Hyperpigmentation induced by topical 5-aminolaevulinic acid plus visible light

Photodynamic therapy (PDT) with 5-aminolaevulinic acid (ALA) is an alternative tool for the treatment of superficial non-melanoma skin cancers. Recently ALA-PDT has been employed with encouraging results also for warts, condylomata and psoriasis. In this study the effects of topical ALA plus irradiation with visible light on intact human skin have been evaluated. Five skin areas (A, B, C, D, and E) on the inner upper part of the arms of five healthy volunteers (skin types III and IV) were treated with (A) ALA 20% in base cream without irradiation, (B) only the vehicle (base cream) without ALA, (C, D and E) ALA cream at the concentrations of 5, 10 and 20%, respectively; all treatments were applied with an occlusive dressing. Four hours after ALA or vehicle application areas B, C, D and E were irradiated with a fixed dose of 40 J/cm(2). ALA penetration through the intact skin was evaluated by in vivo fluorescence determination. The effects on healthy skin were evaluated by clinical and chromometric examinations, light microscopy, immunohistochemistry and electron microscopy. RESULTS: (1) in vivo fluorescence demonstrated that ALA is able to penetrate through the intact skin, when applied with occlusive dressing and induces a classical fluorescence peak due to Protoporphyrin IX (PpIX) formation, which is the active photosensitiser. (2) Skin areas receiving ALA plus irradiation showed erythema and swelling just after the irradiative session and hyperpigmentation 48-72 h later. (3) Colourimetric data confirmed significant skin colour changes: values a* (representing the erythematous changes) increased only on the skin areas where ALA+irradiation were applied and during the 48 h after irradiation, thereafter a* began to decrease; values L* (pigmentation) increased during the 2 weeks following treatment. (4) Histopathological, immunohistochemical (S100, HMB-45) and electron microscopic findings showed an absolute increment of the number of melanocytes, which appeared clearly activated. In conclusion the application of ALA cream followed by irradiation is able to induce a pigmentation response in healthy human skin, at least in skin types III and IV. This melanocytic activation could have a potential for the treatment of skin disorders characterised by hypopigmentation.     

New physically adsorbed polymer coating for reproducible separations of basic and acidic proteins by capillary electrophoresis

In this work, a new physically adsorbed coating for capillary electrophoresis (CE) is presented. The coating is based on a N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EPyM) copolymer synthesized in our laboratory. The capillary coating is simple and easy to obtain as only requires flushing the capillary with a polymer aqueous solution for 2 min. It is shown that by using these coated capillaries the electrostatic adsorption of a group of basic proteins onto the capillary wall is significantly reduced allowing their analysis by CE. Moreover, the DMA-EPyM coating provides reproducible separations of the basic proteins with RSD values for migration times lower than 0.75% for the same day (n = 5) and lower than 3.90% for three different days (n = 15). Interestingly, the electrical charge of the coated capillary wall can be modulated by varying the pH of the running buffer which makes possible the analysis of basic and acidic proteins in the same capillary. The usefulness of this coating is further demonstrated via the reproducible separation of whey (i.e. acidic) proteins from raw milk. The coating protocol should be compatible with both CE in microchips and CE-MS of different types of proteins.     

The thioketone–enethiol tautomerism of aliphatic thiocarbonyls: An ab initio study

Approximate minimum energy reaction paths have been calculated for two thioketone–enethiol tautomeric systems using an ab initio SCF–MO method. The calculations indicate nearly equal stabil ties of the isolated tautomers in both systems and an energy barrier of ca. 85 kcal/mol for their interconversion. This barrier is expected to be significantly lower in solution as a result of solvent–solute interactions.     

Optimized determination of calcium in grape juice,wines, and other alcoholic beverages by atomic absorption spectrometry

This paper describes a study of the different methods of sample preparation for the determination of calcium in grape juice, wines, and other alcoholic beverages by flame atomic absorption spectrometry; results are also reported for the practical application of these methods to the analysis of commercial samples produced in Spain. The methods tested included dealcoholization, dry mineralization, and wet mineralization with heating by using different acids and/or mixtures of acids. The sensitivity, detection limit, accuracy, precision, and selectiviy of each method were established. Such research is necessary because of the better analytical indexes obtained after acid digestion of the sample, as recommended by the European Union, which advocates the direct method. In addition, although high-temperature mineralization with an HNO3-HCIO4 mixture gave the best analytical results, mineralization with nitric acid at 80 degrees C for 15 min gave the most satisfactory results in all cases, including those for wines with high levels of sugar and beverages with high alcoholic content. The results for table wines subjected to the latter treatment had an accuracy of 98.70-99.90%, a relative standard deviation of 2.46%, a detection limit of 19.0 microg/L, and a determination limit of 31.7 microg/L. The method was found to be sufficiently sensitive and selective. It was applied to the determination of Ca in grape juice, different types of wines, and beverages with high alcoholic content, all of which are produced and widely consumed in Spain. The values obtained for Ca were 90.00 +/- 20.40 mg/L in the grape juices, 82.30 +/- 23.80 mg/L in the white wines, 85.00 +/- 30.25 mg/L in the sweet wines, 84.92 +/- 23.11 mg/L in the red wines, 85.75 +/- 27.65 mg/L in the rosé wines, 9.51 +/- 6.65 mg/L in the brandies, 11.53 +/- 6.55 mg/L in the gin, 7.3 +/- 6.32 mg/L in the pacharán, and 8.41 +/- 4.85 mg/L in the anisettes. The method is therefore useful for routine analysis in the quality control of these beverages.     

Study of the first nucleation steps of thin films by XPS inelastic peak shape analysis

The initial steps in the formation of thin films have been investigated by analysis of the peak shape (both inelastic background and elastic contributions) of X‐ray photoelectron spectra. Surface coverage and averaged height of the deposited particles have been estimated for several overlayers (nanometre range) after successive deposition cycles. This study has permitted the assessment of the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of an XPS spectrometer. To check the performance of the method, several materials (i.e. cerium oxide, vanadium oxide and cadmium sulfide) have been deposited on different substrates using a variety of preparation procedures (i.e. thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition). It is shown that the first deposited nuclei of the films are usually formed by three‐dimensional particles whose heights and degree of surface coverage depend on the chemical characteristics of the growing thin film and substrate materials, as well as the deposition procedure. It is concluded that XPS peak shape analysis can be satisfactorily used as a general method to characterize morphologically the first nanometric moieties that nucleate a thin film. Copyright © 2006 John Wiley & Sons, Ltd.     

Regioselective homogeneous hydrogenation of heteroaromatic nitrogen compounds by use of [RuH(CO)(NCMe)2(PPh3)2]BF4 as the precatalyst

Summary The complex [RuH(CO)(NCMe)₂(PPh₃)₂]BF₄ (1) is an efficient and regioselective catalyst precursor for the hydrogenation of polyaromatic nitrogen compounds such as quinoline (Q), isoquinoline (iQ), indole (ln), 5,6- and 7,8-benzoquinoline (BQ) and acridine (A) under relatively mild reaction conditions (125 °C, 4 atm H₂). The order of individual initial rates was: A > Q > 5,6-BQ > 7,8-BQ > ln > iQ, reflecting both steric and electronic effects. For the regioselective homogeneous hydrogenation of A to 9,10-dihydroacridine (DHA) catalysed by complex (1), a kinetic study was carried out; the experimentally determined rate law was r = k ₁ [Ru] [H₂]. These findings are consistent with a mechanism involving the hydrogenation of [RuH(CO)(A)(NCMe)(PPh₃)₂]BF₄ to yield DHA and the unsaturated species [RuH(CO)(NCMe)(PPh₃)₂]BF₄ in the rate-determining step.     

Magnetic properties of biacetyldihydrazone complexes

Summary Magnetic susceptibilities of the biacetyldihydrazone (BdH) complexes [M(BdH)₃](NO₃)₂ (M = Co^II, Ni^II, Cu^II or Zn^II), [Fe(BdH)₃](NO₃)₃, [M(BdH)₃](Ni(dto)₂] (M = Co^II, Ni^II or Zn^II; dto = dithiooxalate), [(BdH)₂Cu(dto)Ni(dto)] and [Fe(BdH)₃]₂[Ni(dto)₂]₃ have been studied in the 4.2–295 K range. Zn^II complexes are diamagnetic, and complexes of Ni^II, Cu^II and Fe^III obey the Curie-Weiss law. The Co^II complexes behave anomalously and the results are interpreted in terms of a high spinlow spin equilibrium.     

Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.     

Constituents of labiatae—XIV: Vierol and powerol,two new diterpenes from Sideritis canariensis

The two new diterpenes, vierol (1) [(?)kaurane-16α,18-diol] and powerol (3) [(?)kaurane-7β,16α-diol] have been isolated from Sideritis canariensis Ait. 1 was obtained by partial synthesis from epicandicandiol (7), and 3 was related with (?)kauranol (6) and (?)kauren-7β-ol acetate (11). Reduction of the acetoxy-aldehyde 14 by the method of Huang-Minlon and posterior acetylation gave 11, (?)isokauren-7β-ol acetate (17) and (?)kauran-7β-ol acetate (18).     

Thermal behaviour of benzenesulfenamides and of their chromium carbonyl complexes

Benzenesulfenamides with the formula R-S-N-(R)₂ (R=C₆H₅ andR=NC₄H₈O, C₇H₇ and C₆H₁₁) and their chromium carbonyl complexes were studied by means of TG and mass spectrometric methods. The thermal behaviour of the compounds the stabilities of free sulfenamides are lower than those observed for the corresponding chromium carbonyl complexes. Combined thermogravimetry — mass spectrometry results suggest that the fragmentation mechanism of the carbonyl complexes involves cleavage of the Cr-S and Cr-CO bonds while that of sulfenamide depends mainly on the dissociation rates of the NR₂ groups.This work was partially supported by the Departamento técnico de Investigation of the Universidad de Chile, Grant Q3280/9324.