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These theoretical findings will enrich the knowledge of biomimetic metal-oxygen chemistry.An aerobic copper-mediated domino reaction for the synthesis of 3-(trifluoromethylseleno)indoles by trifluoromethylselenolation of N-Ts 2-alkynylaniline with [(bpy)CuSeCF3]2 is reported. This reaction proceeds through sequential oxidation, alkyne coordination, and deprotonation followed by reductive elimination. This mild and robust method is highly functional group tolerant and provides straightforward access to 3-(trifluoromethylseleno)indoles in moderate to good yields.This study investigated the in vitro digestion of purified pea fractions (protein isolate and starch) in sponge cakes when compared to unrefined pea flour and to the whole wheat flour and purified maize starch commonly used in the food industry. Proteins in the wheat cake were hydrolysed more rapidly than those in cakes made with either pea flour or a combination of pea proteins and purified starch. In absolute terms, however, more readily bioaccessible protein was released from these pea cakes (by around 40%). By contrast, cakes containing wheat flour or maize starch were more susceptible to amylolysis compared to those based on pea starch in the form of the purified ingredient or whole flour. This could be attributed to a higher proportion of amylose and resistant starch in the pea cakes as well as structural characteristics that might have decelerated enzyme-substrate interactions. Interestingly, similar digestion patterns were observed regarding the purified pea ingredients and unrefined whole pea flour. It was therefore concluded that pea ingredients, and particularly the less purified and thus more sustainable whole pea flour, are promising plant-based alternatives for use in gluten-free baked products.In this work, we report the results from molecular dynamics simulations of lithium salt-ionic liquid electrolytes (ILEs) based either on the symmetric bis[(trifluoromethyl)sulfonyl]imide (TFSI-) anion or its asymmetric analogue 2,2,2-(trifluoromethyl)sulfonyl-N-cyanoamide (TFSAM-). Relating lithium's coordination environment to anion mean residence times and diffusion constants confirms the remarkable transport behaviour of the TFSAM--based ILEs that has been observed in recent experiments for increased salt doping, the lithium ions must compete for the more attractive cyano over oxygen coordination and a fragmented landscape of solvation geometries emerges, in which lithium appears to be less strongly bound. We present a novel, yet statistically straightforward methodology to quantify the extent to which lithium and its solvation shell are dynamically coupled. By means of a Lithium Coupling Factor (LCF) we demonstrate that the shell anions do not constitute a stable lithium vehicle, which suggests for this electrolyte material the commonly termed "vehicular" lithium transport mechanism could be more aptly pictured as a correlated, flow-like motion of lithium and its neighbourhood. Our analysis elucidates two separate causes why lithium and shell dynamics progressively decouple with higher salt content on the one hand, an increased sharing of anions between lithium limits the achievable LCF of individual lithium-anion pairs. On the other hand, weaker binding configurations naturally entail a lower dynamic stability of the lithium-anion complex, which is particularly relevant for the TFSAM--containing ILEs.Electrochemical conversion of carbon dioxide and carbon monoxide into value-added multi-carbon products (C2+) offers a promising approach for artificial oxycarbide recycling. However, C2+ productivity is still limited by gas accessibility inside the catalyst layer. Here, a Cu-PMMA porous hybrid architecture with rich triple-phase boundaries was demonstrated to enhance both gas diffusion and electron transfer, and then, facilitate the kinetics of CO electrolysis. As a result, a high C2+ faradaic efficiency (FE) of 81.6% at a current density of 50 mA cm-2 and a maximum C2+ partial current density of 140 mA cm-2 were achieved, among the best performances for Cu/hybrid catalysts. This study provides a novel strategy for designing electrochemical CO reduction (ECORR) catalysts and paves the way for further developing gas-involving electrocatalysis.Spearmint belongs to the genus Mentha in the family Labiatae (Lamiaceae), which is cultivated worldwide for its remarkable aroma and commercial value. The aromatic molecules of spearmint essential oil, including carvone, carveol, dihydrocarvone, dihydrocarveol and dihydrocarvyl acetate, have been widely used in the flavors and fragrances industry. Besides their traditional use, these aromatic molecules have attracted great interest in other application fields (e.g., medicine, agriculture, food, and beverages) especially due to their antimicrobial, antioxidant, insecticidal, antitumor, anti-inflammatory and antidiabetic activities. This review presents the sources, properties, synthesis and application of spearmint aromatic molecules. Furthermore, this review focuses on the biological properties so far described for these compounds, their therapeutic effect on some diseases, and future directions of research. This review will, therefore, contribute to the rational and economic exploration of spearmint aromatic molecules as natural and safe alternative therapeutics.In recent years, nanodrug delivery systems have attracted increasing attention due to their advantages, such as high drug loading, low toxicity and side effects, improved bioavailability, long circulation time, good targeting and controlled drug release efficiency. Self-assembly technology has developed rapidly in recent decades and plays an important role in the research and development of nanoscience. The combination of nanometer drug delivery and self-assembly technology can realize the self-delivery process of drugs. The facile synthesis process and strong biological affinity can both effectively enhance the therapeutic efficacy and reduce the toxicity of drugs. This combination of technologies has received wide attention in the field of nanobiomedicine. In this review, we summarize the research progress and applications of different types of self-assembled nanodrug delivery systems (amphiphilic block copolymer-based self-assembled drug delivery system, carrier-free nanodrugs, peptide-based self-assembled delivery system, metal-polyphenol self-assembly and natural small-molecule self-assembled nanodrug delivery systems), which are expected to have potential therapeutic value in the field of biomedicine in the future.We show that solid-state NMR spectroscopy is a suitable method for characterizing the structure, hydrogen bond dynamics and phase transition behavior in protic ionic liquids (PILs). Deuteron line shape and spin relaxation time analysis provide a description of the structural and dynamical heterogeneity in the solid state of the model PIL triethyl ammonium bis(trifluoromethanesulfonyl)amide [TEA][NTf2]. Therein, we observed two deuteron quadrupole coupling constant for the ND bond of the TEA cation, indicating differently strong hydrogen bonds to the nitrogen and oxygen atoms of the NTf2 anion, as we could confirm by DFT calculations. The transition processes in the dynamically heterogeneous phase are characterized by two standard molar enthalpies and thus different stages of melting. We provide geometry, rates and energetics of the cation in the solid and liquid states of the PIL. Comparison with PILs having stronger interacting anions shows higher enthalpy change between the solid and liquid states, lower activation barriers of tumbling motion and higher amplitude of librational motion for the TEA cation in the presence of the weakly interacting anion NTf2. We provide reasonable relations between microscopic and macroscopic properties, as is relevant for any kind of application.The photo-reactivity of cobalamins (Cbls) is influenced by the nature of axial ligands and the cofactor's environment. While the biologically active forms of Cbls with alkyl axial ligands, such as methylcobalamin (MeCbl) and adenosylcobalamin (AdoCbl), are considered to be photolytically active, in contrast, the non-alkyl Cbls are photostable. In addition to these, the photolytic properties of Cbls can also be modulated in the presence of molecular oxygen, i.e., under aerobic conditions. Herein, the photoreaction of the MeCbl in the presence of oxygen has been explored using density functional theory (DFT) and time-dependent DFT (TD-DFT). The first stage of the aerobic photoreaction is the activation of the Co-C bond and the formation of the ligand field (LF) electronic state through the displacement of axial bonds. Once the photoreaction reaches the LF excited state, three processes can occur namely the formation of OO-CH3 through the reaction of CH3 with molecular oxygen, de-activation of the Im⋯[CoII(corrin)]⋯CH3+ sub-system from the LF electronic state by changing the electronic configuration from (dyz)1(dz2)2 to (dyz)2(dz2)1 and the formation of the deactivation complex (DC) complex via the recombination of OO-CH3 species with the de-excited [CoII(corrin)] system. In the proposed mechanism, the deactivation of the [CoII(corrin)] subsystem may coexist with the formation of OO-CH3, followed by immediate relaxation of the subsystems in the ground state. Moreover, the formation of the OO-CH3 species followed by the formation of the [CoIII(corrin)]-OO-CH3+ complex stabilizes the system compared to the reactant complex.Fluorescent hydrogels have attracted tremendous attention recently in the field of information security due to the booming development of information technology. Along this line, it is highly desired to improve the security level of concealed information by the advancements of materials and encryption technologies. Here we report multi-level encryption of information in a bilayer hydrogel with shape-morphing ability and patterned fluorescence. This hydrogel is composed of a fluorescence layer containing chromophore units in the poly(acrylic acid) network and an active layer with UV-absorption agents in the poly(N-isopropylacrylamide-co-acrylic acid) network. The former layer exhibits tunable fluorescence tailored by UV light irradiation to induce unimer-to-dimer transformation of the chromophores, facilitating the write-in of information through photolithography. The latter layer is responsive to temperature, enabling morphing of the bilayer hydrogel. Therefore, the bilayer hydrogel encoded with patterned fluorescent patterns can deform into three-dimensional configurations at room temperature to conceal the information, which is readable only after successive procedures of shape recovery at an appropriate temperature and under UV light irradiation from the right direction. The combination of morphing materials and patterned fluorescence as a new avenue to improve the encryption level of information should merit the design of other smart materials with integrated functions for specific applications.Both the liberation and stability of endogenous folate are relevant to the bioaccessibility of folate. Since folates are unstable, in addition to studying the natural folate content in foods, bioaccessibility should be considered. To understand folate changes during digestion, a mixture of standard folate compounds was subjected to a static in vitro gastrointestinal digestion assay. selleck chemical Next, different types of bread were analysed to study how food matrices influence folate bioaccessibility. Folates were identified and quantitated by a UHPLC-PDA/FL method. Folic acid and 10-formylfolic acid were stable throughout the digestion, and the conversions among formyl folates and 5,10-methenyltetrahydrofolate were triggered at the gastric phase. Tetrahydrofolate began to degrade during the oral phase and was lost completely during the gastric phase. During the intestinal phase, 5-methyltetrahydrofolate began to degrade and suffered a 60% loss. With bread matrices, folate conversions and the decrease of reduced folates were also common, but the extent of changes varied.

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