The effects of vehicle and region of application on in vitro penetration of testosterone through canine skin

The effects of the vehicles phosphate-buffered saline (PBS), ethanol (EtOH; 50% in PBS w/w) and propylene glycol (PG; 50% in PBS w/w) and the region of administration on in vitro transdermal penetration of testosterone was investigated in the dog. Skin was harvested from the thorax, neck (dorsal part) and groin regions of greyhounds after euthanasia and stored at -20 degrees C until required. The skin was then de-frosted and placed into Franz-type diffusion cells which were maintained at approximately 32 degrees C by a water-bath. Saturated solutions of testosterone, containing trace amounts of radiolabelled (C-14) testosterone, in each vehicle were applied to the outer (stratum corneum) surface of each skin sample and aliquots of receptor fluid were collected at 0, 2, 4, 8, 16, 20, 22 and 24 h and analysed for testosterone by scintillation counting. The maximum flux (J(max)) of testosterone was significantly higher for all sites when dissolved in a vehicle containing 50% EtOH or 50% PG, compared to PBS. In contrast, higher residues of testosterone were found remaining within the skin when PBS was used as a vehicle. This study shows that variability in percutaneous penetration of testosterone could be expected with formulation design and site of application. (C) 2004 Elsevier Ltd. All rights reserved.

The stability and formulation of topical analgesics

High-performance liquid chromatographic methods are developed for the simultaneous determination of various salicylates, their p-hydroxy isomers and nicotinic acid esters. The method is sensitive enough to detect trace amounts (~µM/L)of the product generated from cross reactivity between the drugs and the vehicle. The developed method also allows analysis of various topical products containing salicylate and nicotinate esters in their formulations. Applying this method, the degradation profiles of salicylates, nicotinates, p-hydroxy benzoate, o-methoxy benzoate and aspirin prodrugs in alkaline media are determined. The profile for alkyl salicylate degradation is found to be first order (A---? B) When the alcoholic radical is similar to that of the ester. In alcohol having a radical different from that of the ester function, the degradation is found to proceed through competitive transesterification and hydrolysis. The intermediates are identified following synthesis and isolation. The rate and extent of transesterification depends on the proportion of alcohol present in the system. Equations are presented to model the time profiles of reactant and product concentration. The reactions are base catalysed and the predominant pathway involves a concerted solvent attack upon the salicylate anion. Competitive hydrolysis of both ester components also follows this mechanism at moderate pH values but rates increase under strongly alkaline conditions as direct hydroxide attack becomes significant. In contrast, transesterification is independent of base concentration once full ionization is accomplished. The competitive hydrolysis is modelled using equations involving the dielectric constant of the medium. A range of other esters are also shown to undergo base-catalysed transesterification. In non-alcoholic solution phenyl salicylate undergoes a concentration-dependent oligomerisation which yields salsalate among the products. Competitive transesterification and hydrolysis also occur in products for topical use which have vehicles based upon alcohol, glycol or glycol polymers. Such reactions may compromise stability assessments, pharmaceutical integrity and delivery profiles.

Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red

A family of titania derived nanocomposites synthesized via sol-gel and hydrothermal routes exhibit excellent performance for the photocatalytic degradation of two important exemplar water pollutants, oxytetracycline and Congo Red. Low loadings of Co3O4 nanoparticles dispersed over the surfaces of anatase TiO2 confer visible light photoactivity for the aqueous phase decomposition of organics through the resulting heterojunction and reduced band gap. Subsequent modification of these Co3O4/TiO2 composites by trace amounts of graphene oxide nanosheets in the presence of a diamine linker further promotes both oxytetracycline and Congo Red photodegradation under simulated solar and visible irradiation, through a combination of enhanced photoresponse and consequent radical generation. Radical quenching and fluorescence experiments implicate holes and hydroxyl radicals as the respective primary and secondary active species responsible for oxidative photodegradation of pollutants.

Red mangroves emit hydrocarbons

The objective of this study is to investigate hydrocarbon species and amounts released by red mangrove foliage and determine if these quantities warrant future research on atmospheric chemical processing of these compounds. The field investigation took place during July 2001 at Key Largo, Florida Bay, Florida. Foliage still attached to plants was enclosed in cuvettes while air of known flow rates circulated around leaves to study, hydrocarbon emissions. Cuvette air samples underwent gas chromatographic analyses to determine species and amounts of hydrocarbons released by mangrove foliage. Red mangrove foliage emits isoprene and trace amounts of the monoterpenes of alpha-pinene, beta-pinene, camphene, and d-limonene. The mangrove flowers released these latter compounds in amounts ranging from 0.5 to 10 mg (monoterpene) per gram of dry biomass per hour. These fluxes are normalized to, the foliage temperature of 30 degreesC. When normalized to the foliage temperature of 30 degreesC and light levels of 1000 mumol m(-2) s(-1), isoprene emission rates as high as 0.092 +/- 0.109 mug (isoprene) per gram of dry biomass per hour were measured. Compared to terrestrial forest ecosystems, red mangroves are low isoprene emitters. During peak flowering periods in the summertime, however, red mangroves may emit sufficient amounts of monoterpenes to alter ground-level ozone concentrations and contribute to biogenic aerosol formation.

The use of quantitative polymerase chain reaction amplification method to determine sex ratio of human spermatozoa in semen and to determine maternal contamination of amniotic fluid samples

We have modified a technique which uses a single pair of primer sets directed against homologous but distinct genes on the X and Y chromosomes, all of which are coamplified in the same reaction tube with trace amounts of radioactivity. The resulting bands are equal in length, yet distinguishable by restriction enzyme sites generating two independent bands, a 364 bp X-specific band and a 280 bp Y-specific band. A standard curve was generated to show the linear relationship between X/Y ratio average vs. %Y or %X chromosomal content. Of the 51 purified amniocyte DNA samples analyzed, 16 samples showed evidence of high % X contamination while 2 samples demonstrated higher % Y than the expected 50% X and 50% Y chromosomal content. With regards to the 25 processed sperm samples analyzed, X-sperm enrichment was evident when compared to the primary sex ratio whereas Y-sperm was enriched when we compared before and after selection samples.

Molecular and isotopic compositions of hydrocarbons at DSDP Site 76-533

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (d13C = -68 per mil; C1/C2 = 5000) was the dominant gas (>90%); (2) little fractionation in the C1/C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experiments; (3) the percent of C3, i-C4, and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) C1/C2 ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also contained trace amounts of saturated, acyclic, cyclic, and aromatic C5-C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (d13C of -68 per mil for methane and a C1/C2 ratio of about 6000). Regular trends in the d13C of methane (about -95 to -60 per mil) and C1/C2 ratios (about 25000 to 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

Clay mineralogy of ODP Leg 178 sites

The clay mineral compositions of upper Miocene to Quaternary sediments recovered at Ocean Drilling Program (ODP) Leg 178, Sites 1095 and 1096, from the continental rise west of the Antarctic Peninsula were analyzed in order to reconstruct the Neogene and Quaternary Antarctic paleoclimate and ice dynamics. The clay mineral assemblages are dominated by smectite, illite, and chlorite. Kaolinite occurs only in trace amounts. Analysis of a surface-sample data set facilitates the assignment of these clay minerals to particular source areas on the Antarctic Peninsula and, thus, the reconstruction of transport pathways. In the ODP cores, clay mineral composition cyclically alternates between two end-member assemblages. One assemblage is characterized by <20% smectite and >40% chlorite. The other assemblage has >20% smectite and <40% chlorite. Illite fluctuates between 30% and 50% without a significant affinity to one end-member assemblage. By comparison with a Quaternary sediment sequence from gravity core PS1565, the clay mineral fluctuations can be ascribed to glacial and interglacial periods, respectively. The cyclic changes in the clay mineral composition suggest that glacial-interglacial cycles, repeated ice advances and retreats, and changes in the Antarctic ice volume were already a main control of the global climate in late Miocene time. Throughout the late Neogene and Quaternary, the clay mineral records in the drift sediments exhibit only slight long-term changes predominantly attributed to local changes in glacial erosion and supply of source rocks. The absence of clear long-term trends associated with major climatic or glaciological changes points to an onset of vast glaciation in the Antarctic Peninsula region before ~9 Ma and to relative stability of the Antarctic ice sheet since then.