Fractioning and Compared 1H NMR and GC-MS Analyses of Lanolin Acid Components.

The management of food and food-related wastes represents a growing global issue, as they are hard to recycle and dispose of. Foremost, waste can serve as an important source of biomasses. Particularly, fat-enriched biomasses are receiving more and more attention for their role in the manufacturing of biofuels. Nonetheless, many biomasses have been set aside over the years. Wool wax, also known as lanolin, has a huge potential for becoming a source of typical and atypical fatty acids. The main aim of this work was to evaluate and assess a protocol for the fractioning of fatty acids from lanolin, a natural by-product of the shearing of sheep, alongside the design of a new and rapid quantitative GC-MS method for the derivatization of free fatty acids in fat mixtures, using MethElute™. As the acid portion of lanolin is characterized by the presence of both aliphatic and hydroxylated fatty acids, we also evaluated a procedure for the parting of these two species, by using NMR spectroscopy, benefitting of the different solubilities of the components in organic solvents. At last, we evaluated and quantified the fatty acids and the α-hydroxy fatty acids present in each attained portion, employing both analytical and synthetic standards. The performed analyses, both qualitative and quantitative, showed a good performance in the parting of the different acid components, and GC-MS allowed to speculate that the majority of α-hydroxylated fatty acids is formed of linear saturated carbon chains, while the totality of properly said fatty acids has a much more complex profile.

Development and validation of multiresidue method for organophosphorus pesticides in lanolin using gas chromatography-tandem mass spectrometry.

Lanolin, also known as wool wax, is derived from sheep and has diverse applications in food, cosmetic, textile and lubricant industries. Owing to its direct contact with human, there is a need of studying pesticide residues as contaminants in lanolin. The present study describes a single novel hyphenated gas chromatography-tandem mass spectrometry (GC-MS/MS) technique for the quantification of 14 organophosphorus (OP) pesticides (tecnazene, propetamphos, diazinon, dichlofenthion, chlorpyrifos methyl, fenchlorphos, malathion, chlorpyrifos, pirimiphos ethyl, bromophos ethyl, tetrachlorvinphos, ethion, phosalone, and coumaphos) in lanolin using electrospray ionization (EI) with multiple reaction monitoring (MRM) acquisition mode. The method is simple in terms of sample preparation steps based on matrix solid-phase dispersion (MSPD). The method was found to be linear over the analytical range of 0.05-2.0 µg/g, with acceptable coefficient of determination (r2  ≥ 0.99) for all the 14 pesticides. The limit of detection (LOD) and limit of quantification (LOQ) of the method were found to be less than 0.05 and 0.1 µg/g, respectively, for all the 14 OP pesticide residues. The precision and accuracy of the method were found to be within the acceptable limits, that is, recoveries in the range of 83.5%-104.1% with less than 12.5% of relative standard deviation for all the pesticides. The multiresidue method for estimating pesticide residues employing GC-MS/MS technique will be useful for OP pesticide levels in large number of lanolin samples.

Eco-friendly sunscreen formulation based on starches and PEG-75 lanolin increases the antioxidant capacity and the light scattering activity in the visible light.

Most modern sunscreens contain physical filters, which scatter the sunlight, increasing the photons' pathway in the upper stratum corneum. This effect can lead to a better efficacy of the UV filters and improve the diffuse reflection. However, the addition of nanosized inorganic UV filters reduces the antioxidant capacity of sunscreen formulations. Two cream formulations (F1, F2) which differ in the ingredient PEG75 Lanolin (F2), have been characterized for their radical protection factor (RPF) and their optical properties in vitro using electron paramagnetic resonance (EPR) spectroscopy and UV/VIS spectrometry. The RPF for PEG-75 Lanolin was also determined. Furthermore, their radical protection properties were analyzed on porcine skin ex vivo after visible light irradiation by EPR. The structure of each formulation in the skin surface was determined by reflectance confocal microscopy in vivo. The addition of lanolin increased the reflectance and reduced the transmittance for visible light, improving the scattering drastically. Besides, the antioxidant capacity was also increased for F2, something unpublished until now. F1 presented a lower scattering provided by starches. The sunscreens showed high scattering properties and antioxidant capacity, especially for F2, which presented the lowest radical formation in the skin model. These results are consistent with the RPF measurements where F2 has a higher RPF value (193 ± 3 × 1014 radicals/mg) than F1 (155 ± 4 × 1014 radicals/mg) and for PEG-75 Lanolin (37 ± 1 × 1014 radicals/mg). The combination of starches and PEG-75 Lanolin is the first solution to provide both, light scattering and antioxidant capacity, in sunscreens.

Separation and purification of lanosterol, dihydrolanosterol, and cholesterol from lanolin by high-performance counter-current chromatography dual-mode elution method.

Lanosterol is a potential drug for cataracts treatment, which can reverse the aggregation of intracrystalline proteins. The low concentration in lanolin calls for high-performance separation methods. In this study, a counter-current chromatography dual-mode elution method was developed for the first time to separate and purify lanosterol from hexane extract of lanolin after saponification, in which the column was first eluted with the lower phase as mobile phase in head-to-tail mode, followed by the upper phase in the tail-to-head mode. High purity of lanosterol, dihydrolanosterol, and cholesterol can be obtained simultaneously. A solvent system composed of n-heptane/acetonitrile/ethyl acetate (5:5:1, v/v/v) was selected and optimized via partition coefficient determination. Compounds such as 111 mg lanosterol, 84 mg dihydrolanosterol, and 183 mg cholesterol with high purity of 99.77, 95.71, and 91.43%, respectively, analyzed by high-performance liquid chromatography were obtained within 80 min from 700 mg crude extract from 1.78 g lanolin. The method was also used to improve the purity of commercial lanosterol product from 66.97 to above 99%. Counter-current chromatography could serve as a potential and powerful technique for commercial production of highly pure lanosterol.

Synthesis and characterization of nanostructured lipid-poloxamer organogels for enhanced skin local anesthesia.

The aim of this study was to synthesize a novel drug delivery system using organogels (ORGs) and characterize its physicochemical properties, in vitro and ex vivo permeation abilities, cytotoxicity and in vivo local anesthetic effects. The ORG formulations contained a mixture of oleic acid-lanolin (OA-LAN), poloxamer (PL407), and the commonly used local anesthetic lidocaine (LDC). The main focus was to evaluate the impact of LAN and PL407 concentrations on the ORG structural features and their biopharmaceutical performance. Results revealed that LDC, OA, and LAN incorporation separately shifted the systems transitions phase temperatures and modified the elastic/viscous moduli relationships (G'/G″ = ~15×). Additionally, the formulation with the highest concentrations of LAN and PL407 reduced the LDC flux from ~17 to 12 µg·cm-2·h-1 and the permeability coefficients from 1.2 to 0.62 cm·h-1 through ex vivo skin. In vivo pharmacological evaluation showed that the ORG-based drug delivery system presented low cytotoxicity, increased and prolonged the local anesthetic effects compared to commercial alternatives. The data from this study indicate that ORG represent a promising new approach to effectively enhance the topical administration of local anesthetics.

Safety Assessment of Polyether Lanolins as Used in Cosmetics.

The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) assessed the safety of 39 polyether lanolin ingredients as used in cosmetics. These ingredients function mostly as hair conditioning agents, skin conditioning agent-emollients, and surfactant-emulsifying agents. The Panel reviewed available animal and clinical data, from previous CIR safety assessments of related ingredients and components. The similar structure, properties, functions, and uses of these ingredients enabled grouping them and using the available toxicological data to assess the safety of the entire group. The Panel concluded that these polyether lanolin ingredients are safe in the practices of use and concentration as given in this safety assessment.

Formulation characteristics and in vitro release testing of cyclosporine ophthalmic ointments.

The aim of the present study was to investigate the relationship between formulation/process variables versus the critical quality attributes (CQAs) of cyclosporine ophthalmic ointments and to explore the feasibility of using an in vitro approach to assess product sameness. A definitive screening design (DSD) was used to evaluate the impact of formulation and process variables. The formulation variables included drug percentage, percentage of corn oil and lanolin alcohol. The process variables studied were mixing temperature, mixing time and the method of mixing. The quality and performance attributes examined included drug assay, content uniformity, image analysis, rheology (storage modulus, shear viscosity) and in vitro drug release. Of the formulation variables evaluated, the percentage of the drug substance and the percentage of corn oil in the matrix were the most influential factors with respect to in vitro drug release. Conversely, the process parameters tested were observed to have minimal impact. An evaluation of the release mechanism of cyclosporine from the ointment revealed an interplay between formulation (e.g. physicochemical properties of the drug and ointment matrix type) and the release medium. These data provide a scientific basis to guide method development for in vitro drug release testing of ointment dosage forms. These results demonstrate that the in vitro methods used in this investigation were fit-for-purpose for detecting formulation and process changes and therefore amenable to assessment of product sameness.

Lanolin-based organogel of salicylic acid: evidences of better dermatokinetic profile in imiquimod-induced keratolytic therapy in BALB/c mice model.

The primary aim of the present study was to develop lanolin-based organogel with enhanced delivery potential and reduced skin irritation for the treatment of hyperkeratotic lesions and scaling. The drug was encapsulated in the lipidic bilayers of organogel. The values of particle size, polydispersity index (PDI), and zeta potential of the developed carrier system was found to be 257.5 nm, 0.272, and -24.9 mV, respectively. The system was pseudoplastic in nature with the yield value of 2.3078 Pa. The skin permeation studies exhibited superiority of the prepared lanolin-based organogel formulation over the conventional gel formulation (CGF). Further, the dermatokinetic studies also confirmed better permeation and enhanced skin bioavailability of SA to epidermis as well as dermis vis-à-vis the CGF. In conclusion, the developed organogel system not only improved the delivery profile of SA but also reduced the skin irritant potential. The current findings can provide a suitable alternative for the development of an effective topical formulation of SA for the treatment of hyperkeratotic lesions.

Exotic Vegetable Oils for Cosmetic O/W Nanoemulsions: In Vivo Evaluation.

Oil-in-water nanoemulsions are stable systems with droplet sizes in the 20-200 nm range. The physicochemical properties of these systems may be influenced by the addition of additives. Thus, the influence of ethoxylated (EL) and acetylated lanolin (AL) addition on the droplet size, pH values, electrical conductivity and stability of nanoemulsions was investigated. Then, effect of nano-emulsions additives with EL (NE-EL) or AL (NE-AL) in hydration, oiliness and pH of the skin were evaluated. Nanoemulsion safety was evaluated through the observation of no undesirable effects after skin formulation application. Both additives caused changes in droplet size and electrical conductivity, but not in pH values. Nanoemulsions containing up to 6.0% ethoxylated lanolin and 2.0% acetylated lanolin remained stable after centrifugation tests. Higher concentrations of the additives made the nanoemulsions unstable. Stability tests showed that ethoxylated lanolin produced more stable nanoemulsions then acetylated lanolin and that the major instability phenomenon occurring in these systems is coalescence at elevated temperatures. Nanoemulsion-based lanolin derivatives increased skin hydration and oiliness and did not change cutaneous pH values. These formulations are non-toxic since they did not cause any irritation on the skin surface after nanoemulsion application, showing potential as carriers for pharmaceuticals and cosmetic applications.

[Intercalation of polystyrene in kaolin via in-situ polymerization].

The synergistic stabilization effect of different metal lanolin fatty acids as natural-based thermal stabilizers for poly (vinyl chloride) (PVC) including calcium lanolin fatty acid (Calan2), zinc lanolin fatty acid (Znlan2) and Lanthanum lanolin fatty acid (Lalan3) were studied. The processability of PVC was tested by torque rheometer, the mechanical properties were studied by universal testing machine, and the coupling effect of product in PVC/CaCO3 was also researched. The results indicated that the properties of Lan/Zn stabilizer was better than Ca/Zn stabilizer and compound lead salt except static stability and dynamic stability.

Contact sensitization to the allergens of European baseline series in patients with chronic leg ulcers.

BACKGROUND AND OBJECTIVE: The pattern of contact sensitization among patients with chronic leg ulcers depends on the local practice of wound treatment along with demographic and clinical confounders. The study was aimed at revealing the associations between chronic leg ulcers and contact sensitization. MATERIAL AND METHODS: Between 2006 and 2008, 35 patients with chronic leg ulcers and surrounding dermatitis and 59 patients with contact dermatitis of the lower leg or foot were prospectively recruited at the Department of Skin and Venereal Diseases, Lithuanian University of Health Sciences. Demographic and clinical data were collected in accordance with the "minimal data set" of the European Surveillance System on Contact Allergy. Patch testing was performed with the allergens of the European baseline series. RESULTS: At least one positive patch test reaction was found in 28 (80%) of the patients with chronic leg ulcers and in 24 (41%) of the patients with dermatitis of the lower leg or foot (P<0.001). Sensitization to some of the most common allergens, namely colophony, Myroxylon pereirae resin, and methyldibromo glutaronitrile, was prevalent in both the groups of patients, whereas sensitization to benzocaine, p-phenylenediamine, and lanolin alcohol was associated with the presence of chronic leg ulcers. Benzocaine was found to be the leading allergen among patients with chronic leg ulcers (positive patch test reactions in 34.4% of the patients). CONCLUSIONS: Contact sensitization to benzocaine, p-phenylenediamine, and lanolin was found to be associated with the presence of chronic leg ulcers.

Multiresidue determination of pesticides in lanolin using matrix solid-phase dispersion.

An efficient, fast, and accurate matrix solid-phase dispersion sample cleanup procedure was developed specifically for the determination of pesticide residues in lanolin. The scope of the method for organophosphorus, organochlorine, and pyrethroid insecticides is the same as that of official methods from various pharmacopeias. After lanolin dispersion on C18 bonded silica, pesticides are eluted with acetonitrile saturated with n-hexane. Recoveries ranged from 83 to 118% with RSD values of < 20% for most pesticides listed, in compliance with the requirements of European and U.S. pharmacopeias.

Lanolin-derived lipid mixtures mimic closely the lipid composition and organization of vernix caseosa lipids.

The aim of the present study was to use semi-synthetic lipid mixtures to mimic the complex lipid composition, organization and thermotropic behaviour of vernix caseosa (VC) lipids. As VC shows multiple protecting and barrier supporting properties before and after birth, it is suggested that a VC substitute could be an innovative barrier cream for barrier deficient skin. Lanolin was selected as the source of the branched chain sterol esters and wax esters--the main lipid classes of VC. Different lipid fractions were isolated from lanolin and subsequently mixed with squalene, triglycerides, cholesterol, ceramides and fatty acids to generate semi-synthetic lipid mixtures that mimic the lipid composition of VC, as established by high-performance thin-layer chromatography. Differential scanning calorimetry and Fourier transform infrared spectroscopy investigations revealed that triglycerides play an important role in the (lateral) lipid organization and thermotropic behaviour of the synthetic lipid mixtures. Excellent resemblance of VC lipids was obtained when adding unsaturated triglycerides. Moreover, these lipid mixtures showed similar long range ordering as VC. The optimal lipid mixture was evaluated on tape-stripped hairless mouse skin in vivo. The rate of barrier recovery was increased and comparable to VC lipid treatment.

Lanolin allergy: history, epidemiology, responsible allergens, and management.

Allergy to lanolin has been recognized by dermatologists for decades. This review summarizes the history, epidemiology, and allergenicity of lanolin and its derivatives. "The lanolin paradox" and the safety of pharmaceutical-grade lanolin products are also discussed.

Equilibrium solubilization of lipophilic therapeutic agents by aqueous solutions of products of catalytic oxyethylation of Croda-type lanolin as model excipients of the class of non-ionic surface active agents.

Research was conducted into the properties and identity of the products of Croda-type hypoallergenic lanolin, which were obtained with the use of a selective catalyst (K-4) and a standard alkaline catalyst (Na/NaOH). The 1HNMR method was employed to assess the content of oxyethylated segments and the analytic level of hydrophilic-lipophilic balance (HLB). Surface activity of products soluble in water with n(TE) > or = 40 was examined and the thermodynamic potential for micelle formation deltaGm(o) was calculated. Basic viscosity and hydrodynamic values were determined for the solubilizers and their micellar adduct with ibuprofen, ketoprofen and naproxen. In addition, the amount of solubilized therapeutic agents c/s/ was examined by means of the spectroscopic method and the micellar partition coefficient--Kw(m) was estimated. The results obtained in the course of research served as a basis for determining the solubilization mechanism and the stability of the micellar adduct for the purpose of application. This enabled the commencement of technological work on the design and manufacture of a model dosage form administered to the skin and containing the products of lanolin oxyethylation.

Development of the novel plant-derived lanolin substitute and its cosmetic applications.

We have developed Bis-beheyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (oligomer ester) as a novel plant-derived lanolin or adsorption refined lanolin substitute with very pale color (GH = 1), low odor, and excellent stability. It is an oligomer ester type phytosterol ester in a paste form synthesized only from plant-derived materials. This oligomer ester has excellent lanolin-like properties such as high water holding capability (200%), excellent moisturizing effect in human use tests excellent gloss in makeup products (superior to lanolin and adsorption refined lanolin) coming from its high refractive index (approx. 1.475 at 60 degrees C), high pigment dispersing ability, excellent foam-stabilizing ability and moisturizing effect in cleansing products and shampoos, emulsion stabilizing effect, skin affinity, e.t.c. And this oligomer ester is much more stable against oxidation than lanolin and adsorption refined lanolin in CDM test. So this oligomer ester is useful for make-up products, cleansing products, skincare products, and haircare products.

Volatile fatty acids as malodorous compounds in wool scouring water and lanolin. Origin and characterisation.

Volatile fatty acids (C2-C7) analysis in wool scouring water and lanolin is presented. These substances are of major interest as malodorous compounds in urban and industrial wastewaters. In this work, they have been analysed in wool scouring water by headspace solid-phase microextraction followed by gas chromatography negative chemical ionisation mass spectrometry. Most of the volatile fatty acids have been identified at microg g(-1) levels. In addition, since lanolin is a major impurity of raw wool, volatile fatty acid patterns of wool scouring water and lanolin have been compared in order to establish the origin of these compounds in the wastewater. Finally, the efficiency of the deodorization step, mandatory to obtain commercial lanolin, has been assessed taking into account the decrease in volatile fatty acid content from the raw wool to the lanolin.

Complete characterisation of lanolin steryl esters by sub-ambient pressure gas chromatography-mass spectrometry in the electron impact and chemical ionisation modes.

Steryl esters occurring in lanolin have been characterised by sub-ambient pressure gas chromatography coupled to mass spectrometry. Electron impact and chemical ionisation modes with different reagent gases have been evaluated in order to carry out unambiguous peak identification. Steryl esters with different sterol (i.e. cholesterol, lanosterol and dihydrolanosterol) and acid moieties either according to carbon number (i.e C10-C23) or isomeric forms (i.e. normal, iso and anteiso) have been identified. Identification of the sterol and acid moieties has been carried out by means of the mass spectral information obtained in the electron impact, chemical ionisation mode either in the positive or negative modes using methane, isobutane and ammonia as reagent gases. Isomeric identification has been achieved by chromatographic retention parameters (i.e. entire-chain length and fractional-chain length) and by the free fatty acid profile also present in lanolin.

Systematic characterisation of long-chain aliphatic esters of wool wax by gas chromatography-electron impact ionisation mass spectrometry.

A detailed structural characterisation of the aliphatic high-molecular-mass esters extracted from raw wool based on high-temperature gas chromatography-electron impact ionisation mass spectrometry is described. The raw wool esters extracted are in the range of C37 to C54 (i.e., molecular mass 550-788). The selected ion chromatogram exhibited four isomers for the esters with an odd number of carbon atoms (i:a, i:n, a:n and n:n) and five for those with an even number of carbon atoms (i:i, a:a, i:n, a:n and n:n). Isomeric structural elucidation is discussed with respect to the long-chain fatty acid and long-chain fatty alcohol structures, on the basis of chromatographic retention behaviour and mass spectral information.