Determination of l-proline based on anodic electrochemiluminescence of CdTe quantum dots

A novel flow injection method for detection of l-proline was proposed in the presence of CdTe quantum dots (QDs). This method is based on the enhanced anodic electrochemiluminescence (ECL) emission of CdTe QDs l-proline in aqueous system. CdTe QDs were modified with thioglycolic acid to obtain stable water-soluble QDs and intensive anodic ECL emission in Na₂CO₃–NaHCO₃ buffer solution at an indium tin oxide (ITO) electrode, which was used for the sensitive detection of ECL enhancement using our homemade flow cell. Under the optimal conditions, the ECL intensity was correlated linearly with the concentration of l-proline over the range of 1.0×10^?8?1.0×10^?4 g mL^?1 (r=0.9996) and the detection limit was 5.0×10^?9 g mL^?1. The relative standard deviation was 1.12% for 6.0×10^?5 g mL^?1 l-proline (n=11). The possible mechanism was discussed. This method put forward a new efficient ECL methodology for enhancement-related determination of l-proline successfully.     

Spectrofluorimetric quantification of bilirubin using yttrium–norfloxacin complex as a fluorescence probe in serum samples

A simple and sensitive spectrofluorimetric method was developed to determine trace amounts of bilirubin (BR) using yttrium (Y³⁺)–norfloxacin (NFLX) complex as a fluorescence (FL) probe. NFLX can form a stable binary complex with Y³⁺ and markedly enhances the weak FL signal of the NFLX. The FL intensity of the Y³⁺–NFLX complex decreased significantly in the presence of BR in a buffer solution at pH=7.2. Under optimal conditions, the FL intensity decreased according to the BR concentration and showed a good linear relationship in the range of 0.03–2.3 μg mL^?1 of BR with a correlation coefficient of 0.9988. The limit of detection for the determination of BR was 2.8 ng mL^?1 with a relative standard deviation (RSD) of 1.55% for five replicate determination of 0.05 μg mL^-1 BR. The presented method offers higher sensitivity with simple instrumentation and was applied successfully in detecting BR at low concentrations.     

Two and four photon absorption and nonlinear refraction in undoped,chromium doped and copper doped ZnS quantum dots

The ZnS quantum dots (QDs) with Cr and Cu doping were synthesized by chemical co-precipitation method. The nanostructures of the prepared undoped and doped ZnS QDs were characterized by UV–vis spectroscopy, Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The sizes of QDs were found to be within 3–5 nm range. The nonlinear parameters viz. Two photon absorption coefficient (β₂), nonlinear refractive index (n₂), third order nonlinear susceptibility (χ³) at wavelength 532 nm and Four photon absorption coefficient (β₄) at wavelength 1064 nm have been calculated by Z-scan technique using nanosecond Nd:YAG laser in undoped, Cr doped and Cu doped ZnS QDs. Higher values of nonlinear parameters for doped ZnS infer that they are potential material for the development of photonics devices and sensor protection applications.     

Gain properties of the transition emissions near the second telecommunication window in Ho3+-doped multicomponent heavy-metal gallate glasses

Efficient infrared emissions near the second telecommunication window in Ho³⁺-doped multicomponent heavy-metal gallate (MHG) glasses have been observed. The maximum stimulated emission cross-sections are calculated to be 2.94×10^?21 and 2.08×10^?21 cm² for 1200 and 1390 nm emissions, respectively. Excitation spectra reveal that the 642 and 538 nm wavelengths are practical pumping conditions for 1.2 and 1.39 μm emissions, respectively. Gain cross-sections are evaluated and positive gain bands have been anticipated. The theoretical gain results indicate that the appealing infrared emissions near the second telecommunication window from Ho³⁺-doped MHG glasses with low maximum phonon energy of ～660 cm^?1 make them attractive in developing ～1.2 μm and E-band (1360–1460 nm) optical amplifiers.     

Ultrasound-assisted copper deposition on a polymer membrane and application for methanol steam reforming

Copper particles were electrolessly deposited on a palladium aerosol activated polymer membrane in the presence of ultrasound. An application of ultrasound introduced a faster deposition (220 μg min^?1 in deposition rate) and finer copper particles (9 nm in crystallite size) than those (11 and 41 μg min^?1; 27 and 32 nm) in the absence of ultrasound (i.e. respectively 20 and 45 °C in bath temperature with mechanical agitation). A better performance of methanol steam reforming (0.59 in mean conversion during 5 h operation; 1.3 and 1.6 times respectively higher than those from 20 to 45 °C cases) at a 300 °C reaction temperature was materialized for the ultrasound application, probably due to a finer (i.e. a more textured) copper particle deposition on a polymer membrane.     

Structural and luminescence properties of Nd3+-doped PbO–B2O3–TiO2–AlF3 glass for 1.07 μm laser applications

Trivalent neodymium doped multi-component lead borate titanate aluminumfluoride (LBTAFNd) glasses were prepared and characterized as a function of Nd³⁺ ions concentration through optical absorption, NIR luminescence and decay measurements. The intensity (Ω_2,4,6) and other radiative parameters were determined within the frame work of Judd–Ofelt theory. The intensities of absorption bands were expressed in terms of experimental oscillator strengths. Reasonably small root mean square deviation of ±0.384×10^?6 obtained between the experimental and calculated oscillator strengths indicates the validity of intensity parameters. Upon 805 nm laser excitation, the NIR emissions at 0.92 μm (⁴F_3/2→⁴I_9/2), 1.07 μm (⁴F_3/2→⁴I_11/2) and 1.35 μm (⁴F_3/2→⁴I_13/2) were observed. The spectroscopic quality factor has been determined from the Ω₄ and Ω₆ intensity parameters as well as the intensities of emission bands centered at 1.07 and 1.35 μm. The decay curves of the ⁴F_3/2 excited state were recorded by monitoring the emission and excitation wavelengths at 1.07 μm and 805 nm, respectively. The decay curves exhibit single exponential behavior for all the glasses. The laser characteristic parameters of ⁴F_3/2→⁴I_11/2 (1.07 μm) transition were determined and compared with other reported glasses.     

Competing nucleation mechanisms and growth of InAsSbP quantum dots and nano-pits on the InAs(100) surface

InAsSbP quantum dots (QDs) and nano-pits (NPs) are grown on a InAs(100) surface by liquid phase epitaxy (LPE). Their morphology, dimensions and distribution density are investigated by high resolution scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and total energy calculations. QDs average density ranges from 5 to 7 × 10⁹ cm^?2, with heights and widths having a Gaussian distribution with sizes from 5 nm to 15 nm and 10 nm to 40 nm respectively. The average pits density is (2–6) × 10¹⁰ cm^?2 with dimensions ranging from 5–30 nm in width and depth. We also find a shift in the absorption edge towards the longer wavelengths together with broadening towards shorter wavelengths indicating that these QDs and lateral overgrown nano-pits are grown at the n-InAs/p-InAsSbP heterojunction interface. Together with total energy calculations, the results indicate that lattice mismatch ratio plays a central role in the growth of these strain-induced nano-objects.     

Determination of nitrofurans in feeds based on silver nanoparticle-catalyzed chemiluminescence

A highly sensitive chemiluminescence (CL) method for the determination of nitrofurans (NFs) was developed based on the enhancement of CL intensity of luminol–H₂O₂–NFs system by silver nanoparticles (AgNPs). It was supposed that the oxygen-related radicals of OH and superoxide radical (O₂^?) could be produced when NFs reacted with H₂O₂. Furthermore, the enhancement mechanism was originated from the reinforcer of AgNPs, which could catalyze the generation of the OH radical. Then OH radicals reacted with luminol anion and HO₂^? to form luminol radical (L^?) and O₂^?. The excited state 3-aminophthalate anion was obtained in the reaction of L^? and O₂^?, which was the emitter (luminophor) in the luminol–H₂O₂ CL reaction system and the maximal emission of the CL spectrum was at 425 nm. The experiments of scavenging oxygen-related radicals were done to confirm these reactive oxygen species participated in the CL reaction. The limits of detection (LOD) (S/N=3) were 8×10^?7 g mL^?1 for furacilin, 8×10^?8 g mL^?1 for furantoin, 4×10^?8 g mL^?1 for furazolidone and 2×10^?7 g mL^?1 for furaltadone. The proposed method was successfully applied to the determination of NFs in feeds and pharmaceutical samples.     

Temperature and concentration quenching of mid-IR photoluminescence in iron doped ZnSe and ZnS laser crystals

Concentration dependences of the mid-IR kinetic of luminescence at ⁵E?⁵T₂ transition in Fe:ZnSe and Fe:ZnS laser samples were studied in 14–300 K temperature ranges. Radiation lifetime in Fe:ZnSe samples measured using low doped samples with iron concentration 0.1×10¹⁸ cm^?3 was estimated to be 57 μs. The magnetic susceptibility for higher doped (C_Fe=38 and 112×10¹⁸ cm^?3) Fe:ZnSe samples was found to consist of a paramagnetic Curie–Weiss behavior arising from the weakly interacting Fe²⁺ ions and a diamagnetic ZnSe contribution plus a temperature-independent, field-dependent contribution possibly arising from very small amounts of aggregated Fe.     

Temperature-dependent photoluminescence of CuInS2 quantum dots

Temperature-dependent photoluminescence (PL) spectroscopy of CuInS₂ core and CuInS₂/ZnS core–shell quantum dots (QDs) was studied for understanding the influence of a ZnS shell on the PL mechanism. The PL quantum yield and lifetime of CuInS₂ core QDs were significantly enhanced after the QD surface was coated with the ZnS shell. The temperature dependences of the PL energy, linewidth, and intensity for the core and core–shell QDs were studied in the temperature range from 92 to 287 K. The temperature-dependent shifts of 98 meV and 35 meV for the PL energies of the QDs were much larger than those of the excitons in their bulk semiconductors. It was surprisingly found that the core and core–shell QDs exhibited a similar temperature dependence of the PL intensity. The PL in the CuInS₂/ZnS core–shell QDs was suggested to originate from recombination of many kinds of defect-related emission centers in the interior of the cores.     

Photolysis of SF6 adsorbed on Si(111)-7 × 7 by monochromatic soft X-ray

Continuous-time photoelectron spectroscopy (PES) and photon-exposure-dependent photon-stimulated desorption (PSD) were employed to investigate the monochromatic soft X-ray-induced dissociation of SF₆ molecules adsorbed on Si(111)-7 × 7 at 30 K (SF₆ dose = 3.4 × 10¹³ molecules/cm², ～ 0.5 monolayer). The photon-induced evolution of adsorbed SF₆ was monitored at photon energies of 98 and 120 eV [near the Si(2p) edge], and sequential valence-level PES spectra made it possible to deduce the photolysis cross section as a function of energy. It was found that the photolysis cross sections for 98 and 120 eV photons are ～ 2.7 × 10^? 17 and ～ 3.7 × 10^?17 cm², respectively. The changes in the F^? and F⁺ PSD ion yields were also measured during irradiation of 120 eV photons. The photon-exposure dependencies of the F^? and F⁺ ion yields show the characteristics: (a) the dissociation of adsorbed SF₆ molecules is ascribable to the substrate-mediated dissociations [dissociative attachment (DA) and dipolar dissociation (DD) induced by the photoelectrons emitting from the silicon substrate]; (b) at early stages of photolysis, the F^? yield is mainly due to DA and DD of the adsorbed SF₆ molecules, while at high photon exposure the F^? formation by electron capture of the F⁺ ion is likely to be the dominant mechanism; (c) the F⁺ ion desorption is associated with the bond breaking of the surface SiF species; (d) the surface SiF is formed by reaction of the surface Si atom with the fluorine atom or F^? ion produced by scission of S–F bond of SF_n (n = 1–6) species.     

Ultrasound assisted combined molecularly imprinted polymer for selective extraction of nicotinamide in human urine and milk samples: Spectrophotometric determination and optimization study

Ultrasound-assisted dispersive solid phase microextraction followed by UV–vis spectrophotometer (UA-DSPME-UV–vis) was designed for extraction and preconcentration of nicotinamide (vitamin B₃) by HKUST-1 metal organic framework (MOF) based molecularly imprinted polymer (MIP). This new material was characterized by FTIR and FE-SEM techniques. The preliminary Plackett–Burman design was used for screening and subsequently the central composite design justifies significant terms and possible construction of mathematical equation which give the individual and cooperative contribution of variables like HKUST-1-MOF-NA-MIP mass, sonication time, temperature, eluent volume, pH and vortex time. Accordingly the optimum condition was set as: 2.0 mg HKUST-1-MOF-NA-MIP, 200 μL eluent and 5.0 min sonication time in center points other variables were determined as the best conditions to reach the maximum recovery of the analyte. The UA-DSPME-UV–vis method performances like excellent linearity (LR), limits of detection (LOD), limits of quantification of 10–5000 μg L⁻¹ with R² of 0.99, LOD (1.96 ng mL⁻¹), LOQ (6.53 μg L⁻¹), respectively show successful and accurate applicability of the present method for monitoring analytes with within- and between-day precision of 0.96–3.38%. The average absolute recoveries of the nicotinamide extracted from the urine, milk and water samples were 95.85–101.27%.     

Synthesis,biocompatibility and luminescence properties of quantum dots conjugated with amino acid-functionalized β-cyclodextrin

A series of CdSe and CdSe/CdS quantum dots (QDs) labeled with amino acid-modified β-cyclodextrin (β-CD) was prepared by a simple ultrasonic method. These amino acid-modified β-CD-coated QDs are very soluble and stable in biological buffer. They also have high colloidal stability and strong optical emission properties that are similar to those of untreated tri-n-octylphosphine oxide (TOPO)-coated QDs. The quantum yields (QYs) of these amino acid-modified β-CD-coated CdSe and CdSe/CdS QDs in biological buffer were found to be very high. In particular, the QYs of the positively charged l-His-β-CD-coated CdSe/CdS QDs were as high as 33.5±1.8%. In addition, the fluorescence lifetime of these QDs was also very long in PBS solutions as determined by frequency domain spectroscopy. For example, the lifetime of l-His-β-CD-coated CdSe/CdS QDs was 8.6 ns. The in vitro cytotoxicity of these QDs in ECV-304, SH-SY5Y and HeLa cells was found to be lower. l-His-β-CD-coated CdSe/CdS QDs were the least cytotoxic (IC₅₀ 95.6±3.2 mg mL^?1 in ECV-304 cells after 48 h). The flow cytometry results show that the positively charged amino acid led to a considerable increase in biocompatibility of QDs. This may be attributed to the presence of an amino acid-modified β-CD outer layer, which enhanced the biocompatibility.     

Optimization of ultrasound-assisted dispersive solid-phase microextraction based on nanoparticles followed by spectrophotometry for the simultaneous determination of dyes using experimental design

A simple, low cost and ultrasensitive method for the simultaneous preconcentration and determination of trace amount of auramine-O and malachite green in aqueous media following accumulation on novel and lower toxicity nanomaterials by ultrasound-assisted dispersive solid phase micro-extraction (UA-DSPME) procedure combined with spectrophotometric has been described. The Mn doped ZnS nanoparticles loaded on activated carbon were characterized by Field emission scanning electron microscopy (FE-SEM), particle size distribution, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) analyses and subsequently were used as green and efficient material for dyes accumulation. Contribution of experimental variables such as ultrasonic time, ultrasonic temperature, adsorbent mass, vortex time, ionic strength, pH and elution volume were optimized through experimental design, and while the preconcentrated analytes were efficiently eluted by acetone. Preliminary Plackett–Burman design was applied for selection of most significant factors and giving useful information about their main and interaction part of significant variables like ultrasonic time, adsorbent mass, elution volume and pH were obtained by central composite design combined with response surface analysis and optimum experimental conditions was set at pH of 8.0, 1.2 mg of adsorbent, 150 μL eluent and 3.7 min sonication. Under optimized conditions, the average recoveries (five replicates) for two dyes (spiked at 500.0 ng mL⁻¹) changes in the range of 92.80–97.70% with acceptable RSD% less than 4.0% over a linear range of 3.0–5000.0 ng mL⁻¹ for the AO and MG in water samples with regression coefficients (R²) of 0.9975 and 0.9977, respectively. Acceptable limits of detection of 0.91 and 0.61 ng mL⁻¹ for AO and MG, respectively and high accuracy and repeatability are unique advantages of present method to improve the figures of merit for their accurate determination at trace level in complicated materials.     

Synthesis,characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb³⁺ doped CaZrO₃ has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO₃:Tb³⁺ exhibits three thermoluminescence (TL) glow peaks at 126 °C, 200 °C and 480 °C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O^? ion. Centre II with an axial symmetric g-tensor with principal values g_=1.9986 and g_?=2.0023 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F⁺ centre appear to correlate with the observed high temperature TL peak in CaZrO₃:Tb³⁺ phosphor.     

Broadband 2.84 μm luminescence properties and Judd–Ofelt analysis in Dy3+ doped ZrF4–BaF2–LaF3–AlF3–YF3 glass

2.84 μm luminescence with a bandwidth of 213 nm is obtained in Dy³⁺ doped (ZrF₄–BaF₂–LaF₃–AlF₃–YF₃) ZBLAY glass. Three intensity parameters and radiative properties have been determined from the absorption spectrum based on the Judd–Ofelt theory. The 2.84 μm emission characteristics and energy transfer mechanism upon excitation of a conventional 808 nm laser diode are investigated. The prepared Dy³⁺ doped ZBLAY glass possessing high predicted spontaneous transition probability (45.92 s^?1) along with large calculated emission cross section (1.17×10^?20 cm²) has potential applications in 2.8 μm laser.     

Preparation of enzyme nanoparticles and studying the catalytic activity of the immobilized nanoparticles on polyethylene films

Using high-intensity ultrasound, in situ generated α-amylase nanoparticles (NPs) were immobilized on polyethylene (PE) films. The α-amylase NP-coated PE films have been characterized by E-SEM, FTIR, DLS, XPS and RBS. The PE was reacted with HNO₃ and NPs of the α-amylase were also deposited on the activated PE. The PE impregnated with α-amylase (4 μg per 1 mg PE) was used for hydrolyzing soluble potato starch to maltose. The immobilization improved the catalytic activity of α-amylase at all the reaction conditions studied. The kinetic parameters, K_m (5 and 4 g L^?1 for the regular and activated PE, respectively) and V_max (5 × 10^?7 mol ml^?1 min^?1, almost the same numbers were obtained for the regular and activated PEs) for the immobilized amylase were found to slightly favor the respective values obtained for the free enzyme (K_m = 6.6 g L^?1, V_max = 3.7 × 10^?7 mol ml^?1 min^?1). The enzyme remained bound to PE even after soaking the PE in a starch solution for 72 h and was still found to be weakly active.     

Luminescence of Eu2+–vc− dipoles and their associates in CsI:Eu crystals

Spectral-kinetics properties of photo-scintillation excited with single light pulses of a nitrogen laser (λ=337.1 nm, t_1/2=5 ns, Q=1 mJ) have been studied in CsI:Eu crystals at temperature within 80–300 K. It is found that the exponential decay of 463 nm emission band has a time constant which grows from 0.85 μs at 78 K to 1.6 μs at 380 K. Such an anomalous temperature behavior of 463 nm emission decay kinetics is discussed in terms of the crystal thermal expansion. It has been proposed that 463 nm emission is caused by a cluster center consisting of three dipoles Eu²⁺v_c^? bounded with each other in a hexagon. Owing to the exchange resonance in the cluster, the energy passes from an excited dipole to a non-excited one and the distance between them gets longer due to thermal expansion of the crystal.     

Yellow-orange light emission from Mn2+-doped ZnS nanoparticles

ZnS nanoparticles with Mn²⁺ doping (1–2.5%) have been prepared through a simple soft chemical route, namely the chemical precipitation method. The nanostructures of the prepared undoped ZnS and Mn²⁺-doped ZnS:Mn nanoparticles have been analyzed using X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–vis spectrophotometer. The size of the particles is found to be in 2–3 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample only exhibits a blue-light emission peaked at ∼365 nm under UV excitation. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn^{2+ 4}T₁–⁶A₁ transition is observed along with the blue emission. The prepared 2.5% Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission at ∼580 nm with the blue emission suppressed.     

A highly luminescent complexes of Eu(III) and Tb(III) with norfloxacin and gatifloxacin doped in sol–gel matrix: A comparable approach of using silica doped Tb(III) and Eu(III) as optical sensor

Highly luminescent complexes of Eu and Tb ions with norfloxacin (NFLX) and gatifloxacin (GFLX) were prepared in sol–gel matrix. The red and green emissions of Eu and Tb ions were obtained by the energy transfer from the triplet state of (NFLX) and (GFLX) to the excited emitting states (⁵D₀ and ⁵D₄) of Eu and Tb, respectively. The intensity of the electric field emission bands (⁵D₀→⁷F₂, 617 nm and ⁵D₄→⁷F₅, 545 nm) of Eu and Tb ions were proportional to the concentration of (NFLX at pH 6.0) and (GFLX at pH 3.5) in acetonitrile with excitation wavelengths (λ_ex) (340 and 395) and (370 and 350 nm) for Eu and Tb ions, respectively. The monitored luminescence intensity of the system showed a good linear relationship with the concentration of NFLX within a range of 5×10^?9–5.8×10^?6 and 5×10^?8–1.0×10^?6 mol L^?1 with a correlation coefficient of 0.990, and for GFLX within a range of 2.4×10^?9–3.2×10^?5 and 5×10^?8–8.0×10^?6 mol L^?1 with a correlation coefficient of 0.995. The detection limit (LOD) was determined as 3.0×10^?9 and 1.0×10^?8 mol L^?1 for NFLX and 1.6×10^?10 and 2.0×10^?8mol L^?1 for GFLX. The limit of quantification (LOQ) is 9×10^?9 and 3.0×10^?8 and 4.8×10^?10 and 6.0×10^?8 in case of Eu and Tb, respectively.