Binding of polyanions by biogenic amines. II. Formation and stability of protonated putrescine and cadaverine complexes with carboxylic ligands

The formation and stability of protonated diamines-carboxylic ligand complexes was studied potentiometrically (H(+)-glass electrode). Species formed are ALH(r) (A=cadaverine, putrescine, L=acetate, malate, tartrate, malonate, citrate, 1,2,3-propanetricarboxylate, 1,2,3,4-butanetetracarboxylate and glutamate; r=1...m+1, where m is the maximum degree of protonation of the carboxylic ligand), and their stability is a function of charges involved in the formation reaction. For the equilibrium H(i)A(i+)+H(j)L((j-z))=ALH((i+j-z))(i+j) the following linear relationships can be written: logK(1j)=-0.25+0.75 |j-z|, logK(2j)=0.50+0.90 |j-z| (by also considering some ethylenediamine and 1,2-diaminopropane complexes). Medium effects were considered. Comparison was made with analogous inorganic polyanion complexes. The simplest relationships -DeltaG(0)=6.5+/-0.3 and -DeltaG(0)=7.9+/-0.6 kJ mol(-1)n(-1) (n=number of possible salt bridges) were found for carboxylic and inorganic anions, respectively.     

Biosensor based on paraffin/graphite modified with sweet potato tissue for the determination of hydroquinone in cosmetic cream in organic phase

An organic-phase biosensor based on paraffin/graphite modified with sweet potato (Ipomoea batatas (L.) Lam.) tissue as the source of peroxidase was developed and used for determining hydroquinone in cosmetic creams. This enzyme in the presence of hydrogen peroxide catalyses the oxidation of hydroquinone to p-quinone which electrochemical reduction back to hydroquinone was obtained at a peak potential of -0.22 V. The recovery of hydroquinone from two samples ranged from 99.1 to 104.1% and a rectilinear analytical curve for hydroquinone concentration from 7.5x10(-5) to 1.6x10(-3) M (r=0.9991) were obtained. The detection limit was 8.1x10(-6) M and relative standard deviation was <1.0% for a solution containing 7.3x10(-4) M hydroquinone and 1.0x10(-3) M hydrogen peroxide in 0.10 M tetrabutylammonium bromide methanol-phosphate buffer solution (95:5% v/v) (n=10). The results obtained for hydroquinone in cosmetic creams using the proposed biosensor are in close agreement with those obtained using a Pharmacopoeia procedure at the 95% confidence level.     

Under pressure: predicting pressurized metered dose inhaler interactions using the atomic force microscope

Drug particulate interactions in pressurized metered dose inhalers (pMDI) may lead to a decrease in aerosolization efficiency and subsequent efficacy in patient treatment. The interactions between salbutamol sulfate (commonly used in Ventolin pMDIs) and a series of pMDI canister materials were investigated using the atomic force microscope (AFM) colloid probe technique. Approximately 4000 individual force-distance curves were determined for a drug probe and three surfaces (10 x 10 mum areas) in situ, in a model propellant. The area under each force-distance curve was integrated to obtain separation energy values. Median separation energy values followed the rank order borosilicate glass > aluminum > PTFE, suggesting PTFE to be the most suitable canister coating.     

Separation and implantation of relativistic86Kr-fragments at the FrS; half-life measurement by ion-β time-correlations

Neutron-rich Co and Fe isotopes produced by⁸⁶Kr projectile fragmentation at 500 MeV/u were separated and identified using the fragment separator (FrS) in a bunched energy mode.⁶⁶Co and⁶⁵Fe ions were selectively implanted in a double PIN-diode array where the-decay signals were measured. The half-lives were deduced from time correlations between implantation and-decay signals. The remeasurement of the⁶⁶Co half-life confirms the isotope identification. The value of the⁶⁵Fe half-life was found to be 0.45±0.15 s.     

SOOT combustion. co and k catalysts supported on different supports

The catalytic combustion of particulate material was studied on cobalt catalysts promoted with potassium using different supports for its preparation. Silica, aluminium oxides and hydroxides, zirconium oxide and hydroxide were used as supports. The catalytic activity for combustion depends on the type of support used, the higher activity corresponding to the supported catalyst on zirconium oxide. TPR studies indicate that the interaction metal/support allows to explain the higher activity of the CoK/SiO₂ catalyst with respect to the CoK/Al₂O₃ but the high activity found in CoK/ZrO₂is not explained by this interaction. In all cases the Co and K improved the performance of the catalysts.     

Encapsulation of cationic ruthenium complexes into a chiral self-assembled cage

A chiral supramolecular assembly encapsulates the two cationic ruthenium sandwich complexes [CpRu(eta(6)-C(6)H(6))](+) and [CpRu(p-cymene)](+). The host-guest complexes K(11)[CpRu(eta(6)-C(6)H(6)) subset Ga(4)L(6)] (2) and K(11)[CpRu(p-cymene) subset Ga(4)L(6)] (3) were characterized by one- and two-dimensional NMR techniques as well as by electrospray mass spectrometry. Encapsulation of the prochiral complex [CpRu(p-cymene)](+) by the chiral host renders enantiotopic protons diastereotopic as evidenced by (1)H NMR spectroscopy.     

Catalytic, asymmetric synthesis of α,α-disubstituted amino acids

Copper(salen) complex 1 has been found to catalyse the asymmetric alkylation of enolates derived from a variety of amino acids. There is a clear relationship between the size of the side chain in the substrate and the enantioselectivity of the process, so that the enantioselectivity decreases in the order alanine>aminobutyric acid>allylglycine>leucine>phenylalanine>valine. A transition state model which accounts for the influence of the size of the side chain on the enantioselectivity of the reactions is presented.     

Structural characterization of chondroitin/dermatan sulfate oligosaccharides from bovine aorta by capillary electrophoresis and electrospray ionization quadrupole time-of-flight tandem mass spectrometry

An analytical approach based on high-performance capillary electrophoresis (CE) in conjunction with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS) has been developed for providing the basis to obtain new insights into the domain structure of the glycosaminoglycan (GAG) moiety of proteoglycans. The feasibility and performance of the off-line CE/ESI-QTOF-MS approach in GAG oligosaccharide analysis were assessed by screening a chondroitin/dermatan sulfate (DS) oligosaccharide mixture obtained from bovine aorta by enzymatic depolymerization by chondroitin B lyase. The CS/DS mixture was analyzed by CE using 50 mM ammonium acetate, pH 12.0, dissolved in aqueous methanol (2:3; v/v), as a CE carrier. Structural identification of the GAG components was achieved using off-line CE/nanoESI-QTOF-MS and-MS/MS experiments. ESI-QTOF instrumental parameters were found to play an important role in the MS screening of the CE-separated GAG species. By optimizing the ESI conditions, oligosaccharides differing in chain length and degree of sulfation could be detected. The building block composition, the size of the carbohydrate chain, as well as structural features of the repeating HexA-GalNAc, HexA-GalNAc(S) units, have been determined using MS/MS by applying collision-induced dissociation at low energies. Cleavage of GAG chains by chondroitin B lyase occurs with formation of structural markers useful for identification of IdoA-containing domains.     

Multistep adsorption of anionic dyes on silica/chitosan hybrid. 1. Comparative kinetic data from liquid- and solid-phase models

In this work, a hybrid silica/chitosan was synthesized and characterized by nitrogen elemental analysis and thermal analysis (TG, DTG, DTA, and DSC) and BET surface area. The hybrid was used in adsorption studies of two anionic dyes from aqueous solutions. A rise of temperature accelerates mass transfer of dyes into the hybrid. However, the maximum adsorption capacities reach similar values from 25 to 55 degrees C. The kinetic data were first evaluated in relation to the decrease of the time-related residual concentration of the dyes in solution, where the second-order model has presented the best fitting. The solid-phase interaction of dye data presents a rough fitting to the traditional first-order Lagergren kinetic model. However, a modified Avrami kinetic equation was successfully fitted to the kinetic quantities, where from five to seven kinetic regions were found. A pore-diffusion model has also demonstrated that the diffusion is the rate-controlling interaction mechanism. However, the experimental-calculated comparative values are the best way to evaluate a specific aqueous- or solid-phase kinetic model.