the 600 nm region from aqueous solutions of Zn7metallothionein (ZnMT) has been studied as a function of the extent of substitution of the ZnMT with Cu+. The steady state emission intensity shows a strong correlation with cluster formation. Analysis of the emission decay curves obtained by single photon-counting techniques using a multiexponential decay function, indicates that three components are responsible for the observed emission intensity. A short lived component exhibits a lifetime of 20 ns, while the two longer lived components exhibit lifetimes in the 1 μ range at room temperature. The longer-lived emission is assigned to the excited triplet states of the CuS chromophore, most probably the metal-centered 3d94s1.  相似文献   

2.
The sensitive and reliable detection of Hg2+ and CN as harsh environmental contaminants are of great importance. In view of this, a novel ‘on–off–on’ fluorescent probe based on nitrogen-rich silicon quantum dots (NR-SiQDs) has been designed for sensitive detection of Hg2+ and CN ions in aqueous medium. NR-SiQDs were synthesized using a facile, one-step, and environment friendly procedure in the presence of 3-aminopropyl trimethoxysilane (APTMS) and ascorbic acid (AA) as precursors, with l -asparagine as a nitrogen source for surface modification. The NR-SiQDs exhibited strong fluorescence emission at 450 nm with 42.34% quantum yield, satisfactory salt tolerance, and superior photostability and pH stability. The fluorescence emission was effectively quenched using Hg2+ (turn-off) due to the formation of a nonfluorescent stable NR-SiQDs/Hg2+ complex, whereas after the addition of cyanide ions (CN), Hg2+ ions could be leached from the surface of the NR-SiQDs and the fluorescence emission intensity of the quenched NR-SiQDs fully recovered (turn-on) due to the formation of highly stable [Hg(CN)4]2− species. After optimizing the response conditions, the obtained limits of detection were found to be 53 nM and 0.46 μM for Hg2+ and CN, respectively. Finally, the NR-SiQD-based fluorescence probe was utilized to detect Hg2+ and CN ions in water samples and satisfactory results were obtained, suggesting its potential application for environmental monitoring.  相似文献   

3.
The pH-dependent heterometallic complex formation with p-sulfonatothiacalix[4]arene (TCAS) as bridging ligand in aqueous solutions was revealed by the use of spectrophotometry, nuclear magnetic relaxation and fluorimetry methods. The novelty of the structural motif presented is that the appendance of emission metal center ([Ru(bpy)3]2+) is achieved through the cooperative non-covalent interactions with the upper rim of TCAS. The second metal block (Fe(III), Fe(II) and Mn(II)), bound with the lower rim of TCAS in the inner sphere coordination mode is serving as quencher of [Ru(bpy)3]2+ emission. The difference between the complex ability of Fe(III) and Fe(II) ions provides pH conditions for redox-dependent emission of [Ru(bpy)3]2+.  相似文献   

4.
Pike olfactory nerves labeled with pyrene and illuminated at 340 nm showed a highly resolved monomer fluorescence emission and a broad excimer emission band at longer wavelength. The excimer formation being controlled by lateral diffusion in the membrane lipids, the ratio of both maxima emission amplitudes is a fluidity parameter and was found to depend on temperature. When these nerves were stimulated, this ratio (F) underwent a small transient decrease (ΔFF range = 10?3 to 10?4), synchronous with the propagated impulse. These findings may be interpreted as a transient decreased fluidity of the membrane lipids during excitation  相似文献   

5.
Hu Y  Yang JP  Liu JS 《Luminescence》2012,27(5):437-440
Mn‐doped willemite (Zn2SiO4:Mn) green phosphor were synthesized by sol–gel technology. The effect of the addition of sodium, as in the composition Zn(1.92 – X) NaXMn0.08SiO4, on the emission behavior was studied. FT–IR and EPR results revealed that sodium ion is incorporated into the lattice and results in the formation of isolated Mn2+ and Mn–Mn pairs. The maximum emission intensity of the sample under ultraviolet (UV) excitation occurred at the sodium concentration of x = ~0.03. The green emission at about 525 nm is assigned to Mn2+–Mn2+ pair centres on nearest neighbour Zn sites. The highest intensity of the green emission for x = ~0.03 is well close to the highest concentration of the Mn2+–Mn2+ pair. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

6.
Here, a simple and portable paper-based analytical device (PAD) based on the inherent capability of carbon quantum dots (CQDs) to serve as a great emitter for the bis(2,4,6-trichlorophenyl)oxalate (TCPO)–hydrogen peroxide (H₂O₂) chemiluminescence (CL) reaction is introduced for the detection of harmful mercury ions (Hg2+). The energy is transferred from the unstable reaction intermediate (1,2-dioxetanedione) to CQDs, as acceptors, and an intensive orange-red CL emission is generated at ~600 nm, which is equal to the fluorescence emission wavelength of CQDs. The analytical applicability of this system was examined for the determination of Hg2+. It was observed that Hg2+ could significantly quench the produced emission, which can be attributed to the formation of a stable and nonluminescent Hg2+–CQDs complex. Accordingly, a simple and rapid PAD was established for monitoring Hg2+, with a limit of detection of 0.04 μg ml−1. No interfering effect on the signal was found from other examined cations, indicating the acceptable specificity of the method. The designed assay was appropriately utilized to detect Hg2+ ions in cosmetic samples with high efficiency. It was characterized by its low cost, ease of use, and was facile but accurate and high selective for the detection of Hg2+ ions. In addition, the portability of this probe makes it suitable for on-site screening purposes.  相似文献   

7.
Isoprene basal emission (the emission of isoprene from leaves exposed to a light intensity of 1000 µmol m?2 s?1 and maintained at a temperature of 30 °C) was measured in Phragmites australis plants growing under elevated CO2 in the Bossoleto CO2 spring at Rapolano Terme, Italy, and under ambient CO2 at a nearby control site. Gas exchange and biochemical measurements were concurrently taken. Isoprene emission was lower in the plants growing at elevated CO2 than in those growing at ambient CO2. Isoprene emission and isoprene synthase activity (IsoS) were very low in plants growing at the bottom of the spring under very rich CO2 and increased at increasing distance from the spring (and decreasing CO2 concentration). Distance from the spring did not significantly affect photosynthesis making it therefore unlikely that there is carbon limitation to isoprene formation. The isoprene emission rate was very quickly reduced after rapid switches from elevated to ambient CO2 in the gas‐exchange cuvette, whereas it increased when switching from ambient to elevated CO2. The rapidity of the response may be consistent with post‐translational modifications of enzymes in the biosynthetic pathway of isoprene formation. Reduction of IsoS activity is interpreted as a long‐term response. Basal emission of isoprene was not constant over the day but showed a diurnal course opposite to photosynthesis, with a peak during the hottest hours of the day, independent of stomatal conductance and probably dependent on external air temperature or temporary reduction of CO2 concentration. The present experiments show that basal emission rate of isoprene is likely to be reduced under future elevated CO2 levels and allow improvement in the modelling of future isoprene emission rates.  相似文献   

8.
Leaf discs, but not detached leaves, exposed to L-methionine or S-methyl-L-cysteine emitted a volatile sulphur compound identified as methanethiol by different trapping systems and by GC. Methanethiol emission was analyzed using pumpkin (Cucurbita pepo) leaf discs. Emission was observed in darkness or light, however methanethiol emission was greately stimulated by light. Light-dependent emission started after a lag-time of 5–6 hr with an emission peak after 36–40 hr. Maximum rates obtained were in the range of 200 pmol methanethiol/min/cm2 leaf area. After a period of 42 hr about 60–80% of total methionine sulphur added was released as methanethiol. Addition of chloramphenicol did not alter the induction period nor the maximum emission rate of methanethiol in response to L-methionine. Emission was also observed in response to S-methyl-L-cysteine; however, the shorter lag-period for methanethiol formation suggests metabolism via a different enzyme system. In a cell-free system of pumpkin leaves methanethiol formation occured in response to L-methionine. Feeding experiments with L-[35S]methionine to leaf discs showed that more than 80% of methanethiol emitted was derived from the labelled methionine fed. These findings suggest that plants have the capacity to degrade L-methionine to methanethiol. Whole leaves fed L-methionine by the petiole system do not emit methanethiol, but this compound is formed and transported into the feeding solution. Thus, methanethiol is also produced by the intact leaf, but, in contrast to sulphide, is not released into the atmosphere. It is suggested that translocation of methanethiol may function as a signal for the regulation of sulphate uptake.  相似文献   

9.
Nanocrystalline SrS phosphors doped with Ce3+ ions at different concentrations (0.5, 1, 1.5 and 2 mol%) are synthesized via the solid‐state diffusion method (SSDM), which is suitable for the large‐scale production of phosphors in industrial applications. The as‐prepared samples are characterized using an X‐ray diffraction (XRD) technique, field emission scanning electron microscopy (FESEM), high‐resolution transmission electron microscopy (HRTEM) and energy‐dispersive X‐ray (EDX) analysis. The optical properties of these phosphors are analyzed using reflectance spectra, photoluminescence spectra and afterglow decay curves. The cubic structure of the SrS phosphor is confirmed by XRD analysis and the crystallite size calculated by Scherer's formula using XRD data shows the nanocrystalline nature of the phosphors. No phase change is observed with increasing concentrations of Ce3+ ions. The surface morphology of the prepared phosphors is determined by FESEM, which shows a sphere‐like structure and good connectivity of the grains. The authenticity of the formation of nanocrystalline phosphors is examined by HRTEM analysis. Elemental compositional information for the prepared phosphors is gathered by EDX analysis. Photoluminescence studies reveal that the emission spectra of the prepared phosphor shows broad band emission centered at 458 and 550 nm due to the transition of electrons from the 5d → 4f energy levels. The afterglow decay characteristics of different as‐synthesized SrS:Ce3+ nanophosphors are conceptually described. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

10.
Frequency up‐conversion (UC) emission from the Nd3+‐Yb3+/Nd3+‐Yb3+‐Li+ co‐doped gadolinium oxide (Gd2O3) phosphors prepared by the solution combustion technique in the visible range have been studied by using 980 nm near infrared (NIR) laser diode excitation. The crystalline structure and formation of the cubic phase has been confirmed with the help of X‐ray diffraction (XRD) studies. XRD peak shifts have been found towards the lower diffraction angle side in the case of the Nd3+‐Yb3+‐Li+ co‐doped phosphors. Surface morphology and particle size information have been observed by using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. Down‐conversion emission study under 351 nm excitation in the visible region for the Nd3+‐Yb3+/Nd3+‐Yb3+‐Li+ co‐doped phosphors has been performed. The UC emission bands lying in the green and red region arising from the Nd3+ ions have been enhanced by ~260 times, ~113 times due to incorporation of Li+ ions in the Nd3+‐Yb3+ co‐doped phosphors. Photometric characterization has been done for the Nd3+‐Yb3+/Nd3+‐Yb3+‐Li+ co‐doped phosphors. The present study suggests the capability of the synthesized phosphors in near‐infrared (NIR) to visible upconverter and luminescent device applications.  相似文献   

11.
Biophotons spontaneously emitted from radish root cells were detected using highly sensitive photomultiplier tube. Freshly isolated radish root cells exhibited spontaneous photon emission of about 4 counts s?1. Addition of hydrogen peroxide to the cells caused significant enhancement in biophoton emission to about 500 counts s?1. Removal of molecular oxygen using glucose/glucose oxidase system and scavengering of reactive oxygen species by reducing agents such are sodium ascorbate and cysteine completely diminished biophoton emission. Spectral analysis of the hydrogen peroxide-induced biophoton emission indicates that biophotons are emitted mainly in green–red region of the spectra. The data provided by electron paramagnetic resonance spin-trapping technique showed that formation of singlet oxygen observed after addition of H2O2 correlates with enhancement in biophoton emission. These observations provide direct evidence that singlet oxygen is involved in biophoton emission from radish root cells.  相似文献   

12.
《Luminescence》2003,18(3):162-172
The reaction of iron(III) tetrakis‐5,10,15,20‐(N‐methyl‐4‐pyridyl)porphyrin (Fe(III)TMPyP) with hydrogen peroxide (H2O2) and the catalytic activity of the reaction intermediates on the luminescent peroxidation of luminol in aqueous solution were studied by using a double‐mixing stopped‐flow system. The observed luminescence intensities showed biphasic decay depending on the conditions. The initial flashlight decayed within <1 s followed by a sustained emission for more than 30 s. Computer deconvolution of the time‐resolved absorption spectra under the same conditions revealed that the initial flashlight appeared during the formation of the oxo–iron(IV) porphyrin, TMPyPFe(IV) = O, which is responsible for the sustained emission. The absorption spectra 0.0–0.5 s did not reproduce well by a simple combination of the two spectra of Fe(III)TMPyP and TMPyPFe(IV) = O, indicating that transient species was formed at the initial stage. Addition of uric acid (UA) caused a significant delay in the initiation of the luminol emission as well as in the formation of the TMPyPFe(IV) = O. Both of them were completely diminished in the presence of UA equimolar with H2O2, while mannitol had no effect at all. The delay of the light emission as well as the appearance of TMPyPFe(IV) = O was directly proportional to the [UA]0 but other kinetic profiles were not changed significantly. Based on these observations and the kinetic analysis, we confirmed the involvement of the oxo–iron(IV) porphyrin radical cation, (TMPyP)·+Fe(IV) = O, as an obligatory intermediate in the rate‐determining step of the overall reaction, Fe(III)TMPyP + H2O2 → TMPyPFe(IV) = O, with a rate constant of k = 4.3 × 104/mol/L/s. The rate constants for the reaction between the (TMPyP)·+Fe(IV) = O and luminol, and between the TMPyPFe(IV) = O and luminol were estimated to be 3.6 × 106/mol/L/s and 1.31 × 104/mol/L/s, respectively. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

13.
Small ligand molecules, which can recognize thermodynamically unstable site within DNA, such as mismatch base pair, abasic site, and single-bulge, have attracted much attention because of their potential diagnostics and biological applications. In this paper, we describe the binding of cationic perylenediimide (cPDI) molecules to thymine-containing mismatch base pair in DNA and the formation of cPDI dimer at the mismatch site. The cPDI dimer exhibits a characteristic excimer emission at 650 nm. For T/T mismatch containing DNA, the switching behavior from the PDI dimer (650 nm) to the monomer (550 nm) emission in specific response to Hg2+ ion was observed.  相似文献   

14.
Čajánek  M.  Hudcová  M.  Kalina  J.  Lachetová  I.  Špunda  V. 《Photosynthetica》1999,37(2):295-306
Effects of short-term exposure to different irradiances on the function of photosystem 2 (PS2) were studied for barley grown at low (LI; 50 μmol m−2 s−1) and high (HI; 1 100 μmol m−2 s−1) irradiances. HI barley revealed higher ability to down-regulate the light-harvesting within PS2 after exposure to high irradiance as compared to LI plants. This ability was estimated from the light-induced decreases of F685/F742 and E476/E436 in emission and excitation spectra of 77 K chlorophyll (Chl) a fluorescence in vivo which was 65 and 10 % for HI plants as compared to 30 and 2 % for LI plants, respectively. For LI plants this protective down-regulation of the light-harvesting of PS2 was saturated at 430 μmol m−2 s−1, and progressive PS2 photodamage was induced at higher irradiances. After exposure of LI segments to 2 200 μmol m−2 s−1 a pronounced maximum at 700 nm appeared in emission spectrum of 77 K Chl a fluorescence. Based on complementary analysis of 77 K excitation spectra measured at the emission wavelength 685 nm we suggest that this emission maximum may be attributed to the formation of aggregates of light-harvesting complexes of PS2 (LHC2) with part of PS2 core during progressive PS2 photodamage. Our results can be explained assuming different contributions of LHC2 and PS2 core to the total nonradiative dissipation of absorbed excitation energy for the LI and HI barley. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

15.
The peroxidase catalyzed aerobic oxidation of aromatic acetaldehydes has been investigated with regard to the formation of electronically excited states because it generates the products expected from the cleavage of an intermediate dioxetane, that is, the aromatic aldehyde and formic acid. Emission was detected with the liquid scintillation counter. Integrated emission, indole-3-aldehyde formation, and O2 uptake strictly correlate with each other, unequivocally indicating that the aromatic aldehyde is generated electronically excited. Although the quantum yield of emission is approximately 5×10?9, the yield of chemiexcitation must be several orders of magnitude higher.  相似文献   

16.
Preparation of the water-soluble, kinetically labile, high-spin iron(II) tetrakis(4-sulfonatophenyl)porphyrin, Fe(II)TPPS4−, has been realized in neutral or weakly acidic solutions containing acetate buffer. The buffer played a double role in these systems: it was used for both adjusting pH and, via formation of an acetato complex, trapping trace amounts of iron(III) ions, which would convert the iron(II) porphyrins to the corresponding iron(III) species. Fe(II)TPPS4− proved to be stable in these solutions even after saturation with air or oxygen. In the absence of acetate ions, however, iron(II) ions play a catalytic role in the formation of iron(III) porphyrins. While the kinetically inert iron(III) porphyrin, Fe(III)TPPS3−, is a regular one with no emission and photoredox properties, the corresponding iron(II) porphyrin displays photoinduced features which are typical of sitting-atop complexes (redshifted Soret absorption and blueshifted emission and Q absorption bands, photoinduced porphyrin ligand-to-metal charge transfer, LMCT, reaction). In the photolysis of Fe(II)TPPS4− the LMCT process is followed by detachment of the reduced metal center and an irreversible ring-opening of the porphyrin ligand, resulting in the degradation of the complex. Possible oxygen-binding ability of Fe(II)TPPS4− (as a heme model) has been studied as well. Density functional theory calculations revealed that in solutions with high acetate concentration there is very little chance for iron(II) porpyrin to bind and release O2, deviating from heme in a hydrophobic microenvironment in hemoglobin. In the presence of an iron(III)-trapping additive that is much less strongly coordinated to the iron(II) center than the acetate ion, Fe(II)TPPS4− may function as a heme model.  相似文献   

17.
A better understanding of nitric oxide (NO) emission from a typical rice-wheat agroecosystem in eastern China is important for calculating the regional inventory and to propose effective NO mitigation options. Nitric oxide flux measurements by static chamber method were made from treatments of conventional nitrogen-fertilizer (NPK plus urea) application, no-nitrogen application, and nitrogen-fertilizer with incorporation of wheat straw residue for an entire rotation period (June 2002 to June 2003). During the wheat growing season two further treatments of fertilizer without crops planted and bare soil without nitrogen (N) fertilization were applied. Total annual NO emissions for the conventional fertilizer, no N fertilizer and fertilizer plus straw application were 0.44?±?0.01, 0.22?±?0.01, and 0.57?±?0.02 kg N ha?1y?1, respectively. On average 27% of this emission occurred during the rice season due to flooding/drainage cycle. The N fertilizer-induced emission factor for the conventional fertilizer treatment was 0.05% of the total N applied. Incorporation of wheat straw in the rice season showed no significant effect on NO flux due to the high C/N ratio of the straw incorporated. During the wheat growing season, NO emissions for all treatments had similar variation pattern controlled by soil moisture dynamics. Total NO emissions in the wheat season for fertilized bare soil (no wheat planted) were 0.389?±?0.01 and 0.21?±?0.01 kg N ha?1 y?1, respectively. The results indicate the importance of N fertilizer and soil moisture to nitrogen loss through the formation of NO.  相似文献   

18.
Spectra of ultraweak chemiluminescence (CL) accompanying auto-oxidation and hydration of cereal products have been measured using single photon counting and cut-off filters. The spectra cover the 380–880 nm spectral range with maxima centred around 600 nm. Analytically pure air-dried carbohydrates like agar, cellulose and nitrocellulose give emission too weak for spectral measurements. The emission from water pure carbohydrates is on average 4–12 times higher and emission spectra are similar to those from cereal products. The effect of free radical scavengers, SOD and O*2 (1Δg)-quenchers on CL spectra indicates a contribution of radical reactions with the participation of excited carbonyls, O2 and excited molecular oxygen dimoles. Moreover, possible mechanisms of chemi-excitation due to a cooperative H-bond formation during the hydration of carbohydrates and/or recombination of trapped radicals and electron-holes are discussed. It is also postulated that the excitation energy transfer to natural sensitizers occuring in cereal products may account for non-specific broad spectra and differences in the intensity of CL. © 1998 John Wiley & Sons, Ltd.  相似文献   

19.
The role of the histone pairs H2A,H2B and H3,H4 in the kinetics of core particle formation was investigated by using N-(1-pyrene)maleimide-labeled histone H3. The excimer emission intensity of a DNA-core histone complex prepared by direct mixing of DNA and histones in 0.2 m-NaCl is reduced by half when H2A,H2B is omitted. Fluorescence quenching studies and lifetime measurements indicate that the emission differences are probably due to static quenching. In a correctly folded nucleosome or a DNA-(H3,H4) complex, the two pyrene rings are buried and are held very close. DNA-(H3,H4) can interact with additional copies of H3,H4, but only when two dimers of H2A,H2B are correctly bound is there a specific twofold increase in excimer emission.The kinetics of the reaction of H3,H4 with DNA in 0.2 m-NaCl were followed by measuring the increase in 460 nm fluorescence. The apparent rate constant of the dominant kinetic component is ~ 2 × 10?1 s?1. If histones H2A,H2B are added immediately after the preparation of the DNA-(H3,H4) complex, an increase in excimer fluorescence is observed, with an apparent rate constant of ~ 6 × 10?3 s?1. However, if histones H2A,H2B are added one hour after DNA-(H3,H4) complex formation, there is no increase in excimer fluorescence. These results suggest that an intermediate involving the H3,H4 tetramer is formed first in nucleosome assembly. In the presence of H2A,H2B, this intermediate evolves to the final folded nucleosome, but in the absence of H2A,H2B it rearranges to an unmaturable dead-end complex. Additional experiments show that a very fast transfer of histone pairs (probably H2A,H2B) can take place between partially reconstituted nucleosomes.  相似文献   

20.
KBaPO4 luminescent powdered phosphors doped with rare earth elements (RE = Sm3+,Eu3+,Dy3+) were successfully synthesized using a wet chemical method to identify the most suitable phosphor for solid‐state lighting based on the measurement of their emission spectra at excitation wavelengths. The X‐ray diffraction pattern of the as‐prepared KBaPO4 was well matched with its standard JCPDS file no. 330996, indicating the formation of the desired compound. Scanning electron microscopy images revealed irregular morphology, the material crystallized particles aggregated and were non‐uniform with particle sizes ranging from 1 to 100 μm. Photoluminescence excitation and emission spectra clearly indicated that the phosphor containing the Sm3+‐activated KBaPO4 phosphors could be efficiently excited at 403 nm and exhibited an emission mainly including two wavelength peaks at 559 nm and 597 nm. The phosphor containing the Eu3+‐activated KBaPO4 phosphors could be efficiently excited at 396 nm and exhibited a bright red emission mainly including two wavelength peaks at 594 nm and 617 nm. The phosphor containing the Dy3+‐activated KBaPO4 phosphors could be efficiently excited at 349 nm and exhibited wavelength peaks at 474 nm and 570 nm.  相似文献   

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