Cyclodextrin effects on physical–chemical properties of novocaine

The UV-vis absorption and the fluorescence emission spectra of novocaine were analysed in aqueous cyclodextrin (CD) solutions. Either the absorbance read at λ_max 290 nm or the fluorescence emission intensity at λ_ems 346 nm increase in the presence of both α- and β-CD due to the formation of 1:1 inclusion complexes. The lower polarity of the CD-cavity sensed by the included drug enhances the emitted fluorescence; in fact, the same effect was observed in aqueous mixtures of acetonitrile, dioxane, or dimethylsulfoxide. The inclusion complex formation between the monocation of novocaine and CDs diminishes the electrical conductance of aqueous solutions of novocaine hydrochloride (NoHCl). Both the nitrosation reaction in aqueous acid medium and the ester hydrolysis in alkaline medium are retarded in the presence of CDs. The strongest effect was observed with β-CD as a consequence of the higher stability inclusion complex.     

Note on a theoretical interpretation of the isotopic ratio vOH/vOD versus vOH in isotopically diluted HDO molecules in solid hydrates

A simple intra- and inter-molecular potential for water molecules engaged in hydrogen bonding has been used in a one-dimensional approximation for a theoretical interpretation of the experimental correlation $\text{v}$_OH/$\text{v}$_OD versus $\text{v}$_OH in solid hydrates. The variation in the equilibrium OH(D) distance has also been considered.     

Calcium oxalate monohydrate precipitation at membrane lipid rafts

The precipitation of calcium oxalate monohydrate (COM) was monitored at a Langmuir monolayer containing lipid raft domains. The raft-forming monolayer consists of a 2:1:1 mixture of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine/sphingomyelin/dihydrocholesterol, where the raft liquid ordered phase is enriched in sphingomyelin and the sterol. COM crystals, monitored by Brewster angle microscopy, appear at the phase boundary between the raft domains and the expanded phase.     

New liquid chromatographic-chemometric approach for the determination of sunset yellow and tartrazine in commercial preparation

A new liquid chromatographic (LC)-chemometric approach was developed for the determination of sunset yellow (SUN) and tartrazine (TAR) in commercial preparations. This approach uses LC and chemometric calibration methods, i.e., classical least-squares (CLS), principal component regression (PCR), and partial-least squares (PLS), simultaneously. The combined LC-chemometric approaches, denoted as LC-CLS, LC-PCR, and LC-PLS, are based on photodiode array (PDA) detection at multiple wavelengths. Optimum chromatographic separation of SUN and TAR with allura red as the internal standard (IS) was obtained by using a Waters Symmetry C18 column, 5 microm, 4.6 x 250 mm, and 0.2 M acetate buffer (pH 5)-acetonitrile-methano-bidistilled water (55 + 20 + 15 + 10, v/v) as the mobile phase at a flow rate of 1.9 mL/min. The LC data sets consisting of the ratios of analyte peak areas to the IS peak area were obtained by using PDA detection at 5 wavelengths (465, 470, 475, 480, and 485 nm). LC-chemometric calibrations for SUN and TAR were separately constructed by using the relationship between the peak-area ratio and the training sets for each colorant. LC-chemometric approaches were tested for different synthetic mixtures containing SUN and TAR in the presence of the IS. These LC-chemometric calibrations were applied to a commercial preparation of the 2 colorants. The experimental results of the LC-chemometric approaches were compared with those obtained by a developed classical LC method using single-wavelength detection.     

Synthesis and photoluminescent properties of 1,1'-binaphthyl-based chiral phenylenevinylene dendrimers

New chiral, soluble binaphthyl derivatives that incorporate stilbenoid dendrons at the 6,6'-positions have been prepared. The synthesis of the new enantiopure dendrimers was performed in a convergent manner by Horner-Wadsworth-Emmons (HWE) reaction of the appropriately functionalized 1,1'-binaphthyl derivative (R)-1 and the appropriate dendrons (R)(2n)G(n)-CHO. Different electroactive units were incorporated in the peripheral positions of the dendrons in order to tune both the optical and electrochemical behavior of these systems. Fluorescence measurements on the chiral dendrimers reveal a strong emission with maxima between 409 and 508 nm depending upon the substitution pattern. Finally, the redox properties of the dendrimers were determined by cyclic voltammetry, showing the influence of the functional groups at the peripheral positions of the dendrimer on the redox behavior of these systems.     

From a biogenetic scenario to a synthesis of the ABC ring of manzamine A

On the basis of a biogenetic proposal for explaining the biogenesis of manzamine A, the cycloaddition of dihydropyridinium salt 26 with diene derivative 5 leads to adducts 27. These adducts, as well as their related and previously described analogues 9, are now shown to be precursors of diene derivatives such as 10, 13, and 28. Treatment of diene 32 with sodium azide resulted in a one-step formation of the tricyclic imino derivative 34. This key intermediate was further transformed into tricyclic derivative 40, which possesses the essential features of the ABC ring of manzamine A.     

Donnan equilibrium of ionic drugs in pH-dependent fixed charge membranes: theoretical modeling

We have studied theoretically the partition equilibrium of a cationic drug between an electrolyte solution and a membrane with pH-dependent fixed charges using an extended Donnan formalism. The aqueous solution within the fixed charge membrane is assumed to be in equilibrium with an external aqueous solution containing six ionic species: the cationic drug (DH(+)), the salt cations (Na(+) and Ca(2+)), the salt anion (Cl(-)), and the hydrogen and hydroxide ions. In addition to these mobile species, the membrane solution may also contain four fixed species attached to the membrane chains: strongly acid sulfonic groups (SO(3)(-)), weakly acid carboxylic groups in dissociated (COO(-)) and neutral (COOH) forms, and positively charged groups (COO...Ca(+)) resulting from Ca(2+) binding to dissociated weakly acid groups. The ionization state of the weak electrolyte groups attached to the membrane chains is analyzed as a function of the local pH, salt concentration, and drug concentration in the membrane solution, and particular attention is paid to the effects of the Ca(2+) binding to the negatively charged membrane fixed groups. The lipophilicity of the drug is simulated by the chemical partition coefficient between the membrane and external solutions giving the tendency of the drug to enter the membrane solution due to hydrophobic interactions. Comparison of the theoretical results with available experimental data allows us to explain qualitatively the effects that the pH, salt concentration, drug concentration, membrane fixed charge concentration, and Ca(2+) binding exert on the ionic drug equilibrium. The role of the interfacial (Donnan) electric potential difference between the membrane and the external solutions on this ionic drug equilibrium is emphasized throughout the paper.     

Molecular dynamics simulations of the dinuclear zinc-beta-lactamase from Bacteroides fragilis complexed with imipenem

Herein, we present results from MD simulations of the Michaelis complex formed between the dizinc beta-lactamase from B. fragilis and imipenem. We considered two catalytically important configurations, which differ in the presence or absence of a hydroxide bridge connecting the two zinc ions in the active site. The structural and dynamical effects induced by substrate binding, the specific roles of the conserved residues and the zinc-bound water molecules, the near attack conformers of the Michaelis complex, and so forth, are discussed in detail. The relative stability of the two configurations was estimated from QM linear scaling calculations on the enzyme-substrate complex combined with Poisson-Boltzmann electrostatic calculations and normal mode calculations. Importantly, we find that the two configurations have similar energies, indicating that these two structures could readily be interchanged, thereby facilitating catalysis. The configuration with the hydroxide bound to the two zinc ions is predicted to be the resting form of the enzyme, while the configuration without the bridge is the reactive form that was found to place the hydroxide in position to attack the carbonyl of the beta-lactam ring. Thus, we propose that the enzyme initiates catalysis by converting from the hydroxide bridge form into the configuration that lacks the hydroxide bridge. This interconversion increases the nucleophilicity of the hydroxide ion and exposes it to the beta-lactam carbonyl, which ultimately facilitates nucleophilic attack. The implications of the observed modes of binding, the possible influence of mutating the Lys184 and Asn193 residues on substrate binding, and the reaction mechanism are also discussed in detail.     

Sensitive determination of diquat by a kinetic method using the stopped-flow mixing technique

A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples.     

Thermal oxidation of cellulose investigated by chemiluminescence. The effect of magnesium and calcium carbonates and of different pHs

Whatman cellulose impregnated with calcium and magnesium carbonates was oxidized and chemiluminescence accompanying this oxidation has been measured. It was shown that magnesium ions in deacidified cellulose pulp promote the light emission significantly. On the other hand, acid papers give the more pronounced light signals at temperatures close to ambient. The relation between chemiluminescence runs and paper degradation has been implicated, with an attempt to extrapolate half-lives of paper samples to conditions close to ambient. To cite this article: J. Rychlý et al., C. R. Chimie 9 (2006).