Search Results (268)

This study investigates how phospholipid headgroups influence passive membrane penetration and structural impact of four nitrogen-, sulfur-, and oxygen-containing heterocycles (NSO-HETs)—N-methyl-2-pyrrolidone (PIR), 1,4-dioxane (DIOX), oxane (OXA), and phenol (PHE). Using all-atom molecular dynamics simulations combined with Accelerated Weight Histogram free energy calculations, the passive transport of NSO-HETs across DPPC, DPPE, DPPA, and DPPG bilayers was characterized. DPPG showed the highest membrane affinity, increasing permeability (logP_memb/bulk) by 27–64% compared to DPPE, associated with the lowest permeability and tightest lipid packing. Free energy barriers are also decreased in DPPG relative to DPPE; PIR’s central barrier dropped from 19.2 kJ/mol (DPPE) to 16.6 kJ/mol (DPPG), while DIOX’s barrier decreased from 7.2 to 5.2 kJ/mol. OXA exhibited the lowest central barriers (1.2–2.2 kJ/mol) and uniquely accumulated at higher concentrations in the bilayer center than in bulk water, with free energy ranging from −3.4 to −5.9 kJ/mol. PHE and OXA caused significant bilayer thinning (up to 11%) and reduced lipid tail order, especially in DPPE and DPPA. Concentration effects were most pronounced in DPPE, where high solute loading disrupted lipid order and altered free energy profiles. These results highlight the crucial role of headgroup identity in modulating NSO-HET membrane permeability and structural changes. Full article

In this work, we described the synthesis of 4-(methoxycarbonyl)phenyl 5-bromofuran-2-carboxylate by reacting 5-bromofuroic acid with methylparaben in the incorporation of DCC/DMAP (Steglich esterification) as coupling agents. Later on, we subsequently synthesized a series of 4-(methoxycarbonyl)phenyl 5-aryl furan-2-carboxylates (5a–5e) through Suzuki coupling catalyzed by palladium (0) between 4-(methoxycarbonyl)phenyl 5-bromofuran-2-carboxylate (3) with several substituted arylated and heteroaryl boronic acids (4). DFT calculations were computed to elucidate electronic structural features of synthesized molecules (5a–5e) and to validate these findings by correlating with theoretical and experimental spectroscopic analysis. Furthermore, geometrical optimization, thermodynamic features, as FMO orbitals, MESP maps, NLO behavior and reactivity descriptors, were also determined from the PBE0 D3BJ/def2-TZVP/SMD_1,4-dioxane theory level to confirm the structural features of synthesized molecules. Full article

Series of pyrene-labeled diols (Py₂-DOs) and polyols (Py-POs) were synthesized by coupling a number (n_PyBA) of 1-pyrenebutyric acids to diols and polyols to yield series of end-labeled linear (n_PyBA = 2) and branched (n_PyBA > 2) oligomers, respectively. Pyrene excimer formation (PEF) between an excited and a ground-state pyrene was studied for the Py₂-DO and Py-PO samples by analyzing their fluorescence spectra and decays in tetrahydrofuran, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide. Global model-free analysis (MFA) of the pyrene monomer and excimer fluorescence decays yielded the average rate constant (<k>) for PEF. After the calculation of the local pyrene concentration ([Py]_loc) for the Py₂-DO and Py-PO samples, the <k>-vs.-[Py]_loc plots were linear in each solvent, with larger and smaller slopes for the Py₂-DO and Py-PO samples, respectively, resulting in a clear kink in the middle of the plot. The difference in slope was attributed to a bias for PEF between pyrenes close to one another on the densely branched Py-PO constructs resulting in lower apparent [Py]_loc and <k> values. This study illustrated the ability of PEF to probe how steric hindrance along a main chain affects the dynamic encounters between substituents in multifunctional oligomers such as diols and polyols. Full article

Understanding the reactivity and the crystallinity of energetic materials in a solvent is significantly important for their synthesis, purification, and recrystallization. Here, the recrystallization of TNBFI (2,4,7,9-tetranitro-10H-benzofuro[3,2-b]indole), a primary explosive with good thermal stability, in different solvents was studied. Four TNBFI solvates, including TNBFI·AC (AC = acetone), TNBFI·2DMSO (DMSO = dimethyl sulfoxide), TNBFI·4DIO (DIO = 1,4-dioxane), and TNBFI·ACN (ACN = acetonitrile), were obtained. The crystal structures of the solvates were determined by single-crystal X-ray diffraction (SCXRD). The molecular packing and intermolecular interactions in the solvate structures were investigated, and their energetic properties were predicted. Among them, TNBFI·ACN showed good detonation performance with a detonation velocity of 6228 m·s⁻¹ and detonation pressure of 16.23 GPa, which was comparable to TNT and with a potential application in both ammunition and industry. These results will be helpful in the synthesis and purification of TNBFI and valuable for the design of the solvate structure for other energetic materials. Full article

Alkaline treatment is well suited for extracting high-molecular-weight hemicelluloses, specifically hardwoods xylans, which, due to their polymer structure and chemical characteristics, enable the production of films with desirable mechanical, barrier, and optical properties for packaging applications. Despite its relevance, the optimization of antisolvent addition has received little attention in the literature. This study explores the use of eucalyptus industrial residue as feedstock, utilizing a statistical design to determine the optimal extraction conditions for hemicelluloses while minimizing the lignin content in the recovered liquor. The process uses alkali loads that are compatible with those in conventional Kraft pulp mills. Optimal extraction conditions involve a temperature of 105 °C, 16.7% NaOH charge, and 45 min at maximum temperature. The resulting liquor was subjected to ethanol precipitation under varying pH conditions (initial pH, 9, 7, 5, and 2) and different ethanol-to-liquor ratios (1:1 to 4:1). The acidification was performed using hydrochloric, sulfuric, and acetic acids. Ethanol served as the main antisolvent, while isopropyl alcohol and dioxane were tested for comparison. Results show that 2.3 ± 0.2% of xylans (based on oven-dry biomass) could be extracted, minimizing lignin content in the liquor. This value corresponds to the extraction of 15.6% of the xylans present in the raw material. The highest xylan precipitation yield (78%) was obtained at pH 7, using hydrochloric acid for pH adjustment and an ethanol-to-liquor ratio of 1:1. These findings provide valuable insight into optimizing hemicellulose recovery through antisolvent precipitation, contributing to more efficient biomass valorization strategies within lignocellulosic biorefineries. Full article

Advanced oxidation processes (AOPs) show significant promise to degrade recalcitrant water contaminants, such as 1,4-dioxane, but slow degradation kinetics limit the energy efficiency of this technology. We realized substantial enhancements in the degradation of 1,4-dioxane (a suspected carcinogen) using gold-coated titanium dioxide (Au/TiO₂) Janus nanoparticles (JNPs) irradiated with above-bandgap ultraviolet (UV) light (peak wavelength, 254 nm). To explain this result, we combined experimental measurements quantifying 1,4-dioxane degradation at varying UV wavelengths with finite-element simulations that provided explanatory insight into the light–matter interactions at play. The enhanced photocatalytic activity at the optimal condition (254 nm light, high intensity, Au/TiO₂) resulted from a larger quantity of photogenerated holes in the TiO₂ capable of reacting with water to form hydroxyl radicals that degrade 1,4-dioxane. This increased production of holes resulted from two sources: (1) more viable electron–hole pairs were created under 254 nm light owing to increased light absorption by the TiO₂ that was localized near the surface; (2) the metal sequestered photogenerated electrons from the TiO₂, which prevented electron–hole pairs from recombining, leaving more holes available to react with water. Our results motivate the exploration of different metal coatings (especially non-precious metals) and suggest a path toward broader implementation of TiO₂-based photocatalytic AOPs, which can effectively remove many water pollutants that survive conventional treatment techniques. Full article

The metabolic cycle of L-proline plays a crucial role in cancer cell survival, proliferation, and metastasis. A key intermediate in the biosynthesis and degradation of proline is 3,4-dihydro-2H-pyrrole-2-carboxylic acid. A direct route for synthesizing substituted derivatives of this acid involves the cyclization of 2-amino-5-oxonitriles. Michael additions of [(diphenylmethylene)amino]acetonitrile to enones in a basic medium—either with aqueous sodium hydroxide or under solid–liquid phase-transfer catalysis conditions using CaO as a base—enable the synthesis of substituted 2-amino-5-oxonitriles as single diastereoisomers or as diastereoisomeric mixtures. Selective removal of the diphenylmethylene-protecting group, followed by in situ cyclization in acidic conditions, yields trans- and cis-3,5-diaryl-3,4-dihydro-2H-pyrrole-2-carbonitriles. The reaction of nitriles with HCl/dioxane/methanol followed by treatment with water produces esters and amides as by-products. In vitro screening of the synthesized compounds against multiple human cancer cell lines revealed that some compounds exhibit a good or high selectivity index. In conclusion, the synthetic schemes presented offer simple and efficient routes for the preparation of the derivatives of substituted 3,4-dihydro-2H-pyrrole-2-carboxylic acids, with some compounds exhibiting promising antiproliferative activity. Full article

Although polyethylene glycol (PEG)-based surfactants are widely used in various industries due to their wide range of hydrophile–lipophile balance (HLB) values, their possible by-product, 1,4-dioxane, has been listed as a reasonably anticipated human carcinogen, which may limit their applications in fields closely related to the human body. Polyglycerol fatty acid esters (PGFEs), a class of surfactants based on polyglycerol (another polyether), also have a wide range of HLB values that can be adjust by varying the degree of polymerization of the polyglycerol, the length of the fatty acid carbon chain, or the degree of esterification, but do not have the risks caused by 1,4-dioxane. In addition, all the raw materials (glycerol and fatty acids) required for the preparation of PGFEs can be obtained via hydrolysis of renewable vegetable oils. Therefore, PGFEs, as new eco-friendly and biodegradable non-ionic surfactants, have been proposed as potential green alternatives to PEG-based non-ionic surfactants. This review summarizes the properties of PGFEs specifically including their HLB, surface properties, phase behaviors, stabilizing effect on foams and emulsions, and stability, and highlights their potential applications in food, cosmetics, and pharmaceuticals observed in the last decade. Full article

Self-assembly of amphiphilic molecules is an important phenomenon attracting a broad range of research. In this work, we study the self-assembly of KTOF₄ sphere–rod amphiphilic molecules in mixed water–dioxane solvents. The molecules are of a T-shaped geometry, comprised of a hydrophilic spherical Keggin-type cluster attached by a flexible bridge to the center of a hydrophobic rod-like oligodialkylfluorene (OF), which consists of four OF units. Transmission electron microscopy (TEM) uncovers self-assembled spherical structures of KTOF₄ in dilute solutions. These spheres are filled with smectic-like layers of KTOF₄ separated by layers of the solution. There are two types of layer packings: (i) concentric spheres and (ii) flat layers. The concentric spheres form when the dioxane volume fraction in the solution is 35–50 vol%. The flat layers are formed when the dioxane volume fraction is either below (20 and 30 vol%.) or above (55 and 60 vol%.) the indicated range. The layered structures show no in-plane orientational order and thus resemble thermotropic smectic A liquid crystals and their lyotropic analogs. The layered packings reveal edge and screw dislocations. Evaporation of the solvent produces a bulk birefringent liquid crystal phase with textures resembling the ones of uniaxial nematic liquid crystals. These findings demonstrate that sphere–rod molecules produce a variety of self-assembled structures that are controlled by the solvent properties. Full article

The reaction of thorium nitrate hydrate with 2,6-dipicolinoylbis(N,N-diethylthiourea), H₂L^pic, results in the hydrolysis of the organic ligand and the formation of [Th(2,6-dipicolinolate)₂(H₂O)₄] (1). Hydrolysis can be avoided by the use of [ThCl₄(DME)₂] (DME = 1,2-dimethoxyethane) as the starting material and the exclusion of water. The product, [Th(L^pic)₃]²⁻ (2), crystallizes as diammonium salt in form of yellow crystals in moderate yields. The thorium ion in the complex is nine-coordinate by the central O,N,O donor atoms of three deprotonated {L^pic}²⁻ ligands. The sulfur atoms of the ligands do not bind to the actinide ion, but establish hydrogen bonds to the ammonium counter ions. A similar coordination sphere is also observed in the uranium(IV) complex [UAu₂(L^pic)₃}] (3), which was obtained from a reaction between H₂L^pic, [U₂I₆(1,4-dioxane)₃] and [AuCl(tht)] (tht = tetrahydrothiophene) in the presence of triethylamine. Charge compensation is established by the linear coordination of two Au⁺ ions between each two sulfur atoms of the ligands. The products have been studied by X-ray diffraction and IR spectroscopy. The actinide ions in both {L^pic}²⁻ complexes have coordination number nine, but establish slightly different coordination spheres. Full article

There is a strong global demand for sulfate-free personal cleansing products. The objective of sulfate-free personal cleansing technology should not be aimed solely at the absence of “sulfate” wording in the list of ingredients, but on the true benefits both in personal use and in environmental effects. These include but are not limited to safety, mildness, and sensory effect for the individual and renewability, low carbon footprint, low water footprint, biodegradability, and sustainability for the environment. In addition, some surfactants or their precursors contain 1,4-dioxane as a by-product of their manufacturing, which is a major safety concern. This paper will deal with sulfate-free cleansing in two parts. Part I will examine the issues surrounding sulfates. Part II will show the benefits of amino acid-based surfactants for cleansing products, and specifically show why glutamates and alaninates are the best choices for safer and more efficacious cleansing. Several metrics will be included to support these conclusions. Full article

In a search for dyes photoactivatable with visible light, fluorenes with substituents at positions 2 and 7 were prepared, and their absorption and emission spectra were studied. In particular, the synthesis route to 9-diazofluorenes with 2-(N,N-dialkylamino) and N-modified 7-(4-pyridyl) substituents was established. These compounds are initially non-fluorescent, undergo photolysis with UV or blue light, and—in non-polar media—provide orange- to red-emitting products with a large separation between absorption and emission bands. Irradiation of non-fluorescent 9-diazoderivative 20 in dioxane with the light of 365 nm or 470 nm was accompanied by strong fluorescence gain (10 to 20 times), orange–red emission, and a large Stokes shift of photoproducts, which structurally relate to fluorescent betaine 13 (model compound without diazo group). Photolysis of 20 in protic solvents (ROH = MeOH, H₂O) provided clean transformation to C⁹-OR derivatives, though the emission gain in protic solvents was low. Full article

A new composite material with enhanced sorption-selective properties for uranium recovery from liquid media has been obtained. Sorbents were synthesized through a polycondensation reaction of a mixture of 4-amino-N’-hydroxy-1,2,5-oxadiazole-3-carboximidamide (hereinafter referred to as amidoxime) and SiO₂ in an environment of organic solvents (acetic acid, dioxane) and highly porous SiO₂. To establish optimal conditions for forming the polymer sorption-active part and the synthesis as a whole, a series of composite adsorbents were synthesized with varying amidoxime/matrix ratios (35/65, 50/50, 65/35). The samples were characterized with FT-IR, XRD, SEM, EDX, XRFES spectroscopy and TGA. Under static conditions of uranium sorption, the dependence of the efficiency of radionuclide recovery from mineralized solutions of various acidities on the ratio of the initial components was established. In the pH range from 4 to 8 (inclusive), the uranium removal efficiency exceeds 95%, while the values of the distribution coefficients (Kd) exceed 10⁴ cm³g⁻¹. It was demonstrated that an increase in the surface development of the sorbents enhances such kinetic parameters of uranium sorption as diffusion rate by 10–20 times compared to non-porous materials. The values of the maximum static capacity exceed 700 mg g⁻¹. The enhanced availability of adsorption centers, achieved through the use of a porous SiO₂ matrix, significantly improves the kinetic parameters of the adsorbents. A composite with optimal physicochemical and sorption properties (amidoxime/matrix ratio of 50/50) was examined under dynamic conditions of uranium sorption. It was found that the maximum dynamic sorption capacity of porous materials is four times greater compared to that of a non-porous adsorbent Se-init. The effective filter cycle exceeds 3200 column volumes—twice that of an adsorbent with a monolithic surface. These results indicate the promising potential of the developed materials for uranium sorption from liquid mineralized media under dynamic conditions across a wide pH range. Full article

New derivatives of the closo-decaborate anion [B₁₀H₉–O(CH₂)₂O(CH₂)₃C(O)–L–OCH₃]²⁻ (An) (1: L = Trp; 2: L = His; 3: L = Met; 4: L = Ala(2-oxopyrrolidin-3-yl) (Pld) were synthesized and isolated as tetraphenylphosphonium salts (Ph₄P)₂An. Anions 1²⁻; 2²⁻; 3²⁻, and 4²⁻ contain a pendant functional group from the L-tryptophan methyl ester, L-histidine methyl ester, L-methionine methyl ester, or methyl 2-amino-3-(2-oxopyrrolidin-3-yl)propanoate (-Trp–OCH₃, -His–OCH₃, -Met–OCH₃, or -Pld–OCH₃) residue, respectively, bonded with the boron cluster anion through the oxybis[(ethane-2,1-diyl)oxy] spacer. This pacer is formed as a result of the nucleophilic opening of the attached dioxane molecule in the [B₁₀H₉O(CH₂)₄O]⁻ starting derivative. Sodium salts of the target compounds were isolated and used in biological experiments. It was established that among compounds Na₂An (An = 1–4), not all are capable of inhibiting the cytopathic effect of the virus in vitro. Sodium salts Na₂An have a low toxic effect on a monolayer of continuous canine embryonic kidney (MDCK) cell line. Compounds Na₂1 and Na₂2 had IC₅₀ of 5.0 and 20.0 μg/mL, respectively, while for compounds Na₂3 and Na₂4, IC₅₀ values could not be achieved at the concentrations studied. The studies performed for molecular docking of the anionic part of 1²⁻ and 2²⁻ with the transmembrane domain of viroporin M2 show some differences in the location of these two ligands inside the M2 canal pore. Full article

ABS plastic is an inexpensive material with attractive physical and chemical properties. Unfortunately, it is susceptible to degradation under UV radiation, so it limits the use of this material outdoors. In this paper, we demonstrate a low-cost approach to reduce the photodegradation of ABS plastic by using additives of kraft lignin and dioxane lignin as UV absorbers. Lignin is an abundant plant polymer, which is a waste product of the pulp and paper industry. Non-regular structure of lignin hampers its use in industry. However, there is possible use of lignin as an addition to enhance the properties of resulting materials. In this study, we obtained composites of ABS and lignin with the hot extrusion method. Adding up to 15% of lignin to ABS plastic does not have a significant negative impact on tensile properties. We irradiated the resulting composites with UV and studied the UV effects on their mechanical properties and chemical structure. Oxidative degradation was characterized by FTIR and 2D NMR methods. The results showed that small lignin additions reduced the photodegradation of ABS. The previously undescribed product of the degradation of the obtained composites was detected with the use of the set of 2D NMR spectra of the composites. We proposed a scheme for the formation of this photodegradation product based on the obtained data. Full article