Kinetics and mechanism of the reaction of an arenediazonium ion with hydrophilic aminocarboxylic acids in aqueous buffered solution

The reaction of 4‐nitrobenzenediazonium ion, 4NBD, with the aminocarboxylic acids (AA) glycine and serine was studied under acidic conditions by using Linear Sweep Voltammetry (LSV), which allows simultaneous monitoring of 4NBD loss and product formation. Voltammograms of the reaction mixture are complex, showing up to five reduction peaks. The reduction peaks at E_p = ?0.5 and ?1.0 V, not detected in the absence of AA, are associated to products formed in the course of the reaction. The variation of their peak current, i_p, with time shows a complex behavior; that of i_p (E_p = ?1.0 V) follows a biphasic profile with i_p increasing with time up to a maximum after which a decrease is detected, suggestive of formation and subsequent decomposition of a transient intermediate, meanwhile i_p (E_p = ?0.5 V) increases with time after an induction period. The peaks at E_p = ?0.1 and ?0.8 V are associated to the reduction of the diazonium group of 4NBD and, in the presence of AA ([AA] >>> [4NBD]), their peak currents decrease exponentially with time following clean first‐order kinetics for more than 3t_1/2. The variation of k_obs with [AA] at a given pH is linear with an intercept equal to zero and that of log(k_obs) with pH at constant [AA] is also linear. Kinetic evidence is consistent with a reaction mechanism involving an irreversible, rate‐limiting bimolecular step which leads to the formation of an unstable triazene, which further decomposes yielding 4‐nitroaniline among other reaction products. Copyright © 2007 John Wiley & Sons, Ltd.     

Some new 4‐coordinated nanostructure cadmium imidazolidine Schiff base complexes: Thermal behavior,antimicrobial, and DNA cleavage potential

In this study, a new series of cadmium halide/pseudohalide complexes with a novel Schiff base ligand containing imidazolidine ring has been successfully synthesized. The structure of the ligand and its complexes was characterized by analysis tools such as Fourier transform infrared, UV‐visible, proton and carbon nuclear magnetic resonance spectra, molar conductance, and thermal analysis. Also cadmium bromide and iodide nanostructure complexes have been prepared via sonochemical method. X‐ray powder diffraction and scanning electron microscopy techniques confirmed nanostructure sheets for these 2 cadmium complexes. All the newly prepared compounds were screened for their antimicrobial activities, against 4 bacterial and 2 fungal strains using disk diffusion and serial dilution methods. The CdL(N₃)₂ and CdLCl₂ complexes showed the best antimicrobial activity as compared with other compounds. Moreover, DNA cleavage potential of all compounds was investigated by agarose gel electrophoresis method. The results showed remarkable ability of some cadmium complexes for DNA cleavage. Furthermore, thermal behaviors of all cadmium complexes were studied in the range of room temperature to 800°C under nitrogen atmosphere. The complexes were thermally decomposed via 2 to 4 steps. Cadmium metal was suggested as final residue at the end of thermal decomposition process.     

Polymer Surface Functionalization Using Plasma,Ultraviolet and Synchrotron Radiation

Polyurethane (PU) and polystyrene (PS) films were functionalized by ultraviolet (UV) or selective synchrotron radiations (SR) in the presence of reactive gases. The UV-PU results were compared with lowpressure plasma treatments of the same films. Oxygen or acrylic acid vapours (AA) were used as reactive gases. X-ray photoelectron spectroscopy measurements of UV modified films in the presence of oxygen or AA matched the RF-plasma treatments results. It is shown that COO and C=O functional groups were incorporated at the polymer surface efficiently with both methodologies. In addition, near-edge X-ray absorption fine structure showed that a thin film of poly(acrylic acid) is formed over the PU and PS films during the UV irradiation in the presence of AA vapours. These results resemble previous AA low-power plasma treatments. PU and PS films were also selectively functionalized by SR using oxygen as reactive gas. Surface concentrations of COO and C=O functional groups were enhanced by C_1s → σ* _C–C excitation after irradiation and oxygen introduction. This efficient surface functionalization was clearly observed in PS films which do not have CO and COO groups in their molecular structure. Excitations involving transitions to π* orbital (π*_C=C, π*_C=O) led to much lower functionalization efficiency. The SR results can be explained by taking into account previous photon stimulated ion desorption studies of polymers. SR results may open new ways to functionalize polymer surfaces selectively and efficiently.     

Photocorrosion of cadmium sulfide: Analysis by photoelectron spectroscopy

Photocorrosion of cadmium sulfide electrodes in aqueous electrolytes leads to sulfate formation in the presence and to sulfur formation in the absence of oxygen. All three sulfur species involved (S²⁻, S⁰ and SO²⁻₄) can be detected on CdS electrodes after treatment in photoelectrochemical cells using AES or XPS. Both, the S2p/3p XPS and the S Auger peaks are broadened on photoelectrochemical oxidized CdS due to deposition of elemental sulfur. The XPS binding energy of the S electrons is shifted by about 1 eV per sulfur oxidation step from around 161.5 eV for S²⁻ to around 163.5 eV for S⁰ and around 168 eV for SO²⁻₄. The results obtained by photoelectron spectroscopy of electrodes transferred from the electrolyte directly into the UHV system without any cleaning and special precautions are in excellent agreement with the predictions based on photoelectrochemical experiments. For example, it could be proved by XPS that sulfur was transformed into sulfate in a reductive oxidation step in the presence of oxygen, leading to the CdS surface being cleaned of S⁰.     

Radiation removal of lead and cadmium complexed with ethylenediamine tetraacetic ACID from aqueous solutions

The removal of lead (100 mg/L) and cadmium (27 mg/L) complexed with ethylenediamine tetraacetic acid (EDTA) in presence of different scavengers has been investigated. The experiments show that in acidic solutions, the EDTA complexed lead may be reduced at a dose of 40 kGy up to 97% without the addition of typical OH radical scavengers such as Na(K) formate. The addition of OH radical scavengers as 1×10⁻³ mol/L HCOOK, 2×10⁻³ mol/L carbonate or 2×10⁻³ mol/L bicarbonate (wide range of pH) results in no further improvement. The bubbling of the solution with nitrogen or oxygen also exhibits no positive effect. On the contrary, saturation with nitrous oxide in the presence of scavengers has a modest positive influence, whereas in the system which is scavenger-free, high negative effect (30 %) was observed. The presence of nitrate (e _aq ⁻ scavenger) appears to be important for an effective reduction of complexed lead. The efficient removal of cadmium complexed with EDTA proceeds up to 96 % at a dose of 40 kGy with an addition of 5×10⁻³ mol/L of carbonate as the OH radical scavenger and simultaneously pH buffer (pH 10.5). After irradiation, the cadmium is present in the final form of CdCO₃.     

Effect of sintering aid (CdCl2) on the optical and structural properties of CdZnS screen-printed film

Sulphides of zinc and cadmium have been utilized effectively in various opto-electronic devices. In the present work cadmium zinc sulphide (Cd_0.4Zn_0.6S) thin film has been deposited on ultra clean glass substrate by a simple inexpensive screen-printing method using cadmium sulphide, zinc sulphide, anhydrous cadmium chloride and ethylene glycol. Cadmium chloride has been used as sintering aid and ethylene glycol as a binder. Effect of sintering aid on the optical and structural properties of prepared cadmium zinc sulphide film has been investigated. The optical band gap (E_g) of the film has been studied by using reflection spectra in wavelength range 325–600 nm. It is found that reflection spectra suffer a drastic fall at two places, which is indicative of two band gaps of film viz. 2.38 eV and 2.9 eV corresponding to CdS and Cd_0.6Zn_0.4S, respectively. This is suggestive of the fact that cadmium zinc sulphide is a wide band gap semiconducting material. X-ray diffraction also confirms the formation of Cd_0.6Zn_0.4S composition.     

Mode of layer displacements in MX2-type crystals

Using van der Waals potential, the relative strengths of interlayer and intralayer bonds have been estimated in the halides of cadmium and lead. The results have been compared with the recent Raman studies of rigid layer modes in MX₂-type layer compounds and X-ray diffraction studies of fused cadmium iodide. It is found that the interlayer bond is relatively much weaker than the intralayer bond. Accordingly, it is concluded that in the polytypic MX₂-type compounds CdI₂, CdBr₂ and PbI₂, only X-X glide takes place in the polytypic transformations observed during crystal growth and during high temperature treatment of the polytypes. The nature of the X-X glide has been examined in detail.     

Structural and impedance spectroscopic studies of samarium modified lead zirconate titanate ceramics

The polycrystalline samples of Pb_1−xSm_x(Zr_0.60Ti_0.40)_1−x/4O₃ (PSZT) where x=0.00, 0.03, 0.06 and 0.09 were prepared by a high-temperature solid-state reaction technique. The preliminary structural analysis using X-ray diffraction (XRD) data collected at room temperature has confirmed the formation of single-phase compounds in tetragonal crystal system. The morphological study of each sample using scanning electron microscope (SEM) has revealed that the grains are uniformly distributed through out the surfaces of the samples. Using complex impedance spectroscopy (CIS) technique, the electrical impedance and modulus properties of the materials were studied in a wide range of temperatures at different frequencies. The impedance analysis indicates the presence of bulk resistive contributions in the materials which is found to decrease on increasing temperature. The nature of variation of resistances with temperature suggests a typical negative temperature coefficient of resistance (NTCR) type behavior of the materials. The complex modulus plots clearly exhibits the presence of grain boundaries along with the bulk contributions in the PSZT materials. The presence of non-Debye type of relaxation has been confirmed by the complex impedance analysis. The variation of dc conductivity (bulk) with temperature demonstrates that the compounds exhibit Arrhenius type of electrical conductivity.     

苯胺和丙烯酸协同聚合一步法制备聚苯胺纳米管

本文通过加入过硫酸铵(APS)引发苯胺和丙烯酸(AA)在水溶液中的协同聚合反应,一步合成出具有中空结构的聚苯胺纳米管. 聚苯胺纳米管的外径平均为180 nm,内径约80 nm,其形成取决于苯胺与丙烯酸的摩尔比(X_{ani/AA}). 当X_{ani/AA}不超过1时,主要得到聚苯胺纳米管. 在三电极体系中测定了所制备的聚苯胺纳米管的电化学性能. 在1 mol/L H₂SO₄为电解液,电流密度为0.5 A/g的条件下,聚苯胺纳米管比电容高达436 F/g,是通常聚苯胺纳米片的七倍. 此外,在0.5 A/g的电流密度下进行500次充放电循环后,其比电容能够保持最初始的89.2%,表现出优异的充放电循环稳定性.     

BaFBr:Eu2+ nanophosphor-SiO2 hybrid entrapped in Anodise Alumina membrane pores array

Sol–gel template method has been used to prepare BaFBr:Eu²⁺ nanophosphor-SiO₂ hybrid entrapped within the nanopores array (of about 200 nm size) of a comercial anodized alumina (AA) membrane. Structural and morphological measurements using electron microscopy (SEM) and X-ray diffraction (XRD) have shown the presence of the BaFBr:Eu²⁺ nanophosphor in the silica xerogel entrapped within the nanopores array; photoluminescence and X-ray excited luminescence measurements have shown Eu²⁺ luminescence at 395 nm accompanied by a broad band due to AA membrane. The method assures a relatively uniform spreading of the BaFBr nanophosphor into the AA membrane pores array without the nanoparticles agglomeration. Preliminary imaging tests have shown a spatial resolution in the micrometer range and even in the submicrometer range can be expected. As BaFBr:Eu²⁺ is a very efficient X-ray phosphor the material might be used as X-ray micro-imaging detector.     

Optical and structural characterization of KBr crystals doped cadmium bromide (CdBr2)

In this paper we demonstrate the presence of CdBr₂ and cadmium aggregates in KBr matrix during Czochralski growth of KBr crystals. The chemical decomposition of CdBr₂ due to high temperature of crystallisation and reformation of cadmium bromide seems to be responsible for this effect.     

Dielectric, modulus and impedance analysis of lead-free ceramics Ba0.8La0.133Ti1−x Sn x O3 (x=0.15 and 0.2)

Titanate barium (BaTiO₃)-type oxide ceramics Ba_0.8La_0.133Ti_1?x Sn _x O₃ (BLTS) (here x=0.15 and 0.2) have been synthesized by the standard solid-state reaction method. Preliminary room temperature X-ray study confirms the formation of single-phase compounds in a rhombohedral crystal system. The electrical properties of BLTS were studied using the ac impedance spectroscopy technique over a wide range of temperature (120–320 K) in the frequency range of 40 Hz to 10 MHz. The presence of a single arc in the complex modulus spectrum at different temperatures confirms the single-phase character of the BLTS compounds.     

Superior selectivity of high-frequency ultrasound toward chorine containing-pharmaceuticals elimination in urine: A comparative study with other oxidation processes through the elucidation of the degradation pathways

This work considered the sonochemical degradation (using a bath-type reactor, at 375 kHz and 106.3 W L^-1, 250 mL of sample) of three representative halogenated pharmaceuticals (cloxacillin, diclofenac, and losartan) in urine matrices. The action route of the process was initially established. Then, the selectivity of the sonochemical system, to degrade the target pharmaceuticals in simulated fresh urine was compared with electrochemical oxidation (using a BDD anode, at 1.88 mA cm⁻²), and UVC/H₂O₂ (at 60 W of light and 500 mol L^-1 of H₂O₂). Also, the treatment of cloxacillin in an actual urine sample by ultrasound and UVC/H₂O₂ was evaluated. More than 90% of the target compounds concentration, in the simulated matrix, was removed after 60 min of sonication. However, the sono-treatment of cloxacillin in the real sample was less efficient than in the synthetic urine. The ultrasonic process achieved 43% of degradation after 90 min of treatment in the actual matrix. In the sonochemical system, hydroxyl radicals in the interfacial zone were the main degrading agents. Meanwhile, in the electrochemical process, electrogenerated HOCl was responsible for the elimination of pharmaceuticals. In turn, in UVC/H₂O₂ both direct photolysis and hydroxyl radicals degraded the target pollutants. Interestingly, the degradation by ultrasound of the pharmaceuticals in synthetic fresh urine was very close to the observed in distilled water. Indeed, the sonodegradation had a higher selectivity than the other two processes. Despite the sono-treatment of cloxacillin was affected by the actual matrix components, this contrasts with the UVC/H₂O₂, which was completely inhibited in the real urine. The sonochemical process led to 100% of antimicrobial activity (AA) elimination after 75 min sonication in the synthetic urine, and ∼ 20% of AA was diminished after 90 min of treatment in the real matrix. The AA decreasing was linked to the transformations of the penicillin nucleus on cloxacillin, the region most prone to electrophilic attacks by radicals according to a density theory functional analysis. Finally, predictions of biological activity confirmed that the sono-treatment decreased the activity associated with cloxacillin, diclofenac, and losartan, highlighting the positive environmental impact of degradation of chlorinated pharmaceuticals in urine.     

The isotopic dependence of the spin-rotation interaction: the rotational spectrum of cadmium hydride in its XΣ state

Far-infrared rotational transitions within the X²Σ⁺ (v=0) state of cadmium hydride (CdH) were recorded over the range N″=2-17 for 12 different isotopomers, using the technique of tunable far-infrared (TuFIR) spectroscopy. The molecule was made by heating cadmium metal in the presence of a DC electric discharge in hydrogen. Fine structure arising from the electron spin-rotation interaction and hyperfine structure from the ¹¹¹Cd, ¹¹³Cd, and ¹H nuclei were resolved and analyzed. All of the isotopic data were fitted together using a Hamiltonian containing mass-independent, Dunham-type rotational parameters U_kl and small correction terms Δ_kl described by Watson [J. Mol. Spectrosc. 80 (1980) 411]. The spin-rotation interaction was modeled in an analogous way using Dunham-like U_γ,kl parameters, and fitting its isotopic dependence properly required the use of four Δ_γ,kl correction terms.     

Luminescent Properties of a Polymer Photoluminescent Composite Containing the Binuclear (EU,TB) Complex as an Emitter

Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu³⁺) to terbium (III) (Tb³⁺) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)₃Phen and Eu_0.5Tb_0.5(AA)₃Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)₃Phen and TCA/Eu_0.5Tb_0.5(AA)₃Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu_0.5Tb_0.5(AA)₃Phen composites the introduced Tb³⁺ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb³⁺ion→Eu³⁺ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu_0.5Tb_0.5(AA)₃Phen composites was noticeably stronger than that of the TCA/Eu(AA)₃Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu_0.5Tb_0.5(AA)₃Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.     

Synthesis, structural and conductivity characterization of alginic acid–Fe3O4 nanocomposite

Alginic acid–Fe₃O₄ nanocomposite is synthesized by the precipitation of Fe₃O₄ in the presence of alginic acid (AA). Structural, surface, morphological, thermal and electrical transport properties of the nanocomposite were performed by XRD, FT-IR, TEM-SEM, TGA and conductivity measurements respectively. FT-IR analysis revealed that Fe₃O₄ NPs are strongly capped with AA and TGA analysis showed that nanocomposite have 80% of Fe₃O₄ content. TEM analysis of Fe₃O₄ NPs show an average particle size of 9.5 nm, and upon nanocomposite formation with AA these particles are observed to form aggregates of ~150 nm. The frequency-dependency of the AC conductivity show electrode polarization effect. Analysis of electrical modulus and dielectric permittivity functions suggest that ionic and polymer segmental motions are strongly coupled. DC electrical conductivity is strongly temperature dependent, and is classified into three regions over a limited temperature range of up to 100 °C.     

Optimisation of the ultrasound-assisted extraction of betalains and polyphenols from Amaranthus hypochondriacus var. Nutrisol

The present study optimised the ultrasound-assisted extraction (UAE) of bioactive compounds from Amaranthus hypochondriacus var. Nutrisol. Influence of temperature (25.86–54.14 °C) and ultrasonic power densities (UPD) (76.01–273.99 mW/mL) on total betalains (BT), betacyanins (BC), betaxanthins (BX), total polyphenols (TP), antioxidant activity (AA), colour parameters (L*, a*, and b*), amaranthine (A), and isoamaranthine (IA) were evaluated using response surface methodology. Moreover, betalain extraction kinetics and mass transfer coefficients (K_La) were determined for each experimental condition. BT, BC, BX, TP, AA, b*, K_La, and A were significantly affected (p < 0.05) by temperature extraction and UPD, whereas L*, a*, and IA were only affected (p < 0.05) by temperature. All response models were significantly validated with regression coefficients (R²) ranging from 87.46 to 99.29%. BT, A, IA, and K_La in UAE were 1.38, 1.65, 1.50, and 29.93 times higher than determined using conventional extraction, respectively. Optimal UAE conditions were obtained at 41.80 °C and 188.84 mW/mL using the desired function methodology. Under these conditions, the experimental values for BC, BX, BT, TP, AA, L*, a*, b*, K_La, A, and IA were closely related to the predicted values, indicating the suitability of the developed quadratic models. This study proposes a simple and efficient UAE method to obtain betalains and polyphenols with high antioxidant activity, which can be used in several applications within the food industry.     

Investigations of Pulse‐Plasma‐Polymer Coating on TiO2 Nanoparticles and Their Dispersion

An amorphous acrylic acid (AA) polymer coating was generated on TiO₂ nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO₂ nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO₂ nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO₂ nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.     

Improved resistive switching performance in Cu-cation migrated MoS2 based ReRAM device incorporated with tungsten nitride bottom electrode

The resistive switching characteristics of sputtered deposited molybdenum disulphide (MoS₂) thin film has been investigated in Cu/MoS₂/W₂N stack configuration for Resistive Random Access Memory (ReRAM) application. The benefits of incorporating tungsten nitride (W₂N) as a bottom electrode material were demonstrate by stability in operating voltages, good endurance (10³ cycles) and long non-volatile retention (10³?s) characteristics. Resistive switching properties in Cu/MoS₂/W₂N structure are induced by the formation/disruption of Cu conducting filaments in MoS₂ thin film. Ohmic law and space charge limited current (SCLC) are observed as dominant conduction mechanism in low resistance state (LRS) and high resistance state (HRS) respectively. This study suggests the application of MoS₂ thin films with W₂N bottom electrode for next generation non-volatile ReRAM application.     

Structural and physical properties of undoped and nickel-doped BaFe2-xNixAs2（x = 0,0.04） single crystals

<正>Single crystals of undoped and nickel-doped BaFe_(2-x)Ni_xAs_2(x=0,0.04) have been grown by FeAs self-flux method.The maximum dimension of the crystal is as large as ~ 1 cm along the ab plane.The crystalline topography of a cleaved crystal surface is examined by scanning electron microscope(SEM).By x-ray powder diffraction(XRD) experiments using pure silicon as an internal standard,precise unit cell parameters(tetragonal at room temperature) are determined:a = 3.9606(4) A(1 A=0.1 nm),c = 13.015(2) A for BaFe_(1.96)Ni_(0.04)As_2 and a = 3.9590(5) A,c = 13.024(1) A for BaFe_2As_2.DC magnetization and transport measurements are performed to check superconducting transition(T_c=15 K for x=0.04) and other subtle anomalies.For BaFe_(0.96)Ni_(0.04)As_2 crystal,the resistance curve at normal state shows two distinct anomalies associated with spin and structure transitions,and its magnetization data above ~ 91 K exhibit a linear temperature dependence due to spin density wave(SDW) instability.