Mechanism of lubrication by tricresylphosphate (TCP)

The coefficient of friction was measured as a function of temperature on a pin-on-disk tribometer. Pins and disks of 440C and 52100 steels were lubricated with tricresylphosphate (TCP), 3.45 percent TCP in squalene, and pure squalene. The M-50 pins and disks were lubricated with 3.45 percent TCP in squalene and pure squalene. Experiments were conducted under limited lubrication conditions in dry ( 100 ppm H2O) air and dry ( pp H2O) nitrogen at 50 rpm (equivalent to a sliding velocity of 13 cm sec) and a constant load of 9.8 N (1 kg). Characteristic temperatures T sub r were identified for TCP on 52100 steel and for squalene on M-50 and 52100 steels, where the friction decreased because of a chemical reaction between the lubricant and the metal surface. The behavior of squalene obscured the influence of 3.45 percent TCP solute on the friction of the system. Wear volume measurements demonstrated that wear was lowest at temperatures just above T sub r. Comparing the behavior of TCP on M-50, 440C, and 52100 steels revealed that the TCP either reacted to give T sub r behavior or produced initial failure in the temperature range 223 + or - 5 C

Paleoproterozic Icehouses and the Evolution of Oxygen Mediating Enzymes: The Case for a Late Origin of Photosystem -- II

Two major geological problems regarding the origin of oxygenic photosynthesis are: (1) identifying a source of oxygen predating biological oxygen production and capable of driving the evolution of oxygen tolerance, and (2) determining when oxygenic photosynthesis evolved. One solution to the first problem is the accumulation of photochemically-produced H2O2 at the surface of glaciers and its subsequent incorporation into ice. Melting at the glacier base would release H2O2, which interacts with seawater to produce O2 in an environment shielded from the lethal levels of ultraviolet radiation needed to produce H2O2. Answers to the second problem are controversial and range from 3.8 to 2.2 Ga. A skeptical view, based on metals that have redox potentials close to oxygen, argues for the late end of the range. The preponderance of geological evidence suggests little or no oxygen in the late Archaean atmosphere (< 1 ppm). The main piece of evidence for an earlier evolution of oxygenic photosynthesis comes from lipid biomarkers. Recent work, however, has shown that 2-methylhopanes, once thought to be unique biomarkers for cyanobacteria, are also produced anaerobically in significant quantities by at least two strains of anoxygenic phototrophs. Sterane biomarkers provide the strongest evidence for a date ≥2.7 Ga but could also be explained by the common evolutionary pattern of replacing anaerobic enzymes with oxygen-dependent ones. Although no anaerobic sterol synthesis pathway has been identified in the modern biosphere, enzymes that perform the necessary chemistry do exist. This analysis suggests that oxygenic photosynthesis could have evolved close in geological time to the Makganyene Snowball Earth Event and argues for a causal link between the two

How does Cross-Linking Effect the Thermal Stability of Polyisoprene

Polyisoprene can be cross-linked by an initial lithiation followed by reaction with both monochloro compounds and dichloro compounds. The monochloro compounds effect crosslinking through a lithium-chlorine exchange route while the use of dichloro compounds links the PIP chains with the spacer between the two chlorine atoms. A significant amount of char is produced from compounds which have been cross-linked with aromatic dihalides while aliphatic dihalides do not produce significant char

Hopanoids Play a Role in Membrane Integrity and pH Homeostasis in Rhodopseudomonas palustris TIE-1

Sedimentary hopanes are pentacyclic triterpenoids that serve as biomarker proxies for bacteria and certain bacterial metabolisms, such as oxygenic photosynthesis and aerobic methanotrophy. Their parent molecules, the bacteriohopanepolyols (BHPs), have been hypothesized to be the bacterial equivalent of sterols. However, the actual function of BHPs in bacterial cells is poorly understood. Here, we report the physiological study of a mutant in Rhodopseudomonas palustris TIE-1 that is unable to produce any hopanoids. The deletion of the gene encoding the squalene-hopene cyclase protein (Shc), which cyclizes squalene to the basic hopene structure, resulted in a strain that no longer produced any polycyclic triterpenoids. This strain was able to grow chemoheterotrophically, photoheterotrophically, and photoautotrophically, demonstrating that hopanoids are not required for growth under normal conditions. A severe growth defect, as well as significant morphological damage, was observed when cells were grown under acidic and alkaline conditions. Although minimal changes in shc transcript expression were observed under certain conditions of pH shock, the total amount of hopanoid production was unaffected; however, the abundance of methylated hopanoids significantly increased. This suggests that hopanoids may play an indirect role in pH homeostasis, with certain hopanoid derivatives being of particular importance

Influence of the sebaceous gland density on the stratum corneum lipidome

The skin surface lipids (SSL) result from the blending of sebaceous and epidermal lipids, which derive from the sebaceous gland (SG) secretion and the permeability barrier of the stratum corneum (SC), respectively. In humans, the composition of the SSL is distinctive of the anatomical distribution of the SG. Thus, the abundance of sebum biomarkers is consistent with the density of the SG. Limited evidence on the influence that the SG exerts on the SC lipidome is available. We explored the differential amounts of sebaceous and epidermal lipids in areas at different SG density with lipidomics approaches. SC was sampled with adhesive patches from forearm, chest, and forehead of 10 healthy adults (8F, 2M) after mechanical removal of sebum with absorbing paper. Lipid extracts of SC were analysed by HPLC/(-)ESI-TOF-MS. In the untargeted approach, the naïve molecular features extraction algorithm was used to extract meaningful entities. Aligned and normalized data were evaluated by univariate and multivariate statistics. Quantitative analysis of free fatty acids (FFA) and cholesterol sulfate (CHS) was performed by targeted HPLC/(-)ESI-TOF-MS, whereas cholesterol and squalene were quantified by GC-MS. Untargeted approaches demonstrated that the relative abundance of numerous lipid species was distinctive of SC depending upon the different SG density. The discriminating species included FFA, CHS, and ceramides. Targeted analyses confirmed that sebaceous FFA and epidermal FFA were increased and decreased, respectively, in areas at high SG density. CHS and squalene, which are biomarkers of epidermal and sebaceous lipid matrices, respectively, were both significantly higher in areas at elevated SG density. Overall, results indicated that the SG secretion intervenes in shaping the lipid composition of the epidermal permeability barrier. © 2018, The Author(s)

Chemical investigation of a biologically active schinus molle L. leaf extract

The pepper tree Schinus molle L. is an evergreen ornamental plant belonging to the Anacardiaceae family, native to South America and widespread throughout the world. It has biological activities and is used in folk medicine. This paper aims to contribute to a deeper knowledge of its chemical composition and biological properties. S. molle leaf extracts were obtained by sequential extraction with solvents of different polarities and subsequently tested on the HL-60 human leukaemia cell line to define a possible cytotoxic activity. Among the investigated extracts, the petroleum ether extract revealed a high cytotoxic activity, and its chemical composition was further investigated. By a silica column chromatography, eight fractions were obtained, and their compositions were determined by GC-MS analysis. Compounds and relative abundance differed widely among the fractions; sesquiterpenes resulted the main component and alcoholic sesquiterpenes the most abundant

Simultaneously hermaphroditic shrimp use lipophilic cuticular hydrocarbons as contact sex pheromones

Successful mating is essentially a consequence of making the right choices at the correct time. Animals use specific strategies to gain information about a potential mate, which is then applied to decision-making processes. Amongst the many informative signals, odor cues such as sex pheromones play important ecological roles in coordinating mating behavior, enabling mate and kin recognition, qualifying mate choice, and preventing gene exchange among individuals from different populations and species. Despite overwhelming behavioral evidence, the chemical identity of most cues used in aquatic organisms remains unknown and their impact and omnipresence have not been fully recognized. In many crustaceans, including lobsters and shrimps, reproduction happens through a cascade of events ranging from initial attraction to formation of a mating pair eventually leading to mating. We examined the hypothesis that contact pheromones on the female body surface of the hermaphroditic shrimp Lysmata boggessi are of lipophilic nature, and resemble insect cuticular hydrocarbon contact cues. Via chemical analyses and behavioural assays, we show that newly molted euhermaphrodite-phase shrimp contain a bouquet of odor compounds. Of these, (Z)-9-octadecenamide is the key odor with hexadecanamide and methyl linoleate enhancing the bioactivity of the pheromone blend. Our results show that in aquatic systems lipophilic, cuticular hydrocarbon contact sex pheromones exist; this raises questions on how hydrocarbon contact signals evolved and how widespread these are in the marine environment