Editor’s Choice Articles

This study aimed to investigate the chemical composition of the leaf essential oil from Ivoirian Isolona dewevrei. A combination of chromatographic and spectroscopic techniques (GC(RI), GC-MS and ¹³C-NMR) was used to analyze two oil samples (S1 and S2). Detailed analysis by repetitive column chromatography (CC) of essential oil sample S2 was performed, leading to the isolation of four compounds. Their structures were elucidated by QTOF-MS, 1D and 2D-NMR as (10βH)-1β,8β-oxido-cadin-4-ene (38), 4-methylene-(7αH)-germacra-1(10),5-dien-8β-ol (cis-germacrene D-8-ol) (52), 4-methylene-(7αH)-germacra-1(10),5-dien-8α-ol (trans-germacrene D-8-ol) (53) and cadina-1(10),4-dien-8β-ol (56). Compounds 38, 52 and 53 are new, whereas NMR data of 56 are reported for the first time. Lastly, 57 constituents accounting for 95.5% (S1) and 97.1% (S2) of the whole compositions were identified. Samples S1 and S2 were dominated by germacrene D (23.6 and 20.5%, respectively), followed by germacrene D-8-one (8.9 and 8.7%), (10βH)-1β,8β-oxido-cadin-4-ene (7.3 and 8.7), 4-methylene-(7αH)-germacra-1(10),5-dien-8β-ol (7.8 and 7.4%) and cadina-1(10),4-dien-8β-ol (7.6 and 7.2%). Leaves from I. dewevrei produced sesquiterpene-rich essential oil with an original chemical composition, involving various compounds reported for the first time among the main components. Integrated analysis by GC(RI), GC-MS and ¹³C-NMR appeared fruitful for the knowledge of such a complex essential oil. Full article

Triazole pesticides are widely used to control grapevine diseases. In this study, we investigated the impact of three triazole pesticides—triadimefon, tebuconazole, and paclobutrazol—on the concentrations of wine aroma compounds. All three triazole pesticides significantly affected the ester and acid aroma components. Among them, paclobutrazol exhibited the greatest negative influence on the wine aroma quality through its effect on the ester and acid aroma substances, followed by tebuconazole and triadimefon. Qualitative and quantitative analysis by solid-phase micro-extraction gas chromatography coupled with mass spectrometry revealed that the triazole pesticides also changed the flower and fruit flavor component contents of the wines. This was attributed to changes in the yeast fermentation activity caused by the pesticide residues. The study reveals that triazole pesticides negatively impact on the volatile composition of wines with a potential undesirable effect on wine quality, underlining the desirability of stricter control by the food industry over pesticide residues in winemaking. Full article

The global SARS-CoV-2 pandemic started late 2019 and currently continues unabated. The lag-time for developing vaccines means it is of paramount importance to be able to quickly develop and repurpose therapeutic drugs. Protein-based biosensors allow screening to be performed using routine molecular laboratory equipment without a need for expensive chemical reagents. Here we present a biosensor for the 3-chymotrypsin-like cysteine protease from SARS-CoV-2, comprising a FRET-capable pair of fluorescent proteins held in proximity by a protease cleavable linker. We demonstrate the utility of this biosensor for inhibitor discovery by screening 1280 compounds from the Library of Pharmaceutically Active Compounds collection. The screening identified 65 inhibitors, with the 20 most active exhibiting sub-micromolar inhibition of 3CL^pro in follow-up EC₅₀ assays. The top hits included several compounds not previously identified as 3CL^pro inhibitors, in particular five members of a family of aporphine alkaloids that offer promise as new antiviral drug leads. Full article

Carbohydrate-derived ionic liquids have been explored as bio-alternatives to conventional ionic liquids for over a decade. Since their discovery, significant progress has been made regarding synthetic methods, understanding their environmental effect, and developing perspectives on their potential applications. This review discusses the relationships between the structural properties of carbohydrate ionic liquids and their thermal, toxicological, and biodegradability characteristics in terms of guiding future designs of sugar-rich systems for targeted applications. The synthetic strategies related to carbohydrate-based ionic liquids, the most recent relevant advances, and several perspectives for possible applications spanning catalysis, biomedicine, ecology, biomass, and energy conversion are presented herein. Full article

New advances in protein post-translational modifications (PTMs) have revealed a complex layer of regulatory mechanisms through which PTMs control cell signaling and metabolic pathways, contributing to the diverse metabolic phenotypes found in cancer. Using conformational templates and the three-dimensional (3D) environment investigation of proteins in patients with colorectal cancer, it was demonstrated that most PTMs (phosphorylation, acetylation, and ubiquitination) are localized in the supersecondary structures (helical pairs). We showed that such helical pairs are represented on the outer surface of protein molecules and characterized by a largely accessible area for the surrounding solvent. Most promising and meaningful modifications were observed on the surface of vitamin D-binding protein (VDBP), complement C4-A (CO4A), X-ray repair cross-complementing protein 6 (XRCC6), Plasma protease C1 inhibitor (IC1), and albumin (ALBU), which are related to colorectal cancer developing. Based on the presented data, we propose the impact of the observed modifications in immune response, inflammatory reaction, regulation of cell migration, and promotion of tumor growth. Here, we suggest a computational approach in which high-throughput analysis for identification and characterization of PTM signature, associated with cancer metabolic reprograming, can be improved to prognostic value and bring a new strategy to the targeted therapy. Full article

The perception of aroma mixtures is based on interactions beginning at the peripheral olfactory system, but the process remains poorly understood. The perception of a mixture of ethyl isobutyrate (Et-iB, strawberry-like odor) and ethyl maltol (Et-M, caramel-like odor) was investigated previously in both human and animal studies. In those studies, the binary mixture of Et-iB and Et-M was found to be configurally processed. In humans, the mixture was judged as more typical of a pineapple odor, similar to allyl hexanoate (Al-H, pineapple-like odor), than the odors of the individual components. To explore the key features of this aroma blend, we developed an in silico approach based on molecules having at least one of the odors—strawberry, caramel or pineapple. A dataset of 293 molecules and their related odors was built. We applied the notion of a “social network” to describe the network of the odors. Additionally, we explored the structural properties of the molecules in this dataset. The network of the odors revealed peculiar links between odors, while the structural study emphasized key characteristics of the molecules. The association between “strawberry” and “caramel” notes, as well as the structural diversity of the “strawberry” molecules, were notable. Such elements would be key to identifying potential odors/odorants to form aroma blends. Full article

Olfactory cues are key drivers of our multisensory experiences of food and drink. For example, our perception and enjoyment of the flavour and taste of a wine is primarily steered by its aroma. Making sense of the underlying smells that drive consumer preferences is integral to product innovation as a vital source of competitive advantage in the marketplace, which explains the intense interest in the olfactory component of flavour and the sensory significance of individual compounds, such as one of the most important apocarotenoids for the bouquet of wine, β-ionone (violet and woody notes). β-Ionone is formed directly from β-carotene as a by-product of the actions of carotenoid cleavage dioxygenases (CCDs). The biological production of CCDs in microbial cell factories is one way that important aroma compounds can be generated on a large scale and with reduced costs, while retaining the ‘natural’ moniker. The CCD family includes the CCD1, CCD2, CCD4, CCD7 and CCD8; however, the functions, co-dependency and interactions of these CCDs remain to be fully elucidated. Here, we review the classification, actions and biotechnology of CCDs, particularly CCD1 and its action on β-carotene to produce the aromatic apocarotenoid β-ionone. Full article

The effects of metal-based Lewis acid (LA) catalysts on the reaction rate and regioselectivity in polar Diels–Alder (P-DA) reactions has been analyzed within the molecular electron density theory (MEDT). A clear linear correlation between the reduction of the activation energies and the increase of the polar character of the reactions measured by analysis of the global electron density transfer at the corresponding transition state structures (TS) is found, a behavior easily predictable by analysis of the electrophilicity ω and nucleophilicity N indices of the reagents. The presence of a strong electron-releasing group in the diene changes the mechanism of these P-DA reactions from a two-stage one-step to a two-step one via formation of a zwitterionic intermediate. However, this change in the reaction mechanism does not have any chemical relevance. This MEDT study makes it possible to establish that the more favorable nucleophilic/electrophilic interactions taking place at the TSs of LA catalyzed P-DA reactions are responsible for the high acceleration and complete regioselectivity experimentally observed. Full article

Over the past three decades, carbon nanotubes and fullerenes have become remarkable objects for starting the implementation of new models and technologies in different branches of science. To a great extent, this is defined by the unique electronic and spatial properties of nanocavities due to the ramified π-electron systems. This provides an opportunity for the formation of endohedral complexes containing non-covalently bonded atoms or molecules inside fullerenes and nanotubes. The guest species are exposed to the force field of the nanocavity, which can be described as a combination of electronic and steric requirements. Its action significantly changes conformational properties of even relatively simple molecules, including ethane and its analogs, as well as compounds with C−O, C−S, B−B, B−O, B−N, N−N, Al−Al, Si−Si and Ge−Ge bonds. Besides that, the cavity of the host molecule dramatically alters the stereochemical characteristics of cyclic and heterocyclic systems, affects the energy of pyramidal nitrogen inversion in amines, changes the relative stability of cis and trans isomers and, in the case of chiral nanotubes, strongly influences the properties of R- and S-enantiomers. The present review aims at primary compilation of such unusual stereochemical effects and initial evaluation of the nature of the force field inside nanotubes and fullerenes. Full article

The use of luminescence in biological systems allows one to diagnose diseases and understand cellular processes. Molecular systems, particularly lanthanide(III) complexes, have emerged as an attractive system for application in cellular luminescence imaging due to their long emission lifetimes, high brightness, possibility of controlling the spectroscopic properties at the molecular level, and tailoring of the ligand structure that adds sensing and therapeutic capabilities. This review aims to provide a background in luminescence imaging and lanthanide spectroscopy and discuss selected examples from the recent literature on lanthanide(III) luminescent complexes in cellular luminescence imaging, published in the period 2016–2020. Finally, the challenges and future directions that are pointing for the development of compounds that are capable of executing multiple functions and the use of light in regions where tissues and cells have low absorption will be discussed. Full article

Pd-catalysed Stille and Suzuki cross-couplings were used to prepare 9-(3-indenyl)-, 6, and 9-(2-indenyl)-anthracene, 7; addition of benzyne led to the 9-Indenyl-triptycenes, 8 and 9. In 6, [4 + 2] addition also occurred to the indenyl substituent. Reaction of 6 through 9 with Cr(CO)₆ or Re₂(CO)₁₀ gave their M(CO)₃ derivatives, where the Cr or Re was complexed to a six- or five-membered ring, respectively. In the 9-(2-indenyl)triptycene complexes, slowed rotation of the paddlewheel on the NMR time-scale was apparent in the η⁵-Re(CO)₃ case and, when the η⁶-Cr(CO)₃ was deprotonated, the resulting haptotropic shift of the metal tripod onto the five-membered ring also blocked paddlewheel rotation, thus functioning as an organometallic molecular brake. Suzuki coupling of ferrocenylboronic acid to mono- or dibromoanthracene yielded the ferrocenyl anthracenes en route to the corresponding triptycenes in which stepwise hindered rotations of the ferrocenyl groups behaved like molecular dials. CuCl₂-mediated coupling of methyl- and phenyl-indenes yielded their rac and meso 2,2′-biindenyls; surprisingly, however, the apparently sterically crowded rac 2,2′-Bis(9-triptycyl)biindenyl functioned as a freely rotating set of molecular gears. The predicted high rotation barrier in 9-phenylanthracene was experimentally validated via the Pd-catalysed syntheses of di(3-fluorophenyl)anthracene and 9-(1-naphthyl)-10-phenylanthracene. Full article

Halloysite aluminosilicate nanotubes loaded with ruthenium particles were used as reactors for Fischer–Tropsch synthesis. To load ruthenium inside clay, selective modification of the external surface with ethylenediaminetetraacetic acid, urea, or acetone azine was performed. Reduction of materials in a flow of hydrogen at 400 °C resulted in catalysts loaded with 2 wt.% of 3.5 nm Ru particles, densely packed inside the tubes. Catalysts were characterized by N₂-adsorption, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray fluorescence, and X-ray diffraction analysis. We concluded that the total acidity and specific morphology of reactors were the major factors influencing activity and selectivity toward CH₄, C_2–4, and C₅₊ hydrocarbons in the Fischer–Tropsch process. Use of ethylenediaminetetraacetic acid for ruthenium binding gave a methanation catalyst with ca. 50% selectivity to methane and C_2–4. Urea-modified halloysite resulted in the Ru-nanoreactors with high selectivity to valuable C₅₊ hydrocarbons containing few olefins and a high number of heavy fractions (α = 0.87). Modification with acetone azine gave the slightly higher CO conversion rate close to 19% and highest selectivity in C₅₊ products. Using a halloysite tube with a 10–20-nm lumen decreased the diffusion limitation and helped to produce high-molecular-weight hydrocarbons. The extremely small C₂–C₄ fraction obtained from the urea- and azine-modified sample was not reachable for non-templated Ru-nanoparticles. Dense packing of Ru nanoparticles increased the contact time of olefins and their reabsorption, producing higher amounts of C₅₊ hydrocarbons. Loading of Ru inside the nanoclay increased the particle stability and prevented their aggregation under reaction conditions. Full article

To determine the impact of oral physiology on the volatility of typical wine aroma compounds, mixtures of a synthetic wine with oral components (centrifuged human saliva (HS), artificial saliva with mucin (AS), and buccal epithelial cells (BC)) were prepared. Each wine type was independently spiked with four relevant wine odorants (guaiacol, β-phenyl ethanol, ethyl hexanoate, and β-ionone). Additionally, the impact of four types of phenolic compounds (gallic acid, catechin, grape seed extract, and a red wine extract) on aroma volatility in the HS, AS, and BC wines was also assessed. Static headspace was measured at equilibrium by solid phase microextraction–GC/MS analysis. Results showed a significant impact of oral components on the volatility of the four tested odorants. Independently of the type of aroma compound, aroma volatility was in general, higher in wines with BC. Moreover, while guaiacol and ethyl hexanoate volatility was significantly lower in wines with HS compared to wines with AS, β-ionone showed the opposite behavior, which might be related to metabolism and retention of mucin, respectively. Phenolic compounds also showed a different effect on aroma volatility depending on the type of compound and wine. Gallic acid had little effect on polar compounds but it enhanced the volatility of the most hydrophobic ones (ethyl hexanoate and β-ionone). In general, flavonoid type polyphenols significantly reduced the volatility of both polar (guaiacol and β-phenyl ethanol) and hydrophobic compounds (β-ionone in HS and BC wines), but through different mechanisms (e.g., π–π interactions and hydrophobic binding for polar and apolar odorants respectively). On the contrary, flavonoids enhanced the volatility of ethyl hexanoate, which might be due to the inhibition exerted on some salivary enzymes (e.g., carboxyl esterase) involved in the metabolism of this odorant molecule. Full article

Catalysts are essential for mediating a controlled polymerization in atom transfer radical polymerization (ATRP). Copper-based catalysts are widely explored in ATRP and are highly efficient, leading to well-controlled polymerization of a variety of functional monomers. In addition to copper, iron-based complexes offer new opportunities in ATRP catalysis to develop environmentally friendly, less toxic, inexpensive, and abundant catalytic systems. Despite the high efficiency of iron catalysts in controlling polymerization of various monomers including methacrylates and styrene, ATRP of acrylate-based monomers by iron catalysts still remains a challenge. In this paper, we review the fundamentals and recent advances of iron-catalyzed ATRP focusing on development of ligands, catalyst design, and techniques used for iron catalysis in ATRP. Full article

Periodic local vibrational modes were calculated with the rev-vdW-DF2 density functional to quantify the intrinsic strength of the X-I⋯OA-type halogen bonding (X = I or Cl; OA: carbonyl, ether and N-oxide groups) in 32 model systems originating from 20 molecular crystals. We found that the halogen bonding between the donor dihalogen X-I and the wide collection of acceptor molecules OA features considerable variations of the local stretching force constants (0.1–0.8 mdyn/Å) for I⋯O halogen bonds, demonstrating its powerful tunability in bond strength. Strong correlations between bond length and local stretching force constant were observed in crystals for both the donor X-I bonds and I⋯O halogen bonds, extending for the first time the generalized Badger’s rule to crystals. It is demonstrated that the halogen atom X controlling the electrostatic attraction between the $\sigma$ -hole on atom I and the acceptor atom O dominates the intrinsic strength of I⋯O halogen bonds. Different oxygen-containing acceptor molecules OA and even subtle changes induced by substituents can tweak the $n\to {\sigma }^{\ast }$ (X-I) charge transfer character, which is the second important factor determining the I⋯O bond strength. In addition, the presence of the second halogen bond with atom X of the donor X-I bond in crystals can substantially weaken the target I⋯O halogen bond. In summary, this study performing the in situ measurement of halogen bonding strength in crystalline structures demonstrates the vast potential of the periodic local vibrational mode theory for characterizing and understanding non-covalent interactions in materials. Full article

We created a new library of disordered patterns and disordered residues in the Protein Data Bank (PDB). To obtain such datasets, we clustered the PDB and obtained the groups of chains with different identities and marked disordered residues. We elaborated a new procedure for finding disordered patterns and created a new version of the library. This library includes three sets of patterns: unique patterns, patterns consisting of two kinds of amino acids, and homo-repeats. Using this database, the user can: (1) find homologues in the entire Protein Data Bank; (2) perform a statistical analysis of disordered residues in protein structures; (3) search for disordered patterns and homo-repeats; (4) search for disordered regions in different chains of the same protein; (5) download clusters of protein chains with different identity from our database and library of disordered patterns; and (6) observe 3D structure interactively using MView. A new library of disordered patterns will help improve the accuracy of predictions for residues that will be structured or unstructured in a given region. Full article

Flow chemistry is an area of contemporary chemistry exploiting the hydrodynamic conditions of flowing liquids to provide particular environments for chemical reactions. These particular conditions of enhanced and strictly regulated transport of reagents, improved interface contacts, intensification of heat transfer, and safe operation with hazardous chemicals can be utilized in chemical synthesis, both for mechanization and automation of analytical procedures, and for the investigation of the kinetics of ultrafast reactions. Such methods are developed for more than half a century. In the field of chemical synthesis, they are used mostly in pharmaceutical chemistry for efficient syntheses of small amounts of active substances. In analytical chemistry, flow measuring systems are designed for environmental applications and industrial monitoring, as well as medical and pharmaceutical analysis, providing essential enhancement of the yield of analyses and precision of analytical determinations. The main concept of this review is to show the overlapping of development trends in the design of instrumentation and various ways of the utilization of specificity of chemical operations under flow conditions, especially for synthetic and analytical purposes, with a simultaneous presentation of the still rather limited correspondence between these two main areas of flow chemistry. Full article

Perylenediimide (PDI) is one of the most important classes of dyes and is intensively explored in the field of functional organic materials. The functionalization of this electron-deficient aromatic core is well-known to tune the outstanding optoelectronic properties of PDI derivatives. In this respect, the functionalization has been mostly addressed in bay-positions to halogenated derivatives through nucleophilic substitutions or metal-catalyzed coupling reactions. Being aware of the synthetic difficulties of obtaining the key intermediate 1-bromoPDI, we will present as an alternative in this review the potential of 1-nitroPDI: a powerful building block to access a large variety of PDI-based materials. Full article

Drug development is one of the most significant processes in the pharmaceutical industry. Various computational methods have dramatically reduced the time and cost of drug discovery. In this review, we firstly discussed roles of multiscale biomolecular simulations in identifying drug binding sites on the target macromolecule and elucidating drug action mechanisms. Then, virtual screening methods (e.g., molecular docking, pharmacophore modeling, and QSAR) as well as structure- and ligand-based classical/de novo drug design were introduced and discussed. Last, we explored the development of machine learning methods and their applications in aforementioned computational methods to speed up the drug discovery process. Also, several application examples of combining various methods was discussed. A combination of different methods to jointly solve the tough problem at different scales and dimensions will be an inevitable trend in drug screening and design. Full article

Transition metal catalysis in modern organic synthesis has largely focused on noble transition metals like palladium, platinum and ruthenium. The toxicity and low abundance of these metals, however, has led to a rising focus on the development of the more sustainable base metals like iron, copper and nickel for use in catalysis. Iron is a particularly good candidate for this purpose due to its abundance, wide redox potential range, and the ease with which its properties can be tuned through the exploitation of its multiple oxidation states, electron spin states and redox potential. This is a fact made clear by all life on Earth, where iron is used as a cornerstone in the chemistry of living processes. In this mini review, we report on the general advancements in the field of iron catalysis in organic chemistry covering addition reactions, C-H activation, cross-coupling reactions, cycloadditions, isomerization and redox reactions. Full article

Mascarpone, a soft-spread cheese, is an unripened dairy product manufactured by the thermal-acidic coagulation of milk cream. Due to the mild flavor and creamy consistency, it is a base ingredient in industrial, culinary, and homemade preparations (e.g., it is a key constituent of a widely appreciated Italian dessert ‘Tiramisù’). Probably due to this relevance as an ingredient rather than as directly consumed foodstuff, mascarpone has not been often the subject of detailed studies. To the best of our knowledge, no investigation has been carried out on the volatile compounds contributing to the mascarpone cheese aroma profile. In this study, we analyzed the Volatile Organic Compounds (VOCs) in the headspace of different commercial mascarpone cheeses by two different techniques: Headspace-Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS-SPME GC-MS) and Proton-Transfer Reaction-Mass Spectrometry coupled to a Time of Flight mass analyzer (PTR-ToF-MS). We coupled these two approaches due to the complementarity of the analytical potential—efficient separation and identification of the analytes on the one side (HS-SPME GC-MS), and effective, fast quantitative analysis without any sample preparation on the other (PTR-ToF-MS). A total of 27 VOCs belonging to different chemical classes (9 ketones, 5 alcohols, 4 organic acids, 3 hydrocarbons, 2 furans, 1 ester, 1 lactone, 1 aldehyde, and 1 oxime) have been identified by HS-SPME GC-MS, while PTR-ToF-MS allowed a rapid snapshot of volatile diversity confirming the aptitude to rapid noninvasive quality control and the potential in commercial sample differentiation. Ketones (2-heptanone and 2-pentanone, in particular) are the most abundant compounds in mascarpone headspace, followed by 2-propanone, 2-nonanone, 2-butanone, 1-pentanol, 2-ethyl-1-hexanol, furfural and 2-furanmethanol. The study also provides preliminary information on the differentiation of the aroma of different brands and product types. Full article

We describe here a mechanistic study of the iron-catalyzed carboazidation of alkenes involving an intriguing metal-assisted β-methyl scission process. Although t-BuO radical has frequently been observed in experiments, the β-methyl scission from a t-BuO radical into a methyl radical and acetone is still broadly believed to be thermodynamically spontaneous and difficult to control. An iron-catalyzed β-methyl scission of t-BuO is investigated in this work. Compared to a free t-BuO radical, the coordination at the iron atom reduces the activation energy for the scission from 9.3 to 3.9 ~ 5.2 kcal/mol. The low activation energy makes the iron-catalyzed β-methyl scission of t-BuO radicals almost an incomparably facile process and explains the selective formation of methyl radicals at low temperature in the presence of some iron catalysts. In addition, a radical relay process and an outer-sphere radical azidation process in the iron-catalyzed carboazidation of alkenes are suggested by density functional theory (DFT) calculations. Full article

There are many areas in medicine and industry where it would be advantageous to orally deliver bioactive proteins and peptides (BPPs), including ACE inhibitors, antimicrobials, antioxidants, hormones, enzymes, and vaccines. A major challenge in this area is that many BPPs degrade during storage of the product or during passage through the human gut, thereby losing their activity. Moreover, many BPPs have undesirable taste profiles (such as bitterness or astringency), which makes them unpleasant to consume. These challenges can often be overcome by encapsulating them within colloidal particles that protect them from any adverse conditions in their environment, but then release them at the desired site-of-action, which may be inside the gut or body. This article begins with a discussion of BPP characteristics and the hurdles involved in their delivery. It then highlights the characteristics of colloidal particles that can be manipulated to create effective BPP-delivery systems, including particle composition, size, and interfacial properties. The factors impacting the functional performance of colloidal delivery systems are then highlighted, including their loading capacity, encapsulation efficiency, protective properties, retention/release properties, and stability. Different kinds of colloidal delivery systems suitable for encapsulation of BPPs are then reviewed, such as microemulsions, emulsions, solid lipid particles, liposomes, and microgels. Finally, some examples of the use of colloidal delivery systems for delivery of specific BPPs are given, including hormones, enzymes, vaccines, antimicrobials, and ACE inhibitors. An emphasis is on the development of food-grade colloidal delivery systems, which could be used in functional or medical food applications. The knowledge presented should facilitate the design of more effective vehicles for the oral delivery of bioactive proteins and peptides. Full article

Eutectic systems offer a wide range of new (green) designer solvents for diverse applications. However, due to the large pool of possible compounds, selecting compounds that form eutectic systems is not straightforward. In this study, a simple approach for preselecting possible candidates from a pool of substances sharing the same chemical functionality was presented. First, the melting entropy of single compounds was correlated with their molecular structure to calculate their melting enthalpy. Subsequently, the eutectic temperature of the screened binary systems was qualitatively predicted, and the systems were ordered according to the depth of the eutectic temperature. The approach was demonstrated for six hydrophobic eutectic systems composed of L-menthol and monocarboxylic acids with linear and cyclic structures. It was found that the melting entropy of compounds sharing the same functionality could be well correlated with their molecular structures. As a result, when the two acids had a similar melting temperature, the melting enthalpy of a rigid acid was found to be lower than that of a flexible acid. It was demonstrated that compounds with more rigid molecular structures could form deeper eutectics. The proposed approach could decrease the experimental efforts required to design deep eutectic solvents, particularly when the melting enthalpy of pure components is not available. Full article

The exceptional reactivity of the azide group makes organic azides a highly versatile family of compounds in chemistry and the material sciences. One of the most prominent reactions employing organic azides is the regioselective copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition with alkynes yielding 1,2,3-triazoles. Other named reactions include the Staudinger reduction, the aza-Wittig reaction, and the Curtius rearrangement. The popularity of organic azides in material sciences is mostly based on their propensity to release nitrogen by thermal activation or photolysis. On the one hand, this scission reaction is accompanied with a considerable output of energy, making them interesting as highly energetic materials. On the other hand, it produces highly reactive nitrenes that show extraordinary efficiency in polymer crosslinking, a process used to alter the physical properties of polymers and to boost efficiencies of polymer-based devices such as membrane fuel cells, organic solar cells (OSCs), light-emitting diodes (LEDs), and organic field-effect transistors (OFETs). Thermosets are also suitable application areas. In most cases, organic azides with multiple azide functions are employed which can either be small molecules or oligo- and polymers. This review focuses on nitrene-based applications of multivalent organic azides in the material and life sciences. Full article

Arene C(sp²)-H bond borylation reactions provide rapid and efficient routes to synthetically versatile boronic esters. While iridium catalysts are well established for this reaction, the discovery and development of methods using Earth-abundant alternatives is limited to just a few examples. Applying an in situ catalyst activation method using air-stable and easily handed reagents, the iron-catalysed C(sp²)-H borylation reactions of furans and thiophenes under blue light irradiation have been developed. Key reaction intermediates have been prepared and characterised, and suggest two mechanistic pathways are in action involving both C-H metallation and the formation of an iron boryl species. Full article

The direct C-H functionalization reaction is one of the most efficient strategies by which to introduce new functional groups into small organic molecules. Over time, iron complexes have emerged as versatile catalysts for carbine-transfer reactions with diazoalkanes under mild and sustainable reaction conditions. In this review, we discuss the advances that have been made using iron catalysts to perform C-H functionalization reactions with diazoalkanes. We give an overview of early examples employing stoichiometric iron carbene complexes and continue with recent advances in the C-H functionalization of C(sp²)-H and C(sp³)-H bonds, concluding with the latest developments in enzymatic C-H functionalization reactions using iron-heme-containing enzymes. Full article

Hydrophilic interaction liquid chromatography (HILIC) and electrospray ionization (ESI) coupled to either Fourier-transform (FT) orbital-trap or linear ion-trap tandem mass spectrometry (LIT-MS/MS) was used to characterize the phospholipidome of yellow lupin (Lupinus luteus) seeds. Phosphatidylcholines (PC) were the most abundant species (41 ± 6%), which were followed by lyso-forms LPC (30 ± 11%), phosphatidylethanolamines (PE, 13 ± 4%), phosphatidylglycerols (PG, 5.1 ± 1.7%), phosphatidic acids (PA, 4.9 ± 1.8%), phosphatidylinositols (PI, 4.7 ± 1.1%), and LPE (1.2 ± 0.5%). The occurrence of both isomeric forms of several LPC and LPE was inferred by a well-defined fragmentation pattern observed in negative ion mode. An unprecedented characterization of more than 200 polar lipids including 52 PC, 42 PE, 42 PA, 35 PG, 16 LPC, 13 LPE, and 10 PI, is reported. The most abundant fatty acids (FA) as esterified acyl chains in PL were 18:1 (oleic), 18:2 (linoleic), 16:0 (palmitic), and 18:3 (linolenic) with relatively high contents of long fatty acyl chains such as 22:0 (behenic), 24:0 (lignoceric), 20:1 (gondoic), and 22:1 (erucic). Their occurrence was confirmed by reversed-phase (RP) LC-ESI-FTMS analysis of a chemically hydrolyzed sample extract in acid conditions at 100 °C for 45 min. Full article

Guanosine- and uridine-rich single-stranded RNA (GU-rich RNA) is an agonist of Toll-like receptor (TLR) 7 and TLR8 and induces strong immune responses. A nanostructured GU-rich RNA/DNA assembly prepared using DNA nanotechnology can be used as an adjuvant capable of improving the biological stability of RNA and promoting efficient RNA delivery to target immune cells. To achieve a sustained supply of GU-rich RNA to immune cells, we developed a GU-rich RNA/DNA hydrogel (RDgel) using nanostructured GU-rich RNA/DNA assembly, from which GU-rich RNA can be released in a sustained manner. A hexapod-like GU-rich RNA/DNA nanostructure, or hexapodRD6, was designed using a 20-mer phosphorothioate-stabilized GU-rich RNA and six phosphodiester DNAs. Two sets of hexapodRD6 were mixed to obtain RDgel. Under serum-containing conditions, GU-rich RNA was gradually released from the RDgel. Fluorescently labeled GU-rich RNA was efficiently taken up by DC2.4 murine dendritic cells and induced a high level of tumor necrosis factor-α release from these cells when it was incorporated into RDgel. These results indicate that the RDgel constructed using DNA nanotechnology can be a useful adjuvant in cancer therapy with sustained RNA release and high immunostimulatory activity. Full article

Human cathepsin L belongs to the cathepsin family of proteolytic enzymes with primarily an endopeptidase activity. Although its primary functions were originally thought to be only of a housekeeping enzyme that degraded intracellular and endocytosed proteins in lysosome, numerous recent studies suggest that it plays many critical and specific roles in diverse cellular settings. Not surprisingly, the dysregulated function of cathepsin L has manifested itself in several human diseases, making it an attractive target for drug development. Unfortunately, several redundant and isoform-specific functions have recently emerged, adding complexities to the drug discovery process. To address this, a series of chemical biology tools have been developed that helped define cathepsin L biology with exquisite precision in specific cellular contexts. This review elaborates on the recently developed small molecule inhibitors and probes of human cathepsin L, outlining their mechanisms of action, and describing their potential utilities in dissecting unknown function. Full article

The oxidative, dearomative cross-dehydrogenative coupling of indoles with various C-H nucleophiles is developed. This process features a broad substrate scope with respect to both indoles and nucleophiles, affording structurally diverse 2,2-disubstituted indolin-3-ones in high yields (up to 99%). The oxidative dimerization and trimerization of indoles has also been demonstrated under the same conditions. Full article

Onion is widely used worldwide in various forms for both food and medicinal applications, thanks to its high content of phytonutrients, such as flavonoids and volatile sulfur compounds. Fresh onion is very perishable and drying is widely applied for extending shelf-life, thus obtaining a very easy-to-use functional food ingredient. The flavonoid and volatile fractions of different onion cuts (flakes, rings) prepared through different drying cycles in a static oven, were characterized by high-performance liquid chromatography with a diode-array detector HPLC-DAD, Head Space-Solid Phase Micro Extraction followed by Gas Chromatography coupled with Mass Spectrometry (HS-SPME-GC-MS) and Head-Space Solid Phase Micro Extraction followed by comprehensive two-dimensional Gas-Chromatography (HS-SPME-GC×GC-TOF). Onion flakes showed a significantly higher flavonoid content (3.56 mg g⁻¹) than onion rings (2.04 mg g⁻¹). Onion flakes showed greater amount of volatile organic compounds (VOCs) (127.26 mg g⁻¹) than onion rings (42.79 mg g⁻¹), with different relative amounts of di- and trisulfides—disulfides largely predominate the volatile fraction (amounts over 60% on the total volatile content), followed by trisulfides and dipropyl disulfide and dipropyl trisulfide were the most abundant VOCs. HS-SPME-GC×GC-TOF allowed for the detection of the presence of allylthiol, diethanol sulfide, 4,6-diethyl1,2,3,5-tetrathiolane, not detected by HS-SPME-GC-MS, and provided a fast and direct visualization and comparison of different samples. These results highlight different nutraceutical properties of dried onion samples processed otherwise, only differing in shape and size, thus pointing out potentially different uses as functional ingredients. Full article

Pharmacophore modeling is usually considered as a special type of virtual screening without probabilistic nature. Correspondence of at least one conformation of a molecule to pharmacophore is considered as evidence of its bioactivity. We show that pharmacophores can be treated as one-class machine learning models, and the probability the reflecting model’s confidence can be assigned to a pharmacophore on the basis of their precision of active compounds identification on a calibration set. Two schemes (Max and Mean) of probability calculation for consensus prediction based on individual pharmacophore models were proposed. Both approaches to some extent correspond to commonly used consensus approaches like the common hit approach or the one based on a logical OR operation uniting hit lists of individual models. Unlike some known approaches, the proposed ones can rank compounds retrieved by multiple models. These approaches were benchmarked on multiple ChEMBL datasets used for ligand-based pharmacophore modeling and externally validated on corresponding DUD-E datasets. The influence of complexity of pharmacophores and their performance on a calibration set on results of virtual screening was analyzed. It was shown that Max and Mean approaches have superior early enrichment to the commonly used approaches. Thus, a well-performing, easy-to-implement, and probabilistic alternative to existing approaches for pharmacophore-based virtual screening was proposed. Full article

Graphene is the prototype of two-dimensional (2D) materials, whose main feature is the extremely large surface-to-mass ratio. This property is interesting for a series of applications that involve interactions between particles and surfaces, such as, for instance, gas, fluid or charge storage, catalysis, and filtering. However, for most of these, a volumetric extension is needed, while preserving the large exposed surface. This proved to be rather a hard task, especially when specific structural features are also required (e.g., porosity or density given). Here we review the recent experimental realizations and theoretical/simulation studies of 3D materials based on graphene. Two main synthesis routes area available, both of which currently use (reduced) graphene oxide flakes as precursors. The first involves mixing and interlacing the flakes through various treatments (suspension, dehydration, reduction, activation, and others), leading to disordered nanoporous materials whose structure can be characterized a posteriori, but is difficult to control. With the aim of achieving a better control, a second path involves the functionalization of the flakes with pillars molecules, bringing a new class of materials with structure partially controlled by the size, shape, and chemical-physical properties of the pillars. We finally outline the first steps on a possible third road, which involves the construction of pillared multi-layers using epitaxial regularly nano-patterned graphene as precursor. While presenting a number of further difficulties, in principle this strategy would allow a complete control on the structural characteristics of the final 3D architecture. Full article

Aryl benzoates are compounds of high importance in organic synthesis. Herein, we report the iron-catalyzed C(sp²)–C(sp³) Kumada cross-coupling of aryl chlorobenzoates with alkyl Grignard reagents. The method is characterized by the use of environmentally benign and sustainable iron salts for cross-coupling in the catalytic system, employing benign urea ligands in the place of reprotoxic NMP (NMP = N-methyl-2-pyrrolidone). It is notable that high selectivity for the cross-coupling is achieved in the presence of hydrolytically-labile and prone to nucleophilic addition phenolic ester C(acyl)–O bonds. The reaction provides access to alkyl-functionalized aryl benzoates. The examination of various O-coordinating ligands demonstrates the high activity of urea ligands in promoting the cross-coupling versus nucleophilic addition to the ester C(acyl)–O bond. The method showcases the functional group tolerance of iron-catalyzed Kumada cross-couplings. Full article

The sweet-mellow taste sensation is a unique and typical feature of premium congou black tea infusions. To explore the key taste-active compounds that influence the sweet-mellow taste, a sensory and molecular characterization was performed on thirty-three congou black tea infusions presenting different taste qualities, including the sweet-mellow, mellow-pure, or less-mellow taste. An integrated application of quantitative analysis of 48 taste-active compounds, taste contribution analysis, and further validation by taste supplementation experiments, combined with human sensory evaluation revealed that caffeine, γ-aminobutyric acid, rutin, succinic acid, citric acid, and gallic acid negatively affect the sweet-mellow taste, whereas glucose, sucrose, and ornithine positively contribute to the sweet-mellow taste of congou black tea infusions. Particularly, rutin, γ-aminobutyric acid, gallic acid, and caffeine, which impart the major inhibitory effect to the manifestation of the sweet-mellow taste, were identified as the key influencing components through stepwise screening and validation experiments. A modest level of these compounds was found to be favorable for the development and manifestation of the sweet-mellow taste. These compounds might potentially serve as the regulatory targets for oriented-manufacturing of high-quality sweet-mellow congou black tea. Full article

Ring-opening polymerization (ROP) of cyclic esters (lactones, lactides, cyclic carbonates and phosphates) is an effective tool to synthesize biocompatible and biodegradable polymers. Metal complexes effectively catalyze ROP, a remarkable diversity of the ROP mechanisms prompted the use of density functional theory (DFT) methods for simulation and visualization of the ROP pathways. Optimization of the molecular structures of the key reaction intermediates and transition states has allowed to explain the values of catalytic activities and stereocontrol events. DFT computation data sets might be viewed as a sound basis for the design of novel ROP catalysts and cyclic substrates, for the creation of new types of homo- and copolymers with promising properties. In this review, we summarized the results of DFT modeling of coordination ROP of cyclic esters. The importance to understand the difference between initiation and propagation stages, to consider the possibility of polymer–catalyst coordination, to figure out the key transition states, and other aspects of DFT simulation and visualization of ROP have been also discussed in our review. Full article

Redox flow batteries (RFBs), provide a safe and cost-effective means of storing energy at grid-scale, and will play an important role in the decarbonization of global electricity networks. Several approaches have been explored to improve their efficiency and power density, and recently, cell geometry modification has shown promise in efforts to address mass transport limitations which affect electrochemical and overall system performance. Flow-by electrode configurations have demonstrated significant power density improvements in laboratory testing, however, flow-through designs with conductive felt remain the standard at commercial scale. Concentration gradients exist within these cells, limiting their performance. A new concept of redistributing reactants within the flow frame is introduced in this paper. This research shows a 60% improvement in minimum V³⁺ concentration within simulated vanadium redox flow battery (VRB/VRFB) cells through the application of static mixers. The enhanced reactant distribution showed a cell voltage improvement by reducing concentration overpotential, suggesting a pathway forward to increase limiting current density and cycle efficiencies in RFBs. Full article

Malaria and cancer are chronic diseases. The challenge with drugs available for the treatment of these diseases is drug toxicity and resistance. Ferrocene is a potent organometallic which have been hybridized with other compounds resulting in compounds with enhanced biological activity such as antimalarial and anticancer. Drugs such as ferroquine were developed from ferrocene and chloroquine. It was tested in the 1990s as an antimalarial and is still an effective antimalarial. Many researchers have reported ferrocene compounds as potent compounds useful as anticancer and antimalarial agents when hybridized with other pharmaceutical scaffolds. This review will be focused on compounds with ferrocene moieties that exhibit either an anticancer or antimalarial activity. Full article

As one of the most efficient pathways to provide clean energy, fuel cells have attracted great attention in both academic and industrial communities. Proton exchange membranes (PEMs) or proton-conducting electrolytes are the key components in fuel cell devices, which require the characteristics of high proton conductivity as well as high mechanical, chemical and thermal stabilities. Organic–inorganic hybrid PEMs can provide a fantastic platform to combine both advantages of two components to meet these demands. Due to their extremely high proton conductivity, good thermal stability and chemical adjustability, polyoxometalates (POMs) are regarded as promising building blocks for hybrid PEMs. In this review, we summarize a number of research works on the progress of POM–polymer hybrid materials and related applications in PEMs. Firstly, a brief background of POMs and their proton-conducting properties are introduced; then, the hybridization strategies of POMs with polymer moieties are discussed from the aspects of both noncovalent and covalent concepts; and finally, we focus on the performance of these hybrid materials in PEMs, especially the advances in the last five years. This review will provide a better understanding of the challenges and perspectives of POM–polymer hybrid PEMs for future fuel cell applications. Full article

Noble gases (Ngs) are the least reactive elements in the periodic table towards chemical bond formation when compared with other elements because of their completely filled valence electronic configuration. Very often, extreme conditions like low temperatures, high pressures and very reactive reagents are required for them to form meaningful chemical bonds with other elements. In this personal account, we summarize our works to date on Ng complexes where we attempted to theoretically predict viable Ng complexes having strong bonding to synthesize them under close to ambient conditions. Our works cover three different types of Ng complexes, viz., non-insertion of NgXY type, insertion of XNgY type and Ng encapsulated cage complexes where X and Y can represent any atom or group of atoms. While the first category of Ng complexes can be thermochemically stable at a certain temperature depending on the strength of the Ng-X bond, the latter two categories are kinetically stable, and therefore, their viability and the corresponding conditions depend on the size of the activation barrier associated with the release of Ng atom(s). Our major focus was devoted to understand the bonding situation in these complexes by employing the available state-of-the-art theoretic tools like natural bond orbital, electron density, and energy decomposition analyses in combination with the natural orbital for chemical valence theory. Intriguingly, these three types of complexes represent three different types of bonding scenarios. In NgXY, the strength of the donor-acceptor Ng→XY interaction depends on the polarizing power of binding the X center to draw the rather rigid electron density of Ng towards itself, and sometimes involvement of such orbitals becomes large enough, particularly for heavier Ng elements, to consider them as covalent bonds. On the other hand, in most of the XNgY cases, Ng forms an electron-shared covalent bond with X while interacting electrostatically with Y representing itself as [XNg]⁺Y⁻. Nevertheless, in some of the rare cases like NCNgNSi, both the C-Ng and Ng-N bonds can be represented as electron-shared covalent bonds. On the other hand, a cage host is an excellent moiety to examine the limits that can be pushed to attain bonding between two Ng atoms (even for He) at high pressure. The confinement effect by a small cage-like B₁₂N₁₂ can even induce some covalent interaction within two He atoms in the He₂@B₁₂N₁₂ complex. Full article

In the last decade, ion mobility spectrometry (IMS) has reemerged as an analytical separation technique, especially due to the commercialization of ion mobility mass spectrometers. Its applicability has been extended beyond classical applications such as the determination of chemical warfare agents and nowadays it is widely used for the characterization of biomolecules (e.g., proteins, glycans, lipids, etc.) and, more recently, of small molecules (e.g., metabolites, xenobiotics, etc.). Following this trend, the interest in this technique is growing among researchers from different fields including food science. Several advantages are attributed to IMS when integrated in traditional liquid chromatography (LC) and gas chromatography (GC) mass spectrometry (MS) workflows: (1) it improves method selectivity by providing an additional separation dimension that allows the separation of isobaric and isomeric compounds; (2) it increases method sensitivity by isolating the compounds of interest from background noise; (3) and it provides complementary information to mass spectra and retention time, the so-called collision cross section (CCS), so compounds can be identified with more confidence, either in targeted or non-targeted approaches. In this context, the number of applications focused on food analysis has increased exponentially in the last few years. This review provides an overview of the current status of IMS technology and its applicability in different areas of food analysis (i.e., food composition, process control, authentication, adulteration and safety). Full article

In the present work, promising proton conducting solid polymer blend electrolytes (SPBEs) composed of chitosan (CS) and methylcellulose (MC) were prepared for electrochemical double-layer capacitor (EDLC) application with a high specific capacitance and energy density. The change in intensity and the broad nature of the XRD pattern of doped samples compared to pure CS:MC system evidencedthe amorphous character of the electrolyte samples. The morphology of the samples in FESEM images supported the amorphous behavior of the solid electrolyte films. The results of impedance and Bode plotindicate that the bulk resistance decreasedwith increasing salt concentration. The highest DC conductivity was found to be 2.81 × 10⁻³ S/cm. The electrical equivalent circuit (EEC) model was conducted for selected samples to explain the complete picture of the electrical properties.The performance of EDLC cells was examined at room temperature by electrochemical techniques, such as impedance spectroscopy, cyclic voltammetry (CV) and constant current charge–discharge techniques. It was found that the studied samples exhibit a very good performance as electrolyte for EDLC applications. Ions were found to be the dominant charge carriers in the polymer electrolyte. The ion transference number (t_ion) was found to be 0.84 while 0.16 for electron transference number (t_el). Through investigation of linear sweep voltammetry (LSV), the CS:MC:NH₄SCN system was found to be electrochemically stable up to 1.8 V. The CV plot revealed no redox peak, indicating the occurrence of charge double-layer at the surface of activated carbon electrodes. Specific capacitance (C_spe) for the fabricated EDLC was calculated using CV plot and charge–discharge analyses. It was found to be 66.3 F g⁻¹ and 69.9 F g⁻¹ (at thefirst cycle), respectively. Equivalent series resistance (R_esr) of the EDLC was also identified, ranging from 50.0 to 150.0 Ω. Finally, energy density (E_d) was stabilized to anaverage of 8.63 Wh kg⁻¹ from the 10th cycle to the 100th cycle. The first cycle obtained power density (P_d) of 1666.6 W kg⁻¹ and then itdropped to 747.0 W kg⁻¹ at the 50th cycle and continued to drop to 555.5 W kg⁻¹ as the EDLC completed 100 cycles. Full article

Cannabis has regained much attention as a result of updated legislation authorizing many different uses and can be classified on the basis of the content of tetrahydrocannabinol (THC), a psychotropic substance for which there are legal limitations in many countries. For this purpose, accurate qualitative and quantitative determination is essential. The relationship between THC and cannabidiol (CBD) is also significant as the latter substance is endowed with many specific and non-psychoactive proprieties. For these reasons, it becomes increasingly important and urgent to utilize fast, easy, validated, and harmonized procedures for determination of cannabinoids. The procedure described herein allows rapid determination of 10 cannabinoids from the inflorescences of Cannabis sativa L. by extraction with organic solvents. Separation and subsequent detection are by RP-HPLC-UV. Quantification is performed by an external standard method through the construction of calibration curves using pure standard chromatographic reference compounds. The main cannabinoids dosed (g/100 g) in actual samples were cannabidiolic acid (CBDA), CBD, and Δ9-THC (Sample L11 CBDA 0.88 ± 0.04, CBD 0.48 ± 0.02, Δ9-THC 0.06 ± 0.00; Sample L5 CBDA 0.93 ± 0.06, CBD 0.45 ± 0.03, Δ9-THC 0.06 ± 0.00). The present validated RP-HPLC-UV method allows determination of the main cannabinoids in Cannabis sativa L. inflorescences and appropriate legal classification as hemp or drug-type. Full article

Food fraud, being the act of intentional adulteration of food for financial advantage, has vexed the consumers and the food industry throughout history. According to the European Committee on the Environment, Public Health and Food Safety, fruit juices are included in the top 10 food products that are most at risk of food fraud. Therefore, reliable, efficient, sensitive and cost-effective analytical methodologies need to be developed continuously to guarantee fruit juice quality and safety. This review covers the latest advances in the past ten years concerning the targeted and non-targeted methodologies that have been developed to assure fruit juice authenticity and to preclude adulteration. Emphasis is placed on the use of hyphenated techniques and on the constantly-growing role of MS-based metabolomics in fruit juice quality control area. Full article

The planning and development of new chiral stationary phases (CSPs) for liquid chromatography (LC) are considered as continuous and evolutionary issues since the introduction of the first CSP in 1938. The main objectives of the development strategies were to attempt the improvement of the chromatographic enantioresolution performance of the CSPs as well as enlarge their versatility and range of applications. Additionally, the transition to ultra-high-performance LC were underscored. The most recent strategies have comprised the introduction of new chiral selectors, the use of new materials as chromatographic supports or the reduction of its particle size, and the application of different synthetic approaches for preparation of CSPs. This review gathered the most recent developments associated to the different types of CSPs providing an overview of the relevant advances that are arising on LC. Full article

We present a Raman study on the phase transitions of organic/inorganic hybrid perovskite materials, CH₃NH₃PbX₃ (X = I, Br), which are used as solar cells with high power conversion efficiency. The temperature dependence of the Raman bands of CH₃NH₃PbX₃ (X = I, Br) was measured in the temperature ranges of 290 to 100 K for CH₃NH₃PbBr₃ and 340 to 110 K for CH₃NH₃PbI₃. Broad ν₁ bands at ~326 cm⁻¹ for MAPbBr₃ and at ~240 cm⁻¹ for MAPbI₃ were assigned to the MA–PbX₃ cage vibrations. These bands exhibited anomalous temperature dependence, which was attributable to motional narrowing originating from fast changes between the orientational states of CH₃NH₃⁺ in the cage. Phase transitions were characterized by changes in the bandwidths and peak positions of the MA–cage vibration and some bands associated with the NH₃⁺ group. Full article

Can two sites of positive electrostatic potential localized on the outer surfaces of two halogen atoms (and especially fluorine) in different molecular domains attract each other to form a non-covalent engagement? The answer, perhaps counterintuitive, is yes as shown here using the electronic structures and binding energies of the interactions for a series of 22 binary complexes formed between identical or different atomic domains in similar or related halogen-substituted molecules containing fluorine. These were obtained using various computational approaches, including density functional and ab initio first-principles theories with M06-2X, RHF, MP2 and CCSD(T). The physical chemistry of non-covalent bonding interactions in these complexes was explored using both Quantum Theory of Atoms in Molecules and Symmetry Adapted Perturbation Theories. The surface reactivity of the 17 monomers was examined using the Molecular Electrostatic Surface Potential approach. We have demonstrated inter alia that the dispersion term, the significance of which is not always appreciated, which emerges either from an energy decomposition analysis, or from a correlated calculation, plays a structure-determining role, although other contributions arising from electrostatic, exchange-repulsion and polarization effects are also important. The 0.0010 a.u. isodensity envelope, often used for mapping the electrostatic potential is found to provide incorrect information about the complete nature of the surface reactive sites on some of the isolated monomers, and can lead to a misinterpretation of the results obtained. Full article

Eight new polymerizable ammonium-TFSI ionic liquids were synthesized and characterized with respect to an application in energy storage devices. The ionic liquids feature methacrylate or acrylate termination as polymerizable groups. The preparation was optimized to obtain the precursors and ionic liquids in high yield. All products were characterized by NMR and IR spectroscopy. Phase transition temperatures were obtained by DSC analysis. Density, viscosity and ionic conductivity of the ionic liquids were compared and discussed. The results reveal that the length of attached alkyl groups as well as the methyl group at the polymerizable function have significant influences on the ionic liquids physicochemical properties. Ionic conductivity values vary between 0.264 mS cm⁻¹ for [C₂N_A,22]TFSI and 0.080 mS cm⁻¹ for [C₈N_MA,22]TFSI at 25 °C. Viscosity values are within a range of 0.762 Pa s for [C₂N_A,22]TFSI and 1.522 Pa s for [C₆N_MA,22]TFSI at 25 °C. Full article

Previous work has demonstrated that a bidentate receptor containing a pair of Sn atoms can engage in very strong interactions with halide ions via tetrel bonds. The question that is addressed here concerns the possibility that a receptor of this type might be designed that would preferentially bind a polyatomic over a monatomic anion since the former might better span the distance between the two Sn atoms. The binding of Cl⁻ was thus compared to that of HCOO⁻, HSO₄⁻, and H₂PO₄⁻ with a wide variety of bidentate receptors. A pair of SnFH₂ groups, as strong tetrel-binding agents, were first added to a phenyl ring in ortho, meta, and para arrangements. These same groups were also added in 1,3 and 1,4 positions of an aliphatic cyclohexyl ring. The tetrel-bonding groups were placed at the termini of (-C≡C-)_n (n = 1,2) extending arms so as to further separate the two Sn atoms. Finally, the Sn atoms were incorporated directly into an eight-membered ring, rather than as appendages. The ordering of the binding energetics follows the HCO₂⁻ > Cl⁻ > H₂PO₄⁻ > HSO₄⁻ general pattern, with some variations in selected systems. The tetrel bonding is strong enough that in most cases, it engenders internal deformations within the receptors that allow them to engage in bidentate bonding, even for the monatomic chloride, which mutes any effects of a long Sn···Sn distance within the receptor. Full article