Hexyl Salicylate Research Articles

Food additive salicylates inhibit human and rat placental 3β-hydroxysteroid dehydrogenase: 3D-QSAR and in silico analysis

The use of salicylates as flavoring agents in food and beverages is common, but their potential to disrupt the endocrine system remains unclear. Human placental 3β-hydroxysteroid dehydrogenase 1 (h3β-HSD1) plays a role in progesterone synthesis and is the potential target. This study evaluated the inhibition of 13 salicylates on h3β-HSD1, structure-activity relationship (SAR) and compared with rat placental homolog r3β-HSD4. Salicylates inhibited h3β-HSD1, depending on carbon chain number in the alcohol moiety and the IC50 values for hexyl, ethylhexyl, homomenthyl, and menthyl salicylates were 53.27, 15.78, 2.35, and 2.31 μM, as mixed inhibitors, respectively, while methyl to benzyl salicylates were ineffective at 100 μM. Interestingly, only hexyl salicylate inhibited r3β-HSD4 with IC50 of 31.05 μM. Bivariate analysis revealed a negative correlation between IC50 and hydrophobicity (LogP), molecular weight, heavy atoms, and carbon number in the alcohol moiety against h3β-HSD1. Docking analysis demonstrated that these salicylates bind to cofactor binding sites or between the steroid and cofactor binding sites. Additionally, 3D-QSAR showed distinct binding via hydrogen bond donors and hydrophobic regions. In conclusion, the inhibition of h3β-HSD1 by salicylates appears to be dependent on factors such as LogP, molecular weight, heavy atoms, and carbon-chain length and there is species-dependent inhibition sensitivity.

Eco-Friendly Fungal Chitosan-Silica Dual-Shell Microcapsules with Tailored Mechanical and Barrier Properties for Potential Consumer Product Applications.

Commercial perfume microcapsules are becoming popular across the globe to fulfill consumers' demands. However, most of microcapsules rely on synthetic polymers and/or animal-sourced ingredients to form the shells. Therefore, replacement of the shell materials is imperative to minimize environmental microplastic pollution, as well as to meeting peoples' needs, religious beliefs, and lifestyles. Herein, we report a methodology to fabricate environmentally benign dual-shell (fungal chitosan-SiO2) microcapsules laden with fragrance oil (hexyl salicylate). Anionically stabilized oil droplets were coated with fungal chitosan via interfacial electrostatic interactions at pH 2, which were then covered by an inorganic coating of SiO2 produced via external alkaline mineralization of sodium silicate. Core-shell microcapsules with a spherical morphology were achieved. Under compression, dual-shell chitosan-SiO2 microcapsules yielded a mean nominal rupture stress of 3.0 ± 0.2 MPa, which was significantly higher than that of single-shell microcapsules (1.7 ± 0.2 MPa). After 20 days in neutral pH water, only ∼2.5% of the oil was released from dual-shell microcapsules, while single-shell microcapsules cumulatively released more than 10%. These findings showed that the additional SiO2 coating significantly enhanced both mechanical and barrier properties of microcapsules, which may be appealing for multiple commercial applications, including cosmetics and detergents.

Environmentally friendly calcium carbonate-polydopamine microcapsules with superior mechanical, barrier, and adhesive properties

There is a rising need to deliver perfume molecules to fabric surfaces during washing cycles to enhance consumers' perception. With upcoming regulations phasing out intentionally produced microplastics by 2027, the focus is on sustainable alternatives to conventional non-biodegradable synthetic microcapsules (e.g. melamine-formaldehyde). Calcium carbonate (CaCO3) has shown promise to form the microcapsule shells due to its environmental benignity, inexpensiveness, and potential for liquid formulations, particularly detergents. Notwithstanding, its inherent porosity undermines the performance of the ensuing microcapsules. Bio-inspired by the adhesive properties of mussel proteins, dopamine is proposed for forming a protective organic coating on CaCO3-based microcapsules. This research aims towards developing primary microcapsules with CaCO3 shells encapsulating hexylsalicylate (HS) as a perfume oil, applying a polydopamine (PDA) coating via oxidative auto-polymerisation of dopamine-hydrochloride (pH 8.5), and conducting a comprehensive analysis of morphological, mechanical, barrier, and adhesive properties through advanced techniques, namely fluorescent-sensing/scanning electron microscopy (SEM), micromanipulation, UV–Vis spectrometry, and a microfluidic chamber fitted with polyethylene-terephthalate (PET) fabrics. The obtained microcapsules (D[3, 2]=31.2 ± 0.4 μm) exhibited a spherical core-shell structure with a smooth PDA-coated surface. Mechanical assessments reveal remarkable rupture stress (2.2 ± 0.3 MPa) comparable to that of commercial microcapsules. After one month in water, ∼40% of HS was released from PDA-coated microcapsules, while the primary ones released the entire amount within 4 h. When mimicking washing conditions (pH 9), the PDA-coated microcapsules demonstrated improved retention (∼60%) on the PET substrate at hydrodynamic shear stress of ∼1 Pa, whereas that of the primary microcapsules was below 10%. Overall, this study suggests the successful fabrication of eco-friendly microcapsules featuring a hybrid inorganic-organic shell, with enhanced mechanical strength, reduced leakage, and improved adhesion, showcasing their potential in applications within the fast-moving consumer goods industry.

Relationship between the Young's Moduli of Whole Microcapsules and Their Shell Material Established by Micromanipulation Measurements Based on Diametric Compression between Two Parallel Surfaces and Numerical Modelling.

Micromanipulation is a powerful technique to measure the mechanical properties of microparticles including microcapsules. For microparticles with a homogenous structure, their apparent Young's modulus can be determined from the force versus displacement data fitted by the classical Hertz model. Microcapsules can consist of a liquid core surrounded by a solid shell. Two Young's modulus values can be defined, i.e., the one is that determined using the Hertz model and another is the intrinsic Young's modulus of the shell material, which can be calculated from finite element analysis (FEA). In this study, the two Young's modulus values of microplastic-free plant-based microcapsules with a core of perfume oil (hexyl salicylate) were calculated using the aforementioned approaches. The apparent Young's modulus value of the whole microcapsules determined by the classical Hertz model was found to be EA = 0.095 ± 0.014 GPa by treating each individual microcapsule as a homogeneous solid spherical particle. The previously obtained simulation results from FEA were utilised to fit the micromanipulation data of individual core-shell microcapsules, enabling to determine their unique shell thickness to radius ratio (h/r)FEA = 0.132 ± 0.009 and the intrinsic Young's modulus of their shell (EFEA = 1.02 ± 0.13 GPa). Moreover, a novel theoretical relationship between the two Young's modulus values has been derived. It is found that the ratio of the two Young's module values (EA/EFEA) is only a function on the ratio of the shell thickness to radius (h/r) of the individual microcapsule, which can be fitted by a third-degree polynomial function of h/r. Such relationship has proven applicable to a broad spectrum of microcapsules (i.e., non-synthetic, synthetic, and double coated shells) regardless of their shell chemistry.

Highly selective water-compatible molecularly imprinted polymers for benzophenone-4

Molecularly imprinting technology was applied for preparing selective sorbents for benzophenone-4 (BP4), an organic UV filter used in sunscreens and cosmetics. Several imprinted polymers were prepared by bulk polymerization, using BP4 as template. Combination of stability (mechanical and chemical), selectivity and robustness of the imprinted polymers with BP4 properties resulted in a successful imprinting process (imprinting factors in range 1.05?2.60). The prepared polymers were characterised by infrared spectroscopy, elemental analysis, conductometric titrations and nitrogen physisorption at 77 K. Adsorption capacities and selectivity towards 7 other organic UV filters (benzophenone-3, benzophenone-8, homosalate, butyl methoxydibenzoylmethane, ethyl hexyl salicylate, ethyl hexyl p-dimethylamino benzoate and ethyl hexyl p-methoxycinnamate) were determined, proving high adsorption capacity and high selectivity for BP4 binding. The highest adsorption capacity was observed for 4-vinylpyridine/ethylene glycol dimethacrylate co-polymer prepared in dimethyl sulfoxide (1.108 mmol g-1). The imprinted polymer with the highest binding capacity was applied to solid phase extraction of BP4 from aqueous solutions with 98.5 % efficiency.

In Vitro and In Vivo Human Body Odor Analysis Method Using GO:PANI/ZNRs/ZIF−8 Adsorbent Followed by GC/MS

Among various volatile organic compounds (VOCs) emitted from human skin, trans-2-nonenal, benzothiazole, hexyl salicylate, α-hexyl cinnamaldehyde, and isopropyl palmitate are key indicators associated with the degrees of aging. In our study, extraction and determination methods of human body odor are newly developed using headspace-in needle microextraction (HS-INME). The adsorbent was synthesized with graphene oxide:polyaniline/zinc nanorods/zeolitic imidazolate framework-8 (GO:PANI/ZNRs/ZIF−8). Then, a wire coated with the adsorbent was placed into the adsorption kit to be directly exposed to human skin as in vivo sampling and inserted into the needle so that it was able to be desorbed at the GC injector. The adsorption kit was made in-house with a 3D printer. For the in vitro method, the wire coated with the adsorbent was inserted into the needle and exposed to the headspace of the vial. When a cotton T-shirt containing body odor was transferred to a vial, the headspace of the vial was saturated with body odor VOCs. After volatile organic compounds were adsorbed in the dynamic mode, the needle was transferred to the injector for analysis of the volatile organic compounds by gas chromatography/mass spectrometry (GC/MS). The conditions of adsorbent fabrication and extraction for body odor compounds were optimized by response surface methodology (RSM). In conclusion, it was able to synthesize GO:PANI/ZNRs/ZIF−8 at the optimal condition and applicable to both in vivo and in vitro methods for body odor VOCs analysis.

734 Development of multicellular organoids for skin injury and disease modeling

Modeling a skin complex layered structure provided tissue-specific functionality is one of the actual challenges in Regenerative Medicine. In this study, we have utilized novel skin organoids (SO) containing the key skin cell types as a tool for in vitro disease modeling and chemical skin irritation testing in immersive conditions. Key human skin cells were induced to form SO and further were exposed to UVB, retinol, 1% Triton solution, Isopropanol, Hexyl Salicylate, 5%KOH on d7. Melanoma cells were added on days 0 and 7 for melanoma modeling.

Fragrance oil microcapsules with low content of formaldehyde: Preparation and characterization

To reduce the residual formaldehyde content in melamine-formaldehyde (MF) microcapsules, glutaraldehyde was introduced to replace a portion of formaldehyde to prepare melamine-glutaraldehyde-formaldehyde (MGF) fragrance oil microcapsules via in-situ polymerization. MGF-lily oil microcapsules were obtained when the concentration of aldehyde groups provided by glutaraldehyde in the total aldehyde groups Cga∕Ca≤ 33.3 mol%. When Cga∕Ca≤ 9.5 mol%, the addition of glutaraldehyde reduced the residual formaldehyde content (235.05 ± 13.14 ppm to 21.79 ± 6.82 ppm) effectively without sacrificing the mechanical properties of microcapsules; it also improved the elasticity of microcapsules, in which Young’s modulus of MF shell was approximately 1.5 times to that of MGF shell. The approach was extended to encapsulate 2-hydroxy-3-(octanoyloxy)propyl decanoate (ODO), hexyl salicylate and lavender oil. All three fragrance oils were encapsulated successfully with low content of formaldehyde; however, the mechanical properties varied due to the difference on the hydrophobicity and viscosity of fragrance oil. This work provided an efficient and universal formaldehyde reduction method to encapsulate hydrophobic fragrance oil, which can not only reduce formaldehyde content but also maintain the mechanical properties and improve the elasticity of microcapsules, which has a potential application in consumer-friendly additives.

Fragrance materials (FMs) affect the larval development of the copepod Acartia tonsa: An emerging issue for marine ecosystems

Fragrance materials (FMs) are used in a variety of detergents and cosmetics, including household and personal care products. Despite their widespread use and the growing evidence of their occurrence in surface waters worldwide, very little is known about their toxicity towards marine species, including a key component of the marine food webs such as copepods. Thus, we investigated the toxicity of six of the more long-lasting and stable commercial fragrances, including Amyl Salicylate (AMY), Oranger Crystals (ORA), Hexyl Salicylate (HEX), Ambrofix (AMB), Peonile (PEO), and Benzyl Salicylate (BZS), to assess their ability to impair the larval development of the calanoid copepod Acartia tonsa. FMs inhibited the development of A. tonsa significantly at concentrations by far lower than the effect-concentrations reported in the literature for aquatic species. The more toxic FMs were HEX (EC50 = 57 ng L−1), AMY (EC50 = 131 ng L−1) and ORA (EC50 = 766 ng L−1), while the other three compounds exerted toxic effects at concentrations higher than 1000 ng L−1 (LOEC at 1000 ng L−1 for PEO and BZS, and at 10,000 ng L−1 for AMB). Early life-stage mortality was unaffected by FMs at all the tested concentrations. A comparison with water concentrations of FMs reported in the literature confirmed that FMs, especially HEX and AMY, may act as contaminants of potential concern in many aquatic habitats, including urban areas and remote and polar environments.

Human Induced Pluripotent Stem Cell-Based Skin for Assessing Transdermal Drug Permeability and Irritancy.

To establish a system for assessing drug permeation and irritation of the skin, the permeation of benzoic acid and isosorbide dinitrate, which are listed in the Pharmacopoeia, and the chemical irritation were evaluated using skin generated from human induced pluripotent stem cells (iPSCs). Multilayer structures and cellular markers (keratin 14 and 10, which are in basal and suprabasal epidermal layers) were clearly detected in our iPSC-based skin. Transepidermal water loss (TEWL) decreased after iPSC-derived keratinocytes were cultured on collagen gels from human primary fibroblasts. These results indicate that the barrier function was partly increased by formation of the living epidermis. The cumulative amount of benzoic acid and isosorbide dinitrate across human iPSC-based skin gradually increased after an initial lag time. Moreover, the irritancy of various chemicals (non-irritants: ultrapure water, allyl phenoxy-acetate, isopropanol, and hexyl salicylate and irritants: 5% sodium dodecyl sulfate (SDS), heptanal, potassium hydroxide (5% aq.) and cyclamen aldehyde) to iPSC-based skin was almost met the irritation criteria of the Organisation for Economic Co-operation and Development (OECD) guideline. The results of our iPSC-based skin evaluation provide useful basic information for developing an assessment system to predict the permeation and safety of new transdermal drugs in human skin.

Synthesis of melamine-formaldehyde microcapsules containing oil-based fragrances via intermediate polyacrylate bridging layers

Abstract A general and versatile strategy to prepare melamine-formaldehyde (MF) microcapsules encapsulating oil-based fragrances by combining solvent evaporation and in situ polymerization was proposed in this work. The oil-based fragrance was pre-encapsulated by an inner polyacrylate membrane via solvent evaporation, followed by in situ polymerization of MF precondensates as an outer shell. The polyacrylate membrane is used as an intermediate bridging layer to stabilize the oil-based fragrance, and to provide driving forces for in situ polymerization of MF precondensates through electrostatic attractions between carboxyl groups and ammonium ions. It was demonstrated that MF microcapsules containing clove oil were prepared successfully. The amount and the composition of the intermediate polyacrylate bridging layer were critical. Smooth and sphere-shaped MF-clove oil microcapsules were prepared when the weight ratio of polyacrylate to clove oil was over 60 wt% and the concentration of acrylic acid (AA) increased to 10 wt% in polyacrylate. In addition, MF microcapsules containing sunflower oil and hexyl salicylate were prepared by using this method. The work suggests that this new approach can be potentially used to encapsulate various core materials, tuning the shell properties of microcapsules such as thickness, mechanical strength and release properties.

Fragrances in the seawater of Terra Nova Bay, Antarctica

Personal Care Products are emerging pollutants whose distribution in the Antarctic and remote environments is still largely unknown. Among PCPs, long-lasting and stable Fragrance Materials were selected to perform a first pilot study on their occurrence in the coastal surface seawater of Terra Nova Bay in the Ross Sea, Antarctica. Ambrofix, Amyl Salicylate, Benzyl Salicylate, Hexyl Salicylate, Lemonile and Okoumal were detected for the first time in Antarctic natural seawater, and reached total concentrations up to 100ngL−1. Treated discharges from the Italian research station Mario Zucchelli (MZS) contain FMs, however concentrations in nearby Tethys Bay increase during the seasonal melt of the sea ice and its snow cover: variability in emissions and distribution, as well as a contribution from atmospheric (long or short-range) transport were hypothesized.

Development of a versatile laboratory experiment to teach the metabolic transformation of hydrolysis

In this paper we describe an easy, reliable, versatile and inexpensive laboratory experiment to teach the metabolic transformation of hydrolysis to Pharmacy students. The experiment does not require the sacrifice of any experimental animal, or any work with organs or tissues, and so can be implemented in a typical university chemistry laboratory. We used acetylsalicylic acid (ASA), hexyl salicylate (HS) and two enzymes, a lipase and an esterase. Since both ASS and HS liberate salicylic acid (SA) upon hydrolysis, students can evaluate the different enzymatic transformations by monitoring the amount of SA liberated. The learning outcomes are an enhanced student understanding of: (1) the process of hydrolysis; (2) the application of enzymatic transformations of molecules from food to xenobiotics; (3) the differences between the general specificity of substrate of both enzymes; (4) the concepts of the lipophilic pocket; (5) the catalytic triad and its regioselectivity in relation to the ester bond. A questionnaire was administered to participating students at three points in time: at the beginning of the module, after enzymatic hydrolysis was taught in class, and after the laboratory experiment. From an analysis of the questionnaire data we conclude that this practical helped Pharmacy students to understand these concepts.

Fragrances as new contaminants in the Venice lagoon

Fragrance Materials (FMs) are omnipresent components of household and Personal Care Products (PCPs). In spite of their widespread use, little is known about their environmental occurrence. We selected 17 among the longest-lasting and most stable fragrance ingredients that are commercially available, namely: Amberketal, Ambrofix, Amyl Salicylate, Benzyl Salicylate, Bourgeonal, Dupical, Hexyl Salicylate, Isobutavan, Lemonile, Mefranal, Myraldene, Okoumal, Oranger Crystals, Pelargene, Peonile, Tridecene-2-Nitrile, Ultravanil. A new analytical method was developed to quantify FMs in water samples and it was applied to perform the first study about the distribution of these compounds in the surface waters of the city of Venice and its lagoon. Total FMs concentrations range from about 30ngL−1 to more than 10μgL−1 in polluted canals during the low tide. Sewage discharges were supposed to be the main sources of the selected FMs in the environment. Salicylates, oestrogenic and allergenic compounds, were in general the most abundant and widespread components. This study reports for the first time the detection of most of the selected FMs in surface waters and represent the first step to understand their environmental fate.

Enhancing plant resistance at the seed stage: low concentrations of methyl jasmonate reduce the performance of the leaf miner Tuta absoluta but do not alter the behavior of its predator Chrysoperla externa.

Plants express inducible direct and indirect defenses in response to herbivory. The plant hormone jasmonic acid (JA) and related signaling compounds referred to as jasmonates play a central role in regulating defense responses to a wide range of herbivores.We assessed whether treating tomato seeds with 0.8mM of methyl jasmonate (MeJA) affected the performance of the leaf miner Tuta absoluta, and whether possible changes in volatile profiles altered the behavior of its predator Chrysoperla externa. MeJA-treatment significantly lengthened larval development and decreased the pupal weight of T. absoluta. Herbivory alone increased the emissions of α-pinene, 6-methyl 5-hepten-2-one, β-myrcene, (E)-β-ocimene, isoterpinolene, TMTT, (Z)-3-hexenyl butyrate, and hexyl salicylate. MeJA seed treatment significantly decreased the emissions of α-cubebene from undamaged and herbivore-infested plants. In addition, the emissions of several compounds were lower in the absence of herbivory. Chrysoperla. externa preferred odors from herbivore-infested plants over those from control plants, regardless of the MeJA-treatment, and they did not show any preference for herbivore-infested plants for any of the MeJA-treatments. Our results show preliminary evidence that the treatment of tomato seeds with MeJA can reduce the performance of Tuta absoluta, and that the chemical differences observed in plant VOC profiles do not alter the behavior of the model predator.

Determination of the shell permeability of microcapsules with a core of oil-based active ingredient

An experimental and theoretical methodology is proposed to calculate the permeability of microcapsules that contain a core of oil-based active ingredient. Theoretical analysis is performed considering the polydispersity of the measurable capsule size, which allows the estimation of the permeability polydispersity via three different methods. The models proposed were applied in order to determine the permeability of melamine-formaldehyde microcapsules with hexyl salicylate as core oil. Release experiments were performed with four different co-solvents (ethanol, propan-1-ol, propan-2-ol and 1,3-butanediol) of different concentration. Permeability values were found to be constant, despite a two order magnitude of difference in the solubility concentrations.

Determination of the elastic properties of single microcapsules using micromanipulation and finite element modeling

Finite element modeling (FEM) has been used to simulate the compression of single elastic core–shell capsules between two parallel plates. FEM allows characterizing the compressions at deformations beyond the wall thickness, when both bending and stretching contribute to the force resisting compression. Due to the incorporation of bending effects, the force deformation profiles of capsules with the same elastic modulus E depend on the wall thickness to capsule radius ratio ( h/r). A model is presented that enables the (i) calculation of h/r from the individual compression force profiles at fractional deformations lower than 0.1, thus applicable for brittle capsules and for elastic–plastic capsules and (ii) calculation of Eh by comparison with FEM data at that h/r. Thus, the model allows the determination of E from compression data alone, as the wall thickness is also determined. The compression of melamine–formaldehyde capsules with a hexyl salicylate core using a micromanipulation technique is given as an example of the application of the model. The estimated wall thickness value, found to be independent of the capsule size, is in excellent agreement with transmission electron microscopy measurements.

Effective and efficient photoluminescence of salicylate-ligating terbium(iii) clusters stabilized by multiple phenyl–phenyl interactions

A luminescent nonanuclear terbium(III) hydroxo cluster, Tb(9)(Hesa)(16)(mu-OH)(10)(NO(3)) (Hesa: hexyl salicylate), stabilized by unique two-way phenyl ring interactions, pi-pi stackings (d = 3.482-3.599 A) and C-H-pi interactions (d = 2.75-3.03 A) between adjacent pairs of salicylates, was structurally characterized based on X-ray analysis, and the favourable absorption change and efficient photoluminescent characteristic were rationalized as being due to J-type pi-pi stackings, which are dramatically enhanced by hexyl groups in hexyl salicylate ligands.