Immobilization and electrochemical redox behavior of cytochrome c on fullerene film-modified electrodes

Two different fullerene film-modified electrodes were prepared and used for surface immobilization and electrochemical property investigation of horse heart cytochrome c (cyt c). Both a pristine fullerene film and fullerene-palladium (C(60)-Pd) polymer film-modified platinum, glassy carbon and indium-tin-oxide (ITO) electrodes were used. The immobilized cyt c was characterized by piezoelectric microgravimetry at a quartz crystal microbalance (QCM), UV-visible absorption, and X-ray photoelectron spectroscopy (XPS), as well as cyclic voltammetry (CV) techniques. The UV-visible spectral studies revealed a small blue shift of both the Soret and Q band of the heme moiety of cyt c, immobilized on the C(60)-Pd polymer film-modified ITO electrode, as compared to the bands of cyt c in solution suggesting that molecules of cyt c are densely packed onto the surface of the modified electrode. The CV studies revealed a quasi-reversible electrode behavior of the heme moiety indicating the occurrence of kinetically hindered electron transfer. A good agreement was found between the values of cyt c electrode surface coverage determined by piezoelectric microgravimetry and cyclic voltammetry. For piezoelectric microgravimetry, these values ranged from 0.5 x 10(-10) to 2.5 x 10(-10) mol cm(-2), depending upon the amount of cyt c present in solution and the time allowed for immobilization, which compared with a value of 3.6+/-0.4 x 10(-10) mol cm(-2) determined by CV. The possible mechanisms of cyt c immobilization on the C(60) film and C(60)-Pd film-modified electrodes are also discussed.     

New strategy for the asymmetric synthesis of phenyl ketone cyanohydrins: quaternization of cyanohydrins derived from 2-p-tolylsulfinyl benzaldehyde

[reaction: see text] Optically pure functionalized cyanohydrins derived from 1-[2-(p-tolylsulfinyl)phenyl] ethanone can be obtained by the reaction of 2-p-tolylsulfinyl benzaldehyde derived cyanohydrins with bases and further treatment with suitable electrophiles. High yields and excellent stereoselectivities (up to de >98%) were obtained for these remote 1,4-asymmetric induction processes controlled by a sulfinyl chiral inductor.     

Potential energy surface for the CCl4 + H --> CCl3 + ClH reaction: kinetics and dynamics study

An analytical potential energy surface for the gas-phase CCl4 + H --> CCl3 + ClH reaction was constructed with suitable functional forms to represent vibrational modes. This surface is completely symmetric with respect to the permutation of the four chlorine atoms and is calibrated with respect to experimental thermal rate constants available over the temperature range 297-904 K. On this surface, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wider temperature range 300-2500 K, therefore obtaining kinetics information at higher temperatures than are experimentally available. This surface was also used to analyze dynamical features, such as tunneling and reaction-path curvature. In the first case, the influence of the tunneling factor is very small since a heavy chlorine atom has to pass through the barrier. In the second, it was found that vibrational excitation of the Cl-H stretching mode can be expected in the exit channel.     

Three isomorphous Ln complexes: {[Ln2(bt)6(bno)(H2O)4]·bno}n (bt is but‐2‐enoate and bno is 4,4′‐bipyridyl N,N′‐dioxide), with Ln = Nd,Er and Y

The polymeric title compounds, namely catena‐poly[[[di‐μ‐but‐2‐enoato‐κ³O:O,O′;κ³O,O′:O′‐bis[diaquadibut‐2‐enoato‐κO;κ²O,O′‐neodymium(III)]]‐μ‐4,4′‐bipyridyl N,N′‐dioxide‐κ²O:O′] 4,4′‐bipyridyl N,N′‐dioxide solvate] and the erbium(III) and yttrium(III) analogues, {[Ln₂(C₄H₅O₂)₆(C₁₀H₈N₂O₂)(H₂O)₄]·C₁₀H₈N₂O₂}_n (Ln = Nd, Er and Y), form from [Ln₂(bt)₆(H₂O)₄] dimers (bt is but‐2‐enoate) bridged by 4,4′‐bipyridyl dioxide (bno) spacers into sets of parallel chains; these linear arrays are interconnected by aqua‐mediated hydrogen bonds into broad two‐dimensional structures, which in turn interact with each other though the hydrogen‐bonded bridged bno solvent units. Both independent bno units in the structures are bisected by symmetry centres.     

Simultaneous determination of hydrogen as its iodine equivalent and of nitrogen by a volumetric method

Summary The method developed for simultaneous determination of hydrogen (by means of an equivalent amount of iodine) and of nitrogen by a volumetric method, is based on a flash combustion technique in a stream of CO₂ (100 ml/min) with controlled addition of O₂ (20%). Hydrogen is determined by conversion of water into hydrogen chloride on anhydrous magnesium chloride heated at 600–650° C, and reaction of the hydrogen chloride with Ag₂OI₂ at 220° C to yield iodine, which is collected on silver and weighed. The precision of the determination of hydrogen is excellent, the standard deviation being 0.008–0.017% abs., about a tenth of that obtained by the classical methods. The error in the determination of hydrogen was ±0.006% abs.

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Gleichzeitige Bestimmung von Wasserstoff als dessen Jodäquivalent und von Stickstoff auf volumetrischem Wege

Zusammenfassung Die entwickelte Methode zur gleichzeitigen Bestimmung von Wasserstoff in Form seines Jodäquivalents und von Stickstoff auf gasvolumetrischem Wege beruht auf der Entflammungsmineralisation im CO₂-Strom (100 cm³/min) mit kontrolliertem Zusatz von O₂ (20%). Der Gasstrom wird zusätzlich über P₂O₅ getrocknet. Die dem Wasserstoff äquivalente Jodmenge wird an metallischem Silber gebunden und gravimetrisch bestimmt, wobei Wasser bei 600–650° C mit Magnesiumchlorid in Chlorwasserstoff übergeführt wird, der nachfolgend bei 220° C mit Ag₂Oj₂ zu Jod umgesetzt wird. Für Verbindungen, die neben C, H, N und O auch Br, Cl, P und S enthalten, werden Wasserstoffresultate mit hoher Präzision erzielt:s _H beträgt 0,008 bis 0,017% absolut und ist etwa 10mal kleiner als bei den üblichen, klassischen Methoden. Die Genauigkeit der Wasserstoffbestimmung entspricht einem mittleren Fehler=±0,006% absolut. Die Resultate für den Wasserstoff und Stickstoff verlangen eine Blindwertkorrektur.

     

Synthesis of 1,2-di-(4-pyridyl)ethylenediamine and related compounds

Hydrolysis of N,N'-diacyl-1,2-di(4-pyridyl)ethylenediamines 1 in aqueous sulfuric acid gave the corresponding imidazolines 3. 1,2-Di-(4-pyridyl)ethylenediamine 2 was prepared in 61 % yield by treating N,N'-di-t-butyl-oxycarbonyl-1,2-di(4-pyridyl)ethylenediamine 4 with trifluoroacetic acid or in 94% yield by the hydrolysis under basic conditions of N,N'-diphthaloylglycyl-1,2-di(4-pyridy)ethylenediamine 13.     

Temperature-induced isomerization of violaxanthin in organic solvents and in light-harvesting complex II

Three main xanthophyll pigments are bound to the major photosynthetic pigment-protein complex of Photosystem II (LHCII): lutein, neoxanthin and violaxanthin. Chromatographic analysis of the xanthophyll fraction of LHCII reveals that lutein appears mainly in the all-trans conformation, neoxanthin in the 9'-cis conformation and major fraction of violaxanthin in the all-trans conformation. Nevertheless, a small fraction of violaxanthin appears always in a cis conformation: 9-cis and 13-cis (approximately 4% and 2% in the darkness, respectively). Illumination of the isolated complex (5 min, 445 nm, 250 micromolm-2s-1) results in the substantial increase in the concentration of the cis steric conformers of violaxanthin: up to 6% of 9-cis and 4% of 13-cis. Similar effect can be obtained by dark incubation of the same preparation for 30 min at 60 degrees C. Heating-induced isomerization of the all-trans violaxanthin can also be obtained in the organic solvent system but the formation of the 9-cis stereoisomer has not been observed under such conditions. The fact that the appearance of the 9-cis form of violaxanthin is specific for the protein environment suggests that violaxanthin may replace neoxanthin in LHCII in the N1 xanthophyll binding pocket and that the protein stabilizes this particular conformation. The analysis of the electronic absorption spectra of LHCII and the FTIR spectra of the protein in the Amid I band spectral region indicates that violaxanthin isomerization is associated with the disaggregation of the complex. It is postulated that this reorganization of LHCII provides conditions for desorption of violaxanthin from the pigment protein complexes, its diffusion within the thylakoid membrane and therefore, availability to the enzymatic deepoxidation within the xanthophyll cycle. It is also possible that violaxanthin isomerization plays the role of a security valve, by consuming an energy of excessive excitations in the antenna pigment network (in particular, exchanged at the triplet state levels).     

Application of the extended RSA models in studies of particle deposition at partially covered surfaces

This paper reviews the application of the extended random sequential adsorption (RSA) approaches to the modeling of colloid-particle deposition (irreversible adsorption) on surfaces precovered with smaller particles. Hard (noninteracting) particle systems are discussed first. We report on the numerical simulations we performed to determine the available surface function, jamming coverage, and pair-correlation function of the larger particles. We demonstrate the effect of the particle size ratio and the small particle surface coverage. We found that the numerical results were in reasonable agreement with the formula stemming from the scaled-particle theory in 2D with a modification for the sphere geometry. Next, we discuss three approximate models of adsorption allowing electrostatic interaction of colloid particles at a charged interface, employing a many-body superposition approximation. We describe two approaches of the effective hard-particle approximation next. We demonstrate the application of the effective hard-particle concept to the bimodal systems and present the effect of electrolyte concentration on the effective particle size ratio. We present the numerical results obtained from the theoretical models of soft-particle adsorption at precovered surfaces. We used the effective hard-particle approximation to determine the corresponding simpler systems of particles, namely the system of hard spheres and the system of hard discs at equilibrium. We performed numerical computations to determine the effective minimum particle surface-to-surface distance, available surface function, jamming coverage, and pair-correlation function of the larger particles at various electrolyte ionic strengths and particle size ratios. The numerical results obtained in the low-surface coverage limit were in good agreement with the formula stemming from the scaled-particle theory with a modification for the sphere geometry and electrostatic interaction. We compared the results of numerical computations of the effective minimum particle surface-to-surface distance obtained using the 2D, 3D, and curvilinear trajectory model. The results obtained with the 3D and curvilinear trajectory models indicate that large-particle/substrate attractive interaction significantly reduces the kinetic barrier to large, charged-particle adsorption at a surface precovered with small, like-charged particles. The available surface function and jamming-coverage values predicted using the simplified 3D and the more sophisticated curvilinear trajectory models are similar, while the results obtained with the 2D model differ significantly. The pair-correlation function suggests different structures of monolayers obtained with the three models. Unlike the three models of the electrostatic interaction, both effective hard-particle approximations give almost identical results. Results of this research clearly suggest that the extended RSA approaches can fruitfully be exploited for numerical simulations of colloid-particle adsorption at precovered surfaces, allowing the investigation of both hard and soft-particle systems.     

A potential model for the study of ices and amorphous water: TIP4P/Ice

The ability of several water models to predict the properties of ices is discussed. The emphasis is put on the results for the densities and the coexistence curves between the different ice forms. It is concluded that none of the most commonly used rigid models is satisfactory. A new model specifically designed to cope with solid-phase properties is proposed. The parameters have been obtained by fitting the equation of state and selected points of the melting lines and of the coexistence lines involving different ice forms. The phase diagram is then calculated for the new potential. The predicted melting temperature of hexagonal ice (Ih) at 1 bar is 272.2 K. This excellent value does not imply a deterioration of the rest of the properties. In fact, the predictions for both the densities and the coexistence curves are better than for TIP4P, which previously yielded the best estimations of the ice properties.     

RP-HPLC study of redox equilibria in vanadium-PAR binary and ternary systems: Direct determination of vanadium in steel

The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C₁₈ column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H₂O₂-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH₂OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH₂OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel.