Advanced analytical approaches consisting of both LC-LTQ-Orbitrap Fourier transformed (FT)-MS and LC-time-of-flight-(TOF)-MS coupled to solid-phase extraction (SPE) NMR were used to obtain more insight into the complex phenolic composition of tea. On the basis of the combined structural information from (i) accurate mass fragmentation spectra, derived by using LC-Orbitrap FTMS n , and (ii) proton NMR spectra, derived after LC-TOFMS triggered SPE trapping of selected compounds, 177 phenolic compounds were annotated. Most of these phenolics were glycosylated and acetylated derivatives of flavan-3-ols and flavonols. Principal component analysis based on the relative abundance of the annotated phenolic compounds in 17 commercially available black, green, and white tea products separated the black teas from the green and white teas, with epicatechin-3,5-di-O-gallate and prodelphinidin-O-gallate being among the main discriminators. The results indicate that the combined use of LC-LTQ-Orbitrap FTMS and LC-TOFMS-SPE-NMR leads to a more comprehensive metabolite description and comparison of tea and other plant samples.

Carbon dots (CDs) are carbon-based fluorescent nanomaterials that are of interest in different research areas due to their low cost production and low toxicity. Considering their unique photophysical properties, hydrophobic/amphiphilic CDs are powerful alternatives to metal-based quantum dots in LED and photovoltaic cell designs. On the other hand, CDs possess a considerably high amount of surface defects that give rise to two significant drawbacks: (1) causing decrease in quantum yield (QY), a crucial drawback that limits their utilization in LEDs, and (2) affecting the efficiency of charge transfer, a significant factor that limits the use of CDs in photovoltaic cells. In this study, we synthesized highly luminescent, water-insoluble, slightly amphiphilic CDs by using a macrocyclic compound, calix[4]pyrrole, for the first time in the literature. Calix[4]pyrrole-derived CDs (CP-DOTs) were highly luminescent with a QY of over 60% and size of around 4–10 nm with graphitic structure. The high quantum yield of CP-DOTs indicated that they had less amount of surface defects. Furthermore, CP-DOTs were used as an additive in the active layer of organic solar cells (OSC). The photovoltaic parameters of OSCs improved upon addition of CDs. Our results indicated that calix[4]pyrrole is an excellent carbon precursor to synthesize highly luminescent and water-insoluble carbon dots, and CDs derived from calix[4]pyrrole are excellent candidates to improve optoelectronic devices.

3A type supramolecular monomers in which three calix[4]­pyrrole units connected to a central benzene unit with varying linker lengths were synthesized through azide–alkyne click reactions between two different azide cores and an alkyne-functionalized calix[4]­pyrrole. These compounds were then complexed with a BB-type monomer tetrabutylammonium suberate in chloroform and acetonitrile via hydrogen bonding between calix[4]­pyrrole units of 3A monomers and carboxylate units of suberate anions, leading to the formation of anion recognition-based supramolecular polymer networks. Owing to the dynamic noncovalent interactions, the resulting systems were found to be responsive against temperature, competing anions, and pH. Rheological analyses of the supramolecular polymer networks revealed that the system with a longer distance between the benzene core and calix[4]­pyrrole units exhibits transient network behavior and viscoelastic self-healing ability below 20% deformation ratio. These systems were also used for the fabrication of hierarchical materials ranging from zero-dimensional (0D) to three-dimensional (3D) by utilizing various methods. This work demonstrates for the first time the preparation of anion recognition-based supramolecular polymer networks based on calix[4]­pyrroles and their utilization in the formation of multiresponsive, self-healing materials for the fabrication of hierarchical materials.

An AB2‐type monomer comprised of a calix[4]pyrrole skeleton and alternating bis‐carboxylate units is reported and used for the construction of a novel supramolecular hyperbranched polymer based on anion recognition ability of calix[4]pyrrole. 1H‐, DOSY‐NMR spectroscopy, viscosity measurements, and dynamic light scattering techniques are used for the characterization of the supramolecular hyperbranched polymer exhibiting thermo‐, pH‐, and chemical responsiveness, as well as concentration dependent morphology tune as inferred from electron microscopy analyses. The present study enriches the field of supramolecular polymers with a new construction motif, building block, and provides a simple approach for the fabrication of smart polymer material with multi‐responsiveness and ‐morphologies.

Flavonoids are a class of natural compounds essentially produced by plants that are part of animal and human diets and have assumed health-promoting benefi ts. Upon human consumption, these fl avonoids are to a modest extent absorbed in the small intestines. The major part arrives in the colon where the microfl ora utilises and converts the fl avonoids to a wide range of products. Many of these products are absorbed in the major intestines and subsequently metabolised by the host. To understand the impact of the microfl ora on the metabolism and possible effects on human health, complete (and quantitative) identifi cation of the microbial as well as human metabolic conversion products of fl avonoids is required. This is a challenging task, as these bioconversion products are often present in relatively small amounts, making classical identifi cation strategies based on (accurate) mass information or nuclear magnetic resonance, not straightforward. In the absence of reference compounds, annotation of a component may be achieved by detailed expert evaluation, e.g. by searching for similar fragmentation patterns in spectral databases of known compounds. However, such manual analysis is a tedious task, and in advanced metabolite profi ling experiments, with large numbers of unknown metabolites, this is a major bottleneck. Therefore, new strategies are needed for quick and reliable identifi cation of the diverse range of molecules in complex matrices (faeces, blood, urine). Intelligent software for annotation and identifi cation of unknowns is crucial to fully exploit complex datasets. We developed a new software tool (MAGMA) for (sub)structure-based annotation of LC-MSn datasets which,