Reply to Sergent et al. Comment on "Balwierz et al. Potential Carcinogens in Makeup Cosmetics. Int. J. Environ. Res. Public Health 2023, 20, 4780".

Comments by Sergent et al. (2023) [...].

Reply to Chaudhuri et al. Comment on "Balwierz et al. Potential Carcinogens in Makeup Cosmetics. Int. J. Environ. Res. Public Health 2023, 20, 4780".

Comments by Chaudhuri et al. (2023) [...].

Natural Ingredients of Transdermal Drug Delivery Systems as Permeation Enhancers of Active Substances through the Stratum Corneum.

In recent years, significant progress has been made in transdermal drug delivery systems, but there is still a search for enhancers that can improve the absorption of active substances through the stratum corneum. Although permeation enhancers have been described in the scientific literature, the use of naturally occurring substances in this role is still of particular interest, because they can offer a high level of safety of use, with a low risk of skin irritation, and high efficiency. In addition, these ingredients are biodegradable, easily available, and widely accepted by consumers due to the growing trust in natural compounds. This article provides information on the role of naturally derived compounds in transdermal drug delivery systems that help them penetrate the skin. The work focuses on the components found in the stratum corneum such as sterols, ceramides, oleic acid, and urea. Penetration enhancers found in nature, mainly in plants, such as terpenes, polysaccharides, and fatty acids have also been described. The mechanism of action of permeation enhancers in the stratum corneum is discussed, and information on the methods of assessing their penetration efficiency is provided. Our review mainly covers original papers from 2017 to 2022, supplemented with review papers, and then older publications used to supplement or verify the data. The use of natural penetration enhancers has been shown to increase the transport of active ingredients through the stratum corneum and can compete with synthetic counterparts.

Bacterial cellulose: Biopolymer with novel medical applications.

Due to the growing importance of green chemistry, the search for alternatives to cellulose has begun, leading to the rediscovery of bacterial cellulose (BC). The material is produced by Gluconacetobacter and Acetobacter bacteria, mainly Komagataeibacter xylinus. It is a pure biopolymer, without lignin or hemicellulose, forming a three-dimensional mesh, showing much lower organization than its plant counterpart. Thanks to its design, it has proven itself in completely unprecedented applications - especially in the field of biomedical sciences. Coming in countless forms, it has found use in applications such as wound dressings, drug delivery systems, or tissue engineering. The review article focuses on discussing the main structural differences between plant and bacterial cellulose, methods of bacterial cellulose synthesis, and the latest trends in BC applications in biomedical sciences.

Nanoparticles coated by chloramphenicol in hydrogels as a useful tool to increase the antibiotic release and antibacterial activity in dermal drug delivery.

BACKGROUND: Nanocarriers for antibacterial drugs became hopeful tools against the increasing resistance of bacteria to antibiotics. This work focuses on a comprehensive study of the applicability and therapeutic suitability of dermal carbopol-based hydrogels containing chloramphenicol carried by various nanoparticles (AuNPs and SiNPs). METHODS: The different forms of carbopol-based drugs for dermal use were obtained. Five different concentrations of chloramphenicol and two types of nanoparticles (silica and gold) in carbopol-based ointments were tested. The influence of different carbopol formulations with nanocarriers on the rheological properties as well as the release profile of active substances and bacteriostatic activity on five reference strains were determined. RESULTS: The properties of the obtained hydrogels were compared to a commercial formulation, and finally it was possible to obtain a formulation that allowed improved antimicrobial activity over a commercially available detreomycin ointment while reducing the concentration of the antibiotic. CONCLUSION: The work indicates that it is possible to reduce the concentration of chloramphenicol by four times while maintaining its bacteriostatic activity, which can improve the patient's safety profile while increasing the effectiveness of the therapy.

Potential Carcinogens in Makeup Cosmetics.

Facial makeup cosmetics are commonly used products that are applied to the skin, and their ingredients come into contact with it for many years. Consequently, they should only contain substances that are considered safe or used within an allowable range of established concentrations. According to current European laws, all cosmetics approved for use should be entirely safe for their users, and the responsibility for this lies with manufacturers, distributors, and importers. However, the use of cosmetics can be associated with undesirable effects due to the presence of certain chemical substances. An analysis of 50 random facial makeup cosmetics commercially available on the European Union market and manufactured in six European countries was carried out, concerning the presence of substances with potential carcinogenic properties, as described in recent years in the literature. Nine types of facial makeup cosmetics were selected, and their compositions, as declared on the labels, were analyzed. The carcinogens were identified with information present in the European CosIng database and according to the Insecticide Resistance Action Committee's (IRAC) classification. As a result, the following potential carcinogens were identified: parabens (methylparaben, propylparaben, butylparaben, and ethylparaben), ethoxylated compounds (laureth-4, lautreth-7, or ethylene glycol polymers known as PEG), formaldehyde donors (imidazolidinyl urea, quaternium 15, and DMDM hydantoin), and ethanolamine and their derivatives (triethanolamine and diazolidinyl urea), as well as carbon and silica. In conclusion, all of the analyzed face makeup cosmetics contain potential carcinogenic substances. The literature review confirmed the suppositions regarding the potential carcinogenic effects of selected cosmetic ingredients. Therefore, it seems necessary to carry out studies on the long-term exposure of compounds present in cosmetics and perhaps introduce stricter standards and laws regulating the potential presence of carcinogens and their activity in cosmetics.

Role of calcium carbonate in the process of heavy metal biosorption from solutions: synergy of metal removal mechanisms.

The effect of calcium carbonate on the removal efficiency of cations of the selected heavy metals Cu, Zn and Pb from aqueous solutions using various biosorbents (BS) was investigated under laboratory static conditions. The main mechanism of biosorption of heavy metal cations is ion exchange, whereas the reaction with calcium carbonate results in precipitation of poorly soluble carbonates and hydroxides of the examined heavy metals. Studies conducted under static conditions have shown that the effect of Cu and Zn cations removal from solutions is better when using a mixture of BS and CaCO3 as compared to the effect of process, in which these two components were used separately. Removal efficiency for Cu and Zn has been shown to increase from 20 to 50% depending on the BS used. For the removal of lead cations, a measurable effect is found only for biosorbents whose active centers are saturated with protons (improvement in removal efficiency by about 20%). A synergy effect in the flow system was also investigated. It was found that under the conditions of the experiment, the addition of powdered CaCO3, in a weight ratio of 1 g CaCO3: 15 g BS, increases the removal efficiency of all the metals studied by 20-30%. It has been shown that an important role in the process of heterophasic ion exchange is played by neutralization of protons-desorbed from the biosorbents-with hydroxide ions released into the solution by partial dissolution of CaCO3 and subsequent hydrolysis reaction.

On the impact of side methyl groups on the structure and vibrational properties of ß-carotenoids. The case of butadiene and isoprene.

Theoretical consideration about the impact of methyl groups on the structure and vibrational properties of ß-carotenoids, using medium size molecules of trans-butadiene and trans-isoprene, are reported. Density functional theory (DFT) calculations with correlation-consistent and polarization-consistent basis sets were applied to trans-1,3-butadiene and trans-isoprene as the smallest building bricks of ß-carotenoids. Their structure and harmonic vibrations were estimated in the complete basis set limit (CBS) using the non-linear least square fit. Optimized geometries and harmonic frequencies, obtained with B3LYP and BLYP density functionals and large basis sets, were favorably reproduced by a significantly faster approach, using a recently modified STO(1M)-3G Slater-type basis set. Selected density functionals with STO(1M)-3G and 6-311++G** basis sets were also successful in predicting ß-carotene structures and harmonic vibrations. This work demonstrates the potential applicability of the proposed level of theory for larger molecules, including ß-carotenoids, present in numerous natural food sources. The proposed scheme of molecular modeling, applied to biologically active compounds in food, could provide a deeper insight into their function in vivo, which is directly related to their structure and spectroscopic properties. It could also support the experimental qualitative analysis, based on peak assignment of ß-carotenoids in various food sources.

Sequential Iron-Catalyzed C(sp2)-C(sp3) Cross-Coupling of Chlorobenzamides/Chemoselective Amide Reduction and Reductive Deuteration to Benzylic Alcohols.

Benzylic alcohols are among the most important intermediates in organic synthesis. Recently, the use of abundant metals has attracted significant attention due to the issues with the scarcity of platinum group metals. Herein, we report a sequential method for the synthesis of benzylic alcohols by a merger of iron catalyzed cross-coupling and highly chemoselective reduction of benzamides promoted by sodium dispersion in the presence of alcoholic donors. The method has been further extended to the synthesis of deuterated benzylic alcohols. The iron-catalyzed Kumada cross-coupling exploits the high stability of benzamide bonds, enabling challenging C(sp2)-C(sp3) cross-coupling with alkyl Grignard reagents that are prone to dimerization and ß-hydride elimination. The subsequent sodium dispersion promoted reduction of carboxamides proceeds with full chemoselectivity for the C-N bond cleavage of the carbinolamine intermediate. The method provides access to valuable benzylic alcohols, including deuterium-labelled benzylic alcohols, which are widely used as synthetic intermediates and pharmacokinetic probes in organic synthesis and medicinal chemistry. The combination of two benign metals by complementary reaction mechanisms enables to exploit underexplored avenues for organic synthesis.

Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts.

The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discussed. In addition, the thermal properties of E-NB copolymers such as the melting and crystallization behavior, like also the heterogeneity of composition described by successive the self-nucleation and annealing (SSA) and the dispersity index (DI) were determined.

2-(1,3-Oxazolin-2-yl)pyridine and 2,6-bis(1,3-oxazolin-2-yl) pyridine.

The data presented in this article are related to research articles "Titanium and vanadium catalysts with oxazoline ligands for ethylene-norbornene (co)polymerization (Ochedzan-Siodlak et al., 2018). For the title compounds, 2-(1,3-oxazolin-2-yl)pyridine (Py-ox) and 2,6-bis(1,3-oxazolin-2-yl)pyridine (Py-box), the single-crystal X-ray diffraction measurement together with NMR, GC, MS, DSC analysis, like also the method of crystallization are presented.

Pyrazole amino acids: hydrogen bonding directed conformations of 3-amino-1H-pyrazole-5-carboxylic acid residue.

A series of model compounds containing 3-amino-1H-pyrazole-5-carboxylic acid residue with N-terminal amide/urethane and C-terminal amide/hydrazide/ester groups were investigated by using NMR, Fourier transform infrared, and single-crystal X-ray diffraction methods, additionally supported by theoretical calculations. The studies demonstrate that the most preferred is the extended conformation with torsion angles ϕ and ψ close to ±180°. The studied 1H-pyrazole with N-terminal amide/urethane and C-terminal amide/hydrazide groups solely adopts this energetically favored conformation confirming rigidity of that structural motif. However, when the C-terminal ester group is present, the second conformation with torsion angles ϕ and ψ close to ±180° and 0°, respectively, is accessible. The conformational equilibrium is observed in NMR and Fourier transform infrared studies in solution in polar environment as well as in the crystal structures of other related compounds. The observed conformational preferences are clearly related to the presence of intramolecular interactions formed within the studied residue. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd.