Separation and determination of the group-type composition of modern base and lubricating oils with a wide range of polarity, especially emitted to the environment.

Lubricating oils are composed of base oils (>85% v/v) and enriching additives (<15% v/v). Three types of base oils may be distinguished: 1) traditional bases (obtained by low-volatile fractions from crude oil distillation refining), 2) synthetic bases (mainly poly-alpha-olefins, sometimes esters, especially succinic acid esters), 3) bases of natural origin (especially obtained from refined plant oils). The bases of natural origin are the only ones recommended for application when lubricating oil may be emitted to the environment (e.g. when the machine with an open cutting system is used). Group-type separation and analysis of group-type composition of base and lubricating oils are of significant importance in quality control and environmental monitoring. Due to the potentially wide range of polarity of the components of base and lubricating oils, group- type separation becomes a difficult separation problem. It is also a serious analytical problem due to the considerable diversity of physicochemical properties. The authors propose a new procedure for the separation and determination of the group-type composition of base and lubricating oils using thin-layer liquid chromatography in normal phase systems (abr. NP-TLC) on silica gel plates impregnated with berberine salt/in the coupling of thin-layer chromatography with flame ionization detection (abr. TLC-FID). A new, effective procedure of TLC plates impregnation with berberine sulphate was presented. The proposed procedure ensures the visualization of all groups of base oils. Extensive experimental research showed that a 2-step development procedure with application of n-hexane up to 100% height of development +15 min and further n-hexane: isopropanol: tri-fluoroacetic acid 96.25: 3: 0.75 (v: v: v) up to 75% height of development is advantageous for the group-type separation, both in TLC-FID and TLC.

Microalgae Biomass as a New Potential Source of Sustainable Green Lubricants.

Lubricants are materials able to reduce friction and/or wear of any type of moving surfaces facilitating smooth operations, maintaining reliable machine functions, and reducing risks of failures while contributing to energy savings. At present, most worldwide used lubricants are derived from crude oil. However, production, usage and disposal of these lubricants have significant impact on environment and health. Hence, there is a growing pressure to reduce demand of this sort of lubricants, which has fostered development and use of green lubricants, as vegetable oil-based lubricants (biolubricants). Despite the ecological benefits of producing/using biolubricants, availability of the required raw materials and agricultural land to create a reliable chain supply is still far from being established. Recently, biomass from some microalgae species has attracted attention due to their capacity to produce high-value lipids/oils for potential lubricants production. Thus, this multidisciplinary work reviews the main chemical-physical characteristics of lubricants and the main attempts and progress on microalgae biomass production for developing oils with pertinent lubricating properties. In addition, potential microalgae strains and chemical modifications to their oils to produce lubricants for different industrial applications are identified. Finally, a guide for microalgae oil selection based on its chemical composition for specific lubricant applications is provided.

Extraction and Characterization of Sesbania cannabina (Retz.) Pers. (Dhaincha) Seed Oil for Potential Engineering Applications.

Sesbania cannabina (Retz.) Pers. (Dhaincha) is a member of family Fabaceae spread over several countries in tropical and subtropical regions of the world. Sesbania aculeata, Sesbania drummondii, Sesbania grandiflora, Sesbania rostrata, Sesbania sesban, and Sesbania speciosa are other members of this family. The agricultural, nutritional and pharmaceutical applications of Sesbania species are known to farmers, villagers, and the tribes since ages and are well studied by researchers. However, the significance of Sesbania as an industrial crop has not been recognized till now. The objective of this study was extraction and characterization of Sesbania cannabina seed oil (SCSO) for potential engineering applications. The seed oil was extracted with hexane in a Soxhlet extractor. Yield was only 2.32% w/w due to long storage at high temperature in seed house. Sesbania cannabina seed oil methyl ester (SCSOME) was prepared via esterification and transesterification for analysis of fatty acid composition of extracted oil. SCSO has high iodine value (118 g I2/100 g) and high saponification value (185.79 mg KOH/g) making the oil suitable for use as candle stocks or in soap making. However, these applications were ruled out on account of being insignificant for oil available in limited quantity. The oil has high viscosity index (174.19), high onset (382°C) and offset (450°C) decomposition temperatures, endothermic nature, and shear rate thickening behaviour. These properties make SCSO a good candidate for application as specialty lubricant required under severe operating conditions of high temperature and high shear rate or as insulating and cooling transformer oil.

Persistence of Polydimethylsiloxane Condom Lubricants.

Polydimethylsiloxane (PDMS) is commonly used to lubricate condoms. The detection of PDMS on swabs from complainants can be used to support an allegation of sexual assault. Previous research has focused on establishing analytical techniques for detecting PDMS. This research examined the persistence of PDMS on the penis, in the vagina, in the mouth, and on skin. The longest PDMS detection times were 20 h on the penis, 35 h in the vagina, and 52 h on skin. PDMS was detected up to 4 h in the mouth if the participant did not eat or drink and up to 9 h if the participant slept. PDMS was not detected in the mouth after eating or drinking. The presence of biological fluids had no detrimental effect on the analysis. Aqueous extraction of swabs for DNA did not remove any significant amount of PDMS; hence, swab remains could be subsequently analyzed for PDMS.

Notochordal cell matrix as a bioactive lubricant for the osteoarthritic joint.

Notochordal cell derived matrix (NCM) can induce regenerative effects on nucleus pulposus cells and may exert such effects on chondrocytes as well. Furthermore, when dissolved at low concentrations, NCM forms a viscous fluid with potential lubricating properties. Therefore, this study tests the feasibility of the use of NCM as a regenerative lubricant for the osteoarthritic joint. Chondrocyte-seeded alginate beads were cultured in base medium (BM), BM with NCM (NCM), or BM with TGF-ß1 (TGF), as well as BM and NCM treated with IL-1ß. NCM increased GAG deposition and cell proliferation (stronger than TGF), and GAG/DNA ratio and hydroxyproline content (similar to TGF). These effects were maintained in the presence of IL-1ß. Moreover, NCM mitigated expression of IL-1ß-induced IL-6, IL-8, ADAMTS-5 and MMP-13. Reciprocating sliding friction tests of cartilage on glass were performed to test NCM's lubricating properties relative to hyaluronic acid (HA), and showed a dose-dependent reduction in coefficient of friction with NCM, similar to HA. NCM has anabolic and anti-inflammatory effects on chondrocytes, as well as lubricating properties. Therefore, intra-articular NCM injection may have potential as a treatment to minimize pain while restoring the affected cartilage tissue in the osteoarthritic joint.

Skin Barrier Restoration and Moisturization Using Horse Oil-Loaded Dissolving Microneedle Patches.

BACKGROUND: Horse oil (HO) has skin barrier restoration and skin-moisturizing effects. Although cream formulations have been used widely and safely, their limited penetration through the stratum corneum is a major obstacle to maximizing the cosmetic efficacy of HO. Therefore, we aimed to encapsulate HO in a cosmetic dissolving microneedle (DMN) for efficient transdermal delivery. METHODS: To overcome these limitations of skin permeation, HO-loaded DMN (HO-DMN) patches were developed and evaluated for their efficacy and safety using in vitro and clinical studies. RESULTS: Despite the lipophilic nature of HO, the HO-DMN patches had a sharp shape and uniform array, with an average length and tip diameter of 388.36 ± 16.73 and 38.54 ± 5.29 µm, respectively. The mechanical strength of the HO-DMN patches was sufficient (fracture force of 0.29 ± 0.01 N), and they could successfully penetrate pig skin. During the 4-week clinical evaluation, HO-DMN patches caused significant improvements in skin and dermal density, skin elasticity, and moisturization. Additionally, a brief safety assessment showed that the HO-DMN patches induced negligible adverse events. CONCLUSION: The HO-DMNs are efficient, safe, and convenient for wide use in cosmetic applications for skin barrier restoration and moisturization.

Slippery when sticky: Lubricating properties of thin films of Taxus baccata aril mucilage.

Mucilage is hydrogel produced from succulent plants and microorganisms displaying unique adhesiveness and slipperiness simultaneously. The objective of this study is to establish an understanding on the lubricating mechanisms of the mucilage from Taxus baccata aril as thin, viscous lubricant films. Oscillation and flow rheological studies revealed that T. baccata mucilage is shear-thinning, thixotropic, and weak hydrogel that is highly stretchable under shear stress due to its high density physical crosslinking characteristics. In addition, T. baccata mucilage showed a distinct Weissenberg effect, i.e., increasing normal force with increasing shear rate, and thus it contributes to deplete the lubricant from tribological interfaces. Lubrication studies with a number of tribopairs with varying mechanical properties and surface wettability have shown that the lubricity of T. baccata mucilage is most effectively manifested at soft, hydrophilic, and rolling tribological contacts. Based on tenacious spreading on highly wetting surfaces, slip plane can be formed within mucilage hydrogel network even when the lubricating films cannot completely separate the opposing surfaces. Moreover, highly stretchable characteristics of mucilage under high shear enhance smooth shearing of two opposing surfaces as lubricating film.

Utilization of banana peel as a novel substrate for biosurfactant production by Halobacteriaceae archaeon AS65.

In this study, biosurfactant-producing bacteria was evaluated for biosurfactant production by using banana peel as a sole carbon source. From the 71 strains screened, Halobacteriaceae archaeon AS65 produced the highest biosurfactant activity. The highest biosurfactant production (5.30 g/l) was obtained when the cells were grown on a minimal salt medium containing 35 % (w/v) banana peel and 1 g/l commercial monosodium glutamate at 30 °C and 200 rpm after 54 h of cultivation. The biosurfactant obtained by extraction with ethyl acetate showed high surface tension reduction (25.5 mN/m), a small critical micelle concentration value (10 mg/l), thermal and pH stability with respect to surface tension reduction and emulsification activity, and a high level of salt tolerance. The biosurfactant obtained was confirmed as a lipopeptide by using a biochemical test FT-IR, NMR, and mass spectrometry. The crude biosurfactant showed a broad spectrum of antimicrobial activity and had the ability to emulsify oil, enhance PAHs solubility, and oil bioremediation.

Enhancing trimethylolpropane esters synthesis through lipase immobilized on surface hydrophobic modified support and appropriate substrate feeding methods.

Candida sp. 99-125 lipase immobilized on surface hydrophobic modified support and appropriate substrate feeding methods were used to improve the synthesis of tri-substituted trimethylolpropane (TMP) esters, which can be used as raw materials for biodegradable lubricants. The proposed novel production method is environmentally friendly. Lipase was adsorbed on surface hydrophobic silk fibers that were pretreated by amino-modified polydimethylsiloxane. A 5-level-4-factors central composite model, including reaction time, temperature, enzyme amount, and molar ratio of fatty acid to TMP, was designed to evaluate the interaction of process variables in the enzymatic esterification. The water activity was kept constant using a LiCl-saturated salt solution. Under the optimum conditions with 30% enzyme amount and substrates molar ratio 8.4 at 45°C for 47h, the total conversion of caprylic acid is 97.3% and the yield of tri-substituted TMP esters is 95.5%. The surface hydrophobic treatment resulted in less cluster water accumulated on the surface immobilized lipase, which was demonstrated by near-infrared spectra. Consequently, the optimum temperature and water tolerance of immobilized lipase were increased. Two TMP-feeding methods were used to maintain high molar ratio of fatty acid to TMP, and increase the final tri-substituted TMP esters content exceeding 85% (w/w) in reactant.

Effect of unconventional carbon sources on biosurfactant production and its application in bioremediation.

The potential of an alkaliphilic bacterium Klebsiella sp. strain RJ-03, to utilize different unconventional carbon sources for the production of biosurfactant was evaluated. The biosurfactant produced using corn powder, potato peel powder, Madhuca indica and sugarcane bagasse containing medium, exhibited significantly higher viscosity and maximum reduction in surface tension as compared to other substrates. Among several carbon substrates tested, production of biosurfactant was found to be the highest with corn powder (15.40 ± 0.21 g/l) as compared to others. The comparative chemical characterization of purified biosurfactant was done using advance analytical tools such as NMR, FT-IR, SEM, GPC, MALDI TOF-TOF MS, GC-MS, TG and DSC. Analyses indicated variation in the functional groups, monosaccharide composition, molecular mass, thermostability. Higher yield with cheaper raw materials, noteworthy stress tolerance of CP-biosurfactant toward pH and salt as well as compatibility with chemical surfactants and detergents revealed its potential for commercialization and application in bioremediation.

Semi-permeable membrane retention of synovial fluid lubricants hyaluronan and proteoglycan 4 for a biomimetic bioreactor.

Synovial fluid (SF) contains lubricant macromolecules, hyaluronan (HA), and proteoglycan 4 (PRG4). The synovium not only contributes lubricants to SF through secretion by synoviocyte lining cells, but also concentrates lubricants in SF due to its semi-permeable nature. A membrane that recapitulates these synovium functions may be useful in a bioreactor system for generating a bioengineered fluid (BF) similar to native SF. The objectives were to analyze expanded polytetrafluoroethylene membranes with pore sizes of 50 nm, 90 nm, 170 nm, and 3 microm in terms of (1) HA and PRG4 secretion rates by adherent synoviocytes, and (2) the extent of HA and PRG4 retention with or without synoviocytes adherent on the membrane. Experiment 1: Synoviocytes were cultured on tissue culture (TC) plastic or membranes +/- IL-1beta + TGF-beta1 + TNF-alpha, a cytokine combination that stimulates lubricant synthesis. HA and PRG4 secretion rates were assessed by analysis of medium. Experiment 2: Bioreactors were fabricated to provide a BF compartment enclosed by membranes +/- adherent synoviocytes, and an external compartment of nutrient fluid (NF). A solution with HA (1 mg/mL, MW ranging from 30 to 4,000 kDa) or PRG4 (50 microg/mL) was added to the BF compartment, and HA and PRG4 loss into the NF compartment after 2, 8, and 24 h was determined. Lubricant loss kinetics were analyzed to estimate membrane permeability. Experiment 1: Cytokine-regulated HA and PRG4 secretion rates on membranes were comparable to those on TC plastic. Experiment 2: Transport of HA and PRG4 across membranes was lowest with 50 nm membranes and highest with 3 microm membranes, and transport of high MW HA was decreased by adherent synoviocytes (for 50 and 90 nm membranes). The permeability to HA mixtures for 50 nm membranes was approximately 20 x 10(-8) cm/s (- cells) and approximately 5 x 10(-8) cm/s (+ cells), for 90 nm membranes was approximately 35 x 10(-8) cm/s (- cells) and approximately 19 x 10(-8) cm/s (+ cells), for 170 nm membranes was approximately 74 x 10(-8) cm/s (+/- cells), and for 3 microm membranes was approximately 139 x 10(-8) cm/s (+/- cells). The permeability of 450 kDa HA was approximately 40x lower than that of 30 kDa HA for 50 nm membranes, but only approximately 2.5x lower for 3 microm membranes. The permeability of 4,000 kDa HA was approximately 250x lower than that of 30 kDa HA for 50 nm membranes, but only approximately 4x lower for 3 microm membranes. The permeability for PRG4 was approximately 4 x 10(-8) cm/s for 50 nm membranes, approximately 48 x 10(-8) cm/s for 90 nm membranes, approximately 144 x 10(-8) cm/s for 170 nm membranes, and approximately 336 x 10(-8) cm/s for 3 microm membranes. The associated loss across membranes after 24 h ranged from 3% to 92% for HA, and from 3% to 93% for PRG4. These results suggest that semi-permeable membranes may be used in a bioreactor system to modulate lubricant retention in a bioengineered SF, and that synoviocytes adherent on the membranes may serve as both a lubricant source and a barrier for lubricant transport.