Abstract  Compatibility between oligomers and polymers was systematically assessed using differential scanning calorimetry (DSC) and was correlated with similarity in saturation and solubility parameter. These measurements enabled validation of detailed volume of mixing calculations using Statistical Association Fluid Theory (SAFT-γ Mie) and molecular dynamics (MD) simulations, which can be used to predict behaviour beyond the experimentally accessible conditions. These simulations confirmed that squalane is somewhat more compatible with poly(isoprene), "PI" than poly(butadiene), "PB", and further enabled prediction of the temperature dependence of compatibility. Surface and interfacial segregation of a series of deuterated oligomers was quantified in rubbery polymer films: PI, PB and hydrogenated poly(isoprene) "hPI". A striking correlation was established between surface wetting transition and mixtures of low compatibility, such as oligo-dIB in PB or PI. Segregation was quantified normal to the surface by ion beam analysis and neutron reflectometry and in some cases lateral segregation was observable by AFM. While surface segregation is driven by disparity in molecular weight in highly compatible systems this trend reverses as critical point is approached, and surface segregation increases with increasing oligomer molecular weight.

Abstract  Double oxide,SrxCa1-xCuOy has a layered structure in which Ca(Sr) is sandwiched between CuO2 layers. This crystal structure is expected to give low friction due to its low shear strength between laminas, In this work, various kind of SrxCa1-xCuOy with x=0.0 to 1.0 were prepared from SrCO3, CaCO3 and CuO by sintering method. The compositions of these products were examined by X-ray diffraction. The sample powders were blended in oil (squalane) and grease, and their load carrying capacities were evaluated by a cylinder-on-plate type tribometer and a four-ball machine, respectively. As a result of the tests, SrxCa1-xCuOy with x=0.0, 0.14, 0.90 and 1.0 showed low friction (about 0.1) and high load carrying capacity (4900 N). It was found from SEM and EPMA results that the worn surface was smooth, and that a thin solid lubricating him containing Ca, Sr and Cu was formed on the rubbing counterface. Also, the oxides with x=0.9 and 1.0 showed superior properties under extreme pressure in four-ball machine testing.

Abstract    Squalene (SQ), a precursor of sterols and terpenoids is a functional lipid of high importance in the food and pharmaceutical sectors. SQ oxidation studies are rather limited compared with those for other olefins. The aim of the present study was to monitor the formation of SQ oxidation products under different conditions (temperature, air supply), to characterise the most abundant of them by spectroscopic techniques and then examine their pro-oxidant activity in a model lipid substrate. Squalane (SQA), the saturated analogue of SQ, was used as a reference compound. FT-MIR analysis indicated the presence of alcohols, epoxides, aldehydes, and ketones. GC-MS was used to characterise SQ primary oxidation and scission products. The presence of epoxides was further confirmed by means of 1H NMR and 13C NMR spectroscopy. It could be argued that SQ stability is due to its stereochemistry and specifically to the presence of methyl groups next to the double bonds. The pro-oxidant activity of SQ oxidation products was evident at 62 and 40°C and suppressed only in the presence of primary antioxidants, not of SQ. The present work adds to the characterisation of SQ oxidised products. To our knowledge their pro-oxidant activity has never been examined before. Practical applications: Characterisation of squalene oxidation products and assessment of their activity as pro-oxidants present both scientific interest regarding the kinetics and product identity as well as a practical impact in case this bioactive lipid is provided for consumption as a functional product. In the past, cholesterol oxidation products and more recently phytosterol ones attracted the interest of researchers, who studied the stability of the respective parent compounds for food safety reasons. Monitoring of the formation of SQ oxidation products under different conditions (temperature, air supply) and chemical characterisation of the most abundant of them by spectroscopic techniques. Examination of their pro-oxidant activity in a model lipid substrate. Squalene may exert a weak antioxidant activity due to competitive oxidation phenomena with the lipid substrate while its oxidation products have a pro-oxidant activity on purified olive oil model substrate that was suppressed only in the presence of primary antioxidants. [PUBLICATION ABSTRACT]

Abstract  Squalene is a natural triterpenoid present virtually in all taxonomic groups. Its use for improving human health is rooted in ancient human history as several Pacific nations consumed the oil from livers of deep-sea sharks with high squalene content to improve their health and extend the life. In addition to the use as nutritional supplement, this molecule finds today many applications in pharmacology and cosmetics, or as a valuable industrial lubricant. Broad application potential of squalene is related to its physico-chemical characteristics, antioxidant activity and to its ability to interact with cell membranes. The industrial use of squalene is limited by short natural resources. Even today squalene is acquired mainly from shark liver oil; however, this source is no more tenable from the environmental viewpoint. Plant sources (e.g. olives, amaranth seeds) and particularly microbial production are thus gaining importance as promising alternatives for extended industrial use of squalene.

Abstract  We demonstrate the first capture and analysis of secondary organic aerosol (SOA) on a droplet suspended in an aerosol optical tweezers (AOT). We examine three initial chemical systems of aqueous NaCl, aqueous glycerol, and squalane at ∼75% relative humidity. For each system we added α-pinene SOA-generated directly in the AOT chamber-to the trapped droplet. The resulting morphology was always observed to be a core of the original droplet phase surrounded by a shell of the added SOA. We also observed a stable emulsion of SOA particles when added to an aqueous NaCl core phase, in addition to the shell of SOA. The persistence of the emulsified SOA particles suspended in the aqueous core suggests that this metastable state may persist for a significant fraction of the aerosol lifecycle for mixed SOA/aqueous particle systems. We conclude that the α-pinene SOA shell creates no major diffusion limitations for water, glycerol, and squalane core phases under humid conditions. These experimental results support the current prompt-partitioning framework used to describe organic aerosol in most atmospheric chemical transport models and highlight the prominence of core-shell morphologies for SOA on a range of core chemical phases.

Abstract  Gelatin capsules containing squalane partially purified bone morphogenetic protein (BMP) complex were placed on the perimuscular membrane of rats. Two kinds of control, gelatin capsules containing only BMP and those bearing squalane only, were used. The embedded areas were histopathologically examined at 3 and 6 wk after the operation. The observations revealed that the squalane/BMP complex elicited wide heterotopic bone formation with bone marrow tissue, suggesting that squalane is a possible carrier of BMP for clinical applications.

Abstract  Over the past several years, we have conducted a variety of elastic neutron diffraction and quasielastic neutron scattering experiments to study the structure and the dynamics of films of two intermediate-length alkane molecules (C sub( n)H sub(2n+2)), adsorbed on a graphite basal-plane surface. The two molecules are the normal alkane n-tetracosane [n-CH sub( 3)(CH sub(2)) sub(22)CH sub(3)] and the branched alkane squalane (C sub(30)H sub(62) or 2, 6, 10, 15, 19, 23-hexamethyltetracosane) whose carbon backbone is the same length as teteracosane. The temperature dependence of the monolayer structure of tetracosane and squalane was investigated using elastic neutron diffraction and evidence of two phase transitions was observed. Both the low-coverage tetracosane (C sub( 24)H sub(50)) and squalane (C sub(30)H sub(62)) monolayers have crystalline-to-"smectic" and "smectic"-to-isotropic fluid phase transitions upon heating. The diffusive motion in the tetracosane and squalane monolayers has been investigated by quasielastic neutron scattering. Two different quasielastic neutron scattering spectrometers at the Center for Neutron Research, National Institute of Standards and Technology (NIST) have been used. The spectrometers differ in both their dynamic range and energy resolution allowing molecular motions to be investigated on time scales in the range 10 super(-13)--10 super( -9) s. On these time scales, we observe evidence of translational, rotational, and intermolecular diffusive motions in the tetracosane and squalane monolayers. We conclude that the molecular diffusive motion in the two monolayers is qualitatively similar. Thus, despite the three methyl sidegroups at each end of the squalane molecule, its monolayer structure, phase transitions, and dynamics are qualitatively similar to that of a monolayer of the unbranched tetracosane molecules. With the higher resolution spectrometer at NIST, we have also investigated the molecular diffusive motion in multilayer tetracosane films. The analysis of our measurements indicates slower diffusive motion in the bottom layer of a bilayer tetracosane film compared to that in a monolayer, while the rate of diffusive motion in the bottom two layers of the trilayer film is comparable to that in a monolayer.

Abstract  Squalane is obtained by hydrogenation from squalene, an unsaturated terpene hydrocarbon found mainly in shark liver oil. It is a very stable liquid, and has a remarkably low capacity to irritate the skin. Squalane is used as an important component in various kinds of cosmetics and has a considerably beneficial effect on faecal excretion of the highly toxic 2, 3, 4, 7, 8-pentachlorodibenzofuran (PenCDF). The distribution, excretion and subacute toxicity of squalane after oral administration has already been examined. We considered that squalane, applied subcutaneously, might be an effective carrier of drugs. Furthermore, we found an application of squalane as a carrier of bone morphogenetic protein (BMP). As there were no data on the tissue reaction to squalane administered subcutaneously, we decided to make a histopathological evaluation of squalane fluid in vivo (DBO).

Abstract  Female mice were given 100 mg HCB/kg body weight i.p. and fed diets containing 0, 2.5, 5.0, and 7.5% of squalane. After 3 weeks samples of liver, blood and abdominal fat were analysed for HCB as well as for squalane. HCB concentrations were significantly lowered as compared to controls in all tissues and at all dietary concentrations of squalane to a maximum of about 36% in fat, 44% in liver and 47% in blood. The effect of squalane upon HCB concentrations was strongly dose dependent in abdominal fat. In contrast, no significant differences were seen with liver and blood between animals fed 5.0 or 7.5% of squalane. Squalane was detected in considerable amounts in the livers (50-100 ppm) but not in abdominal fat (less than 1 ppm) of mice fed squalane.

Abstract  Microfluidized squalene or squalane emulsions are efficient adjuvants, eliciting both humoral and cellular immune responses. Microfluidization stabilizes the emulsions and allows sterilization by terminal filtration. The emulsions are stable for years at ambient temperature and can be frozen. Antigens are added after emulsification so that conformational epitopes are not lost by denaturation and to facilitate manufacture. A Pluronic block copolymer can be added to the squalane or squalene emulsion. Soluble antigens administered in such emulsions generate cytotoxic T lymphocytes able to lyse target cells expressing the antigen in a genetically restricted fashion. Optionally a relatively nontoxic analog of muramyl dipeptide (MDP) or another immunomodulator can be added; however, the dose of MDP must be restricted to avoid systemic side effects in humans. Squalene or squalane emulsions without copolymers or MDP have very little toxicity and elicit potent antibody responses to several antigens in nonhuman primates. They could be used to improve a wide range of vaccines. Squalene or squalane emulsions have been administered in human cancer vaccines, with mild side effects and evidence of efficacy, in terms of both immune responses and antitumor activity.

Abstract  This study focused on an investigation into the experimental quantities inherent in the determination of partition coefficients from gas-liquid chromatographic measurements through the use of capillary columns. We prepared several squalane a (2,6,10,15,19,23-hexamethyltetracosane) a containing columns with very precisely known phase ratios and determined solute retention and hold-up times at 30, 40, 50 and 60 degree C. We calculated infinite dilution partition coefficients from the slopes of the linear regression of retention factors as a function of the reciprocal of the phase ratio by means of fundamental chromatographic equations. In order to minimize gasasolid and liquid-solid interface contributions to retention, the surface of the capillary inner wall was pretreated to guarantee a uniform coat of stationary phase. The validity of the proposed approach was first tested by estimating the partition coefficients of n-alkanes between n-pentane and n-nonane, for which compounds data from the literature were available. Then partition coefficients of sixteen aliphatic alcohols in squalane were determined at those four temperatures. We deliberately chose these highly challenging systems: alcohols in the reference paraffinic stationary phase. These solutes exhibited adsorption in the gas-liquid interface that contributed to retention. The corresponding adsorption constant values were estimated. We fully discuss here the uncertainties associated with each experimental measurement and how these fundamental determinations can be performed precisely by circumventing the main drawbacks.

Abstract  Among several bacterial species belonging to the general Gordonia, Mycobacterium, Micromonospora, Pseudomonas, and Rhodococcus, only two mycobacterial isolates, Mycobacterium fortuitum strain NF4 and the new isolate Mycobacterium ratisbonense strain SD4, which was isolated from a sewage treatment plant, were capable of utilizing the multiply branched hydrocarbon squalane (2,6,10,15,19, 23-hexamethyltetracosane) and its analogous unsaturated hydrocarbon squalene as the sole carbon source for growth. Detailed degradation studies and high-pressure liquid chromatography analysis showed a clear decrease of the concentrations of squalane and squalene during biomass increase. These results were supported by resting-cell experiments using strain SD4 and squalane or squalene as the substrate. The degradation of acyclic isoprenoids and alkanes as well as of acids derived from these compounds was also investigated. Inhibition of squalane and squalene degradation by acrylic acid indicated the possible involvement of beta-oxidation in the degradation route. To our knowledge, this is the first report demonstrating the biodegradation of squalane by using defined axenic cultures.

Abstract  1. The intestinal excretion of hexachlorobenzene (HCB) was studied in rats using the method of pendular perfusion. One and four weeks after i.p. application of 100 micrograms HCB/kg body weight segments of jejunum, ileum and colon were perfused with light liquid paraffin or squalane for 5 h. 2. The highest amount of HCB was excreted into jejunum, followed by ileum and colon. After 5 h HCB concentration in jejunal perfusion medium equals that in plasma. 3. Serosal tissue of intestinal segments contained higher HCB concentrations as compared to mucosa. 4. Paraffin treatment decreased the HCB content in both serosal and mucosal tissue of jejunum and ileum but not of colon.

Abstract  The efficacy of a new vaccine preparation against Epstein-Barr (EB) virus was investigated in cotton-top tamarins. The vaccine consists of fast protein liquid chromatography-purified EB virus membrane antigen glycoprotein of 340 Kd (MA gp340) mixed with a synthetic muramyl dipeptide adjuvant emulsified in squalane containing a pluronic polymer; it is suitable for both scaled-up batch production and eventual administration to man. Vaccinated tamarins rapidly developed ELISA detectable high titre antibodies to MA gp340, and their sera became strongly EB virus-neutralising. After challenge with a massive 100% carcinogenic dose of EB virus, the vaccinated tamarins had a strikingly low level of circulating EB virus-carrying mononuclear cells, in contrast to a control animal, and remained entirely free of tumours. This first-generation vaccine has thus been validated in experimental animals and the way opened for a phase I human trial.

Abstract  The ability of nontoxic monophosphoryl lipid A (MPL) to stimulate nonspecific resistance against viral infection was investigated. Mice pretreated intravenously with squalane-in-water emulsions of MPL, alone or in combination with other immunostimulants, were given an aerosol of influenza virus three weeks after the pretreatment. Complete protection against lethal influenza virus infection was conferred when MPL was combined with trehalose dimycolate (TDM). The protective activity of MPL plus TDM combination was corroborated by a significant reduction of the lung virus titers. Combination of lower doses of MPL with TDM extracted from Mycobacterium bovis, but not with that of M. phlei, induced significant resistance to influenza virus. Preparations containing MPL alone, or combined with mycobacterial cell wall skeleton or muramyl dipeptide, were not effective. The adjuvant activity of MPL on bivalent influenza subunit vaccine was also studied. The primary antibody responses to influenza A and influenza B antigens were enhanced by the addition of MPL and were higher than the vaccine associated with aluminum hydroxide. The adjuvant activity of MPL was confirmed by the elevated secondary response. High levels of circulating antibodies were still present in the MPL group when antibody titers in the controls were waning.

Abstract    The solute retention mechanism in gas-liquid chromatography was studied for the hydrocarbon solute-nonpolar stationary liquid phase (squalane) system. The retention volume of the solute and the specific surface area of the liquid-coated, modified alumina were determined as a function of the liquid loading. On the basis of the previous reasoning, distribution constants for the bulk solution partition and some adsorption equilibria taking part in the solute retention could be estimated. The results prove to be quite different from those of the polar liquid phases used previously: that is, squalane formed a bulk liquid layer on the modified alumina after the solid support was completely covered with the monolayer.

Abstract  Squalane and Squalene have been identified as natural components of human sebum. Both ingredients are used in a variety of cosmetics at concentrations ranging from 5 0.1 to > 504b. Animal studies indicate Squalene is slowly absorbed through the skin, while both compounds are poorly absorbed from the gastrointestinal tract. The acute animal toxicity of these ingredients by all routes is low. Both compounds are nonirritants to rabbit skin and eye at 100% concentration. Formulations containing Squalene indicate it is not a significant human skin irritant or sensitizer. limited contact sensitization tests indicate Squalene is not a significant contact allergen or irritant. It is concluded that both Squalane and Squalene are safe as cosmetic ingredients in the present practices of use and concentration.

Abstract  We have used friction force microscopy to probe friction laws for nanoasperities sliding on atomically flat substrates under controlled atmosphere and liquid environment, respectively. A power law relates friction force and normal load in dry air, whereas a linear relationship, i.e., Amontons' law, is observed for junctions fully immersed in model lubricants, namely, octamethylciclotetrasiloxane and squalane. Lubricated contacts display a remarkable friction reduction, with liquid and substrate specific friction coefficients. Comparison with molecular dynamics simulations suggests that load-bearing boundary layers at junction entrance cause the appearance of Amontons' law and impart atomic-scale character to the sliding process; continuum friction models are on the contrary of limited predictive power when applied to lubrication effects. An attempt is done to define general working conditions leading to the manifestation of nanoscale lubricity due to adsorbed boundary layers.

Abstract  Collisions of hyperthermal oxygen atoms, with an average translational energy of 520 kJ mol(-1), on continuously refreshed ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][NTf2]) and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C(12)mim][NTf2]), were studied with the use of a beam-surface scattering technique. Time-of-flight and angular distributions of inelastically scattered O and reactively scattered OH and H2O were collected for various angles of incidence with the use of a rotatable mass spectrometer detector. For both O and OH, two distinct scattering processes were identified, which can be empirically categorized as thermal and non-thermal. Non-thermal scattering is more probable for both O and OH products. The observation of OH confirms that at least some reactive sites, presumably alkyl groups, must be exposed at the surface. The ionic liquid with the longer alkyl chain, [C(12)mim][NTf2], is substantially more reactive than the liquid with the shorter alkyl chain, [emim][NTf2], and proportionately much more so than would be predicted simply from stoichiometry based on the number of abstractable hydrogen atoms. Molecular dynamics models of these surfaces shed light on this change in reactivity. The scattering behavior of O is distinctly different from that of OH. However, no such differences between inelastic and reactive scattering dynamics have been seen in previous work on pure hydrocarbon liquids, in particular the benchmark, partially branched hydrocarbon, squalane (C30H62). The comparison between inelastic and reactive scattering dynamics indicates that inelastic scattering from the ionic liquid surfaces takes place predominantly at non-reactive sites that are effectively stiffer than the reactive alkyl chains, with a higher proportion of collisions sampling such sites for [emim][NTf2] than for [C(12)mitn][NTf2].

Abstract  A new approach was undertaken to increase the bifunctionality of USY zeolite based catalyst. Nickel metallic phase was first impregnated onto USY zeolite and composite catalysts NiMo/[gamma-Al2O3+ (Ni)/USY] were prepared from these zeolites. Catalytic properties in toluene hydrogenation and squalane (2,6,10,15,19,23-hexamethyltetracosane) hydrocracking (HCK) were investigated.

Enhanced conversion and middle distillate (MD) selectivity was obtained for catalysts on which nickel has been impregnated on the zeolite powder. These enhancements are ascribed to an increased proximity between the hydrogenation/dehydrogenation (H/DH) function and the acid sites resulting in a more efficient synergy between these two functions. (C) 2011 Elsevier B.V. All rights reserved.

Abstract  Squalane, an emollient used in cosmetics, will be the first product of a biotechnology pilot plant now being started up by Nucelis Inc, a spin-off from Cibus. The plant will use Cibus' Rapid Trait Development System (RTDS), a new gene-editing technology to enable naturally occurring yeast to increase their production of squalene, the precursor of squalane. RTDS differs from genetically modified organisms in that it does not involve the introduction of foreign genes into a microorganism, says Sean O'Connor, president of Nucelis.

Abstract  Liquid-liquid extraction was investigated for use with surfactant enhanced subsurface remediation. A surfactant liquid-liquid extraction model (SLLEM) was developed for batch equilibrium conditions based on contaminant partitioning between micellar, water, and solvent phases. The accuracy of this fundamental model was corroborated with experimental results (using naphthalene and phenanthrene as contaminants and squalane as the extracting solvent). The SLLEM model was then expanded to nonequilibrium conditions. The effectiveness of this nonequilibrium model was corroborated with experimental results from continuous flow hollow fiber membrane systems. The validated models were used to conduct a sensitivity analysis evaluating the effects of surfactants on the removal of the contaminants in liquid-liquid extraction systems. In addition, liquid-liquid extraction is compared to air stripping for surfactant-contaminant separation. Finally, conclusions are drawn as to the impact of surfactants on liquid-liquid extraction processes, and the significance of these impacts on the optimization of surfactant-enhanced subsurface remediation.

Abstract  PURPOSETo develop a multi-compartmental vaccine delivery system for safe and efficient delivery of the gp100 peptide antigen in melanoma immunotherapy.METHODSWater-in-oil-in-water (W/O/W) multiple emulsion-based multi-compartmental vaccine delivery system containing the gp100 peptide was prepared by a two-step emulsification method. In vivo prophylactic and active immunization effectiveness of the novel squalane oil-containing gp100 vaccine was evaluated in the murine B16 melanoma model and compared with that of an incomplete Freund's adjuvant (IFA)-based vaccine.RESULTSMorphological evaluation of the W/O/W multiple emulsions showed that the oil-droplets were homogenously dispersed with the gp100 peptide encapsulated in an inner aqueous phase. Immunization with the gp100 peptide delivered in the W/O/W multiple emulsions-based vaccine resulted in increased protection against tumor challenge compared to IFA-based vaccine (p < 0.05, n = 8) signifying induction of enhanced anti-tumor immunity. In addition, serum Th1 cytokine levels and immuno-histochemistry of excised tumor tissues indicated activation and local infiltration of antigen specific cytotoxic T-lymphocytes into and/or surrounding the tumor mass. Moreover, the newly developed vaccine formulation did not induce any overt systemic toxicity.CONCLUSIONNovel W/O/W multiple emulsions-based vaccine efficiently delivers the gp100 peptide antigen to induce cell-mediated anti-tumor immunity and offers an alternate, safe vaccine delivery system.

Abstract  A series of Miocene/Pliocene halite deposits (with extremely low organic carbon contents) from the Sdom Formation (Dead Sea Basin, Israel) have been studied. Distributions and delta(13)C contents of biomarkers have been determined using GC-MS and irm-GCMS analyses, respectively. The hydrocarbon fractions consist mainly of pristane, phytane and C-21 to C-25 regular isoprenoids. The predominance of C21+ regular isoprenoids in the Dead Sea halites and other hypersaline deposits indicate that these components could be derived from ether-bound membrane lipids of halophilic archaea. The lack of intact ether-bound lipids in the polar fractions indirectly infers that such components have already been released at early stages of diagenesis. Their delta(13)C contents are enriched in C-13, by UP to 7 parts per thousand, compared to the biomarkers of presumed phytoplanktonic origin (i.e. steranes and hopanes) within the same sediment sample, in agreement with a source other than algae and cyanobacteria, thus, tentatively assigned as halophilic archaea. Based on biomarker distributions, delta(13)C contents and mineral compositions, these sediments appear to have been deposited in a salinity stratified water body with a bottom water brine. Continual evaporation and deposition of the higher salts (i.e. carnallites) are favourable conditions for the growth of halophilic archaeal communities. (C) 1998 Elsevier Science Ltd. All rights reserved.