Electrochemical degradation of the Acid Blue 62 dye on a β-PbO<Subscript>2</Subscript> anode assessed by the response surface methodology

The electrochemical degradation of the anthraquinonic dye Acid Blue 62 in a filter-press reactor on a Ti/Pt/β-PbO₂ anode was investigated using the response surface methodology with the variables: current density, pH, [NaCl], and temperature. The system’s modeling was carried out with the charge required for 90% decolorization (Q ⁹⁰) and the chemical oxygen demand removal percentage after a 30 min electrolysis (COD ³⁰), with good correlations between predicted and observed values. Best conditions for decolorization were attained in acidic solutions (pH = 4) with medium to high [NaCl] (1.0–2.0 g L⁻¹) and lower temperature due to the prevalent oxidant species HOCl and Cl₂. Optimal conditions for COD ³⁰ removal were attained at high current densities in pH > 5 solutions with high [NaCl], when the prevalent oxidant species are HOCl and OCl⁻. The lowest charge per unit volume of the electrolyzed solution necessary for total mineralization was attained at pH 11.     

On the activation and physical degradation of boron-doped diamond surfaces brought on by cathodic pretreatments

The electrochemical activation and physical degradation of boron-doped diamond (BDD) electrodes with different boron doping levels after repeated cathodic pretreatments are reported. Galvanostatic cathodic pretreatment passing up to −14000 C cm⁻² in steps of −600 C cm⁻² using −1 A cm⁻² caused significant physical degradation of the BDD surface, with film detachment in some areas. Because of this degradation, a great increase in the electrochemically active area was observed in Tafel plots for the hydrogen evolution reaction (HER) in acid media. The minimum cathodic pretreatment needed for the electrochemical activation of the BDD electrodes without producing any observable physical degradation on the BDD surfaces was determined using electrochemical impedance spectroscopy (EIS) measurements and cyclic voltammetry: −9 C cm⁻², passed at −1 A cm⁻². This optimized cathodic pretreatment can be safely used when electrochemical experiments are carried out on BDD electrodes with doping levels in the range between 800 and 8000 ppm.     

Manganese oxide precipitated into activated carbon electrodes for electrochemical capacitors

Manganese oxide was prepared at different pH and temperatures and then precipitated into activated carbon by the chemical impregnation method. Size distributions of manganese oxide sol were also measured by light scattering. The electrodes were annealed in nitrogen gas at different temperatures. In addition, electrochemical characterization was carried out using cyclic voltammetry (CV) at a scan rate of 25 mV s⁻¹ and chronopotentiometry (CP) with constant-current (10 mA cm⁻²). Maximum capacitance of 461.3 F g⁻¹ was obtained in a 0.1 M Na₂SO₄ solution for manganese oxide prepared under optimum conditions (pH = 13.11 and T = 25 oC) and annealed at a temperature of 195 oC. The manganese oxide particle size decreased with annealing. This probably leads to increased specific capacitance. Using X-ray photoelectron spectroscopy (XPS) the results reveal that manganese oxide species are transformed from hydroxide to oxide after annealing.     

Application of a Handheld Portable Mid-Infrared Sensor for Monitoring Oil Oxidative Stability

This study evaluated the capabilities of a handheld mid-infrared (MIR) spectrometer combined with multivariate analysis to characterize oils, monitor chemical processes occurring during oxidation, and to determine fatty acid composition. Vegetable oils (corn, peanut, sunflower, safflower, cottonseed, and canola) were stored at 65 °C for 30 days to accelerate oxidation reactions. Aliquots were drawn at 5 day intervals and analyzed by benchtop and portable handheld mid-infrared devices (4,000–700 cm⁻¹) and reference methods (IUPAC 2301 [1], 2302 [1]; AOCS Cd 8-58 [2]; and Shipe 1979 [3]). PLSR and soft independent modeling of class analogy (SIMCA) models were developed for oil classification and estimation of oil stability parameters. Models developed from MIR spectra obtained with a benchtop spectrometer equipped with a 3-bounce ATR device resulted in superior discriminative performances for classifying oils as compared to those obtained from handheld spectra (single-bounce ATR). Models developed from reference tests and handheld spectra showed prediction errors (SECV) of 1 meq/kg for peroxide value, 0.09% for acid value and 2% for determination of unsaturated fatty acids in different oils. Spectral regions ~3,012–2,850 cm⁻¹ (C–H stretching bands/shoulders of fatty acids), ~1,740 cm⁻¹ (C=O stretching of esters), and ~1,114 cm⁻¹ (–C–O stretching) were found to be important for prediction. Handheld-FTIR instruments combined with multivariate-analysis showed promise for determination of oil quality parameters. Portability and ease-of-use makes the handheld device a great alternative to traditional methods.     

Electrochemical pretreatment of distillery wastewater using aluminum electrode

Electrochemical (EC) oxidation of distillery wastewater with low (BOD₅/COD) ratio was investigated using aluminum plates as electrodes. The effects of operating parameters such as pH, electrolysis duration, and current density on COD removal were studied. At a current density of 0.03 A cm⁻² and at pH 3, the COD removal was found to be 72.3%. The BOD₅/COD ratio increased from 0.15 to 0.68 for an optimum of 120-min electrolysis duration indicating improvement of biodegradability of wastewater. The maximum anodic efficiency observed was 21.58 kg COD h⁻¹ A⁻¹ m⁻², and the minimum energy consumption observed was 0.084 kWh kg⁻¹ COD. The kinetic study results revealed that reaction rate (k) decreased from 0.011 to 0.0063 min⁻¹ with increase in pH from 3 to 9 while the k value increased from 0.0035 to 0.0102 min⁻¹ with increase in current density from 0.01 to 0.03 A cm⁻². This study showed that the COD reduction is more influenced by the current density. The linear and the nonlinear regression models reveal that the COD reduction is influenced by the applied current density.     

Effects of temperature and current density on zinc electrodeposition from acidic sulfate electrolyte with [BMIM]HSO<Subscript>4</Subscript> as additive

The effects of temperature and current density on cathodic current efficiency, specific energy consumption, and zinc deposit morphology during zinc electrodeposition from sulfate electrolyte in the presence of 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM]HSO₄) as additive were investigated. The highest current efficiency (93.7%) and lowest specific energy consumption (2,486 kWh t⁻¹) were achieved at 400 A m⁻² and 313 K with addition of 5 mg dm⁻³ [BMIM]HSO₄. In addition, the temperature dependence of some kinetic parameters for the zinc electrodeposition reaction was experimentally determined. Potentiodynamic polarization sweeps were carried out to obtain the expression for each parameter as a function of temperature. In the condition studied, the exchange current density depended on temperature as ln(i ₀) = −a/T + b and the charge transfer coefficient was constant. Moreover, the adsorption of the additive on cathodic surface obeyed the Langmuir adsorption isotherm. The associated thermodynamic parameters indicated the adsorption to be chemical.     

Catalyst electrode preparation for PEM fuel cells by electrodeposition

The preparation of catalyst electrodes by electrodeposition for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) has been studied. This work looks at the potential to apply the electrodeposition technique, in the forms of direct current (DC) and pulse plating electrodepositions, to prepare Pt and Pt–Co alloy catalysts for membrane electrode assemblies (MEAs). The preparation of the non-catalyst layer was found to be important for the electrodeposition of Pt catalysts. The activities of the electrodeposited catalysts, both pure Pt and Pt–Co alloy, produced by pulse plating are substantially higher than that of the Pt catalyst produced by DC electrodeposition. The improvement in electroactivity towards the ORR of the electrodeposited catalysts produced by pulse plating is likely due to the finer structures of electrodeposited catalysts which contain smaller catalyst particles compared to those produced by DC electrodeposition. A maximum performance towards the ORR in PEMFCs was achieved from the catalysts prepared by pulse plating using a charge density of 2 C cm⁻², a pulse current density of 200 mA cm⁻², a 5% duty cycle and a pulse frequency of 1 Hz.     

Molecular Spin Ladders Constructed from [Ni(dmit)2]− Building Blocks: Synthesis, Structure and Physical Properties

Abstract  A new ion-pair complex [1-(4-bromobenzyl)-3-methylpyridinium][Ni(dmit)₂] (1), in which dmit = 4,5-dimercapto-1,3-dithiole-2-thione, has been synthesized and structurally characterized. The anions of [Ni(dmit)₂]⁻ stack into dimers, which further construct into a two-leg ladder through lateral S···S interactions. The weak H-bonding interactions of C–H···S and van de Waals interactions between anion and cations were observed. The magnetic susceptibilities measured from 2–300 K indicate an AFM exchange interaction domination and an AFM ordering below ~8 K. The best fit to magnetic susceptibility above 40 K, using a dimer model with s = ?, gives rise to Δ/k_B = 29.8 K, zJ′ = −0.72 K, C = 3.40 × 10⁻³ emu K mol⁻¹ and χ ₀ = −5.8 × 10⁻⁶ emu mol⁻¹ with a fixed g = 2.0. Cyclovoltammetry revealed two quasi-reversible one-electron steps, which are attributed to Ni(IV/III) and Ni(III/II) redox couples. Graphical Abstract  [A novel complex [1-(4-bromobenzyl)-3-methylpyridinium][Ni(dmit)₂] has been synthesized and structurally characterized. The anions of [Ni(dmit)₂]⁻ stack into dimers, which further construct into two-leg ladder through lateral S···S interactions. The weak H–bonding interactions of C–H···S and van de Waals interactions between anion and cations were observed. Moreover, its magnetic property and electrochemical property have been investigated] .     

Electrocatalytic oxidation of glutathione at carbon paste electrode modified with 2,7-<Emphasis Type="Italic">bis</Emphasis> (ferrocenyl ethyl) fluoren-9-one: application as a voltammetric sensor

Electrooxidation of glutathione (GSH) was studied at the surface of 2,7-bis (ferrocenyl ethyl) fluoren-9-one modified carbon paste electrode (2,7-BFEFMCPE). Cyclic voltammetry (CV), double potential-step chronoamperometry, and differential pulse voltammetry (DPV) were used to investigate the suitability of this ferrocene derivative as a mediator for the electrocatalytic oxidation of GSH in aqueous solutions with various pH. Results showed that pH 7.00 is the most suitable pH for this purpose. At the optimum pH, the oxidation of GSH at the surface of this modified electrode occurs at a potential of about 0.410 V versus Ag|AgCl|KCl_sat. The kinetic parameters such as electron transfer coefficient, α = 0.61, and rate constant for the chemical reaction between GSH and redox site in 2,7-BFEFMCPE, k _h = 1.73 × 10³ cm³ mol⁻¹ s⁻¹, were also determined using electrochemical approaches. Also, the apparent diffusion coefficient, D _app, for GSH was found to be 5.0 × 10⁻⁵ cm² s⁻¹ in aqueous buffered solution. The electrocatalytic oxidation peak current of GSH showed a linear dependence on the glutathione concentration, and linear calibration curves were obtained in the ranges of 5.2 × 10⁻⁵ M to 4.1 × 10⁻³ M and 9.2 × 10⁻⁷ M to 1.1 × 10⁻⁵ M with cyclic voltammetry and differential pulse voltammetry methods, respectively. The detection limits (3σ) were determined as 1.4 × 10⁻⁵ M and 5.1 × 10⁻⁷ M for the CV and DPV methods, respectively. This method was also examined as a selective, simple, and precise new method for voltammetric determination of GSH in real sample such as hemolysed erythrocyte.     

Electrochemical recycling of cobalt from spent cathodes of lithium-ion batteries: its application as supercapacitor

The supercapacitive behavior of the metallic cobalt recycled from Li-ion batteries has been studied in this work. The reversibility of both redox process (Co^II/Co^III) and (Co^III/Co^IV) in KOH 6 mol L⁻¹ is very high and promising for capacitive applications in electrochemical devices. The specific capacitances calculated from cyclic voltammetry and electrochemical impedance spectroscopy show a good agreement, giving the value of 625 Fg⁻¹. The electrode morphology presents a high porosity, thus an electrical equivalent circuit composed of two parallel resistance and capacitance elements in series was proposed. The specific capacitance values calculated from charge/discharge curves at 0.23 and 2.3 mA/cm² are 601 and 384 Fg⁻¹, respectively. Thereby, it was observed that metallic cobalt recycled from ion-Li batteries is compatible with other supercapacitive materials. This shows that cobalt recycling from Li-ion batteries is economically and environmentally viable for application in supercapacitor devices.     

A Novel Dinucleating Ligand-Containing Hexabenzimidazoles and Its Dinuclear Zinc Complex Bridged by a Carboxylate Group for the Hydrolysis of 2-Hydroxypropyl-p-nitrophenyl phosphate

A dinuclear zinc(II) complex with the ligand bis{tris[2-(1-methylbenzimidazole-2-yl)ethyl]-methylamine}nitrilotriacetic acid sodium salt, L, was synthesized and characterized. Complex formation of L with Zn²⁺ in aqueous acetone was studied by Zn²⁺ titration using ¹H NMR and UV–vis spectroscopies. Analysis of the titration data indicates the formation of a dizinc complex. The ν_as(COO⁻) and ν_s(COO⁻) stretches were observed at 1572 and 1450 cm⁻¹, respectively. The low separation of the stretches, Δ_exp = 115 cm⁻¹, is an indication of chelating coordination of the carboxylate group between the two zinc(II) ions. The catalytic activity of [LZn₂]³⁺ 1, as a model for phosphatase that catalyze chemical transformation of phosphate ester, in the hydrolysis of the RNA model, 2-hydroxypropyl p-nitrophenyl phosphate, was examined in aqueous acetone buffer solution, pH 7.0–9.5. The mechanism of the catalytic hydrolysis suggests that the rate of acceleration is due to what is called double Lewis acid activation.     

Long-term tillage,straw management and N fertilization effects on quantity and quality of organic C and N in a Black Chernozem soil

Soil, crop and fertilizer management practices may affect the amount and quality of organic C and N in soil. A long-term field experiment (growing barley, wheat, or canola) was conducted on a Black Chernozem (Albic Argicryoll) loam at Ellerslie, Alberta, Canada, to determine the influence of 19 (1980 to 1998) or 27 years (1980 to 2006) of tillage (zero tillage [ZT] and conventional tillage [CT]), straw management (straw removed [S_Rem]and straw retained [S_Ret]) and N fertilizer rate (0, 50 and 100 kg N ha⁻¹ in S_Ret and 0 kg N ha⁻¹ in S_Rem plots) on total organic C (TOC) and N (TON), and light fraction organic C (LFOC) and N (LFON) in the 0–7.5 and 7.5–15 cm or 0–5, 5–10 and 10–15 cm soil layers. The mass of TOC and TON in soil was usually higher in S_Ret than in S_Rem treatment (by 3.44 Mg C ha⁻¹ for TOC and 0.248 Mg N ha⁻¹ for TON after 27 years), but there was little effect of tillage and N fertilization on these parameters. The mass of LFOC and LFON in soil tended to increase with S_Ret (by 285 kg C ha⁻¹ for LFOC and 12.6 kg N ha⁻¹ for LFON with annual rate of 100 kg N ha⁻¹ for 27 years)_, increased with N fertilizer application (by 517 kg C ha⁻¹ for LFOC and 36.0 kg N ha⁻¹ for LFON after 27 years), but was usually higher under CT than ZT (by 451 kg C ha⁻¹ for LFOC and 25.3 kg N ha⁻¹ for LFON after 27 years). Correlations between soil organic C or N fractions were highly significant in most cases. Linear regressions between crop residue C input and soil organic C or N were significant in most cases. The effects of tillage, straw management and N fertilizer on soil were more pronounced for LFOC and LFON than TOC and TON, and also in the surface layers than in the deeper layers. Tillage and straw management had little or no effect on C:N ratios, but the C:N ratios in light organic fractions significantly decreased with increasing N rate (from 20.06 at zero-N to 18.91 at 100 kg N ha⁻¹). Compared to the 1979 results, in treatments that did not receive N fertilizer (CTS_Rem0, CTS_Ret0, ZTS_Rem0 and ZTS_Ret0), CTS_Rem0 resulted in a net decrease in TOC concentration (by 1.9 g C kg⁻¹) in the 0–15 cm soil layer in 2007 (after 27 years), with little or no change in the CTS_Ret0 and ZTS_Rem0 treatments, while there was a net increase in TOC concentration (by 1.2 g C kg⁻¹) in the ZTS_Ret0 treatment. Straw retention and N fertilizer application at 50 and 100 kg N ha⁻¹ rates showed a net positive effect on TOC concentration under both ZT (ZTS_Ret50 by 2.3 g C kg⁻¹ and ZTS_Ret100 by 3.1 g C kg⁻¹) and CT (CTS_Ret50 by 3.5 g C kg⁻¹ and CTS_Ret100 by 1.6 g C kg⁻¹) treatments in 2007 compared to 1979 data. In conclusion, the findings suggest that retention of straw, application of N fertilizer and elimination of tillage would improve soil quality, and this might increase the potential for N supplying power of the soil and sustainability of crop productivity.     

Preparation of Pt–Co alloy catalysts by electrodeposition for oxygen reduction in PEMFC

Direct current (DC) and pulse current (PC) electrodeposition of Pt–Co alloy onto pretreated electrodes has been conducted to fabricate catalyst electrodes for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). The effect of plating mode and pulse plating parameters on the Pt–Co alloy catalyst structure, composition and electroactivity for the ORR in PEMFC has been investigated. The electrodeposited Pt–Co alloy catalyst indicates higher electrocatalytic activity towards the ORR than the electrodeposited Pt catalyst. The activity of the electrodeposited Pt–Co catalysts is further improved by applying the current in a pulse waveform pattern. The electrodeposition mode and the pulse plating parameters do not have the significant effect on the Pt:Co composition of deposited catalysts, but show the substantial effect on the deposit structures produced. The Pt–Co catalysts prepared by PC electrodeposition have finer structures and contain smaller Pt–Co catalyst particles compared to that produced by DC electrodeposition. By varying the Pt concentration in deposition solution, the Pt:Co composition of the electrodeposited catalyst that exhibits the highest activity is found. The Pt–Co alloy catalyst with the Pt:Co composition of 82:18 obtained at the charge density of 2 C cm⁻², the pulse current density of 200 mA cm⁻², 5% duty cycle and 1 Hz was found to yield the best electrocatalytic activity towards the ORR in PEMFC.     

Synthesis of a novel amphiphilic polymer containing nucleobases in the self-organized nanospheres

A simple strategy to achieve molecular recognition in water is to make the polymers self-organized into nanospheres which could incorporate the functional groups containing hydrogen bonding sites into hydrophobic-lipophilic regions. A novel amphiphilic polymer, Poly(polyoxyethylene-600)-oxy-5-(6-(1-thymine)hexyl)) isophthaloyl (PPETHI), has been synthesized. The PPETHI polymer could self-organize into nanospheres in dilute aqueous solution, which were 150–300 nm in diameter as estimated by SEM. The isophthaloyl with side hexyl thymine of the polymer self-organized into hydrophobic regions and the PEG surrounded it. Molecular recognition between thymine in PPETHI polymer and adenine substrate has been studied by FT-IR. The FT-IR studies demonstrate that C₄=O of thymine has recognized with N-H of adenine through complementary nucleobases. It shows that the typical characteristic band at 3,352 cm⁻¹ of N-H stretching vibration of adenine shifted to 3,373 cm⁻¹ and the band at 1,685 cm⁻¹ of C₄=O of thymine shifted to 1,680 cm⁻¹. To confirm the formation of hydrogen bonds, the N-H band at 3,373 cm⁻¹ and C₄=O band at 1,680 cm⁻¹ have retrieved to 3,312 cm⁻¹ and 1,685 cm⁻¹ respectively upon heating to 115 °C or higher by means of variable temperature FT-IR. The formations of hydrogen-bonds between thymine in the polymer and adenine substrate in nanospheres were confirmed. It could enhance their interaction and loading capacity.     

Electrochemical recycling of cobalt from spent cathodes of lithium–ion batteries: its application as coating on SOFC interconnects

In this work the metallic cobalt was electrodeposited on 430 steel in order to obtain a low electrical resistance film made to Co₃O₄. Pure cobalt was obtained by acidic dissolution of lithium cobalt oxide (LiCoO₂) present in exhausted Li-ion battery cathode. The electrodeposition was performed with a 96% efficiency at a potential of 1.50 V versus Ag/AgCl. The electrodeposited cobalt showed the face-centered cubic (23%) and hexagonal centered (77%) phases. After oxidation at 850 °C for 1000 h in air, the cobalt layer was transformed into the Co₃O₄ phase. On the other hand, a sample without cobalt showed the usual Cr₂O₃ and FeCr₂O₄ phases. After 1000 h at 850 °C, in air the area specific resistance of the sample with the cobalt oxide layer was 0.038 Ω cm⁻², while it was 1.30 Ω cm⁻² for the bare sample.     

Studies of some operating parameters and cyclic voltammetry for a direct ethanol fuel cell

A direct ethanol fuel cell (DEFC) of 5 cm² membrane-electrode area was studied systematically by varying the catalyst loading, ethanol concentration, temperature and different Pt based electro-catalysts (Pt–Ru/C, Pt-black High Surface Area (HSA) and Pt/C). A combination of 2 M ethanol at the anode, pure oxygen at the cathode, 1 mg cm⁻² of Pt–Ru/C (40%:20%) as the anode and 1 mg cm⁻² of Pt-black as the cathode gave a maximum open circuit voltage (OCV) of 0.815 V, a short circuit current density of 27.90 mA cm⁻² and a power density of 10.3 mW cm⁻². The optimum temperatures of the anode and cathode were determined as 90 °C and 60 °C, respectively. The power density increased with increase in ethanol concentration and catalyst loading at the anode and cathode. However, the power density decreased slightly beyond 2 M ethanol concentration and 1 mg cm⁻² catalyst loading at the anode and cathode. These results were validated using cyclic voltammetry at single electrodes under similar conditions to those of the DEFC.     

Determination of hydrogenation ability and exchange current of H<Subscript>2</Subscript>O/H<Subscript>2</Subscript> system on hydrogen-absorbing metal alloys

A detailed analysis of potential versus time measurements at galvanostatic charge/discharge conditions (external current change from −1 to +1 mA cm⁻²) for two La–Ni alloys in Ar-saturated 0.1 M KOH solution is presented. It is shown that passivation of the electrodes does not affect the potential jump as a result of current switching over. The value of potential jump allows to calculate the exchange current density for H₂O/H₂ system on the tested material. Anodic potential of the hydrogenated electrode (at i _a = const) linearly increases with logarithm of time which allows to evaluate precisely time necessary for oxidation of hydrogen absorbed during cathodic charging. The method described enables to determine effectiveness of hydrogen absorption by materials applied for negative electrodes of NiMH batteries.     

Structural Analysis of Highly Relaxed GaSb Grown on GaAs Substrates with Periodic Interfacial Array of 90° Misfit Dislocations

We report structural analysis of completely relaxed GaSb epitaxial layers deposited monolithically on GaAs substrates using interfacial misfit (IMF) array growth mode. Unlike the traditional tetragonal distortion approach, strain due to the lattice mismatch is spontaneously relieved at the heterointerface in this growth. The complete and instantaneous strain relief at the GaSb/GaAs interface is achieved by the formation of a two-dimensional Lomer dislocation network comprising of pure-edge (90°) dislocations along both [110] and [1-10]. In the present analysis, structural properties of GaSb deposited using both IMF and non-IMF growths are compared. Moiré fringe patterns along with X-ray diffraction measure the long-range uniformity and strain relaxation of the IMF samples. The proof for the existence of the IMF array and low threading dislocation density is provided with the help of transmission electron micrographs for the GaSb epitaxial layer. Our results indicate that the IMF-grown GaSb is completely (98.5%) relaxed with very low density of threading dislocations (10⁵ cm⁻²), while GaSb deposited using non-IMF growth is compressively strained and has a higher average density of threading dislocations (>10⁹ cm⁻²).     

Syntheses and Characterizations of Three Cu(II) Complexes with 2,2′-Bipyridine-3,3′-dicarboxylate and <Emphasis Type="Italic">N</Emphasis>-Donor Ancillary Ligands

Abstract  

Three novel inorganic–organic hybrid frameworks of [Cu(BPDC)(2,2′-bipy)] (1), [Cu(BPDC)(BIB)₂ ·H₂O]_n (2) and [Cu(BPDC)(4,4′-bipy)]_n (3) (BPDC²⁻ = 2,2′-bipyridine-3,3′-dicarboxylate; 2,2′-bipy = 2,2′-bipyridine; BIB = 1,2-bis(imidazol-1-ylmethyl)benzene; 4,4′-bipy = 4,4′-bipyridine) were prepared. The three complexes have been characterized by the elemental analyses, IR spectra, TGA and the single crystal X-ray diffraction. Two intramolecular Cu(II) centers of 1 are encircled by two BPDC²⁻ ligands forming an 18-membered ring, which is further assembled into a three-dimensional (3D) supramolecular architecture through the C–H···O hydrogen-bonding interactions. Complex 2 possesses a two-dimensional layer network, while complex 3 is a three-dimensional polymer composed of Cu-BPDC helical chains bridged by 4,4′-bipy. In addition, the electrochemistry of complex 1 was investigated.     

Adsorptive stripping voltammetric determination of podophyllotoxin,an antitumour herbal drug,at multi-walled carbon nanotube paste electrode

Adsorption stripping voltammetry, a very sensitive electroanalytical method, was employed to determine podophyllotoxin, a kind of antitumour herbal drug at a multi-wall carbon nanotube (MWCNT)-modified carbon paste electrode (CPE) surface. In the following anodic sweep from 0.5 to 1.5 V, podophyllotoxin, adsorbed at the MWCNT-modified CPE surface, was oxidized and yielded a sensitive oxidation peak with E _1/2/E _p approximately 1.16 V/1.18 V over the scan rates of 10–120 mV s⁻¹. From CV and SWV studies of podophyllotoxin in the acetate buffers of various pH values, it was found that protons were involved in the oxidation of the drug at the H⁺/e⁻ ratio of one (∆E _p/pH = 56 mV at 25 °C). Its electrochemical behaviour was irreversible. The experimental conditions, such as supporting electrolyte, pH value, accumulation time, ionic strength and scan rate, were optimized for the measurement of podophyllotoxin. The best results were obtained in 0.02 M acetate/acetic acid buffer (pH 4.6) containing 0.04 M KCl (1:49, v/v) for 60 s accumulation. The oxidation peak current varies linearly with the concentration of podophyllotoxin over the range of 199–1796 pg mL⁻¹. The limits of detection and quantification of the pure drug are 4.5 and 14.96 pg mL⁻¹, with the correlation coefficient, r = 0.998 and the relative standard deviation, RSD = 1.3% (n = 5). This new method was successfully applied to the determination of podophyllotoxin in a plant sample of the rhizome of Podophyllum hexandrum. Recoveries were 99.173–101.231%. The relative standard deviations of intraday and interday analyses for podophyllotoxin were 0.55 and 0.61%, respectively (n = 3).