A Procedure for Transforming Impedance Spectra for the Determination of Mechanism of Electrochemical Reactions

Transformation of impedance spectra into relaxation time spectra (RTS) is used for determining contributions of individual processes of the oxygen electroreduction reaction (OER) to the polarization resistance of the electrochemical cell. The transformation technique involves the solution of the convolution equation found with the aid of a modified Van Cittert iteration algorithm checked on model impedance spectra. The technique, when used to analyze impedance spectra of electrochemical cells air|Pt|YSZ|YSZ + Pt|air, shows that the conversion of a globular structure of the YSZ + Pt cermet layer to a columnar one is accompanied by a change of peak amplitudes in RTS. The revealed RTS dynamics when heated to 750°C is compared with peculiarities of individual processes in OER.     

Thermal studies on some organotin(IV) complexes with piperidine and 2-aminopyridine dithiocarbamates

The complexes of piperidine dithiocarbamate, 2-aminopyridine dithiocarbamate and organotin(IV) of the type R₃Sn(L¹), R₂Sn(L¹)₂, R₃Sn(L²), R₂Sn(L²)₂, [R=C₆H₅CH₂ (benzyl), p-ClC₆H₄CH₂ (p-chlorobenzyl), L ¹=sodium piperidine dithiocarbamate and L ²=sodium 2-aminopyridine dithiocarbamate] have been synthesised and characterised by spectral studies (IR, UV, ¹H NMR). Thermogravimetric (TG) and differential thermal analytical (DTA) studies have beeen carried out for these complexes and from the TG curves, the order and apparent activation energy for the thermal decomposition reactions have been elucidated. The various thermal studies have been correlated with some structural aspects of the complexes concerned. From DTA curves, the heat of reaction has been calculated.     

Construction of recombinant Escherichia coli strais for production of poly-(3-hydroxybutyrate-co-3-hydroxyvalerate)

Plastic wastes constitute a worldwide environmental problem, and the demand for biodegradable plastics has become high. One of the most important characteristics of microbial polyesters is that they are thermoplastic with environmentally degradable properties. In this study, pUC 19/PHA was cloned and transformed into three different Escherichia coli strains. Among the three strains that were successfully expressed in the production of polyhydroxyalkanoates (PHA), E. coli HMS174 had the highest yield in the production of poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (P[HB-HV]). The cell dry weight and PHA content of recombinant HMS174 reached as high as 10.27 g/L and 43% (w/w), respectively, in fed-batch fermentor culture. The copolymer of PHA, P(HB-HV), was found in the cells, and the biopolymers accumulated were identified and analyzed by gas chromatography, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. We demonstrated clearly that the E. coli host for PHA production has to be carefully selected to obtain a high yield. The results obtained indicated that a superior E. coli with high PHA production can be constructed with a desirable ratio of P(HB-HV), which has potential applications in industry and medicine.     

Viscosity of aqueous solutions of polysaccharides and hydrophobically modified polysaccharides: Application of Fedors equation

Amphiphilic polysaccharides have been obtained by hydrophobic modification of a neutral bacterial polysaccharide, dextran. Various amounts and types of aliphatic hydrocarbon groups have been attached to dextran.The solution behaviour of unmodified dextran samples and amphiphilic dextran derivatives is characterized by viscometric measurements. The overall viscosity behaviour of unmodified polysaccharides is described up to C × [η] = 3, using the equation of Fedors [Fedors RF. Polymer 1979;20:225] which involves only a concentration parameter. The latter is shown to depend on the hydrodynamic volume of the macromolecules in solution.The equation of Fedors is shown to conveniently estimate the viscosity behaviour of amphiphilic dextran derivatives up to C × [η] = 1. The interdependence between Fedors parameter and other viscometric characteristics (intrinsic viscosity, Huggins coefficient) is evidenced. These results are extended to the data of other authors.     

Influence of extractions on physicochemical characterization and bioactivity of Piper nigrum oils: Study on the non-isothermal decomposition kinetic

Black pepper oils have been investigated frequently in the recent years. However, there is a significant variation in physicochemical properties and bioactivity of oils depended on extraction techniques. In this study, the systemic investigation of four various extraction methods was performed to evaluate the physicochemical characterizations, antioxidant and antibacterial activity. The investigation of ¹H NMR, FTIR and UV–Vis spectra confirmed presence of non-volatile components in oils extracted through supercritical CO₂ and hexane-soaking extractions which induced their typical thermal properties. The isothermal behaviour of extracted oils related to evaporation was within range of 3.2–7.3% (w/w) at 27 °C. The SEM images of the black pepper confirmed different operation manners of mechanism between extractions using the solvents and heating process. The lowest MIC for both essential oils from conventional hidrodistillation and microwave-assisted hidrodistillation against two bacteria including E. coli and B. subtilis were found to be 137 µg mL⁻¹. The non-isothermal decomposition kinetics were investigated on the essential oil of microwave-assisted hydrodistillation extraction. The activation energies and pre-exponent factors of non-isothermal decomposition were found to be in range of 36.5–73.7 KJ mol⁻¹ and 4.98 × 10³–1.97 × 10⁸ s⁻¹, respectively, dependent on conversional fractions of the oil. The results revealed that chemical components, physicochemical properties and bioactivity of black pepper essential oils depended on the extraction techniques.     

Diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide

The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities.     

Monolayer adsorption isotherms and a disordered medium model

A model of disordered medium is proposed to describe the monolayer adsorption isotherm on heterogeneous surfaces. The model is based on the premise that adsorption medium consists of separate regions in each of which there is a permanent local equilibrium constant, the character of the changes of which is determined by the disorder parameter of the medium. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 189–193, May–June, 2006.     

Polymerization of methyl methacrylate by 2‐pyrrolidinone and n‐dodecyl mercaptan

The bulk polymerization of methyl methacrylate initiated with 2‐pyrrolidinone and n‐dodecyl mercaptan (R‐SH) has been explored. This polymerization system showed “living” characteristics; for example, the molecular weight of the resulting polymers increased with reaction time by gel permeation chromatographic analysis. Also, the polymer was characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR techniques. The polymer end with the iniferter structures was found. By the initial‐rate method, the polymerization rate depended on [2‐pyrrolidinone]^1.0 and [R‐SH]⁰. Combining the structure analysis and the polymerization‐rate expression, a possible mechanism was proposed. n‐Dodecyl mercaptan served dual roles—as a catalyst at low conversion and as a chain‐transfer agent at high conversion. Finally, the thermal properties were studied, and the glass‐transition temperature and thermal‐degradation temperature were, respectively, 25 and 80–100 °C higher than that of the azobisisobutyronitrile system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3692–3702, 2002     

Adsorption of p-Nitrophenol in Untreated and Treated Activated Carbon

The adsorption of p-nitrophenol in one untreated activated carbon (F100) and three treated activated carbons (H₂, H₂SO₄ and Urea treated F100) was carried out at undissociated and dissociated conditions.To characterize the carbon, N₂ and CO₂ adsorption were used. X-ray Photoelectron Spectroscopy (XPS) was used to analyze the surface of the activated carbon.The experimental isotherms are fitted via the Langmuir homogenous model and Langmuir binary model. Variation of the model parameters with the solution pH is studied. Both Q _max and the adsorption affinity coefficient (K ₁) were dependent on the PZC of the carbons and solution pH. The Effect of pH must be considered due to its combined effects on the carbon surface and on the solute molecules. Adsorption of p-nitrophenol at higher pH was found to be dependent on the concentration of the anionic form of the solute.     

Thermal And Structural Characterization of Commercial α-, β-, and γ-Cyclodextrins

α-, β-, and γ-cyclodextrins (CDs) marketed by five different companies were characterized from the thermal and structural point of view. Three αCD samples showed two-step DSC dehydration profiles and their XRD patterns were characteristic for αCD⋅6H₂O form I, whereas one brand with an apparent three-step DSC dehydration behaviour was a mixture of αCD⋅6H₂O form I and anhydrous αCD. The differences in the DSC profiles after dehydration and EGA onset decomposition temperatures recorded for the five βCD brands were attributed to different manufacturing and purification processes. The five γCDs brands showed a common thermal behaviour and very similar XRD patterns. The patterns did not match the idealized pattern of γCD⋅14.1H₂O, indicating the occurrence of two different hydrated crystal structures. This revised version was published online in August 2006 with corrections to the Cover Date.