Hydrothermal synthesis of functionalized CdS nanoparticles and their application as fluorescence probes in the determination of uracil and thymine

A novel, sensitive, and convenient method for the determination of uracil and thymine by functionalized CdS nanoparticles (NPs) was proposed. CdS NPs were prepared by hydrothermal process and modified with thioglycollic acid (TGA) in aqueous solution. The fluorescence intensity of functionalized CdS NPs was quenched in the presence of uracil or thymine. Under optimal conditions, the relative fluorescence intensity (F₀/F) was proportional to the concentration in the range of 9.0×10^?6–1.0×10^?4 mol/L for uracil (r=0.9985) and 8.8×10^?7–1.5×10^?4 mol/L for thymine (r=0.9960). The corresponding detection limits were 9.6×10^?7 mol/L and 3.2×10^?7 mol/L, respectively. In addition, the possible quenching mechanism was also discussed.     

Ultrasonic assisted-Fenton-like degradation of nitrobenzene at neutral pH using nanosized oxides of Fe and Cu

Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe₂O₃ and CuO were prepared, characterized and tested in degradation of NB (10 mg L⁻¹) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H₂O₂ after 10 min of sonication in presence of α-Fe₂O₃ (1.0 g L⁻¹), (k = 0.58 min⁻¹) and after 25 min in case of CuO (k = 0.126 min⁻¹). α-Fe₂O₃ showed also effective degradation under the conditions of 0.1 g L⁻¹ oxide and 5.0 mM of H₂O₂, even though with a lower rate constant (0.346 min⁻¹). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.     

Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)

Phase transformations in squaric acid (H₂C₄O₄) have been investigated by thermogravimetry and differential scanning calorimetry with different heating rates β. The mass loss in TG apparently begins at onset temperatures T_di=245±5 °C (β=5 °C min^?1), 262±5 °C (β=10 °C min^?1), and 275±5 °C (β=20 °C min^?1). A polymorphic phase transition was recognized as a weak endothermic peak in DSC around 101 °C (T_c⁺). Further heating with β=10 °C min^?1 in DSC revealed deviation of the baseline around 310 °C (T_i), and a large unusual exothermic peak around 355 °C (T_p), which are interpreted as an onset and a peak temperature of thermal decomposition, respectively. The activation energy of the thermal decomposition was obtained by employing relevant models. Thermal decomposition was recognized as a carbonization process, resulting in amorphous carbon.     

Green synthesis of finely-dispersed highly bactericidal silver nanoparticles via modified Tollens technique

In this article, we represent a versatile and effective technique which using non-toxic chemicals to prepare stable aqueous dispersions of silver nanoparticles (NPs) via modified Tollens process. It was shown that as-prepared silver colloids consisted of finely-dispersed NPs with average diameter about 10 nm and a relatively narrow size distribution. Moreover, they could be stored very stable after several months without observation of aggregates or sedimentation. In comparison with previous works where Tollens process was being used, we for the first time applied UV-irradiation simultaneously with glucose reduction of silver salt through NPs preparation. The colloidal solutions of silver NPs were found to exhibit a high antibacterial activity against gram-negative Escherichia coli. The concentration of silver leading to a complete inhibition of bacteria growth was revealed as low as at 1.0 μg ml⁻¹ and found much lower compared to earlier reports. These advantages of aqueous dispersions of silver NPs make them ideal for green industrial, medicinal, microbiological and other applications.     

Ce0.8Sm0.2O1.9 synthesis for solid oxide fuel cell electrolyte by ultrasound assisted co-precipitation method

In this study, the synthesis of Ce_0.8Sm_0.2O_1.9 (SDC) solid electrolyte by the ultrasound assisted co-precipitation method was accomplished to explore the effects of ultrasound power, ultrasound pulse ratio and probe type upon the ionic conductivity of SDC as well as the lattice parameter, the microstructure and the density. Fine powders of uniform crystallite sizes (average 11.70 ± 0.62 nm) were obtained, needing lower sintering temperature. The SDC powders were successfully sintered to a relative density of over 95% at 1200 °C (5 °C min^?1) for 6 h. The micrograph of SDC pellets showed non-agglomerated and well-developed grains with average size of about 200 nm. X-ray diffraction analysis showed that the lattice parameter increased with increasing acoustic intensity and reached a maximum for the 14.94 W cm^?2. Further, a linear relationship was detected between the lattice parameter and the ionic conductivity, inspiring a dopant like effect of US on the electrolyte properties. The highest ionic conductivity as σ_800°C = 3.07 × 10^?2 S cm^?1 with an activation energy E_a = 0.871 kJ mol^?1 was obtained with pulsed ultrasound for an acoustic intensity of 14.94 W cm^?2, using 19 mm probe and 8:2 pulse ratio.     

Preparation and photocatalytic degradation of erbium doped titanium dioxide nanorods

Photocatalytic degradation of methylene blue (MB) in water was examined using Er³⁺-doped TiO₂ (Er–TiO₂) nanorods prepared by a sol–gel derived electrospinning, calcination, and subsequent mechanical grinding. Different concentrations of Er dopant in the range of 0–1.0 mol% were synthesized to evaluate the effect of Er content on the photocatalytic activity of TiO₂. Among Er³⁺–TiO₂ catalysts, the 0.7 mol% Er³⁺–TiO₂ catalyst showed the highest MB degradation rate. The degradation kinetic constant (k) increased from 1.0 × 10^?3 min^?1 to 5.1 × 10^?3 min^?1 with the increase of Er³⁺ doping from 0 to 0.7 mol%, but decreased down to 2.1 × 10^?3 min^?1 when Er³⁺ content was 1.0 mol%. It can be concluded that the degradation of MB under UV radiation was more efficient with Er³⁺–TiO₂ catalyst than with pure TiO₂. The higher activity might be attributed to the transition of 4f electrons of Er³⁺ and red shifts of the optical absorption edge of TiO₂ by erbium ion doping.     

Ultra-fast grain boundary diffusion and its contribution to surface segregation on a martensitic steel. Experiments and modeling

Phosphorus surface segregation was measured by Auger Electron Spectroscopy on a 17-4 PH martensitic stainless steel at 450, 550 and 600 °C. Surface segregation was shown to be much faster than expected which was attributed to a high contribution of phosphorus diffusion along the former austenitic grain boundaries. A model of surface segregation was developed following the Darken–du Plessis approach and taking account of both bulk and grain boundary solute diffusion. The phosphorus grain boundary diffusion coefficient in 17-4 PH was estimated: D_GB^< = 6.2 10⁴ exp(? 157 kJ mol^? 1/RT)cm² s^? 1. It is found to be more than three orders of magnitude higher in 17-4 PH steel than in α-iron.     

Ultrasonic and DFT study of intermolecular association through hydrogen bonding in aqueous solutions of d(−)-arabinose

The experimental measurements of density, viscosity and ultrasonic velocity of aqueous d-arabinose solutions were carried out as functions of concentration (0.1 ≤ m [mol kg^? 1] ≤ 1.0) and temperature (303.15 ≤ T [K] ≤ 323.15). The isentropic compressibility (β_s), acoustic impedance (Z), hydration number (H_n), intermolecular free length (L_f), classical sound absorption (α/f²)_class and shear relaxation time (τ) were calculated by using the measured data. These parameters have been interpreted in terms of solute–solvent interactions. The quantum chemical calculations were performed to study the hydrogen bonding in interacting complex formed between α-D-arabinopyranose in ¹C₄ conformation and water molecules. Computations have been done by using Density Functional Theory (DFT) method at B3LYP/6-31+g(d) level of theory to study the equilibrium structure of α-d-arabinose, α-D-arabinopyranose–water interacting complex and vibrational frequencies. The solution phase study was carried out using Onsager's reaction field model in water solvent. The computed and scaled vibrational frequencies are in good agreement with the main features of the experimental spectrum when seven water molecules are considered explicitly with α-D-arabinopyranose in ¹C₄ conformation. The interaction energy (E_total), hydrogen bond lengths and dipole moment (μ_m) of the interacting complex are also presented and discussed with in the light of solute–solvent interactions.     

Study on the kinetics properties of lithium hexafluorophosphate thermal decomposition reaction

The thermal decomposition of lithium hexafluorophosphate was studied by using C80 calorimeter, and the samples were heated at a 0.2 K·min^− 1 heating rate from ambient temperature to 573 K in pressure-sensitive transducer fitted and sealed vessel with argon atmosphere. It is found that LiPF₆ decomposes near 433 K, and the gas product PF₅ causes the pressure increasing. The LiPF₆ decomposition reaction order is calculated based on the pressure data by two methods, its average value is n = 1.5, then, the reaction is assumed to be dependent on the Arrhenius law and mass action law, and thus the activation energy and pre-exponential factor were calculated to be E = 104.2 kJ·mol^− 1, A = 1.12 × 10⁷ s^− 1, respectively.     

An oxygen permeable membrane La0.8Sr0.2(Ga0.8Mg0.2)1 − xCrxO3 − δ for a reduced atmosphere

Mixed electron hole and oxide ion conducting perovskite-type oxides, La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ (0 ≤ x ≤ 1.0)_, were prepared by solid state reaction. The phase stability and the oxygen permeation properties of the oxides were examined as a function of the content of Cr. La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ has a perovskite related tetragonal phase with x = 0.1 to 0.8. The total electrical conductivity of La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ increases with increasing x. The oxygen permeation flux across the La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ membranes at higher temperatures increases with x up to x = 04. The maximum oxygen permeation flux of 1.6 × 10^? 7 mol^? 1 cm^? 2 at 1100 °C in a oxygen activity gradient of air/10^? 2 Pa is observed in La_0.8Sr_0.2(Ga_0.8Mg_0.2)_0.6Cr_0.4O_3 ? δ. This perovskite-type oxide is stable under an oxygen partial pressure of 7 × 10^? 10 Pa at 1000 °C.     

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.     

Sono-assisted preparation of highly-efficient peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2

Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs) with much improved peroxidase-like activity were successfully prepared through an advanced reverse co-precipitation method under the assistance of ultrasound irradiation. The characterizations with XRD, BET and SEM indicated that the ultrasound irradiation in the preparation induced the production of Fe₃O₄ MNPs possessing smaller particle sizes (16.5 nm), greater BET surface area (82.5 m² g^?1) and much higher dispersibility in water. The particle sizes, BET surface area, chemical composition and then catalytic property of the Fe₃O₄ MNPs could be tailored by adjusting the initial concentration of ammonia water and the molar ratio of Fe²⁺/Fe³⁺ during the preparation process. The H₂O₂-activating ability of Fe₃O₄ MNPs was evaluated by using Rhodamine B (RhB) as a model compound of organic pollutants to be degraded. At pH 5.4 and temperature 40 °C, the sonochemically synthesized Fe₃O₄ MNPs were observed to be able to activate H₂O₂ and remove ca. 90% of RhB (0.02 mmol L^?1) in 60 min with a apparent rate constant of 0.034 min^?1 for the RhB degradation, being 12.6 folds of that (0.0027 min^?1) over the Fe₃O₄ MNPs prepared via a conventional reverse co-precipitation method. The mechanisms of the peroxidase-like catalysis with Fe₃O₄ MNPs were discussed to develop more efficient novel catalysts.     

Interactions between 4-(2-dimethylaminoethyloxy)-N-octadecyl-1,8-naphthalimide and serum albumins: Investigation by spectroscopic approach

A novel 4-(2-dimethylaminoethyloxy)-N-octadecyl-1,8-naphthalimide (DON) has been synthesized as a spectrofluorimetric probe for the determination of proteins. Photophysics of DON in different solvents has been delineated in this paper. Progressive redshift with polarity of solvents in emission and absorption spectra hints at intramolecular charge transfer. The interactions of DON with serum albumins (i.e., human serum albumin (HSA) and bovine serum albumin (BSA)) were studied by fluorescence and absorption spectroscopy. Fluorescence data revealed that the quenching of HSA/BSA by DON were static quenching and the DON–HSA/BSA complexes were formed. The binding constant (K_b) for HSA and was found to be 8.44×10^?4 and 60.26×10^?4 M^?1 and the number of binding sites (n) were 1.00 and 1.40, respectively. The thermodynamic parameters, ΔH and ΔS, for the DON–HSA system was calculated to be ?14.83 kJ mol^?1 and 23.61 J mol^?1 K^?1, indicating the hydrogen bonds and hydrophobic interactions were the dominant intermolecular force. ΔH and ΔS for the binding of DON with BSA was ?60.08 kJ mol^?1 and ?90.7441 mol^?1 K^?1, suggesting the hydrogen bonds and van der Waals force played the main role in the interaction. The results of displacement experiments showed that DON bound HSA/BSA occurred at the Trp-214 proximity, located in subdomain IIA of the serum albumin structure (the warfarin binding pocket). The effect of DON on the conformation of HSA was also analyzed by synchronous and three-dimensional fluorescence spectra. The fluorescence of DON could be quenched by HSA, based on which, a fluorometric method for the determination of microamount protein using DON in the medium of HCl?Tris buffer solution (pH=7.4) was developed. The linear range of the calibration curves was 0.1–10.0 μM for HSA, 0.1–11.2 μM for BSA and 0.2–9.7 μM for egg albumin (EA). The detection limit (3σ) for HSA was 1.12×10^?10 M, for BSA it was 0.92×10^?10 M and for EA it was 4.33×10^?10 M. The effect of metal cations on the fluorescence spectra of DON in ethanol was also investigated. The method has been applied to detect the total proteins in human serum samples and the results were in good agreement with those reported by the hospital.     

Superconductivity in Nb2InC

In this work the Nb₂InC phase is investigated by X-ray diffraction, heat capacity, magnetic and resistivity measurements. Polycrystalline samples with Nb₂InC nominal compositions were prepared by solid state reaction. X-ray powder patterns suggest that all peaks can be indexed with the hexagonal phase of Cr₂AlC prototype. The electrical resistance as a function of temperature for Nb₂InC shows superconducting behavior below 7.5 K. The M(H) data show typical type-II superconductivity with H_C1 ～ 90 Oe at 1.8 K. The specific heat data are consistent with bulk superconductivity. The Sommerfeld constant is estimated as γ ～ 12.6 mJ mol^?1 K^?1.     

Reduction of thin-film ceria on Pt(111) by supported Pd nanoparticles probed with resonant photoemission

Local defects present in CeO_2 ? x films result in a mixture of Ce³⁺ and Ce⁴⁺ oxidation states. Previous studies of the Ce 3d region with XPS have shown that depositing metal nanoparticles on ceria films causes further reduction, with an increase in Ce³⁺ concentration. Here, we compare the use of XPS and resonant photoemission spectroscopy (RESPES) to estimate the concentration of Ce³⁺ and Ce⁴⁺ in CeO_2 ? x films grown on Pt (111), and the variation of this concentration as a function of Pd deposition. Due to the nature of the electronic structure of CeO_2 ? x, resonant peaks are observed for the 4d–4f transitions when the photon energy matches the resonant energy; (hν = 121.0 eV) for Ce³⁺ and (hν = 124.5 eV) for Ce⁴⁺. This results in two discrete resonant photoemission peaks in valence band spectra. The ratio of the difference of these peaks with off-resonance scans gives an indication of the relative contribution of Ce³⁺. Results from RESPES indicate reduction of CeO_2 ? x on deposition of Pd, confirming earlier findings from XPS studies.     

Spectroscopic studies on the interaction of bovine serum albumin with ginkgolic acid: Binding characteristics and structural analysis

The interaction between ginkgolic acid (GA, C15:0) and bovine serum albumin (BSA) is investigated by several spectroscopic methodologies. At first, the binding characteristics of GA and BSA are determined by fluorescence emission spectra. It is showed that GA quenches the fluorescence of BSA and the static quenching constant K_LB is 11.7891×10⁴ L mol^?1 s^?1 at 297 K. GA and BSA form a 1:1 complex with a binding constant of 9.12×10⁵ L mol^?1. GA binds to the Sudlow's drug binding site II in BSA, and the binding distance between them is calculated as 1.63 nm based on the Förster theory. The thermodynamic parameters indicate that the interaction between BSA and GA is driven mainly by hydrophobic forces. On the other hand, structural analysis indicates that GA binding results in an increased hydrophobicity around the tryptophan residues of BSA as revealed by the synchronous fluorescence spectra, and a decrease in α-helix as revealed by the far-UV CD spectra. In addition, ANS, UV–vis and RLS experiments confirmed that GA binding causes a certain structural changes in BSA. These findings provide the binding information between BSA and GA, and may be helpful for pharmacokinetics and the design of dosage forms of GA.     

DFT study of carbon monoxide adsorption on α-Al2O3(0001)

The adsorption of CO on α-Al₂O₃(0001) was studied using the DFT-GGA computational method and on α-Al₂O₃ powder experimentally by Infra red spectroscopy. The core and valence level regions of α-Al₂O₃(0001) single crystal surface were also studied experimentally. Ar ions sputtering of the surface results in a slight but reproducible decrease in the XPS O2p lines in the valence band regions due to preferential removal of surface (and near surface) O atoms. Core level XPS O1s and Al2p further confirmed oxygen depletion with an associated surface stoichiometry close to Al₂O_2.9. The adsorption energy of CO was computed and found equal to 0.52 eV for θ = 0.25, it decreased to 0.42 eV at θ = 1. The IR frequency of νCO was also computed and in all cases it was blue shifted with respect to gas phase CO. The shift, Δν, decreased with increasing coverage where it was found equal to 56 cm^? 1 for θ = 0.25 and decreased to 30 cm^? 1 for θ = 1. Structural analyses indicated that the change in the adsorption energy and the associated frequency shift is due to surface relaxation upon adsorption. Experimentally the adsorption of CO gave rise to one main IR peak at 2154 cm^? 1 at 0.3 Torr and above. Two far smaller peaks are also seen at lower pressures of 0.03–0.2 Torr at 2189 and 2178 cm^? 1. The isosteric heat of adsorption was computed for the IR band at 2154 cm^? 1 and was found equal to 0.2 eV which did not change with coverage in the investigated range up to θ = 0.6.     

Rapid preparation of high electrochemical performance LiFePO4/C composite cathode material with an ultrasonic-intensified micro-impinging jetting reactor

A joint chemical reactor system referred to as an ultrasonic-intensified micro-impinging jetting reactor (UIJR), which possesses the feature of fast micro-mixing, was proposed and has been employed for rapid preparation of FePO₄ particles that are amalgamated by nanoscale primary crystals. As one of the important precursors for the fabrication of lithium iron phosphate cathode, the properties of FePO₄ nano particles significantly affect the performance of the lithium iron phosphate cathode. Thus, the effects of joint use of impinging stream and ultrasonic irradiation on the formation of mesoporous structure of FePO₄ nano precursor particles and the electrochemical properties of amalgamated LiFePO₄/C have been investigated. Additionally, the effects of the reactant concentration (C = 0.5, 1.0 and 1.5 mol L⁻¹), and volumetric flow rate (V = 17.15, 51.44, and 85.74 mL min⁻¹) on synthesis of FePO₄·2H₂O nucleus have been studied when the impinging jetting reactor (IJR) and UIJR are to operate in nonsubmerged mode. It was affirmed from the experiments that the FePO₄ nano precursor particles prepared using UIJR have well-formed mesoporous structures with the primary crystal size of 44.6 nm, an average pore size of 15.2 nm, and a specific surface area of 134.54 m² g⁻¹ when the reactant concentration and volumetric flow rate are 1.0 mol L⁻¹ and 85.74 mL min⁻¹ respectively. The amalgamated LiFePO₄/C composites can deliver good electrochemical performance with discharge capacities of 156.7 mA h g⁻¹ at 0.1 C, and exhibit 138.0 mA h g⁻¹ after 100 cycles at 0.5 C, which is 95.3% of the initial discharge capacity.     

Enhanced OH radical generation by dual-frequency ultrasound with TiO2 nanoparticles: Its application to targeted sonodynamic therapy

The present study demonstrated the enhanced hydroxyl (OH) radical generation by combined use of dual-frequency (0.5 MHz and 1 MHz) ultrasound (US) and titanium dioxide (TiO₂) nanoparticles (NPs) as sonocatalyst. The OH radical generation became the maximum, when 0.5 MHz US was irradiated at an intensity of 0.8 W/cm² and 1 MHz US was irradiated at intensities at 0.4 W/cm² in the presence of TiO₂ NPs under the examined conditions. After incorporation of TiO₂ NPs modified with targeting protein pre-S1/S2, HepG2 cancer cells were subjected to the dual-frequency US at optimum irradiation intensities (“targeted-TiO₂/dual-US treatment”). Growth of the HepG2 cells was reduced by 46% compared with the control condition after irradiation of dual-frequency US for 60 s with TiO₂ NPs incorporation. In contrast, HepG2 cell growth was almost the same as that in the control condition when cells were irradiated with either 0.5 MHz or 1 MHz ultrasound alone without TiO₂ NP incorporation.     

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.