Search Results (82)

The ongoing exploration of planets such as Mars is producing a wealth of data to define habitable environments beyond the Earth. The inferred presence of neutral to alkaline aqueous fluids on Mars in its early history suggests that many potentially habitable environments existed on the planet. Terrestrial analogues with similar chemical and physical properties are being explored and characterized in order to assess their suitability for triggering the Origin of Life on Mars. Recently, a novel Mars analogue site has been identified in the Bagno dell’Acqua Lake, which is located in the island of Pantelleria in Sicily (Italy). We report here that microbialite from the Bagno dell’Acqua Lake acts as an efficient catalyst for prebiotic processes, starting from a ternary mixture of well-recognized chemical precursors, including ammonium formate, diaminomalonitrile, and alpha-amino acids. Under thermal conditions, significant amounts of building blocks of both RNA and PNA were obtained. Furthermore, samples of the water from the Bagno dell’Acqua Lake have been found to promote the polymerization of the H-form of 3′,5′-cyclic GMP, resulting in the generation of RNA oligomers of up to 15 units in length. Full article

Furfural is a fascinating bio-based platform molecule that can be converted into useful cyclic compounds, among others. In this work, the hydrogenative rearrangement-dehydration of furfural towards cyclopentanone using a commercially available Pt/C catalyst was investigated in terms of its reaction performance to assess its feasibility as an industrial process. However, acquiring an acceptable cyclopentanone yield proved very difficult, and the reaction was constrained by unforeseen parameters, such as the relative liquid volume in the reactor and the substrate concentration. Most strikingly, the sacrificial formation of furanoic oligomers that precipitated onto the catalyst’s surface was a troublesome key factor that mediated the product’s selectivity versus the carbon mass balance. By applying a biphasic water–toluene solvent system, the yield of cyclopentanone was somewhat improved to a middling 59%, while tentatively positive distributions of reaction components over these solvent phases were observed, which could be advantageous for anticipated down-stream processing. Overall, the sheer difficulty of controlling this one-pot cascade transformation towards a satisfactory product output under rather unfavorable reaction parameters renders it unsuitable for industrial process development, and a multi-step procedure for this chemical transformation might be considered instead. Full article

A novel biodegradable food packaging material based on cassava thermoplastic starch (TPS) and polybutylene adipate terephthalate (PBAT) blends containing food preservatives was successfully developed using blown-film extrusion. This active packaging is designed to enhance the appearance, taste, and color of food products, while delaying quality deterioration. However, the incorporation of food preservatives directly influences consumer perception, as well as health and safety concerns. Therefore, this research aims to assess the risks associated with both intentionally added substances (IAS) and non-intentionally added substances (NIAS) present in the developed active packaging. The migration of both intentionally and non-intentionally added substances (IAS and NIAS) was evaluated using gas chromatography–mass spectrometry (GC-MS) and ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS). Fifteen different volatile compounds were detected, with the primary compound identified as 1,6-dioxacyclododecane-7,12-dione, originating from the PBAT component. This compound, along with others, resulted from the polymerization of adipic acid, terephthalic acid, and butanediol, forming linear and cyclic PBAT oligomers. Migration experiments were conducted using three food simulants—95% ethanol, 10% ethanol, and 3% acetic acid—over a period of 10 days at 60 °C. No migration above the detection limits of the analytical methods was observed for 3% acetic acid and 10% ethanol. However, migration studies with 95% ethanol revealed the presence of new compounds formed through interactions between the simulant and PBAT monomers or oligomers, indicating the packaging’s sensitivity to high-polarity food simulants. Nevertheless, the levels of these migrated compounds remained below the regulatory migration limits. Full article

This paper elucidates the consecutive chain transfer reaction, initially to (p-vinylphenyl) methyl dichlorosilane (or (p-vinylbenzyl) methyl dichlorosilane), followed by hydrogen, during metallocene-catalyzed propylene polymerization by an isospecific metallocene catalyst (i.e., rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, I)/ activated with methylaluminoxane (MAO), rendering a catalytic access styryldichlorosilane capped isotactic polypropylenes (iPP). The PP molecular weight is inversely related to the molar ratio of [(p-vinylphenyl) methyl dichlorosilane]/[propylene] and [(p-vinylbenzyl) methyl dichlorosilane]/[propylene]. Every polypropylene chain formed presents a terminal (p-vinylphenyl) methyl dichlorosilane (or (p-vinylbenzyl) methyl dichlorosilane) unit. Hydrogen enhances the concentration of the starting arm polymer for the subsequent synthesis of the star polymer by increasing the incorporation of the chain terminal group. In order to create star polymers with isotactic polypropylene(iPP) as the arm and a siloxane cross-linking structure as the core, the terminal dichlorosilane iPP unit can work up (with water) to create cyclic siloxane oligomer interlinkages between iPP chains. Full article

The complex of hypofluorous acid with acetonitrile—HOF•CH₃CN—is the only substance possessing a truly electrophilic oxygen. This fact makes it the only tool suitable for transferring oxygen atoms to sites that are not accessible to this vital element. We will review here most of the known organic reactions with this complex, which is easily made by bubbling dilute fluorine through aqueous acetonitrile. The reactions of HOF•CH₃CN with double bonds produce epoxides in a matter of minutes at room temperature, even when the olefin is electron-depleted and cannot be epoxidized by any other means. The electrophilic oxygen can also substitute deactivated tertiary C-H bonds via electrophilic substitution, proceeding with full retention of configuration. Using this complex enables transferring oxygen atoms to a carbonyl and oxidizing alcohols and ethers to ketones. The latter could be oxidized to esters via the Baeyer–Villiger reaction, proving once again the validity of the original Baeyer mechanism. Azines are usually avoided as protecting groups for carbonyl since their removal is problematic. HOF•CH₃CN solves this problem, as it is very effective in recreating carbonyls from the respective azines. A bonus of the last reaction is the ability to replace the common ¹⁶O isotope of the carbonyl with the heavier ¹⁷O or ¹⁸O in the simplest and cheapest possible way. The reagent can transfer oxygen to most nitrogen-containing molecules. Thus, it turns practically any azide or amine into nitro compounds, including amino acids. This helps to produce novel α-alkylamino acids. It also attaches oxygen atoms to most tertiary nitrogen atoms, including certain aromatic ones, which could not be obtained before. HOF•CH₃CN was also used to make five-member cyclic poly-NO derivatives, many of them intended to be highly energetic materials. The nucleophilic sulfur atom also reacts very smoothly with the reagent in a wide range of compounds to form sulfone derivatives. While common sulfides are easily converted to sulfones by many orthodox reagents, electron-depleted ones, such as R_f-S-Ar, can be oxidized to R_f-SO₂-Ar only with this reagent. The mild reaction conditions also make it possible to synthesize a whole range of novel episulfones and offer, as a bonus, a very easy way to make S^xO₂, x being any isotope variation of oxygen. These mild conditions also helped to oxidize thiophene to thiophen-S,S-dioxide without the Diels–Alder dimerizations, which usually follow such dioxide formation. The latter reaction was a prelude to a series of preparations of [all]-S,S-dioxo-oligothiophenes, which are important for the efficient preparation of active layers in field-effect transistors (FETs), as such oligomers are considered to be important for organic semiconductors for light-emitting diodes (LEDs). Several types of these oligothiophenes were prepared, including partly or fully oxygenated ones, star-oligothiophenes, and fused ones. Several [all]-S,S-dioxo-oligo-thienylenevinylenes were also successfully prepared despite the fact that they also possess carbon–carbon p centers in their molecules. All oxygenated derivatives have been prepared for the first time and have lower HOMO-LUMO gaps compared to their parent compounds. HOF•CH₃CN was also used to oxidize the surface of the nanoparticles of oligothiophenes, leaving the core of the nanoparticle unchanged. Several highly interesting features have been detected, including their ability to photostimulate the retinal neurons, especially the inner retinal ones. HOF•CH₃CN was also used on elements other than carbon, such as selenium and phosphor. Various selenides were oxidized to the respective selenodioxide derivatives (not a trivial task), while various phosphines were converted efficiently to the corresponding phosphine oxides. Full article

Organic electroactive materials (OEMs) offer advantages such as cost-effectiveness, environmental sustainability, and simplified end-of-life processing compared to inorganic electrode materials. Aqueous electrolytes further enhance sustainability and safety relative to organic electrolytes. Investigating the electrochemical properties of OEMs in aqueous media provides valuable insights into their redox behavior and stability under such conditions. However, challenges remain, including low electronic conductivity and structural stability concerns, while aqueous rechargeable batteries (ARBs) face inherent energy density limitations. Tetrathiafulvalene (TTF) has been previously reported as an electrode material for ARBs, while its oligomers have been proposed for organic electrolyte batteries. This study focuses on the synthesis and characterization of two new dissymmetric TTF derivatives—cyanobenzene tetrathiafulvalene pyrazine (CNB-TTF-Pz) (1) and 4-cyanobenzene tetrathiafulvalene pyrazine (4-CNB-TTF) (2)—as well as one symmetric TTF derivative, dipyrazine tetrathiafulvalene ((Pz)₂-TTF) (3). Their electrochemical behavior in aqueous lithium and potassium nitrate electrolytes was systematically characterized using cyclic voltammetry. The study provides insights into the redox properties and electroactivity of these compounds, highlighting challenges related to low electronic conductivity and redox potentials close to the water stability limits. These findings contribute to broadening our understanding of the electrochemical properties of TTF derivatives in aqueous electrolytes and offer a preliminary assessment of their potential application as electrodes for ARBs. Full article

In this work, the fracture mechanism of winding carbon-fiber-reinforced plastics (CFRPs) based on epoxy matrices reinforced by polysulfone film was investigated. Two types of polymer matrices were used: epoxy oligomer (EO) cured by iso-methyltetrahydrophthalic anhydride (iso-MTHPA), and EO-modified polysulfone (PSU) with active diluent furfuryl glycidyl ether (FGE) cured by iso-MTHPA. At the winding stage, the reinforcing film was placed in the middle layer of the CFRP. The fracture toughness G_IR of the obtained CFRP was determined by the double-cantilever beam delamination method. Additionally, the effect of cyclic loading on the fracture toughness of CFRP reinforced with polysulfone film was investigated. It was shown that heterogeneous structures arising from the dissolution of the polysulfone film in the epoxy binder during the curing process increase the fracture toughness of CFRP from 0.5 kJ/m² to 1.2 kJ/m². Application of cyclic loads had little effect on the fracture toughness value. As a result of this study, it was revealed that the macrocrack propagates near the reinforcement layer along the diffusion zone, which has a phase organization of the type PSU matrix–EO dispersion. Full article

Entropy-Driven Ring-Opening Polymerisation represents an attractive mechanism to produce high-performance polymeric materials as it can be performed using neat, low-viscosity precursors and without the production of by-products or release of volatiles. Macrocyclic oligomers (MCOs) of polyether ketone ketone (PEKK) were synthesised and investigated as an in situ method of forming this high-performance thermoplastic. Cyclic oligomers were successfully synthesised by pseudo-high dilution methods, and the reaction conditions were optimised through careful addition of starting materials and carbonate base selection. These novel compounds were characterised, X-ray crystal structures were obtained, and the synthesis method was extended from the homopolymers to MCOs with the structural isomers predominantly used in industry. PEKK formed from MCOs were characterised by DSC, TGA and GPC and found to have similar glass transitions and molecular weight averages to those of a commercial PEKK polymer. Full article

Ladder oligomers containing calixarene skeletons in the main chain—calix[4]resorcinarene (CRA) ladder macromolecules with open chain and cyclic macromolecules with double ring-like (Noria-type) topologies—bring particular research attention as functional materials with various applications. However, there is still a remarkable lack of studies into the synthesis of fully water-soluble derivatives of these interesting macromolecules. Research on this topic would allow their bio-based research and application niche to be at least revealed. In the present study, a strategy for the synthesis of water-soluble polyglycidol-derivatized calix resorcinarene ladder oligomers with open chain and cyclic structures is introduced. A grafting from approach was used to build branched or linear polyglycidol chains from the ladder scaffolds. The novel structures were synthesized in quantitative yields and fully characterized by NMR, FTIR and UV–vis spectroscopy, gel permeation chromatography, MALDI-TOF mass spectrometry, analytical ultracentrifugation, and static light scattering to obtain the molar mass characteristics and composition. The biocompatibility and toxicity of the two polyglycidol-derivatized oligomers were investigated and the concentration dependence of the survival of three cell lines of human origin determined. The selective apoptosis effect at relatively low dissolve concentrations toward two kinds of cancerous cell lines was found. Full article

This study introduces a metal-free binary catalytic system for coupling CO₂ with cyclohexane oxide (CHO) under mild conditions, allowing for tunable product selectivity. Using trans-cyclohexane diol (trans-CHD) and phosphazene superbase (P₄) as catalysts, the system selectively produces cyclic carbonates and oligocarbonates at 1 bar CO₂ pressure and 80 °C. By adjusting the catalyst ratio, varying proportions of cis-cyclohexane carbonate (cis-CHC), trans-cyclohexane carbonate (trans-CHC), and oligocarbonate are achieved, with 51 mol% CHO conversion and respective selectivities of 36%, 31%, and 33%. The catalytic efficiency and precise control of product outcomes underscore this system’s potential. Full article

Eugenol-containing oligoorganosilsesquioxanes were synthesized by the method of hydrolytic polycondensation in an active medium under various reaction conditions. The obtained products were characterized by ²⁹Si NMR spectroscopy and MALDI-TOF spectrometry. It was shown that factors such as the reaction temperature, polycondensation duration, and molar ratio between the initial alkoxysilane monomer and acetic acid may affect the molecular weight characteristics and molecular structure of the formed oligomer, like the content of stressed cyclic units (T₃, DTT, TDT) and unstressed silsesquioxane units T_nD_m. In particular, an increase in the ratio of the initial reagents led to an increase in the content of silsesquioxane T_n fragments from 28.2%_mol to 41.7%_mol, while the number of strained cyclic structures decreased by more than two times. An increase in the synthesis time is of no particular practical value since it was found that the composition of the oligomers synthesized for 6 h and 12 h was practically identical, as was that of the oligomers synthesized for 24 h and 48 h. A noticeable transition in the oligomer composition was observed only when the synthesis time was changed from 12 h to 24 h. Finally, it was shown that the choice of synthesis temperature had the strongest effect on the oligomer composition. The oligomer synthesized at 95 °C contained the highest amount of silsesquioxane T_n fragments, >77%_mol, while a T_n fragment content of ~42%_mol was observed during the synthesis at 117 °C. It was shown that silsesquioxanes are devitrified at room temperature (T_g from −6.4 to −10.6 °C), and their thermal stability in an inert atmosphere is 300 °C. The synthesized oligomers, due to the presence of hydroxyl-containing eugenol units, may be promising binders and additives for functional epoxy–silicone paints and coating materials. Full article

Superhydrophobic strain sensors are highly promising for human motion and health monitoring in wet environments. However, the introduction of superhydrophobicity inevitably alters the mechanical and conductive properties of these sensors, affecting sensing performance and limiting behavior monitoring. Here, we developed an alkylated MXene–carbon nanotube/microfiber composite material (AMNCM) that is simultaneously flexible, superhydrophobic, and senses properties. Comprising a commercially available fabric substrate that is coated with a functional network of alkylated MXene/multi-walled carbon nanotubes and epoxy–silicone oligomers, the AMNCM offers high mechanical and chemical robustness, maintaining high conductivity and strain sensing properties. Furthermore, the AMNCM strain sensor achieves a gauge factor of up to 51.68 within a strain range of 80–100%, and exhibits rapid response times (125 ms) and long-term stability under cyclic stretching, while also displaying superior direct/indirect anti-fouling capabilities. These properties position the AMNCM as a promising candidate for next-generation wearable devices designed for advanced environmental interactions and human activity monitoring. Full article

Polyglycolic acid (PGA) is a biologically friendly material with a wide range of applications. The production of dimethyl oxalate using coal-based syngas and the hydrogenation of dimethyl oxalate can produce the polymerization raw material of PGA, glycolide, which requires a methyl glycolate polymerization and depolymerization process. The intermediate products of the production process were analyzed using gas chromatogram-mass spectrometry (GC-MS) and Orbitrap mass spectrometry (Orbitrap MS), which revealed the presence of cyclic and linear PGAs with different capped ends. The impurities present in the oligomer were mostly methyl-capped PGA and were retained in the subsequent depolymerization process to glycolide, solvent washing can be used to remove this part of the impurity and ultimately obtain a refined glycolide product. Furthermore, it is proposed that the use of the specialized Kendrick Mass Defect (KMD) to plot and analyze PGA compounds obtained using mass spectrometry can enable the direct classification of PGAs without the need for exact molecular formula assignment. Full article

Since the discovery of metal-catalyzed azide–alkyne cycloadditions, 1,2,3-triazoles have been widely used as linkers for various residues. 1,2,3-Triazole is an aromatic five-membered cyclic compound consisting of three nitrogen and two carbon atoms with large dipoles that absorb UV light. In the past decade, we have been working on the synthesis of dense triazole polymers possessing many 1,2,3-triazole residues linked through a carbon atom in their backbone as a new type of functional polymer. Recently, we reported that stereoregular dense triazole uniform oligomers exhibit a circular dichroism signal based on the chiral arrangement of two neighboring 1,2,3-triazole residues. In this study, to investigate the chiral conformation of two neighboring 1,2,3-triazole residues in stereoregular dense triazole uniform oligomers, density functional theory (DFT) calculations were performed using 1,2,3-triazole diads with different substitution positions and conformations as model compounds and compared with our previous results. Full article

On-surface polymerization of functional organic molecules has been recently recognized as a promising route to persistent low-dimensional structures with tailorable properties. In this contribution, using the coarse-grained Monte Carlo simulation method, we study the initial stage of the Ullmann coupling of doubly halogenated chrysene isomers adsorbed on a catalytically active (111) crystalline surface. To that end, we focus on the formation of labile metal-organic precursor structures preceding the covalent bonding of chrysene monomers. Four monomeric chrysene units with differently distributed halogen substituents were probed in the simulations, and the resulting precursor structures were compared and quantified. Moreover, the effect of (pro)chirality of chrysene tectons on the structure formation was elucidated by running separate simulations in enantiopure and racemic systems. The calculations showed that suitable manipulation of the halogen substitution pattern allows for the creation of diverse precursor architectures, ranging from straight and winded chains to cyclic oligomers with enantiopure, racemic, and nonracemic composition. The obtained findings can be helpful in developing synthetic strategies for covalent polymers with predefined architecture and functionality. Full article