Use of certain alcohol ethoxylates to maintain protease stability in the presence of anionic surfactants

Anionic surfactants, including linear alkylbenzene sulfonate (LAS), are known to decrease the stability of detergent proteases, possibly by hastening autoproteolytic processes. Thus, protease shelf life in enzyme-containing, heavy-duty liquid laundry detergents (HDL) is typically maintained by adding stabilizers, by limiting the level of interfering anionics, or by utilizing more compatible anionics, such as alcohol ethoxysulfates (AES). This study examines the stability of Savinase^® detergent protease in HDL formulations based on LAS and containing different alcohol ethoxylates (AE) for protection against protease inactivation. Dose response curves demonstrated that all commonly used anionic surfactants except AES promote loss of protease activity. In HDL formulations with equal percentage compositions of LAS and AE, the structure of the selected AE was found to have a profound influence on protease stability. Inclusion of AE with chain length ≥C₁₄ and ethoxylate levels >70% resulted in greater protease stability. HDL containing LAS and these protective AE could be formulated to achieve protease stability matching those of simulated commercial products. Unlike polyhydric stabilizers, the AE by themselves confer no additional stability to the protease. It is more likely that the stabilizing effect of the “protective” AE is due to decreased availability of LAS to the protease.     

Correlations between the Type of Aggregates in the Bulk Phase and the Functionality and Safety of All-Purpose Cleaners

The article shows that the type and concentration of inorganic salt can be translated into the structure of the bulk phase and the performance properties of ecological all-purpose cleaners (APC). A base APC formulation was developed. Thereafter, two types of salt (sodium chloride and magnesium chloride) were added at various concentrations to obtain different structures in the bulk phase. The salt addition resulted in the formation of spherical micelles and—upon addition of more electrolyte—of aggregates having a lamellar structure. The formulations had constant viscosities (ab. 500 mPa·s), comparable to those of commercial products. Essential physical-chemical and performance properties of the four formulations varying in salt types and concentrations were evaluated. It was found that the addition of magnesium salt resulted in more favorable characteristics due to the surface activity of the formulations, which translated into adequately high wettability of the investigated hydrophobic surfaces, and their ability to emulsify fat. A decreasing relationship was observed in foaming properties: higher salt concentrations lead to worse foaming properties and foam stability of the solutions. For the magnesium chloride composition, the effect was significantly more pronounced, as compared to the sodium chloride-based formulations. As far as safety of use is concerned, the formulations in which magnesium salt was used caused a much lesser irritation compared with the other investigated formulations. The zein value was observed to decrease with increasing concentrations of the given type of salt in the composition.     

The Irritant Effects of Pharmaceutically Applied Surfactants

Dermal or transdermal medication may lead to irritant contact dermatitis. However, little information is available on the irritant effect of surfactants which are applied in topical formulations. Our aim was to examine the irritant effect of the most frequent compounds in topical products. A murine model was applied. The following compounds were examined: sodium lauryl sulphate (SLS), polyethoxylated (40EO) hydrogenated castor oil and sucrose laurate. SLS led to severe erythema, increase in transepidermal water loss (TEWL) and induced necrosis and accumulation of neutrophylic granulocytes and lymphocytes. Exposure to sucrose laurate resulted in an elevation of TEWL, but histology did not reveal impairment of the skin structure. Application of polyethoxylated (40EO) hydrogenated castor oil was not accompanied by tissue damage. Special attention should be paid to the irritant effect of SLS. Polyethoxylated (40EO) hydrogenated castor oil seems to be a non-irritant agent and sucrose laurate is also a promising candidate for application in topical preparations.     

Effect of Hydrophobic Plant Extract on the Physicochemical Properties of a Transparent Fabric Softener

This article investigates the effect of hydrophobic supercritical CO₂ raspberry seed extracts on the physicochemical and functional properties of a modern, transparent fabric softener. The addition of a hydrophobic extract to a transparent softener formulation increased the turbidity and dynamic viscosity of the product compared to the reference formulation (with no added extract). In addition, fabric rinsed in a bath containing the transparent fabric softener enriched with the hydrophobic extract was characterized by a higher degree of softness and slightly lower values of fabric rewettability (two parameters determining the usable properties of this type products) in relation to the values determined for a fabric exposed to the rinsing process in an aqueous solution of the transparent fabric softener without added extract. The results obtained in the assessment of physicochemical properties point to the modification of the structure of fabric softener resulting from the growth of surfactant aggregates due to solubilization of the hydrophobic extract. As a consequence, the deposit—an adsorption layer of surfactants (responsible for key characteristics relevant to the performance of this type of products) remaining on the fabric after the rinsing process—is modified.     

Formulation of ultralow interfacial tension systems using extended surfactants

Inspired by the concept of lipophilic and hydrophilic linkers, extended surfactants have been proposed as highly desirable candidates for the formulation of microemulsions with high solubilization capacity and ultralow interfacial tension (IFT), especially for triglyceride oils. The defining characteristic of an extended surfactant is the presence of one or more intermediate-polarity groups between the hydrophilic head and the hydrophobic tail. Currently only limited information exists on extended surfactants; such knowledge is especially relevant for cleaning and separation applications where the cost of the surfactant and environmental regulations prohibit the use of concentrated surfactant solutions. In this work, we examine surfactant formulations for a wide range of oils using dilute solutions of the extended surfactant classes sodium alkyl polypropyleneoxide sulfate (R-(PO) _x −SO₄Na), and sodium alkyl polypropyleneoxide-polyethyleneoxide sulfate (R-(PO) _y -(EO) _z −SO₄Na). The IFT of these systems was measured as a function of electrolyte and surfactant concentration for polar and nonpolar oils. The results show that these extended surfactant systems have low critical micelle concentrations (CMC) and critical microemulsion concentrations (CμC) compared with other surfactants. We also found that the unique structure of these extended surfactants allows them to achieve ultralow IFT with a wide range of oils, including highly hydrophobic oils (e.g., hexadecane), triolein, and vegetable oils, using only ppm levels of these extended surfactants. It was also found that the introduction of additional PO and EO groups in the extended surfactant yielded lower IFT and lower optimum salinity, both of which are desirable in most formulations. Based on the optimum formulation conditions, it was found that the triolein sample used in these experiments behaved as a very polar oil, and all other vegetable oils displayed very hydrophobic behavior. This unexpected triolein behavior is suspected to be due to uncharacterized impurities in the triolein sample, and will be further evaluated in future research.     

Characterization of novel soybean‐oil‐based thermosensitive amphiphilic polymers for drug delivery applications

Hydrolyzed polymers of soybean oil (HPSO) and of epoxidized soybean oil (HPESO) were developed previously. Owing to their natural food origin and biocompatibility, we exploited further their potential as a drug delivery system and pharmaceutical excipients. This work aimed to investigate self‐assembly, thermal transition, interaction with various drugs and surface activity of these novel amphiphilic polymers. The critical micelle concentration of HPSO and HPESO was determined by the surface tension method. The molecular interaction between HPESO and anticancer drug doxorubicin HCl was examined. The effect of the polymers on the solution contact angle and surface energy of compressed tablets of hydrophobic drugs ibuprofen and nifedipine was measured. The thermal transition temperatures T_tr (cloud points) of the polymers in aqueous solutions increased with increasing polymer concentration. HPSO exhibited lower T_tr than HPESO. The critical micelle concentration was found to be 0.05 mg mL^?1 for HPSO and 0.08 mg mL^?1 for HPESO. Strong molecular interactions between HPESO and doxorubicin were observed. Both polymers reduced the interfacial energy and contact angles of drug tablets with more effect on ibuprofen tablets with the use of HPSO. These results suggest that the novel soybean‐oil‐based amphiphilic polymers have great potential for drug delivery and pharmaceutical formulations. Copyright © 2012 Society of Chemical Industry     

15-Lipoxygenase-Mediated Modification of HDL3 Impairs eNOS Activation in Human Endothelial Cells

Caveolae are cholesterol and glycosphingolipids-enriched microdomains of plasma membranes. Caveolin-1 represents the major structural protein of caveolae, that also contain receptors and molecules involved in signal transduction pathways. Caveolae are particularly abundant in endothelial cells, where they play important physiological and pathological roles in regulating endothelial cell functions. Several molecules with relevant functions in endothelial cells are localized in caveolae, including endothelial nitric oxide synthase (eNOS), which regulates the production of nitric oxide, and scavenger receptor class B type I (SR-BI), which plays a key role in the induction of eNOS activity mediated by high density lipoproteins (HDL). HDL have several atheroprotective functions, including a positive effect on endothelial cells, as it is a potent agonist of eNOS through the interaction with SR-BI. However, the oxidative modification of HDL may impair their protective role. In the present study we evaluated the effect of 15-lipoxygenase-mediated modification of HDL₃ on the expression and/or activity of some proteins localized in endothelial caveolae and involved in the nitric oxide generation pathway. We found that after modification, HDL₃ failed to activate eNOS and to induce NO production, due to both a reduced ability to interact with its own receptor SR-BI and to a reduced expression of SR-BI in cells exposed to modified HDL. These findings suggest that modification of HDL may reduce its endothelial-protective role also by interfering with vasodilatory function of HDL.     

Freeze casting for near‐net‐shaping of dense zirconium diboride ceramics

Zirconium diboride (ZrB₂) was formed into dense complex shapes using freeze casting as a near‐net‐shaping technique. Aqueous‐based formulations were compared with nonaqueous (cyclohexane) based formulations in terms of rheological behavior, particle packing in the green body, sintered density, macroscale porosity, and cracking. The influence of particle solids concentration and freezing rate was investigated. The aqueous formulations were found to be deficient in that they produced macroscale porosity that could not be eliminated during sintering resulting in low density and large pores in the final shaped objects. The nonaqueous‐based system was able to produce complex shaped objects with significantly reduced macroscale porosity. The higher concentration of solids in the nonaqueous‐based formulations was primarily responsible for the reduced macroscale porosity and enabled higher sintered densities (up to 90%‐91.5% of theoretical density for fast freezing). The microstructure of the ZrB₂ formed at fast freezing rates and high solids content typically had isolated pores in the order of 5‐10 μm in size, mainly found along grain boundaries (grain sizes between 20 and 50 μm). Although this rapid freezing produced denser components, it tended to produce objects with internal cracks. When slower freezing rates were used, intricate complex shaped objects could be produced without cracks but their density was only between 65% and 80% of theoretical density.     

Profiling of skin anti-aging related proteins in human dermal fibroblasts by decursin in <Emphasis Type="Italic">Angelica gigas</Emphasis> Nakai

The extract of Angelica gigas Nakai by supercritical CO₂ increased the expression of collagen synthesis-related proteins in human dermal fibroblast, including type 1(α-2) collagen chain precursor (pI 9.08, MW 129.7), procollagen C-endopeptidase (pI 7.40, MW 47.97), and prolyl 4-hydroxylase (pI 5.49, MW 60.90). It also increased the expression level of interaction-related proteins, α-actinin (pI 5.47, MW 105.5), integrin-β1 (pI 5.27, MW 88.46). The expression levels of these proteins by pure decursin were similar to those by supercritical fluid extract. By the dose concentration experiment, decursin in A. gigas was found to play the major role in expression level increases. Proteome analysis proved that decursin in A. gigas promoted synthesis of proteins related to skin anti-aging in human dermal fibroblasts.     

Amphoterics in household detergents

Amphoteric surfactants are widely known for their extreme skin kindness, decreasing the irritation of otherwise irritant surfactants, especially anionics, giving low-irritant shampoo ingredients. New high quality amphoteric compounds have been developed. These new amphoterics offer exciting possibilities in several new application areas. Considerable development work has been undertaken to investigate new detergent formulations based on these novel amphoterics. Because of the very low concentration of Ampholak 7TX, the formulations give most effective products with low biological load. Data concerning the increasingly important subject of biodegradability and toxicity are shown. This includes both primary and inherent biodegradability and toxicity of metabolites.     

Alterations in the High Density Lipoprotein Phenotype and HDL-Associated Enzymes in Subjects with Metabolic Syndrome

Patients with metabolic syndrome (MetS) usually have low high density lipoprotein cholesterol (HDL-C) levels. We determined the HDL distribution profile as well as the HDL-related lipoprotein associated phospholipase A₂ (HDL-LpPLA₂) and paraoxonase-1 (PON1) activities in subjects with MetS (n = 189) but otherwise healthy. Age and sex-matched individuals (n = 166) without MetS served as controls. The lower HDL-C concentration in MetS patients was due to a reduction in both large and small HDL subclasses (P < 0.001 and P < 0.05, respectively). As the number of MetS components increased, the HDL phenotype comprised of a greater percentage of small HDL-3 and less large HDL-2 subclasses, resulting in a decreased HDL-2/HDL-3 ratio (P < 0.001 for all trends). Multivariate analysis revealed that HDL-2 levels and the HDL-2/HDL-3 ratio significantly and independently correlated with HDL-C (positively) and TG (negatively) levels. HDL-3 concentration significantly and independently positively correlated with HDL-C and TG levels. HDL-LpPLA₂ activity was decreased in MetS patients (P < 0.01), a phenomenon that may contribute to the defective antiatherogenic activity of HDL in MetS. PON1 activity did not differ between groups. We conclude that MetS, in addition to the decrease in HDL-C concentration, is associated with alterations in the HDL phenotype, which is comprised of a greater percentage of small HDL subclasses. Furthermore, HDL-LpPLA₂ activity is decreased in MetS patients.     

Design and Engineering of “Green” Nanoemulsions for Enhanced Topical Delivery of Bakuchiol Achieved in a Sustainable Manner: A Novel Eco-Friendly Approach to Bioretinol

In the present work, we establish novel “environmentally-friendly” oil-in-water nanoemulsions to enhance the transdermal delivery of bakuchiol, the so-called “bioretinol” obtained from powdered Psoralea corylifolia seeds via a sustainable process, i.e., using a supercritical fluid extraction approach with pure carbon dioxide (SC-CO₂). According to Green Chemistry principles, five novel formulations were stabilized by “green” hybrid ionic surfactants such as coco-betaine—surfactin molecules obtained from coconut and fermented rapeseed meal. Preliminary optimization studies involving three dispersion stability tests, i.e., centrifugation, heating, and cooling cycles, indicated the most promising candidates for further physicochemical analysis. Finally, nanoemulsion colloidal characterization provided by scattering (dynamic and electrophoretic light scattering as well as backscattering), microscopic (transmission electron and confocal laser scanning microscopy), and spectroscopic (UV–Vis spectroscopy) methods revealed the most stable nanocarrier for transdermal biological investigation. In vitro, topical experiments provided on human skin cell line HaCaT keratinocytes and normal dermal NHDF fibroblasts indicated high cell viability upon treatment of the tested formulation with a final 0.02–0.2 mg/mL bakuchiol concentration. This excellent biocompatibility was confirmed by ex vivo and in vivo tests on animal and human skin tissue. The improved permeability and antiaging potential of the bakuchiol-encapsulated rich extract were observed, indicating that the obtained ecological nanoemulsions are competitive with commercial retinol formulations.     

人血高密度脂蛋白治疗冠心病的疗效观察

应用人血高密度脂蛋白治疗冠心病患者52例,按1974年及1979年全国冠心病普查和预防座谈会上制订的疗效判定标准,总有效率为100％。治疗后胸闷,气短,乏力症状消失,心慌有了明显改善。心绞痛消失或改善者为100％。心电图恢复或改善者为90.4％,而用硝酸酯和硝苯吡啶常规治疗的对照组,心绞痛和心电图改善者分别为66.6％和50％,HDL明显优于常规药物。应用HDL治疗后心功能和超声心动图有了变化,ICT/LVET和左室舒末内径明显缩小,心功能和超声心动图改善分别为76.92％和57.84％。血脂浓度降低显著,总胆固醇下降高达34.8～43.0％,甘油三酯下降17.0～21.4％。治疗52例,未见有任何副作用。     

Effects of nonionic surfactant on the rheological property of associative polymers in complex formulations

The rheological properties of hydrophobically modified ethoxylated urethane (HEUR) were investigated in the presence of a nonionic surfactant, polyoxyethylene stearyl ether (C₁₈(EO)₂₀). The presence of nonionic surfactants played an important role in tuning the rheological properties of HEUR aqueous solutions. Observing both plateau modulus and viscoelastic relaxation time of HEUR aqueous solutions with varying the concentration of C₁₈(EO)₂₀ allowed us to demonstrate that C₁₈(EO)₂₀ readily interacts with the hydrophobic segments of HEUR polymers, which eventually formed a strong micellar network. Moreover, the micellar network formed at a critical concentration of C₁₈(EO)₂₀, ∼0.6% w/v, was indeed stable against both ionic strength and pH in the aqueous medium and complex formulations, such as a colloid suspension and an oil-in-water emulsion, thus providing more practical applications as thickeners for a wide variety of complex formulations.     

Effect of different skin permeation enhancers on peel strength of an acrylic PSA

Different amounts of two skin permeation enhancers, Oleic acid (OA) and Propylene glycol (PG), were mixed thoroughly with solution of a commercial acrylic pressure sensitive adhesive (Duro‐Tak). Films with different adhesive layer thickness (30 and 60 μm) were prepared by casting of formulations with a film applicator on a PET 80‐μm film and drying of solvents. Peel test was done on different formulations according to ASTM D3330. Surface study and thermal analysis were used for explaining the results. It was shown that the effect of interfacial work of adhesion on peel strength was too low to be considered. PG had no significant effect on peel strength, which was related to effect of hydrogen bonds between PG and copolymer chains acting as crosslinks. OA decreased peel strength significantly, which is due to important changes in copolymer structure. These changes can be found by relatively sharp drop in T_g values. Adhesive–cohesive transition occurred in OA formulations as a result of OA crystals formation. OA migration to surface in concentrations of more than 10 (w/w %) was confirmed by results of DSC and surface study. In contrast with PG, doubling of thickness had no effect on peel strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2987–2991, 2003     

Effects of diet and high density lipoprotein subfractions on the removal of cellular cholesterol

The effects of isocaloric substitutions of dietary polyunsaturated and saturated fat on the composition and function of plasma high density lipoproteins (HDLs) were studied in 3 normal subjects who were fed saturate-rich and polyunsaturate-rich diet programs. Compared to the saturated diets (P/S=0.4), polyunsaturated fat diets (P/S=4 or 2) reduced both plasma cholesterol and triglyceride levels. In 2 of the subjects, HDL cholesterol concentrations increased with polyunsaturated fat caused a reduction in HDL fatty acyl content of oleate and an increase in linoleate. To determine whether the altered composition affected the removal of cell membrane cholesterol, HDL and their subfractions, HDL₂ and HDL₃, which were isolated from each of the diets, were incubated with Ehrlich ascites cells in vitro. The cells were prelabeled with [³H] cholesterol, and the release of labeled cholesterol from the cells into the medium containing the various HDL fractions was determined. HDL, irrespective of the type of dietary fat, caused a release of [³H] cholesterol from the cells into the medium. The amount of [³H] cholesterol recovered in the medium was dependent on the absolute concentration of HDL cholesterol added to the cells and was independent of the type of diet. These results indicate that HDL facilitates the removal of cholesterol from cells, but that the amount and rate of removal are independent of the changes in HDL composition that can be obtained by dietary perturbations.     

Optimized Microemulsion Systems for Detergency of Vegetable Oils at Low Surfactant Concentration and Bath Temperature

Triglycerides and vegetable oils are amongst the most difficult oils to remove from fabrics due to their highly hydrophobic nature; this is all the more challenging as cold water detergency is pursued in the interest of energy efficiency. Recently, extended surfactants have produced very encouraging detergency performance at ambient temperature, especially at low surfactant concentration. However, the salinity requirement for extended surfactants was excessive (4–14%) and there is limited research on extended‐surfactant‐based microemulsions for cold water detergency (below 25 °C). Therefore, extended‐surfactant‐based microemulsions are introduced in this study for cold temperature detergency of vegetable oils with promising salinity and surfactant concentration. The overall goal of this study is to explore the optimized microemulsion formulations with low surfactant and salt concentration using extended surfactant for canola oil detergency at both 25 and 10 °C. It was found that microemulsion systems achieved good performances (higher than those of commercial detergents) corresponding to IFT value 0.1–1 mN/m with the surfactant concentration as low as 10 ppm and 4% NaCl at 25 °C, and as low as 250 ppm and 0.1% (1000 ppm) NaCl at 10 °C. In addition, microemulsion systems were investigated with a different salt (CaCl₂, or water hardness, versus NaCl) at 10 °C, demonstrating that 0.025% CaCl₂ (250 ppm) can produce good detergency; this is in the hardness range of natural water. These results provide qualitative guidance for microemulsion formulations of vegetable oil detergency and for future design of energy‐efficient microemulsion systems.     

Effects of estrogens and progestins on high density lipoproteins

High density lipoprotein (HDL) levels are known to be higher in women than in men, and to increase with estrogen use. To assess the effects of estrogens on HDL subspecies, analytic ultracentrifuge measurements of HDL were compared in 11 menopausal estrogen users and 16 controls. The difference in mean schlieren patterns between the groups showed a significantly higher level of HDL with flotation rate (F _1.20 ^o )>1.5 (predominantly HDL₂) in the users. This was similar to the difference in HDL seen between nonusers of hormones and age-matched males. A previous study had shown that users of combination oral contraceptives had increased levels of HDL with F _1.20 ^o ≤3.5 (primarily HDL₃) suggesting that the estrogen effect on HDL is altered by the presence of added progestin. The progrestin effect was studied here in more detail in two women with type V hyperlipoproteinemia treated with norethindrone acetate. Reduction in serum triglyceride was accompanied by a reduction in HDL, predominantly in the less dense species (HDL₂). Among groups of oral contraceptive and noncontraceptive estrogen and progestin users whose HDL-cholesterol levels have been reported recently, there was a direct correlation (r=0.86, p<.001) between mean HDL-cholesterol and triglyceride levels. Endogenous hormonal influences on HDL were assessed by serum hormone and lipoprotein measurements at weekly intervals during two consecutive menstrual cycles in four healthy females. An increase in HDL of highest flotation rate (F _1.20 ^o 5–9) was seen, which corresponded with the time of ovulation raising the possibility of pituitary as well as gonadal hormone effects on HDL.     

Effect of poly(ethylene glycol) on the hydrophobic interactions and rheology of proanthocyanidin biopolymers from Pinus radiata

The rheology of solutions of extracts from the bark of Pinus radiata was investigated in the presence of poly(ethylene glycol)s (PEGs) of different molecular weights. PEG with a molecular weight of 4600 (1% w/w) was sufficient to reduce the viscosity of a concentrated (40% w/w) pine tannin extract by one order of magnitude. The reduction of the viscosity was due to the inhibition of molecular association via hydrogen bonding and hydrophobic interactions between tannin and PEG and depended on the molecular weight of PEG. PEG effectively reduced the viscosity of polyphenolic tannins but retained high reactivity toward paraformaldehyde for adhesive formulations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1254–1260, 2005     

Irritant action of binary soap mixtures on skin

Conclusions Evidence is offered in support of the following: (1) sodium laurate-sodium caprylate mixtures appear to be highly irritant to the skin of both sexes, (2) sodium ricinoleate binary mixtures with sodium laurate, sodium caprylate, and sodium oleate show a definite irritant action on human skin, (3) sodium linoleate binary mixtures with sodium laurate, sodium caprylate, and sodium oleate indicate a decreased irritant action, (4) sodium laurate-sodium myristate binary mixtures tend to be much less irritant to skin than can be predicted from their respective irritant powers. This investigation was made possible by a fellowship grant received from The Procter & Gamble Company, Cincinnati, Ohio. Presented at 19th Annual Fall Meeting, American Oil Chemists’ Society, Chicago, Ill., on November 7–9, 1945.