Fluorescent Carbon Dot as Nanosensor for Sensitive and Selective Detection of Cefixime Based on Inner Filter Effect

Here a simple and sensitive fluorescent assay for detecting Cefixime based on inner filter effect (IFE) has been proven, which is conceptually different from the previously reported CEF fluorescent assays. In this sensing platform, fluorescent carbon dots (CDs) were prepared by one-pot synthesis and was directly used as fluorophore in IFE. The method is based on the complexation reaction between cefixime and palladium ion in the presence of acidic buffer solution (pH 4). The Pd(II)-CEFcomplex was capable of functioning as a powerful absorber in IFE to influence the excitation of fluorophore (CDs). Production Pd(II)-CEFcomplex induced the absorption band transition from 310 to 400 nm, which resulted in the complementary overlap with the excitation spectra of CDs. Due to the competitive absorption, the excitation of CDs was significantly weakened, resulting in the quenching of CDs. The present IFE-based sensing strategy showed a good linear relationship from 0.2 × 10^?6 M to 8 × 10^?6 M (R² = 0.987) and provided an exciting detection limit of 0.5 × 10^?7 (3δ/slope). The proposed method has been successfully applied for the determination of cefixime in raw milk and human urine samples.     

Measurements of carbon monoxide mixing ratios in Houston using a compact high-power CW DFB-QCL-based QEPAS sensor

Measurements of carbon monoxide (CO) mixing ratios in Houston, Texas, during the period from May 16, 2013 to May 28, 2013 were performed using a sensitive, selective, compact, and portable quartz-enhanced photoacoustic spectroscopy (QEPAS)-based CO sensor employing a high-power continuous wave (CW) distributed feedback quantum cascade laser (DFB-QCL). The minimum detectable CO concentration was 3 ppbv for the strong, interference-free R(6) absorption line at 2,169.2 cm^?1 and a 5 s data acquisition time. The average CO concentration during the measurement period was 299.1 ± 81.4 ppb with observed minimum and maximum values of 210.5 and 4,307.9 ppb, respectively. A commercially available electrochemical sensor was employed in-line for simultaneous measurements to confirm the response of the CW DFB-QCL-based QEPAS sensor to variations of the CO mixing ratios. Moderate agreement (R ² = 0.7) was found between both sets of CO measurements.     

Hyperfine interactions in intermetallic rare earth-gallium compounds studied by 111 Cd PAC

Magnetic and electric hyperfine interaction of the nuclear probe ¹¹¹In/¹¹¹Cd in intermetallic compounds of the rare earth-gallium system have been investigated by perturbed angular correlation (PAC) spectroscopy. The PAC measurements, supported by X-ray diffraction, provide evidence for a marked phase preference of ¹¹¹In for hexagonal RGa₂ over orthorhombic RGa and of RGa₃ with the L12 structure over RGa₂. In the case of SmGa₂, the magnetic hyperfine field B_hf, the electric quadrupole interaction and the angle β between B_hf and the symmetry axis of the electric field gradient have been determined as a function of temperature. The angle β?=?0 is consistent with the results of previous magnetization studies. Up to T?≤?17 K the magnetic hyperfine field has a constant value of B_hf?=?3.0(2) T. The rapid decrease at higher T gives the impression of a first-order transition with an order temperature of T_N?=?19.5 K. In the RKKY model of indirect 4f interaction the ratio T_C/B_hf(0) is a measure of the coupling constant. For ¹¹¹Cd:SmGa₂ (T_C/B_hf(0)~6.5 K/T) this ratio is significantly smaller than for the same probe in other R intermetallics (SmAl₂ ~9.5 K/T, Sm₂In ~13.5 K/T).     

Potential dependent EIS investigation of FeF<Subscript>3</Subscript> · 0.33H<Subscript>2</Subscript>O/C nano-composite synthesized by one-step solid-state method

To further study the lithium ion transportation behavior of cathode material FeF₃?·?0.33H₂O/C synthesized by a simple one-step chemico-mechanical method, the Electrochemical impedance spectrum (EIS) measured at series of open-circuit voltages were investigated in detail. The results showed that the EIS profiles of FeF₃?·?0.33H₂O/C materials were strongly potential dependent. The equivalent circuit parameters obtained by fitting the experimental data as a function of open-circuit voltage (OCV) level were depicted. The ohmic resistance R0, solid electrolyte inter-phase resistance R _SEI, electronic conduction resistance R _E, charge transfer resistance R _R, and Q parameter of CPE circuit characteristic of Li⁺ diffusion Q _diff all showed a sudden change at the OCV level 2.5 V. Ohmic resistance R0 had a relatively lower resistance of ca. 10 Ω above OCV level 2.5 V and a higher resistance of about 40 Ω below 2.5 V. Similar situation was also observed for R _SEI, which was around 20 Ω above 2.5 V and soared up quickly when the equilibrium potential fell below 2.5 V. Similar variations were also observed for R _E and R _R. A high resistance of ca. 410 and 520 Ω was obtained at OCV level 2.05 V, respectively. Q _diff showed a convex profile, which matched the variation of Li⁺ diffusion coefficient well.     

X-ray structure refinement and ionic conductivity of Na6.69Ca3.355(SO4)6Cl0.77F0.63

The structure of Na_6.69Ca_3.355(SO₄)₆Cl_0.77F_0.63, isostructural with fluorapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed a space group P6₃/m with lattice parameters of a?=?9.477 (2) Å, c?=?6.865 (5) Å. Final refinement led to R _F?=?1.83 % and R _B?=?7.64 %. The location of Na⁺ ions in the M (2) sites surrounding the channels was related particularly to the high polarizability of the Ca²⁺. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at σ _500 °C?=?1.03?×?10^?5?S?cm^?1 and E_a?=?0.70 eV.     

Synthesis,DNA/HSA Interaction Spectroscopic Studies and In Vitro Cytotoxicity of a New Mixed Ligand Cu(II) Complex

A new mixed ligand copper(II)-dipeptide complex with 2-(2′-pyridyl)benzothiazole (pbt), [Cu(Gly-L-leu)(pbt)(H₂O)]·ClO₄ (Gly-L-leu = Glycyl-L-leucine anion) was synthesized and characterized by various physico-chemical means. The DNA binding and cleavage properties of the complex investigated by viscosity, agarose gel electrophoresis and multi-spectroscopic techniques (UV, circular dichroism (CD) and fluorescence) showed that the complex was bound to CT-DNA through intercalation mode with moderate binding constant (K _b = 3.132 × 10⁴ M^?1), and cleaved pBR322 DNA efficiently (~ 5 μM) in the presence of Vc, probably via an oxidative mechanism induced by ?OH. Additionally, the interaction of the complex with human serum albumin (HSA) was explored by UV-visible, CD, fluorescence, synchronous fluorescence and 3D fluorescence spectroscopy. The complex exhibits desired affinity to HSA through hydrophobic interaction. Moreover, the cytotoxicity of the complex against three human carcinoma cell lines (HeLa, HepG2 and A549) was evaluated by MTT assay, which showed that the complex had effective cytotoxicity and higher inhibition toward A549 cell lines with IC₅₀ of 38.0 ± 3.2 μM.     

Δ Isobar Degrees of Freedom in the 3He Transverse Electron Scattering Response Function

The importance of Δ(1232) isobar degrees of freedom is investigated for the transverse (e, e′) response of ³He in the quasi-elastic peak region and beyond (considered momentum transfer range: 500 ≤ q ≤ 1,000 MeV/c). Besides Δ isobar currents (Δ-IC) meson exchange currents and relativistic corrections to the nucleonic one-body current are included. The calculation is carried out by using the Lorentz integral transform (LIT) method. Results for the transverse response function R _T are presented up to q = 700 MeV/c, whereas for higher q only some preliminary results for the LIT of R _T are discussed. In the quasi-elastic peak region Δ-IC enhance R _T by about 5% and tend to cancel three-nucleon force effects. One observes an excellent agreement with experimental R _T results. Particularly strong Δ-IC contributions are found for transitions into the final state with isospin T = 3/2, which is only reachable in three-body break-up reactions.     

Selective Spectrofluorimetric Method with Enhanced Sensitivity for Determination of Silodosine in Dosage Form and Human Plasma. Application to Stability Studies and Content Uniformity Testing

A novel, sensitive and selective spectrofluorimetric method has been developed and validated for determination of silodosine (SLD) in its dosage form and human plasma. The method is based on nucleophilic substitution reaction of SLD with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride) in presence of 5.0 × 10^?4 M sodium carbonate (pH 10.50) to yield a highly fluorescent derivative that was measured at 435 nm after excitation at 347 nm. The different experimental parameters affecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence-concentration plot was rectilinear over the range 30.0–200.0 ng ml^?1, with a correlation coefficient of 0.9979. The limits of detection (LOD) and quantification (LOQ) were found to be 5.44 and 16.47 ng ml^?1, respectively. The proposed method was validated according to ICH guidelines, and successfully applied to the assay of commercial capsules as well as content uniformity testing. The high sensitivity of the proposed method allowed its successful application to the analysis of SLD in spiked human plasma with % recovery of 92.88 ± 1.05–100.73 ± 0.75%, (n = 6). The application of the proposed method was further extended to stability studies of SLD after exposure to different forced degradation conditions, such as acidic, alkaline and oxidative conditions, according to ICH guidelines, where this work describe the first attempt for selective spectrofluorimetric determination of silodosine in plasma and in the presence of its oxidative degradation.     

Fabrication and characterization of Ni-SSZ/SSZ/LSM-SSZ anode-supported SOFCs by tape casting and single-step co-sintering techniques

In this work, Ni-10 % Sc₂O₃-stabilized ZrO₂ (SSZ)/SSZ/La_0.8Sr_0.2MnO_3-δ (LSM)-SSZ anode-supported solid oxide fuel cells (SOFCs) have been successfully prepared by tape casting and single-step co-sintering procedures. The structure contains Ni-SSZ anode substrate and Ni-SSZ anode functional, dense SSZ electrolyte, LSM-SSZ cathode functional, and LSM-SSZ cathode layers were successfully prepared at 1250, 1300, and 1350 °C, respectively. The microstructures of the single cells were examined by SEM. There were some close pores in electrolyte of Cell-1250, and the cathode particle size obviously increased in Cell-1350. Therefore, Cell-1300 showed the optimal cell performance, the maximum power density attained 920 mW cm^?2 at 800 °C. The impedance analysis demonstrated that the co-sintered temperatures have effects on not only the polarization resistance R _P of a single cell but also its overall ohmic resistance R _S . The results indicate that the tape casting and single-step co-sintering methods are both time saving and feasible for the development of anode-supported SOFCs.     

Influence of differential stress on the galvanic interaction of pyrite–chalcopyrite

The effect of stress action on pyrite–chalcopyrite galvanic corrosion was investigated using polarization curves and electrochemical impedance spectroscopy (EIS) measurements. When stress increased from 0 to 4?×?10⁵ Pa, the corrosion current density of pyrite–chalcopyrite increased from 5.678 to 6.719 μA cm^?2, and the corrosion potential decreased from 281.634 to 270.187 mV, accompanied by a decrease in polarization resistance from 25.09 to 23.79 Ω·cm². EIS results show there have three time constants in the Nyquist diagrams, which indicated the presence of different steps during the corrosion process. Stress dramatically enhanced pyrite–chalcopyrite galvanic corrosion by affecting the Cu_1???x Fe_1???y S₂ film and the double layer, whereas had little impact on the adsorption species. When the stress changed from 0 to 4?×?10⁵ Pa, the pore resistance and capacitance of the Cu_1???x Fe_1???y S₂ film, R _p and Q _p, changed by 25.72 and 72.28 %, respectively. The adsorption species resistance, R _sl, and capacitance, Q _sl, only changed by 9.77 and 2.31 %, respectively.     

Use and Evaluation of Newly Synthesized Fluorescence Probes to Detect Generated OH• Radicals in Fibroblast Cells

Reactive oxygen species (ROS) are pro-oxidant molecules synthesized in body with various functions and are essential for life. Increasing in reactive oxygen species or decreasing in antioxidants level cause oxidative stress which is very harmful. OH? radical is one of ROS’s, with tendency to bind to lipids, DNA and proteins which cause irreversible damage in cells. The most devastating consequences related to excess OH? radicals occur via direct binding to nucleic acids and proteins. Quantification of this high reactive radical with short life time is difficult. Electron Spin Resonance, Fluorescence, and Luminescence Spectroscopy are commonly used to determine the level of ROS. Fluorescence Probes have higher specificity and sensitivity with their excellent sensors to detect ROS’s compare to the other methods. Also, there are different probes specifically designed for each radical. The purpose of this study was to identify the probe better suiting for detection of OH? radical levels. The two most recommended fluorescence probes, 2-[6-(4 V-Hydroxy) phenoxy-3H-xanthen-3-on-9-yl]benzoic acid (HPF) and coumarin-3-carboxylic acid (3-CCA) to determine OH? radical levels were compared. Following the formation of OH? radical with Fenton reaction, HPF and 3-CCA probes were added to cells and spectrofluorometric measurements were performed in their respective wavelengths. The mean amplitude of fluorescence for HPF was 32.72?±?2.37 F.I (n?=?40) and for 3-CCA was 52.11?±?0.5 F.I (n?=?40). This difference was statistically significant. 3-CCA also demonstrated more stable measurements at different days compered to HPF.     

Measurement of the pH value in pork meat early postmortem by Raman spectroscopy

The pH of a muscle is an accepted parameter to identify normal and deviating meat qualities. In this work, Raman spectroscopy is shown to be suitable for the non-invasive measurement of the early postmortem pH of meat. Raman spectra of ten pork semimembranosus muscles were recorded with a portable handheld device 0.5–24 h postmortem. The spectra were correlated with pH and lactate kinetics measured in parallel. Seven of the muscles were normal, two exhibited accelerated glycolysis and one showed absence of acidification. The pH decline with time could be calculated from the Raman spectra with the Henderson–Hasselbalch equation using only two signals of phosphate vibrations at 980 and 1,080 cm^?1 with a close correlation for each muscle, but larger variations between animals. More robust and better correlations for all muscles were obtained with a linear model based on 11 signals from lactate, lactic acid, phosphate, a carbonyl band and nucleotides resulting in R ² = 0.78 and RMSECV = 0.2 or a partial least-square model using the complete spectrum (R ² = 0.94 and RMSECV = 0.2). These results show the potential of Raman spectroscopy for an online detection of the pH and thus meat qualities during meat processing.     

Low-Lying S-States of Two-Electron Systems

The energies of the low-lying bound S-states of some two-electron systems (treating them as three-body systems) like negatively charged hydrogen, neutral helium, positively charged-lithium, beryllium, carbon, oxygen, neon, argon and negatively charged muonium and exotic positronium ions have been calculated employing hyperspherical harmonics expansion method. The matrix elements of two-body interactions involve Raynal–Revai coefficients which are particularly essential for the numerical solution of three-body Schr?dinger equation when the two-body potentials are other from Coulomb or harmonic. The technique has been applied for to two-electron ions ¹H^? (Z = 1) to ⁴⁰Ar¹⁶⁺ (Z = 18), negatively charged-muonium Mu^? and exotic positronium ion Ps^?(e ⁺ e ^? e ^?) considering purely Coulomb interaction. The available computer facility restricted reliable calculations up to 28 partial waves (i.e. K _m  = 28) and energies for higher K _m have been obtained by applying an extrapolation scheme suggested by Schneider.     

Tailored Nitroxide Radicals and Biradical Containing <Superscript>13</Superscript>C Enriched Acetylene Groups: ENDOR and DFT Investigation

A specially synthesized nitroxide biradical R₅-C≡¹³C-(p-C₆H₄)₂-¹³C≡C-R₅ (B4) and two radicals, R₅-C≡¹³CH (RCC) and R₅-C≡¹³C-C₆H₅ (RCCPh), where R₅ is 1-oxyl-2,2,5,5-tetramethyl-pyrroline group, have been studied by X- and W-band electron paramagnetic resonance (EPR) spectroscopy, and by W-band electron-nuclear double resonance (ENDOR). Spin density distribution and hyperfine splitting (hfs) constants on ¹³C atoms were experimentally determined and also calculated using ORCA 3.0.3 program package. The biradical and radicals geometries were optimized on UKS/B3LYP/cc-pVDZ level. Hfs constants were calculated using density functional theory (DFT) with PBE0 functional and N07D, and were compared with the experimental value of the hfs constant on ¹³C atoms, measured from ENDOR spectra. It is concluded that at small values of the exchange integral as J ≤ a/2 ≈ 7–8 G, the current quantum chemical approaches do not allow determining precise values of the hfs constants on the ¹³C atoms in the bridge connecting two paramagnetic nitroxide rings of the biradical.     

Ultrasonic preparation of tetraoxalyl ethylenediamine melamine resin-coated multiwalled carbon nanotubes for trace Ni(II) sensing

Under an aid of ultrasonic, tetraoxalyl ethylenediamine melamine resin-coated multiwalled carbon nanotubes were prepared for Ni(II) sensing in aqueous solution. The processes involved the fabrication of tetraoxalyl ethylenediamine melamine resin by one pot way, the coating of tetraoxalyl ethylenediamine melamine resin at multiwalled carbon nanotubes (MWCNTs), and the determination of Ni(II). The present materials were carefully examined by Fourier transform infrared spectroscopy, field emission scanning electron microscope, and electrochemistry techniques. A great deal of amorphous microsphere could be observed for tetraoxalyl ethylenediamine melamine resin with an average diameter of 1.2 μm, and MTE could evenly adhere at the surface of MWCNTs by the ultrasonic. Tetraoxalyl ethylenediamine melamine resin-coated multiwalled carbon nanotube-modified paraffin-impregnated graphite electrode was successfully used for the determination of Ni(II) by differential pulse adsorptive anodic stripping voltammetry. The current responses (?0.3 V) were linearly increased depending on the concentration from 1?×?10^?11 to 3?×?10^?10 M (i (μA)?=?11.1?+?7.9 c (1?×?10^?12 M); R?=?0.9901, 3σ?=?7?×?10^?12 M).     

RF-sputtered LiCoO2 thick films: microstructure and electrochemical performance as cathodes in aqueous and nonaqueous microbatteries

Films of LiCoO₂ are prepared on metallized silicon substrates using RF-magnetron sputtering technique. The microstructural properties of the films are investigated by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The films deposited at a substrate temperature of 250 °C with subsequent annealing at 650 °C exhibited hexagonal layered structure with R $ \overline 3 $ m symmetry. The kinetics of lithium ions in LiCoO₂ film cathode host matrix and its cycleability are studied in aqueous Pt//LiCoO₂ and nonaqueous Li//LiCoO₂ cell. Both the electrochemical cells at same current density of 50 μA cm^?2 delivered the same initial discharge capacity of about 60 μA h?cm^?2 μm^?1 with a chemical diffusion coefficient of ca. 10^?11 cm² s^?1 for Li⁺ ions. The capacity fade rates for the Pt//LiCoO₂ and Li//LiCoO₂ cells, in average are 3.0 and 0.15 % per cycle, respectively, for the first 20 cycles. The Pt//LiCoO₂ cell is found to be advantageous for small number of cycles and is cost effective than the Li//LiCoO₂ cell.     

EPR Study of γ-Irradiated UHMWPE Doped with Vitamin E: Assessment of Thermal Effects on the Organic Radicals During Vitamin E Diffusion

Thermal effects on ultra-high-molecular-weight polyethylene (UHMWPE) residual radicals during the vitamin E diffusion process were studied in detail. Electron paramagnetic resonance (EPR) technique showed a significant reduction in concentrations of radiation-induced primary (alkyl (–CH₂– ^?CH–CH₂–), allyl (–CH₂–^?CH=CH–CH–CH₂–) and polyenyl (–^?CH–[CH=CH–] _m –) with m > 3) radicals for both control and vitamin E-doped samples. The concentrations of radiation-induced primary radicals (RIPRs) were found to decrease proportionally with the heat/diffusion time. While the EPR spectra of the control samples showed only polyethylene (PE) radicals, the spectra of vitamin E-doped samples were found to exhibit vitamin E radicals in addition to PE radicals. Of particular interest, the heat involved during vitamin E diffusion plays a significant role in reducing the radiation-induced primary radicals of UHMWPE. For 120 min of heat/diffusion time, the available quantity of primary radicals in control samples were found to be ~7.5 % of initial radicals. The leftover amounts of these primary radicals for vitamin E-doped samples were approximately ~10.0 %. In addition to this, EPR power saturation techniques were also used to assess the effects of initial heat/diffusion treatment on the oxygen-induced residual radicals (OIRRs): R₁ (–^?CH–[CH=CH–] _m –) with m > 3 and R₂ (^?OCH–[CH=CH–] _m –) with m = 2 or 3. It was found that the concentration of OIRRs also decreases proportionally with initial heat/diffusion time. The remaining amount of OIRRs relative to leftover RIPRs after heat/diffusion was found to be approximately 4.0 % in controls and was still found to be 10.0 % in vitamin E-doped UHMWPE. This may indicate that vitamin E slows down the oxidation processes, which may contribute to the strong oxidation resistance of vitamin E-doped UHMWPE.     

Threshold 3He and 3H Transverse Electron Scattering Response Functions

The threshold transverse response functions R _T (q, ω) for ³He and ³H are calculated using the AV18 nucleon–nucleon potential, the UrbanaIX three-body force, and the Coulomb potential. Final states are completely taken into account via the Lorentz integral transform technique. Consistent two-body π- and ρ-meson exchange currents as deduced using the Arenhövel-Schwamb technique are included. The convergence of the method is shown and a comparison of the corresponding MEC contribution is made to that of a consistent MEC for the meson theoretical r-space BonnA potential. The response R _T is calculated in the threshold region at q = 174, 324, and 487 MeV/c and compared with available data. The strong MEC contributions in the threshold region are nicely confirmed by the data at q = 324 and 487 MeV/c although some differences between theoretical and experimental results remain. A comparison is also made with other calculations, where the same theoretical input is used. The agreement is generally rather good, but leaves also some space for further improvement.     

Effects of Al doping for Li[Li0.09Mn0.65*0.91Ni0.35*0.91]O2 cathode material

Li-rich Mn-based Li[Li_0.09Mn_{0.65*(0.91???x)} Ni_{0.35*(0.91???x)} Al _x ]O₂ cathode materials have been prepared by traditional solid-state reaction. The lattice parameters a, c, and V have decreased, but c/a increased with the increase of Al doping. All the samples show analogy morphology of a quasi-spherical shape. Li[Li_0.09Mn_0.591Ni_0.319]O₂ sample shows a higher initial discharge capacity of 239.4 mAh?g^?1 at 20 mA?g^?1, while Li[Li_0.09Mn_0.582Ni_0.314Al_0.015]O₂ sample presents a higher discharge capacity of 170.1 mAh?g^?1 and ratio of 72.0 % with 200 vs. 20 mA?g^?1. The solid electrolyte interface resistance (R _SEI) and charge transfer process resistance (R _ct ) values are relatively smaller for Al-doped samples than those of non-doped samples. Almost no reduction is observed after 24-time cycles in different discharge rates for the samples prepared.     

Total cross sections for 4,6He + 28Si reactions measured at 10–28 MeV/A

New results on the energy dependence of the total cross section (σ _R) for ⁶He scattering on ²⁸Si in the incident energy range 10–28 MeV/A are obtained. The α-particle-production cross sections for the ²⁸Si(⁶He, ⁴He)X channel are measured as well. The secondary beam of ⁶He with an intensity of up to 5×10⁴ particle/s was generated by bombarding a thick beryllium target with ～32-MeV/A ⁷Li ions. In the energy region below 17 MeV/A, σ _R increases sharply. The experimental dependences of the total cross sections are compared with the results of σ _R calculations using the double-folding potential within the optical model. The energy dependence of σ _R for ⁶He differs from that for the neighboring nuclei, which can be associated with the structural features of the former nucleus. The energy spectra of α particles produced in the ⁶He interactions with silicon indicate two mechanisms of their production: transfer reaction and ⁶He breakup in the field of the ²⁸Si nucleus.