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Both condensed and hydrolysable tannins represent versatile natural polyphenolic structures exhibiting a broad range of activities that could be exploited in various fields including nutraceutics, cosmesis, consumer care, household and pharmaceutical applications. Various tannins are commercially available nowadays for use in such application fields. We have analysed a representative selection of commercially available condensed and hydrolysable tannins for structural features and purity. Using a combination of quantitative31 P NMR spectroscopy, HSQC measurements, MALDI-ToF analyses, gel permeation chromatography and wet chemical analysis, detailed structural characterisations and descriptions were possible, allowing for verification and falsification of claimed structural features.

Novel valorization routes for tannins were opened by the development of a simple, straightforward, robust, and flexible approach to the selective functionalization of condensed and hydrolyzable tannins. Irrespective of the different degrees of polymerization, different commercial tannins were efficiently functionalized by the generation of an ether linkage bound to a short linker carrying the desired functional group. Functionalizations could be realized at varying degrees of technical loadings, i.e., amounts of introduced tannin-alien functionalities per number of phenolic hydroxyl groups. The same strategy was found suitable for the synthesis of polyethylene glycol-functionalized tannin copolymers. Condensed tannins functionalized with carboxylic acid moieties could be converted into a tannin-oligopeptide hybrid.

The generation of peptidomimetic substructures for medicinal chemistry purposes requires effective and divergent synthetic methods. We present in this work an efficient flow process that allows quick modulation of reagents for Joullié-Ugi multicomponent reaction, using spiroindolenines as core motifs. This sterically hindered imine equivalent could successfully be diversified using various isocyanides and amino acids in generally good space-time yields. A telescoped flow process combining interrupted Fischer reaction for spiroindolenine synthesis and subsequent Joullié-Ugi-type modification resulted in product formation in very good overall yield in less than 2 hours compared to 48 hours required in batch mode. The developed protocol can be seen as a general tool for rapid and facile generation of peptidomimetic compounds. We also showcase preliminary biological assessments for the prepared compounds.

Privileged scaffolds as starting points toward biologically active molecules represent a neuralgic point in drug discovery. The ability of synthetic chemists concerned with their generation should be flanked by robust technologies enabling the efficient synthesis and decoration of large libraries for extensive screenings and for scale-up processes. The use of continuous flow chemistry in the pharmaceutical chemistry sector may facilitate privileged scaffold generation and implementation of more efficient multistep transformations which can contribute to developing green and sustainable processes. This review discusses the use of flow chemistry applied to the synthesis of privileged scaffolds, considering also sustainability and green chemistry aspects. Flow protocols are discussed in a unified fashion such as to facilitate effective comparison between both the various chemical approaches used on the one hand, and the chosen technical solutions across the various works on the other hand. The review also offers an authors’ perspective on potential future directions in the field.

Microcapsules of sulfited Acacia mearnsii tannin (AmST-MCs) were generated for the first time via the sonochemical method. Their stability profile was assessed and set in the general context of tannin microcapsules (TMCs) generated under the same experimental conditions. The analytical data gathered in this work indicate an excellent stability of TMCs over time as well as under high temperature and pressure, which is a major milestone toward the meaningful applications of TMCs in industrial, pharmaceutical, and biomedical applications in which sterilization of TMCs might be a prerequisite. Active release is shown to be efficiently triggered by varying pH and/or salinity, with different profiles for TMCs from sulfited and nonsulfited species. Surfactants also affect the stability of TMCs significantly, with effects eventually amplifiable by pH and the inherent kosmotropic and chaotropic characteristics of salt components in solutions.

Eucalyptus nitens wood samples were subjected to consecutive stages of hydrothermal processing for hemicellulose solubilization and delignification with an ionic liquid, i.e., either 1-butyl-3-methylimidazolium hydrogen sulfate or triethylammonium hydrogen sulfate. Delignification experiments were carried out a 170 °C for 10–50 min. The solid phases from treatments, i.e., cellulose-enriched solids, were recovered by centrifugation, and lignin was separated from the ionic liquid by water precipitation. The best delignification conditions were identified on the basis of the results determined for delignification percentage, lignin recovery yield, and cellulose recovery in solid phase. The lignins obtained under selected conditions were characterized in deep by 31P-NMR, 13C-NMR, HSQC, and gel permeation chromatography. The major structural features of the lignins were discussed in comparison with the results determined for a model Ionosolv lignin.

Recently reported acetosolv soft- and hardwood lignins as well as ionosolv soft- and hardwood lignins were transformed into monomeric aromatic compounds using either a vanadate or a molybdate-based catalyst system. Monomers were generated with remarkable, catalyst-dependent selectivity and high depolymerisation yields via oxidative exo- and endo-depolymerisation processes. Using the vanadate-hydrogen peroxide system on acetosolv pine lignin, vanillin and isovanillin were produced as main products with depolymerisation yields of 31%. Using the molybdate system on acetosolv and ionosolv lignin, vanillic acid was the practically exclusive product, with depolymerisation yields of up to 72%. Similar selectivities, albeit with lower depolymerisation yields of around 50% under standardised conditions, were obtained for eucalyptus acetosolv lignin, producing vanillin and syringaldehyde or vanillic acid as products, by using the vanadate- or the molybdate-based systems respectively.

Thymol and the corresponding brominated derivatives constitute important biological active molecules as antibacterial, antioxidant, antifungal, and antiparasitic agents. However, their application is often limited, because their pronounced fragrance, their poor solubility in water, and their high volatility. The encapsulation of different thymol derivatives into biocompatible lignin-microcapsules is presented as a synergy-delivering remedy. The adoption of lignosulfonate as an encapsulating material possessing relevant antioxidant activity, as well as general biocompatibility allows for the development of new materials that are suitable for the application in various fields, especially cosmesis. To this purpose, lignin microcapsules containing thymol, 4-bromothymol, 2,4-dibromothymol, and the corresponding O-methylated derivatives have been efficiently prepared through a sustainable ultrasonication procedure. Actives could be efficiently encapsulated with efficiencies of up to 50%. To evaluate the applicability of such systems for topical purposes, controlled release experiments have been performed in acetate buffer at pH 5.4, to simulate skin pH: all of the capsules show a slow release of actives, which is strongly determined by their inherent lipophilicity.

This study demonstrates the effects of structural variations of lignins isolated via an organosolv process from different woody and herbaceous feedstocks on their thermal stability profiles. The organosolv lignins were first analysed for impurities, and structural features were determined using the default set of gel permeation chromatography, FT-IR spectroscopy, quantitative 31P NMR spectroscopy and semi-quantitative 1H-13C HSQC analysis. Pyrolysis-, O2-and CO2-reactivity of the organosolv lignins were investigated by thermogravimetric analysis (TGA), and volatile formation in various heating cycles was mapped by head-space GC-MS analysis. Revealed reactivities were correlated to the presence of identified impurities and structural features typical for the organosolv lignins. Data suggest that thermogravimetric analysis can eventually be used to delineate a lignin character when basic information regarding its isolation method is available.

Lignins were fractionated in a segmented continuous flow fractionation (SCFF) approach using isocratic or gradient elution profiles of different solvent systems at various flow rates and temperatures against adjustable pressure regimes. Superior control of parameters such as temperature and pressure in combination with the possibility of freely combinable solvent gradients allowed facile fractionation and generation of industrially interesting fractions differing in molecular weight properties and/or in physicochemical properties in a process that could be fully remotely controlled for automation and performance. Scale-up of the process was possible in linear and parallel mode. Analyses of the realised fractions by standardised gel permeation chromatography and 31P NMR spectroscopy protocols showed that the SCFF of lignins delivered fractions that could be similar to conventional batch fractions, as well as novel/altered fractions available by applying overheated solvents in pressurised systems.

Two different organosolv lignins (OSLs), that is, wheat straw and corn stover OSLs, were chemically and enzymatically functionalized. Functional groups were attached via the formation of stable ether bonds exploiting the reactivity of free phenolic OH groups along the lignin backbone. The functional groups introduced a range from compact charged and chargeable building blocks for the generation of surface-active lignins to oligomeric and polymeric species used in lignin block-copolymer productions. Combination of selected functions led to novel charged or chargeable polymeric lignin-based materials. Products could be realized with different degrees of technical loadings in terms of introduced functional groups.

One of the outstanding analytical problems in X-ray single-particle imaging (SPI) is the classification of structural heterogeneity, which is especially difficult given the low signal-to-noise ratios of individual patterns and the fact that even identical objects can yield patterns that vary greatly when orientation is taken into consideration. Proposed here are two methods which explicitly account for this orientation-induced variation and can robustly determine the structural landscape of a sample ensemble. The first, termed common-line principal component analysis (PCA), provides a rough classification which is essentially parameter free and can be run automatically on any SPI dataset. The second method, utilizing variation auto-encoders (VAEs), can generate 3D structures of the objects at any point in the structural landscape. Both these methods are implemented in combination with the noise-tolerant expand-maximize-compress (EMC) algorithm and its utility is demonstrated by applying it to an experimental dataset from gold nanoparticles with only a few thousand photons per pattern. Both discrete structural classes and continuous deformations are recovered. These developments diverge from previous approaches of extracting reproducible subsets of patterns from a dataset and open up the possibility of moving beyond the study of homogeneous sample sets to addressing open questions on topics such as nanocrystal growth and dynamics, as well as phase transitions which have not been externally triggered.

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The hippocampal formation (HF) processes spatial memories for cache locations in food-hoarding birds. Hoarding is a seasonal behavior, and seasonal changes in the HF have been described in some studies, but not in others. One potential reason is that birds may have been sampled during the seasonal hoarding peak in some studies, but not in others. In this study, we investigate the seasonal changes in hoarding and HF in willow tits (Poecile montanus). We compare this to seasonal changes in HF in a closely related non-hoarding bird, the great tit (Parus major). Willow tits near Oulu, Finland, show a seasonal hoarding peak in September and both HF volume and neuron number show a similar peak. HF neuronal density also increases in September, but then remains the same throughout winter. Unexpectedly, the great tit HF also changes seasonally, although in a different pattern: the great tit telencephalon increases in volume from July to August and decreases again in November. Great tit HF volume follows suit, but with a delay. Great tit HF neuron number and density also increase from August to September and stay high throughout winter. We hypothesize that seasonal changes in hoarding birds’ HF are driven by food-hoarding experience (e.g., the formation of thousands of memories). The seasonal changes in great tit brains may also be due to experience-dependent plasticity, responding to changes in the social and spatial environment. Large-scale experience-dependent neural plasticity is therefore probably not an adaptation of food-hoarding birds, but a general property of the avian HF and telencephalon.

Nature offers a diverse set of renewable biopolymers, among them the variety of natural polyphenols, whose structural diversity provides opportunities for further manipulation like the generation of chemicals and novel functional materials. These land‐based renewable biomaterials exhibit also a wide range of heterogeneous intrinsic reactivities and activities that render them ideal starting oligomeric and polymeric materials for the generation of multifunctional supramolecular structures as well as the development of high value-added materials. Lignins in particular display a variety of common physico‐chemical features that can be of enormous interest with respect to their eventual use in the pharmaceutical area. These natural polyphenols possess some interesting pharmaceutical properties such as antioxidant, anti‐inflammatory, antibacterial and eventually antiviral activities. In addition, based on their chemical features, i.e., oligomers and/or polymers of monolignol C9-building blocks. lignins can be exploited in the pharmaceutical sector mainly as material for generation of matrices and carriers for drug delivery. The present work attempts a review of the state of the art in lignin use in pharmaceutical applications.

An analytical approach based on phenol fluorescence labeling with the dansyl fluorophore coupled with gel permeation chromatography using UV and fluorescence detection was applied in an effort to increase the understanding of the phenolic group distribution in different lignin specimens. Selective derivatization with dansyl chloride of lignin phenolic functionalities was quantitatively achieved under mild reaction conditions and was applied to acidolytic and kraft lignins from softwood and hardwood and to kraft lignin fractions obtained by solvent fractionation. Acetylated lignins and labeled lignins were analyzed to discern the lignin aromatic skeleton input from the response of dansyl-linked phenols, successively, allowing for estimation of the phenolic group distribution as a function of molecular weight for different lignins before and after solvent fractionation.

Background Given the high prevalence of Cluster-C Personality Disorders (PDs) in clinical populations, disease burden, high societal costs and poor prognosis of comorbid disorders, a major gain in health care can be achieved if Cluster-C PDs are adequately treated. The only controlled cost-effectiveness study published so far found Individual Schema Therapy (IST) to be superior to Treatment as Usual (TAU). Group ST (GST) might improve cost-effectiveness as larger numbers can be treated in (>50%) less time compared to IST. However, to date there is no RCT supporting its (cost-) effectiveness. The overall aim of this study is to assess the evidence for GST for Cluster-C PDs and to improve treatment allocation for individual patients. Three main questions are addressed: 1) Is GST for Cluster-C PDs (cost-) effective compared to TAU? 2) Is GST for Cluster-C PDs (cost-) effective compared to IST? 3) Which patient-characteristics predict better response to GST, IST, or TAU? Methods In a multicenter RCT, the treatment conditions GST, IST, and TAU are compared in 378 Cluster-C PD patients within 10 sites. GST and IST follow treatment protocols and are completed within 1 year. TAU is the optimal alternative treatment available at the site according to regular procedures. Severity of the Cluster-C PD is the primary outcome, assessed with clinical interviews by independent raters blind for treatment. Functioning and wellbeing are important secondary outcomes. Assessments take place at week 0 (baseline), 17 (mid-GST), 34 (post-GST), 51 (postbooster sessions of GST), and 2 years (FU). Patient characteristics predicting better response to a specifc treatment are studied, e.g., childhood trauma, autistic features, and introversion. A tool supporting patients and clinicians in matching treatment to patient will be developed. An economic evaluation investigates the cost-effectiveness and costutility from a societal perspective. A process evaluation by qualitative