Analysis and quantification of parabens in cosmetic products by utilizing hollow fibre-supported liquid membrane and high performance liquid chromatography with ultraviolet detection

A simple and direct method based on hollow fibre-supported liquid membrane (HFSLM) extraction and liquid chromatography equipped with a UV detector was developed for analysis and quantification of parabens in cosmetic products. The parabens analysed included methyl, ethyl, propyl, isobutyl and butyl paraben. The HFSLM extraction was carried out by employing di- n -hexyl ether as organic liquid that was immobilized in the hollow fibre membrane. The HFSLM extraction is simple, cheap, minimizes the use of solvents and uses disposable material. In an investigation of 11 paraben-containing cosmetic products, the levels of parabens (sum of all parabens in a product) ranged from 0.43% to 0.79% (w/w) for skin care products, 0.07–0.44% for hair fixing gels and 0.30–0.52% for soap solutions. The levels of individual parabens in individual cosmetic products ranged between 0.03% and 0.42% w/w for skin care products, 0.07% and 0.26% w/w for hair fixing gels and between 0.11% and 0.34% w/w for soap solutions. Parabens were found in the highest concentrations in skin care products followed by soap solutions and the least amounts were found in hair fixing gels. Of the paraben-containing products tested, all of them contained methyl paraben and about 90% contained propyl paraben in addition to methyl paraben. One product contained all the parabens analysed.     

Sensitive determination of parabens in soy sauces by capillary zone electrophoresis with amperometric detection

A high-performance capillary zone electrophoresis with amperometric detection (CZE-AD) method has been developed for the separation and sensitive determination of the preservatives methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP) in soy sauce samples. The effects of several factors such as the pH and concentration of running buffer, the separation voltage, the applied potential and the injection time on CZE-AD were investigated. Under the optimum conditions, four preservatives can be well separated within 16 min at the separation voltage of 16 kV in a 80 mmol/L borax running buffer (pH 9.94), and adequate extraction was obtained with ethanol for the determination of the above four parabens. Satisfactory recovery (95.0–102.0%), repeatability of the peak current (≤2.4%) and migration time (≤0.5%) of four analytes, as well as detection limits (5.7 × 10⁻⁸–4.4 × 10⁻⁸ g/mL) for the method, were achieved. This proposed procedure has been successfully used for the analysis of paraben preservatives in soy sauce samples, and the content of EP was from 0.08 to 0.14 mg/mL in the tested samples.     

Percutaneous absorption of parabens from cosmetic formulations

Absorption through human skin of a series of six p -hydroxy-benzoates (parabens) was studied in vitro. A diffusion chamber was used, where the receiving phase was a physiological solution of albumin. Maximum fluxes and permeability constants of the parabens were measured from different vehicles representing hydrophilic and lipophilic phases, and from different types of common commercial cosmetic emulsions, each containing a known quantity of a single member of the series. Significant skin absorption was observed, depending upon the partition coefficient (log P octanol/water) of the permeant, composition and time of storage of the emulsions. Fluxes from all types of emulsions were higher for methyl paraben and decreased with the increasing lipophilic character of the preservative. Comparatively, fluxes from oil/water emulsions were higher than from water/oil emulsions. Moreover, a clear dependence of preservatives'percutaneous absorption on the time of storage was observed, the fluxes becoming constant after about three months after the time of preparation. The relationship between preservative activity and percutaneous absorption is discussed.     

Elastic vesicles as topical/transdermal drug delivery systems

Skin acts a major target as well as a principle barrier for topical/transdermal drug delivery. Despite the many advantages of this system, the major obstacle is the low diffusion rate of drugs across the stratum corneum. Several methods have been assessed to increase the permeation rate of drugs temporarily. One simple and convenient approach is application of drugs in formulation with elastic vesicles or skin enhancers. Elastic vesicles are classified with phospholipid (Transfersomes((R)) and ethosomes) and detergent-based types. Elastic vesicles were more efficient at delivering a low and high molecular weight drug to the skin in terms of quantity and depth. Their effectiveness strongly depends on their physicochemical properties: composition, duration and application volume, and entrapment efficiency and application methods. This review focuses on the effect of elastic liposomes for enhancing the drug penetration and defines the action mechanism of penetration into deeper skin.     

A novel polymer anti-irritant barrier film for cosmetics

Currently, we encounter many chemical substances that can affect the skin through contact in our daily life. To keep these irritants away from us, it is very effective to create a dermal barrier film that can prevent penetration of irritants into the skin. For the purpose, we evaluated the permeation characteristics of currently available film-forming polymers, but almost all were found ineffective as barriers. Our investigation led us to fluoroalkylacrylate–polyglycolmethacrylate–alkylmethacrylate–copolymer (F–copolymer), a new acrylic copolymer. This polymer is soluble in water and can easily be incorporated into various cosmetic products. It consists of hydrophilic and lipophilic groups with fluorine units, and forms a durable, continuous film that is resistant to both water and oil upon drying. Testing on human subjects has demonstrated F-copolymer's effectiveness in countering irritation caused by water-soluble materials, including methyl paraben, lactic acid, and oil-soluble materials, like butyl paraben and methyl saricylate.     

Effect of the Parabens With and Without Nitrite on Clostridium botulinum and Toxin Production in Canned Pork Slurry

Antimiciobials were evaluated in thioglycollate broth at pH 6.5 for the ability to inhibit growth and toxin production by C. botulinum 12885A and ATCC 7949 (Type B). Methyl, ethyl, propyl, and butyl parabens (0.1%) and sorbic acid (0.2%) were effective in inhibiting growth of C. botulinum 12885A and ATCC 7949 in broth. Ethyl, propyl, and butyl parabens (0.1%) and sorbic acid (0.2%) inhibited toxin production by both strains in culture medium. Ethyl, propyl, butyl parabens (0.1%) and sorbic acid (0.2%) were individually added to a comminuted pork slurry having salt and sugar, with or without 40 ppm sodium nitrite. Cans were inoculated with a mixture of C. botulinum 12885A and ATCC 7949 spores. The canned product was abused by holding at 27°C and was observed over a 3-month period for swollen cans. Swollen cans were examined for botulinal toxin by the mouse bioassay. Propyl and butyl paraben did not inhibit or delay toxin production. Ethyl paraben with or without nitrite delayed toxin production for 4 wk. Sorbic acid inhibited toxin for 3 wk; when 40 ppm nitrite was added to the sorbic acid treatment, toxin production was delayed for 4 wk.     

Gross adhesive penetration in furfurylated, <Emphasis Type="Italic">N</Emphasis>-methylol melamine-modified and heat-treated wood examined by fluorescence microscopy

This study investigated the radial penetration of three conventional cold-set wood adhesives [emulsion polymer isocyanate (EPI), poly (vinyl acetate) (PVAc), one-component polyurethane (PU)] into various degrees of furfurylated and N-methylol melamine-modified (NMM) Scots pine, and heat-treated Scots pine and beech based on measurements of effective (EP) and maximum penetration (MP) from microscopic observations. EP of EPI adhesive decreased after modification with higher concentration of furfuryl alcohol while an improved penetration was recorded for PVAc into furfurylated wood. A deeper penetration was observed for all adhesives into wood treated with lower concentration of furfuryl alcohol. The EP of EPI and PU adhesives reduced after NMM treatment but it increased in the case of PVAc. In spite of reduction of EP of PU after NMM treatment, it represented a deeper penetration among all adhesives possibly due to its lower molecular weight. For Scots pine, increasing the treatment temperature improved EP of all adhesives while for beech, the EP of PU and PVAc increased largely in the case of samples treated at 195 °C. Visual analysis of fluorescence microscopy pictures provided more detailed information on modality of penetration. The results are useful for understanding the interaction among common adhesives and modified materials, and can be used in future research to explain the bonding behavior of modified wood.     

Chewing activity,saliva production,and ruminal pH of primiparous and multiparous lactating dairy cows

Four multiparous (MP) and four primiparous (PP) ruminally cannulated lactating Holstein cows were used in a double 4 x 4 Latin square design to study the chewing behavior, saliva production, and ruminal pH of cows in the first or subsequent lactation. Cows were fed one of four diets; three total mixed rations containing 40, 50, or 60% silage (DM basis), and a separate ingredient diet containing 50% concentrate. Dry matter intake was higher for MP cows than for PP cows (19.2 vs. 17.1 kg/d) but not as a percentage of body weight (2.97 +/- 0.06%). Multiparous cows spent more time eating than PP cows (260 vs. 213 min/d, respectively), even after adjustment for dry matter intake (13.8 vs. 12.4 min/kg DM). Multiparous cows also spent more time ruminating per day than PP cows (560 vs. 508 min/d, respectively). Eating salivation rate was not affected by parity, but resting salivation rate was higher for MP cows than for PP. Although MP cows spent more time chewing than PP cows, total daily saliva production was only numerically higher for MP cows because the increase in saliva produced during chewing was accompanied by a decrease in saliva produced during resting. Furthermore, pH profiles tended to be lower for MP cows than for PP cows. Multiparous cows may have a greater risk of incurring acidosis than PP cows because increased salivary secretion associated with increased chewing may not sufficiently compensate the increment of fermentation acids produced in the rumen due to high feed intake.     

A physico-chemical properties based model for estimating evaporation and absorption rates of perfumes from skin

Because of their potential for inducing allergic contact dermatitis (ACD) if used improperly, perfumes are carefully assessed for dermal safety prior to incorporation into cosmetic products. Exposure assessment for these materials often involves the conservative assumption of 100% absorption of each component. This report describes an improved method to estimate the absorption and evaporation of perfume ingredients from skin, based on their physico-chemical properties. The effect of environmental variables such as temperature and wind velocity can be accounted for in a logical way. This was accomplished using a first-order kinetic approach expected to be applicable for small doses applied to skin. Skin penetration rate was calculated as a fraction of the maximum flux estimated from the compound's lipid solubility, S(lip) (represented by the product of octanol/water partition coefficient, K(octt), and water solubility, S(w)), and molecular weight, MW. Evaporation rates were estimated from a modified Henry's Law approach with a stagnant boundary layer whose thickness is a function of surface airflow, v. At a given value of v, evaporation rate was assumed proportional to the ratio P(vp)/S(lip), where P(vp) is the vapour pressure of the ingredient at skin temperature, T. The model predicts a relationship for total evaporation from skin of the form %evap = 100x/(k+x) where x = P(vp)MW(2.7)/(K(oct)S(w)) and k is a parameter which depends only on v and T. Comparison with published data on perfume evaporation from human skin in vivo showed good agreement between theory and experiment for two closely related perfume mixtures (r(2) = 0.52-0.74, s = 12-14%, n = 10). Thus, the method would seem to have a good prospect of providing skin absorption estimates suitable for use in exposure assessment and improved understanding of dose-related contact allergy.     

In vitro induction of apoptosis, necrosis and genotoxicity by cosmetic preservatives: application of flow cytometry as a complementary analysis by NRU

Preservatives are used in cosmetics to prevent microbial contamination; however, some preservatives are not free of allergenic and cytotoxic potential. Allergenicity and cytotoxicity potential values are major aspects of preservative safety, which determine limitations and maximum concentration dose in a cosmetic product. The purpose of this study was to investigate and compare the in vitro apoptosis, necrosis and genotoxicity-inducing potential of five different types of preservatives: Phenoxyethanol (PE), Propylparaben (PP), Methylparaben (MP), Benzyl Alcohol (BA) and Ethylhexyl Glycerine (EG). In vitro experiments were carried out on human dermal fibroblasts by a quantitative flow cytometry method, using specific cell markers (Annexin V, Propidium Iodide and H2AX). We compared the resulting cell viability by means of neutral red uptake (NRU) and established the IC(50) . Our results showed that PE, PP, MP and BA have similar cytotoxic mechanisms (high apoptosis and necrosis levels only at the test concentration of 1%), whereas EG showed only an apoptosis pathway. For genotoxicity, both parabens yielded the highest values. Results obtained by flow cytometry for necrosis were comparable to those produced by NRU; however, NRU does not distinguish apoptosis from necrosis. We propose that flow cytometry is a more sophisticated methodology for understanding the cytotoxic mechanisms of cosmetic preservatives and can be used to complement the NRU.     

Effect of water and salt content on protein solubility and water retention of meat preblends

Different preblend water contents at a constant ionic strength were investigated to determine if increasing water availability would increase protein solubility and water retention in meat preblends. Four salt levels (0, 2, 4 and 8%) and four water levels (0, 20, 40 and 80% formulation water) were used with ground bovine semimembranosus muscle that had been frozen once. Ground muscle was mixed with either NaCl alone (0% formulation water) or NaCl and brine (20, 40 and 80% formulation water) for the 2, 4 and 8% NaCl treatments. Distilled water was used for the 0% NaCl treatment. The mixtures were stored at 5°C for 12 h. Following storage, the water/brine content was standardized, and protein solubility and water retention were measured. Elevating the water content of preblends, in which the salt concentration had been standardized, increased the water retained during centrifugation (P < 0·05). Although not statistically significant, a similar trend was observed for protein solubility. Four percent NaCl produced the greatest protein dissolution and water retention.     

真空冷冻干燥大蒜粉对Fenton氧化体系中牦牛肉肌原纤维蛋白乳化特性的影响

用牦牛肉分离肌原纤维蛋白（myofibrillar protein,MP）和牦牛肉脂肪,向牦牛肉MP中分别添加质量分数为0%、0.2%、0.5%和1.0%的真空冷冻干燥（vacuum freeze-dried,VFD）大蒜粉,并构建Fenton氧化体系,测定牦牛肉MP在4 ℃环境中氧化12 h后的活性巯基含量、蛋白质溶解性、表面疏水性以及牦牛肉MP乳液的界面吸附蛋白百分比、乳液黏度、乳化活性、乳液稳定性（澄清指数、积分透光率、沉降速率）和微观结构,研究VFD大蒜粉对氧化体系中牦牛肉MP乳化特性的影响。结果表明：高添加量的VFD大蒜粉（0.5%、1.0%）能显著增强Fenton氧化体系中牦牛肉MP的乳化活性、乳化稳定性和乳液中油相分布均匀性（P＜0.05）;其中,添加0.5% VFD大蒜粉对Fenton氧化体系中牦牛肉MP的保护效果较强,能使牦牛肉MP的活性巯基含量增加1.55 倍、蛋白质溶解性增加19%、表面疏水性降低25.41%;添加1.0% VFD大蒜粉对Fenton氧化体系中牦牛肉MP的乳化特性改善作用较强,能使牦牛肉MP乳液的黏度增加1.02 倍、乳化活性增加49.80%,澄清指数、积分透光率以及沉降速率分别降低17.06%、37.44%和50.79%。说明VFD大蒜粉能显著改善Fenton氧化体系中牦牛肉MP的乳化特性,但作用效果与添加量相关,当添加质量分数为1.0%的VFD大蒜粉时,其改善作用较强。     

Dose-response of the cultured bovine lens to butyl, methyl and propyl parabens

Pre-screening of cosmetic ingredients is vital for consumer safety. Previous in vivo techniques, such as the Draize test, have proved to be unreliable in predicting ocular irritancy and therefore there is a need for alternate testing methodologies. One such test is the scanning laser in vitro assay system which quantifies irritancy based on the focusing ability of the cultured bovine lens. In combination with confocal microscopy, a more thorough documentation of ocular irritancy can be achieved. This study investigates the response of cultured bovine lenses over time to butyl, methyl and propyl parabens, which are common antimicrobial agents found in cosmetic and ophthalmic products. The focusing ability of the lens was measured with an automated laser scanner over a period of 96 h. At 120 h post-treatment, the lenses were analysed by using a confocal laser scanning microscope to determine the characteristics of nuclei, and the morphology and distribution of mitochondria within the lenses. Irritancy to the three parabens was investigated at both an optical and cellular level. Each of the parabens was tested at 0.002% and 0.2%, where the 0.2% butyl paraben was found to be the most irritating.     

安石榴苷与焦磷酸钠对肌原纤维蛋白氧化稳定性及凝胶性能的影响

研究添加安石榴苷、焦磷酸钠（sodium pyrophosphate,SPP）及其组合（P＋SPP）对肌原纤维蛋白（myofibrillar protein,MP）氧化稳定性和凝胶性能的影响。结果表明,安石榴苷和SPP添加均能有效抑制氧化诱导的蛋白羰基含量上升及自由氨基含量下降,且P＋SPP组合添加效果最佳;但所有添加剂均无法有效抑制氧化诱导的巯基含量降低。添加安石榴苷促进了氧化诱导的蛋白结构展开、显著抑制了蛋白粒径增大（抑制率为10.50%）,对于蛋白溶解度和热诱导凝胶过程中的流变学特性无显著影响,但明显降低了氧化MP凝胶的蒸煮损失和质构劣变。SPP添加同样促进了蛋白结构展开、抑制了蛋白粒径增大（抑制率为17.65%）、提高了氧化MP的溶解度（提高了9.78%）,显著改变了热诱导凝胶过程中MP的流变学行为,致使热诱导凝胶的蒸煮损失降低了42.56%,但明显降低了凝胶强度等质构指标。P＋SPP对MP凝胶性能的影响整体与SPP单独添加类似。因此,本研究抗氧化剂使用显著提高了MP的氧化稳定性及凝胶持水性,但凝胶的质构特性与抗氧化剂的种类密切相关。     

藜麦蛋白对低钠盐体系中猪肉肌原纤维蛋白凝胶特性的影响

分别将3%、6%、9%和12%藜麦蛋白添加到低钠盐（0.40 mol/L NaCl、0.10 mol/L KCl和0.05 mol/L CaCl2）猪肉肌原纤维蛋白（myofibrillar protein,MP）体系中,考察藜麦蛋白添加量对复合蛋白溶液/凝胶的理化性质、蛋白二级结构、化学作用力和微观结构的影响。结果表明：藜麦蛋白的添加提高了MP的凝胶强度、保水性和动态流变特性,这是因为藜麦蛋白提高了复合蛋白溶液的蛋白溶解度和ζ-电位绝对值,降低了蛋白粒径;复合蛋白体系中的化学作用力以二硫键和疏水作用为主,但是藜麦蛋白的添加提高了离子键和氢键含量;藜麦蛋白促进了无规则卷曲向β-折叠和α-螺旋转化,增加了凝胶的稳定性;扫描电镜显示,藜麦蛋白提高了复合凝胶的致密程度。综上,藜麦蛋白作为一种优质植物蛋白,可以增强MP的凝胶特性,特别是当藜麦蛋白添加量为6%～9%时,对低钠盐体系中MP凝胶特性的改善效果较好。     

Effects of using plum puree on some properties of low fat beef patties

The purpose of this study was to determine the effects of using different amounts of plum puree (5%, 10% or 15%) on some properties of low fat beef patties. Plum puree (PP) was used as an extender in beef patties. Moisture content decreased with increasing concentration of plum puree. Increasing amounts of PP decreased beef patty pH. The highest cooking yield and moisture retention were found in 5% PP samples. Diameter reduction increased and thickness reduction decreased with increasing amounts of PP. The addition of PP to the formulation significantly affected the colour of samples. TBARS values of control samples were higher than in PP added samples at the end of the storage period. Higher PP concentrations in the formulations led to increased juiciness and texture scores. The results indicated that 5% or 10% plum puree can be used as an extender in low fat beef patties.     

对羟基苯甲酸甲酯对果蝇的毒性与雌激素作用

探讨对羟基苯甲酸甲酯(MP)对果蝇生长发育与生殖的影响。用含不同MP 浓度的培养基喂饲果蝇,统计并分析果蝇亲代与子代产卵量、发育周期、出蛹与羽化量及体重。结果表明,0.2%MP 对果蝇有明显的毒性作用,降低了产卵量、出蛹及羽化量和雄蝇体重,延长了发育周期,而低浓度MP 具有潜在的雌激素作用,0.02%MP可提高子代产卵量、出蛹及羽化量,缩短生长周期。     

Determination of Six Paraben Residues in Fresh-cut Vegetables Using QuEChERS with Multi-walled Carbon Nanotubes and High-Performance Liquid Chromatography–Tandem Mass Spectrometry

In this study, an optimized QuEChERS sample preparation method was developed to analyze residues of six parabens: methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, and isobutylparaben in five fresh-cut vegetables (potato, broccoli, carrot, celery, and cabbage) with high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). Homogenized samples were extracted using acetonitrile, and the extracts were cleaned with the novel sorbent multi-walled carbon nanotubes (MWCNTs). MWCNTs provided 84–94% removal of chlorophyll and lower matrix effects (MEs) compared to commonly used primary-secondary-amine (PSA) sorbent. Selected parabens were separated by HPLC with isocratic elution using acetonitrile and 0.1% (v/v) formic acid solution and determined by triple quadrupole MS/MS. The method validation results showed that recoveries were at 70–120% with RSDs <20%. Calibration curves showed linear responses of six parabens with R ² > 0.99. Fifty fresh-cut vegetable samples from different farmer markets in Beijing, China were collected to measure the paraben residues, and only one sample was tested positive with methylparaben concentration at 81 μg/kg.     

Effect of parity and stage of lactation on feed sorting behavior of lactating dairy cows

The objectives of this study were to determine if feed sorting differs between primiparous (PP) and multiparous (MP) cows, if sorting changes from the period of peak lactation to peak dry matter intake (DMI), and whether feed sorting affects efficiency of production. Data on DMI, milk production, feed sorting (particle size of offered and refused feed), and energy status (plasma nonesterified fatty acid, β-hydroxybutyrate, insulin and glucose concentration) were collected on 30 PP and 30 MP lactating Holstein dairy cows, individually housed and fed in tie-stalls, during 3 wk (wk 2, 6, and 10) over 10 wk of a lactation study. Cows averaged 53, 81, and 109 ± 10 d in milk (DIM) at the beginning of each of the 3 recording weeks. To determine sorting, feed samples were separated with a particle separator that had 3 screens (19, 8, and 1.18 mm) and a bottom pan, resulting in 4 fractions (long, medium, short, fine). Over the study period, MP cows consumed more DM and produced more milk than did the PP cows, but had similar efficiency of production (kg of milk/kg of DMI), and similar levels of plasma indicators of energy status. Across the study period, DMI increased, whereas milk yield decreased, resulting in decreased efficiency of milk production as cows moved further into lactation. All cows had higher nonesterified fatty acid and lower insulin concentrations in plasma at 53 DIM compared with at 81 and 109 DIM, suggesting they were mobilizing more body fat at that earlier stage of lactation. Across periods, all cows sorted against the longest ration particles, did not sort the medium ration particles, and sorted for fine ration particles; as a result, all cows consumed less neutral detergent fiber (NDF) and physically effective NDF (proportion of NDF retained on the 19- and 8-mm screens of the particle separator) than predicted. Greater selection against the longest ration particles was associated with greater efficiency of milk production; however, this sorting pattern also tended to be associated with lower milk fat percentage. The extent of the observed sorting against the longest, physically effective ration particles and for the finest ration particles was greater for PP cows than for MP cows across all 3 observation periods. Feed sorting remained consistent in cows across the DIM evaluated in this study and that this sorting behavior can affect the efficiency of milk production as well as milk fat percentage. Further, PP cows engage in more sorting of their ration than MP cows.     

滚揉腌制条件对猪肉加工特性的影响

研究了滚揉时间和食盐浓度,滚揉时间和焦磷酸盐（PP）浓度以及PP、三聚磷酸盐（TPP）、六偏磷酸盐（HMP）和滚揉时间对肉块腌制液吸收保留和蒸煮得率的影响。以猪里脊肉为研究材料,垂直于肌纤维方向切成2cm肉块和腌制液混合滚揉腌制,研究不同处理条件下,腌制液吸收百分比、腌制液吸收率、腌制液保留量、腌制液保留百分比及蒸煮得率的变化情况。试验结果表明,随着滚揉时间、食盐浓度和PP浓度增加,腌制液吸收百分比逐渐增加,分别达到了38．7％和38．2％,但腌制液吸收率在滚揉2h内是较大的,随着滚揉时间的延长逐渐减小。不同磷酸盐都提高了腌制液的吸收百分比和腌制液保留量,它们对腌制液吸收百分比和保留量的影响效益顺序是：PP〉TPP〉HMP。除了空白处理组外,随着滚揉时间、食盐浓度和PP浓度的增加,蒸煮得率逐渐增加,分别达到了94．6％和113．5％。不同磷酸盐都提高了滚揉腌制肉块的蒸煮得率,它们对蒸煮得率的影响效益顺序是PP〉TPP〉HMP。随着滚揉时间的延长,蒸煮得率分别达到了106．7％、102．5％、88．2％。