Ionization and Partitioning Profiles of Zwitterions: The case of the anti-inflammatory drug azapropazone

Azapropazone ( 1 ) is a non-steroidal anti-inflammatory drug (NSAID) whose chemical structure is markedly different from that of other agents in this class and challenges our understanding of structure-activity and structure-permeation relationships. Using a variety of experimental and computational techniques, we studied 1 for its molecular structure in the gas phase and non-protic polar solvents, protonation/deprotonation equilibra, tautomerism, and pH-lipophilicity profiles (octan-1-ol/H₂O and dodecane/H₂O). Other NSAIDs and model compounds were also examined for comparison. Due to its very low acidic pK_a1, 1 exists in the physiological pH range as a zwitterion and as an anion. Some pharmacological implications of these findings are discussed.     

The Zeeman effect in spin-allowed and forbidden doublet-doublet transitions in orthorhombic rotating molecules

Theoretical predictions of the Zeeman effect on spin-allowed and forbidden doublet-doublet transitions in near-symmetric top molecules are reported, with the assistance of computer simulations of band profiles. Bandwidths in the high-field limit have been determined. Marked differences have been found between the behavior of spin-allowed and forbidden transitions. The intermediate-field effect on spin-allowed transitions is sensitive to the relative energy order of the zero-field spin components of the rotational sublevels in the combining vibronic states. In the high-field limit the rotational components of spin-allowed transitions give rise to a single band, corresponding to ΔM_S = 0, whereas the bands with ΔM_S = ±1 are also expected in spin-forbidden transitions. The applicability to actual cases is finally discussed.     

Optimization of the separation of flavonoids using solvent-modified micellar electrokinetic chromatography

In this work the separation of eighteen flavonoids was attempted using reduced-flow micellar elektrokinetic chromatography (RF-MEKC) electrolytes modified by selected solvents with differing properties: methanol (MeOH), acetonitrile (ACN) and tetrahydrofuran (THF). Structural aspects such as unsaturation of the C ring, number and position of OH groups, methylation and glycosylation as well as solvent effects and their impact on the electrophoretic behavior of flavonoids were addressed. By evaluating the electropherograms obtained from mixture-designed electrolytes and searching for changes in the critical pairs, a favorable separation condition was achieved using 20 mmol/L phosphate buffer at pH 2.5 containing 50 mmol/L sodium dodecyl sulfate (SDS), 15% ACN and 5% THF (one critical pair) in less than 12 min with 1.5% coefficient of variation (CV) for retention factor and 3% CV for peak area (n = 5). The applicability of the proposed separation condition was demonstrated by the inspection of flavonoids in herbal extracts of Neem.     

Identification and composition of cuticular hydrocarbons of the major Afrotropical malaria vector Anopheles gambiae s.s. (Diptera: Culicidae): analysis of sexual dimorphism and age-related changes

Forty-eight cuticular hydrocarbons (CHCs) were characterized by gas chromatography-mass spectrometry from the epicuticular surface of the major Afrotropical malaria vector Anopheles gambiae. The hydrocarbons identified were 14 n-alkanes, 16 monomethyl alkanes, 13 dimethyl alkanes, 5 alkenes, with main-chain lengths ranging from C(17) to C(47), and the results are consistent with those from other Culicidae species. Qualitative differences were not observed between laboratory pools of three females and males, between different age-groups (0-16 days) and between single field specimens, whereas quantitative differences in CHC profiles were observed. Differences between sexes were more marked in individuals aged 0-2 days than in older ones. Both sexes undergo strong CHC profile changes with age, and individuals aged 0-2 days differ remarkably from the older ones. The possibility of exploiting these changes for estimating the age of mosquito was explored through multivariate analyses of the relative abundance of the compounds, using either the whole CHC profile or a subset of CHCs. Such a method allows us to assign more than 85% of females and 75% of males to the correct age-group. Although preliminary, these results show that the method is promising, as it has already been shown in Aedes aegypti and An. stephensi. The correct determination of the vector age (particularly in the case of the An. gambiae complex of sibling species) provides valuable information in malaria epidemiology and in evaluation of the effectiveness of vector control strategies. Further efforts will be made to validate this method on single specimens reared in seminatural conditions before being proposed to medical entomologists working in the Afrotropical region.     

Su un caso di non esistenza e su uno di esistenza e unicità della soluzione di un problema della magnetoidrodinamica stazionaria

Riassunto In questa nota si affrontano alcune questioni di esistenza e unicità della soluzione classica del problema del moto stazionario di un fluido omogeneo, incomprimibile, perfetto, elettricamente condutore attorno ad un ostacolo dielettrico e scarico in un punto del quale è situato un dipolo magnetico. Precisamente, si dimostra dapprima che, nel caso in cui il fluido abbia conduttività finita, il problema suddetto non ammette soluzione se al campo cinetico e al campo magnetico sono imposte condizioni all'infinito alquanto restrittive. Si dimostra poi che opportune ipotesi all'infinito assicurano l'esistenza e l'unicità della soluzione del medesimo problema nel caso in cui il fluido sia un conduttore perfetto.

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Summary This paper deals with some questions of classical solution existence and uniqueness for the problem of the steady flow of an homogeneous, incompressible, perfect, electrically conducting fluid past a dielectric and discharged obstacle in which a magnetic dipole is situated. More precisely, in the first place the non-existence of solutions of the above mentioned problem is proved for fluids of finite conductivity, if rather restrictive conditions are placed on behavior of the kinetic and magnetic fields at infinity. In the next place an existence and uniqueness theorem is established for perfectly conducting fluids.