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1.
Taking into account the recognition element for sensors linked to molecular imprinted polymers (MIPs), a proliferation of interest has been witnessed by those who are interested in this subject. Indeed, MIP nanoparticles are theme which recently has come to light in the literature. In this study, we have proposed a novel thiol ligand-capping method with polymerizable methacryloylamidocysteine (MAC) attached to gold nanoparticles, reminiscent of a self-assembled monolayer. Furthermore, a surface shell by synthetic host polymers based on molecular imprinting method for recognition has been reconstructed. In this method, methacryloyl iminodiacetic acid-chrome (MAIDA–Cr(III)) has been used as a new metal-chelating monomer via metal coordination–chelation interactions and dipicolinic acid (DPA) which is the main participant of Bacillus cereus spores has been used as a template. Nanoshell sensors with templates produce a cavity that is selective for DPA. The DPA can simultaneously chelate to Cr(III) metal ion and fit into the shape-selective cavity. Thus, the interaction between Cr(III) ion and free coordination spheres has an effect on the binding ability of the gold nanoparticles nanosensor. The interactions between DPA and MIP particles were studied observing fluorescence measurements. DPA addition caused significant decreases in fluorescence intensity because they induced photoluminescence emission from Au nanoparticles through the specific binding to the recognition sites of the crosslinked nanoshell polymer matrix. The binding affinity of the DPA imprinted nanoparticles has been explored by using the Langmuir and Scatchard methods and the analysis of the quenching results has been performed in terms of the Stern–Volmer equation.  相似文献   

2.
Lanthanide(III) complexes of 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (H3DO3A) are suggested as sensors for sensitive luminescence-based determination of a carbonate anion. Thermodynamic study of association of [Eu(H2O)2(DO3A)] with bidentate anionic ligands using luminescence spectroscopy reveals an affinity order CO 3 2? > oxalate2? > picolinate? > phthalate2? ≈ citrate3?; presumably as a consequence of an increasing chelate ring size. The ternary [Eu(DO3A)(picolinate)]? and [Tb(DO3A)(picolinate)]? complexes show improved photophysical properties due to the antenna effect of the picolinate anion. High quenching effect of carbonate anion and, to a lesser extent also oxalate, enables construction of a linear calibration plot utilizing optimized experimental conditions (e.g. c LnL?=?0.1 mM, c picolinate?=?2–5 mM, pH?=?7.4, λ exc?=?286 nm, etc.) for carbonate determination in solution. Both sensors show a comparable sensitivity and the detection limit of about 0.4 mM. In order to improve the photophysical properties of Ln(III) sensor by shift of excitation wavelength about 40 nm to VIS range, the isoquinoline-3-carboxylic acid (IQCA) as antenna ligand was employed instead of picolinic acid. The analysis of commercial samples of European mineral waters was carried out and they were compared to the results obtained by capillary isotachophoresis to confirm there is no inherent (systematic) error to the present analysis. The Ln(III) sensor with IQCA is recommended since it has a better robustness than that with picolinate. The present analytical method is simple and rapid, and it is useful for sensitive determination of bicarbonate/carbonate concentration in water samples under aerobic conditions.  相似文献   

3.
The luminescence decay times τlum of the complexes of the ions Tb(III), Eu(III), Sm(III), Dy(III), and Yb(III) with dipicolinic acid (DPA) dissolved in protonated and deuterated water, methanol, and dimethyl sulfoxide are measured. The values of τlum for crystals H3[Ln(DPA)3nH2O and their aqueous solutions coincide, which points to the identity of the environment in the nearest spheres of an ion in both cases. A comparison of τlum of solutions of the complexes in H2O and D2O, as well as in CH3OH, CH3OD, CD3OD, DMSO-h 6, and DMSO-d 6 shows that the molecular groups in the second and third spheres of an ion, exhibiting high-frequency vibrations, have a noticeable effect on the rate constants of nonradiative transitions k nr in the ion. From this comparison, some inferences on the structure of the solvate shell of the Ln(DPA) 3 3? complexes in the solvents used are made. The contributions to k nr of Eu(III), Tb(III), Sm(III), Dy(III), Nd(III), and Yb(III) made by OH and CH groups located at different distances from the ion are estimated. It is demonstrated that the dependence of k nr on the distance to the OH and CH groups is steeper for the Eu(III) and Tb(III) ions than for the remaining ions.  相似文献   

4.
A simple, sensitive, and accurate spectrofluorimetric method was developed for the determination of citalopram in bulk and pharmaceutical preparations. The method is based on the enhancement of the weak fluorescence signal (FL) of the Tb (III)-citalopram system in the presence of silver nanoparticles. Fluorescence intensities were measured at 555 nm after excitation at 281 nm. Prepared silver nanoparticles (AgNPs) were characterized by UV-Visible spectra and transmission electron microscopy (TEM). Various factors affecting the formation of citalopram-Tb (III)-AgNPs complexes were studied and optimized. The fluorescence intensity versus concentration plot was linear over the range 0.02–14 μg?mL?1, with an excellent correlation coefficient of 0.9978. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 7.15?×?10?6?μg?mL?1 and 2.38?×?10?5?μg?mL?1 respectively. The proposed method was found to have good reproducibility with a relative standard deviation of 3.66 % (n?=?6). The interference effects of common excipients found in pharmaceutical preparations were studied. The developed method was validated statistically by performing recoveries studies and successfully applied for the assay of citalopram in bulk powder and pharmaceutical preparations. Percent recoveries were found to range from 98.98 % to 100.97 % for bulk powder and from 96.57 % to 101.77 % for pharmaceutical preparations.  相似文献   

5.
We report blend-based plastic polymer electrolyte (i.e., polyethylene oxide (PEO)–polydimethyl siloxane (PDMS)–lithium hexafluorophosphate (LiPF6)) with substantial improvement in DC conductivity at ambient and subambient temperatures when compared with literature reports. Conductivity variation with salt concentration, investigated within ±30 °C range, indicates an optimum conductivity of 5.6?×?10?5 S cm?1 at 30 °C for Ö/Li ~10 with a further lowering by one order at 0 °C and it remains unaltered at ?10 °C. Enhanced conductivity in this blend electrolyte, though lower than two copolymer counterparts, is attributed to very low glass transition temperatures of the host polymers. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggest an effective blending between the two polymers with an effective interaction between the Li salt and the blend polymer matrix. Raman spectroscopy results indicated that cation (Li+) coordination occurs at the C=Ö site in PEO out of the two electron-rich sites (i.e., CÖ and Si–Ö–Si) in the PEO–PDMS blend. The blend electrolytes are predominantly ionic (t ion ~97 %).  相似文献   

6.
A novel ligand with double sulfinyl groups, bis(benzylsulfinyl)methane, was synthesized by a new method and its two lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1HNMR and UV spectra. The results indicated that the composition of these complexes was REL2.5(ClO4)3·3H2O (RE = Tb (III), Dy (III), L = C6H5CH2SOCH2SOCH2C6H5). The FT-IR results revealed that the perchlorate group was bonded with the lanthanide ion by the oxygen atoms, and the coordination was bidentate. The fluorescent spectra illustrated that both the Tb (III) and Dy (III) complexes displayed characteristic fluorescence in solid state, especially for the Tb (III) complex, the peak of 5D4 → 7 F5 of the Tb (III) ion in 544 nm was stronger than that of others. It indicated that the Tb (III) complex could emit purer green fluorescence. By analysis fluorescence and phosphorescence spectra, it was found that the ligand had the advantage to absorb energy and transfer it to the Tb (III) and Dy (III) ions. The phosphorescence spectra and fluorescence lifetimes of the complexes were also measured.  相似文献   

7.
Studies into the suitability of a novel, widely tunable telecom L-band (1,563–1,613 nm) digital supermode distributed Bragg reflector (DS-DBR) laser for cavity ring-down spectroscopy (CRDS) are presented. The spectrometer comprised of a 36.6?cm long linear cavity with ring-down times varying between 19–26 μs across the 50 nm DS-DBR wavelength range due to changes in the cavity mirror reflectivities with wavelength. The potential of such a broadband, high-resolution CRD spectrometer was illustrated by investigating several transitions of CO2 in air, a 5 % calibrated mixture and breath samples. Allan variance measurements at a single wavelength indicated an optimal minimum detectable absorption coefficient (α min) of 3 × 10?10 cm?1 over 20 s.  相似文献   

8.
Absorption and luminescence properties of silver nanoclusters embedded in SiO2 matrixes were studied experimentally. Thin SiO2 films with different amount of silver were produced by co-deposition of Ag and SiO2 onto the silica substrates in vacuum. The thus obtained films possess three peaks in absorption spectra at 297, 329 and 401 nm and two peaks in luminescence spectra at about 500 and 650 nm. We ascribed these spectral features to silver nanoclusters of different sizes that present in the film. Thermal annealing transforms both absorption and emission spectra of the films. Lager clusters that are formed after annealing possess one absorption band at 350–450 nm and one luminescence band at 510 nm. The luminescence was observed only in samples with the silver content of less than 2.2%. Quenching of the luminescence in samples with higher concentration of silver is due to the presence of larger particles with plasmonic properties.  相似文献   

9.
New phenomena – the first order magnetic phase transitions were observed in nanoclusters and nanostructures. For isolated ferrihydrite nanoclusters (d ~ 1–2 nm) in porous materials, for α-,γ-Fe2O3 nanoclusters (d ~ 20–50 nm) and for composites of nanostructured metallic Eu with additives of α-, γ-Fe2O3 nanoclusters and adamantane the critical temperatures (T C, T N) and magnetic cluster critical sizes (R cr) were determined by means of thermodynamic models and Mössbauer spectroscopy. The first order magnetic phase transitions (jump-like) proceed by such a way when magnetization and magnetic order disappear by jump without superparamagnetic relaxation. According to thermodynamic model predictions the cluster and interface defects were suggested to play the main role in magnetic behavior. Thus, for the defective α-, γ-Fe2O3 nanoclusters, at RR cr, the presence of the first order (jump-like) magnetic phase transition was described in terms of magnetic critical size of cluster. The action of high pressure (up to 2 GPa) with shear (120–240°) was effective for defect generation and nanostructure formation. For nanosystems including iron oxide nanoclusters, adamantane and metallic europium and subjected to shear stress under high pressure loading the critical value of defect density was estimated by the study of the character of magnetic phase transition. First-to-second-order (nanostructured metallic Eu) and second-to-first-order (α-, γ-ferric oxide nanoclusters) changes of the character of magnetic phase transition were shown to accompany by the variation of critical temperatures compared to the corresponding bulk values.  相似文献   

10.
An innovative spectroscopic system based on an external cavity quantum cascade laser (EC-QCL) coupled with a mid-infrared (mid-IR) fiber and quartz enhanced photoacoustic spectroscopy (QEPAS) is described. SF6 has been selected as a target gas in demonstration of the system for trace gas sensing. Single mode laser delivery through the prongs of the quartz tuning fork has been obtained employing a hollow waveguide fiber with inner silver–silver iodine (Ag–AgI) coatings and internal core diameter of 300 μm. A detailed design and realization of the QCL fiber coupling and output collimator system allowed almost practically all (99.4 %) of the laser beam to be transmitted through the spectrophone module. The achieved sensitivity of the system is 50 parts per trillion in 1 s, corresponding to a record for QEPAS normalized noise-equivalent absorption of 2.7 × 10?10 W cm?1 Hz?1/2.  相似文献   

11.
Li WX  Guo L  Chen LJ  Shi XY 《Journal of fluorescence》2008,18(6):1043-1049
A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1H NMR and UV spectra. The results indicated that the composition of these complexes is REL5(ClO4)3·3H2O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C6H5COCH2SOCH2COC6H5). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (5D4) of Tb (III) than that (5D0) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.  相似文献   

12.
A novel Aryl amide ligand H2L and its eight complexes, [LnH2L(NO3)2·H2O]NO3 [Ln=Sm(III), Er(III), Tb(III), Dy(III), La(III), Gd(III), Nd(III), and Pr(III)], are presented. The ligand and complexes were synthesized and characterized based on elemental analyses, molar conductance, IR, 1H and 13C-NMR, UV–VIS., and TGA studies. The conductivity data show a 1:1 electrolytic nature with a general formula [LnH2L(NO3)2·2H2O]NO3 The IR spectra reveal coordination of the ligand through the azomethine nitrogen and the phenolic hydroxyl of the ligand to the lanthanide ion. The coordinated nitrate ions behave in a bidentate fashion. The thermal decomposition studies indicate the presence of two water molecules in the inner coordination sphere. Under the excitation at 319 nm, the luminescence emission properties for Sm, Tb, and Dy complexes are observed. These observations show that the ligand favors energy transfers to the emitting energy level of these lanthanide ions. Furthermore, the antioxidant activity of the ligand and its Ln(III) complexes was determined by DPPH radical scavenging method, which indicates that the Ln(III) complexes exhibit more effective antioxidant activity than the ligand alone.  相似文献   

13.
We studied sensitization of Eu(III) and Tb(III) ions by molecules of 1,10-phenanthroline and 2,2-bipyridil in D2O and d 6-ethanol and the influence of Nd(III), Pr(III), Sm(III), Gd(III), and Ho(III) ions on the luminescence intensity I lum and lifetime τlum of Eu(III) and Tb(III) in solutions. The stability constants of complexes of Eu(III) and Gd(III) with 2,2′-bipyridil are measured by spectrophotometric and luminescence methods. It is shown that luminescence of Eu(III) is quenched by Gd(III) ions at the ion concentration equal to 10?2–10?1 M, which is caused by competing between these ions for a sensitizer. At the concentration of Ln(III) ions equal to 10?6?10?3 M, the sensitized luminescence of Eu(III) and Tb(III) was quenched and τlum decreased in the presence of Nd(III) ions, whereas in the presence of Gd(III) the luminescence intensity increased. It is proved that a bridge that connects the two ions upon energy transfer is formed by hydroxyl groups. The intensity of luminescence of Eu(III) and Tb(III) in aqueous solutions and its lifetime decreased in the presence of hydroxyl groups, while upon addition of Gd(III) to these solutions these quantities were restored. We also found that the addition of Gd(III) to deoxygenated ethanol solutions of 2,2′-bipyridil and Eu(III) slows down photochemical and thermal reactions between bipyridil and Eu(III), resulting in the increase in the luminescence intensity of Eu(III).  相似文献   

14.
Complexes Eu(TTA)3phen and Eu(MBTA)3phen, as well as complexes Tb(MBTA)3phen and Tb(TTA)3phen, which do not luminesce in solutions, are shown to luminesce in polymer films (TTA is thenoyltrifluoroacetone, MBTA is n-methoxybenzoyltrifluoroacetone, and phen is o-phenanthroline). Luminescence of complexes of Eu and Tb in films of a polymer, poly(methylene-bis-anthranilamide) 1,6-hexamethylenedicarboxylic acid (PAA-5), having a high concentration of functional anthranilate groups, is studied. From the behavior of the luminescence intensity (I lum), the luminescence decay time, and the luminescence spectra of complexes of these lanthanides in polymer films, the following regular features were revealed. (i) During the film preparation at 90°C, Ln complexes are attached to PAA-5 via anthranilate groups. (ii) Irradiation of these films in the range of the absorption band of ligands (TTA or MBTA) leads to deactivation of the electronic excitation of ions according to the diketone detachment mechanism and to further binding of complexes to polymers. In this case, I lum(Eu(III)) decreases because the introduction of anthranilate groups of the polymer into the first coordination sphere of Eu(III) complexes enhances the nonradiative deactivation of these ions, whereas I lum(Tb(III)) increases since the introduction of these groups suppresses the nonradiative deactivation of Tb complexes through triplet states of ligands (TTA and MBTA). (iii) Upon storage of films in the dark (20°C), complexes detach themselves from the polymer and return to their initial structure. In PAA-5 films into which Eu and Tb complexes were simultaneously introduced, the color of the emission from the irradiation spot changes from red to green.  相似文献   

15.
Two 2D rare earth terbium and dysprosium coordination polymers with 2,4-pyridinedicarboxylate and oxalate anions have been synthesized by hydrothermal method, the formula is {[RE(pda)(ox)0.5(H2O)4]·2H2O}n (RE = Tb (1) and Dy (2); H2pda = 2,4-pyridinedicarboxylic acid; ox = oxalate anion). The two complexes are isomorphic and crystallized in monoclinic system, P21/c space group. Each pda anion connects two rare earth ions with 2- carboxyl group and the nitrogen atom but the 4- carboxyl group does not coordinate with rare earth ions. Each ox anion connects two rare earth ions by μ 2-bridge way. Both the complexes exhibit intense characteristic luminescence of Tb(III) or Dy(III) ion with excitation of UV-rays.  相似文献   

16.
(100) Oriented Pb x Sr1?x TiO3 (PSTO) thin films are prepared on indium tin oxide (ITO)/glass substrates by sol–gel technique while inserting doped PbTiO3 (PTO)-inducing layer in between. The effect of tensile stress in PSTO on tunability and (100) orientation of the thin films was investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscope, and atomic force microscope, respectively. Results show that PSTO thin film deposited on doped PTO has (100) oriented structure while it is randomly oriented when deposited directly on the ITO/glass substrate. Lattice mismatch between PSTO and PTO appears, in which the in-plane lattice constant c is 0.3922–0.3924 nm in the former and 4.02–4.07 nm in the latter, respectively, contributing tensile stress in the PSTO due to different lattice constants between them. The stress in the PSTO thin film is 3.04, 3.15, 3.59 and 4.47 GPa when the doped PTOs are Fe–PTO, Tb–PTO, Co–PTO and Zn–PTO, respectively. The orientation degrees of PSTO thin films are from 89.63, 90.31, 91.92 to 93.29 % with increasing stress of PSTO on Fe–PTO, Tb–PTO, Co–PTO and Zn–PTO, respectively. Tunabilities of the well-oriented PSTO thin films increase in ascending order of 63 < 65 < 69 < 73 % when induced by oriented PTO layers of Fe–PTO, Tb–PTO, Co–PTO and Zn–PTO, respectively, which is in accordance with the degree of (100) orientation appearing in the thin films. The high tunability appears in the PSTO thin film while high (100) orientation is derived from the tensile stress. It is much higher than that of randomly oriented PSTO thin film.  相似文献   

17.
We have successfully observed high-resolution spectra of spin-forbidden electric quadrupole transition (1 S 03 D 2) in ytterbium (174Yb) atoms. The differential light shifts between the 1 S 0 and the 3 D 2 states in a far-off resonant trap at 532 nm are also measured. For the spectroscopy, we developed simple, narrow-linewidth, and long-term frequency stabilized violet diode laser systems. Long-term drifts of the excitation laser (404 nm) is suppressed by locking the laser to a length stabilized optical cavity. The optical path length of the cavity is stabilized to another diode laser whose frequency is locked to a strong 1 S 01 P 1 transition (399 nm) of Yb. Both lasers are standard extended-cavity diode lasers (ECDLs) in the Littrow configuration. Since the linewidth of a violet ECDL (~10 MHz) is broader than a typical value of a red or near infra-red ECDL (<1 MHz), we employ optical feedback from a narrow-band Fabry–Perot cavity to reduce the linewidth. The linewidth is expected to be <20 kHz for 1 ms averaging time, and the long-term frequency stability is estimated to be ~200 kHz/h.  相似文献   

18.
In this paper, a gate-all-around junctionless tunnel field effect transistor (JLTFET) based on heterostructure of compound and group III–V semiconductors is introduced and simulated. In order to blend the high tunneling efficiency of narrow band gap material JLTFETs and the high electron mobility of III–V JLTFETs, a type I heterostructure junctionless TFET adopting Ge–Al x Ga1?x As–Ge system has been optimized by numerical simulation in terms of aluminum (Al) composition. To improve device performance, we considered a nanowire structure, and it was illustrated that high-performance logic technology can be achieved by the proposed device. The optimal Al composition founded to be around 20 % (x = 0.2). The numerical simulation results demonstrate that the proposed device has low leakage current I OFF of ~1.9 × 10?17, I ON of 4 µA/µm, I ON/I OFF current ratio of 1.7 × 1011 and subthreshold swing SS of 12.6 mV/decade at the 40 nm gate length and temperature of 300 K.  相似文献   

19.
Fast ionic solid specimens of a new binary system namely (BiI3) x –(Ag2CrO4)100?x , where x?=?10, 20, 30, 40, 50, 60, 70, 80, and 90 mol%, were synthesized by melt quenching method. Detailed structural, thermal, and electrical transport properties evaluated by means of X-ray diffraction analysis, Fourier transform infrared spectroscopic investigations, and differential scanning calorimetry in conjunction with complex impedance analysis carried out over the frequency range 1 MHz–20 Hz and in the temperature region 298–430 K indicated the composite nature of such superionic solids consisting of glassy and crystalline phases and possessing electrical conductivities of the order 10?6–10?3 Scm?1 at 298 K. The best conducting composition of the present binary system has been identified as the specimen containing 30 mol% BiI3 and exhibiting a room-temperature electrical conductivity of 7.1?×?10?3 Scm?1 with an activation energy of 0.12 eV for silver ionic transport as confirmed by Wagner's polarization and E.M.F. techniques.  相似文献   

20.
This work reports on the photoluminescent properties of three new lanthanide complexes with acetoacetanilide (aaa), a β-diketonate ligand. The complexes have the general molecular formulae [RE(aaa)3(H2O)], they are soluble in organic solvents such as ethanol and chloroform and insoluble in water. The energy of the triplet state was determined at about 4,700 cm?1 higher than the 5D4 emitting level of the Tb(III) ion, leading to an absolute quantum yield of 22 % for the [Tb(aaa)3(H2O)] complex. The photoluminescent properties were studied and the luminescence parameters of the [Eu(aaa)3(H2O)] complex were experimentally determined. The photostabilities of the complexes under continuous UV irradiation were measured and the data indicate low stability of the [Tb(aaa)3(H2O)] complex when the system is excited at the band attributed to energy transfer from the ligand to terbium(III) ion. However, its photostability is significantly improved under inert atmosphere.  相似文献   

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