Onset of hydrogen bonded collective network of water in 1,4-dioxane

We have studied the evolution of water hydrogen bonded collective network dynamics in mixtures of 1,4-dioxane (Dx) as the mole fraction of water (X(w)) increases from 0.005 to 0.54. The inter- and intramolecular vibrations of water have been observed using terahertz time domain spectroscopy (THz-TDS) in the frequency range 0.4-1.4 THz (13-47 cm(-1)) and Fourier transform infrared (FTIR) spectroscopy in the far-infrared (30-650 cm(-1)) and mid-infrared (3000-3700 cm(-1)) regions. These results have been correlated with the reactivity of water in these mixtures as determined by kinetic studies of the solvolysis reaction of benzoyl chloride (BzCl). Our studies show an onset of intermolecular hydrogen bonded water network dynamics beyond X(w) ≥ 0.1. At the same concentration, we observe a rapid increase of the rate constant of solvolysis of BzCl in water-Dx mixtures. Our results establish a correlation between the onset of collective hydrogen bonded network with the solvation dynamics and the activity of clustered water.     

Time-dependent interactions of the two porphyrinic compounds chlorin e6 and mono-L-aspartyl-chlorin e6 with phospholipid vesicles probed by NMR spectroscopy

The distribution processes of chlorin e6 (CE) and monoaspartyl-chlorin e6 (MACE) between the outer and inner phospholipid monolayers of 1,2-dioleoyl-phosphatidylcholine (DOPC) vesicles were monitored by 1H NMR spectroscopy through analysis of chemical shifts and line widths of the DOPC vesicle resonances. Chlorin adsorption to the outer vesicle monolayer induced changes in the DOPC 1H NMR spectrum. Most pronounced was a split of the N-methyl choline resonance, allowing for separate analysis of inner and outer vesicle layers. Transbilayer distribution of the chlorin compounds was indicated by time-dependent characteristic spectral changes of the DOPC resonances. Kinetic parameters for the flip-flop processes, that is, half-lives and rate constants, were obtained from the experimental data points. In comparison to CE, MACE transbilayer movement was significantly reduced, with MACE remaining more or less attached to the outer membrane layer. The distribution coefficients for CE and MACE between the vesicular and aqueous phase were determined. Both CE and MACE exhibited a high affinity for the vesicular phase. For CE, a positive correlation was found between transfer rate and increasing molar ratio CE/DOPC. Enhanced membrane rigidity induced by increasing amounts of cholesterol into the model membrane was accompanied by a decrease of CE flip-flop rates across the membrane. The present study shows that the movement of porphyrins across membranes can efficiently be investigated by 1H NMR spectroscopy and that small changes in porphyrin structure can have large effects on membrane kinetics.     

2-DE and MALDI-TOF-MS analysis of therapeutic fusion protein abatacept

2-DE and MALDI-TOF MS are useful techniques for the quality evaluation of medicinal products derived from recombinant DNA technology. The principal objective of this study has been to evaluate the suitability of 2-DE in combination with MALDI-TOF MS for the quality study of the therapeutic recombinant protein, abatacept. 1-DE SDS-PAGE, under reducing and nonreducing conditions, and 2-DE analysis were used for the assessment of M(r) , pI, and enzymatic deglycosylation efficiency of abatacept. 2-DE allowed the assessment of product identity, purity, charge heterogeneity, isoform pattern, and post-translational modifications. Furthermore, optimization of the deglycosylation procedure, charge heterogeneity, and sample preparation for the subsequent MALDI-TOF MS analysis has been addressed. PMF analysis allowed rapid identity confirmation of abatacept.     

Electrodeposition of polyaniline–carbon nanotubes composite films and investigation on their role in corrosion protection of austenitic stainless steel by SNIFTIR analysis

Composite films of polyaniline (PANI) and carbon nanotubes (CNTs) were prepared by electrochemical co-deposition from solutions of the corresponding monomer containing two different kinds of CNTs. The first type was commercial (diameter = 110–170 nm, length = 5–9 μm) and the second one was home-made (diameter = 30 nm, length = 5–20 μm). The electrochemical behaviour of PANI–CNTs composite films was investigated with Cyclic Voltammetry and the surface morphology was analysed by Scanning Electron Microscopy (SEM). Subtractively Normalised Interfacial FT-IR procedure was used to investigate the presence of corrosion products when the films were deposited on stainless steel substrates and exposed to acid environment. The spectral investigations were utilised to understand the role of composite films in the corrosion protection and to discriminate the best performance CNTs.     

Systematic generation of relativistic gaussian basis sets

A method for the Gaussian basis set generation for molecular relativistic Dirac-Fock calculations is proposed. The basis set exponents are obtained in the process of stochastic optimization (a hybrid of simplex and simulated annealing optimization techniques has been employed) of a functional defined as the sum of squares of differences between the numerical relativistic atomic wave functions and the wave functions obtained using the Gaussian function expansion. After this pre-optimization step the exponents are refined by ordinary gradient energy-functional based procedure. The present method seems to be very effective and robust. As an example the optimized basis sets of atoms from H (Z=1) to Ar (Z=18) are presented. Results of the Dirac-Fock calculations for all atoms under study are presented and compared with the numerical Dirac-Fock results and results obtained using the Gaussian basis sets according to Okada et al.: J. Chem. Phys.93 (1990) 5013. Slovak Grant Agency has funded the work reported in this paper, project No. 1/4205/98.     

Development of Agglomerate Size and Structure during spherical agglomeration in suspension

During the spherical agglomeration process, a suspended solid is agglomerated by adding a binding liquid. First, mircoagglomerates or flocs are produced, which are compacted in the course of the process. Agglomerate size was evaluated by laser diffraction spectrometry, image analysis was used to determine the size and some adequately defined shape parameters calculated by Fourier analysis of the particle contour. The shape analysis confirms the visual observations; the compaction of the flocs is expressed by the corresponding change of the shape parameters. The influence of several process parameters on changes in agglomerate shape can be described quantitatively and help to gain an insight into agglomeration mechanisms. The particle size distributions determined by image analysis and laser diffraction spectrometry hardly differ for fairly spherical flocs or agglomerates. Concerning the size distribution of the irregular flocs, laser diffraction spectrometry measures larger particles than image analysis.     

Preparation of Synthetic and Natural Derivatives of Flavonoids Using Suzuki–Miyaura Cross-Coupling Reaction

Herein, we report the use of the Suzuki–Miyaura cross-coupling reaction for the preparation of a library of synthetic derivatives of flavonoids for biological activity assays. We have investigated the reactivity of halogenated flavonoids with aryl boronates and with boronyl flavonoids. This reaction was used to prepare new synthetic derivatives of flavonoids substituted at C-8 with aryl, heteroaryl, alkyl, and boronate substituents. The formation of flavonoid boronate enabled a cross-coupling reaction with halogenated flavones yielding biflavonoids connected at C-8. This method was used for the preparation of natural compounds including C-8 prenylated compounds, such as sinoflavonoid NB. Flavonoid boronates were used for the preparation of rare C-8 hydroxyflavonoids (natural flavonoids gossypetin and hypolaetin). A series of previously unknown derivatives of quercetin and luteolin were prepared and fully characterized.