Simultaneous fractionation of multiple classes of polyphenols from honeybush tea using solid-phase extraction

The structural diversity of polyphenols and the inherent limitations of current extraction techniques pose a challenge to extract polyphenols using a simple and green method. Hence, in this study, a method was developed to simultaneously fractionate multiple classes of polyphenols by only varying ethanol-water solutions. Honeybush tea, which is rich in polyphenols, was selected as a model for this study. Solvent extraction followed by solid-phase extraction (SPE) was developed to obtain a polyphenol-rich fraction from six honeybush samples. Based on a gradient elution programme (10%, 30%, 50%, 70% and 90% (v/v) ethanol-water solution) of SPE, the Strata X cartridge showed a better recovery of most targeted polyphenols under 0.9 mL of the drying volume and 1 mL min⁻¹ of the dispensing speed. The elution programme for fractionating most polyphenols was as follows: single elution with 50% ethanol, followed by twice elution with 70% ethanol. The antioxidant capacity was used to analyse the differences among the polyphenol-rich fractions from six honeybush samples. Principal component analysis (PCA) revealed that unfermented C. genistoides (GG) has the greatest antioxidant capacity among the honeybush species studied. Additionally, mangiferin, isomangiferin and vicenin-2 were the main contributors to the antioxidant capacity in six honeybush fractions according to the correlation study.     

Superconducting Quantum Metamaterials from High Pressure Melt Infiltration of Metals into Block Copolymer Double Gyroid Derived Ceramic Templates

Mesoscale order can lead to emergent properties including phononic bandgaps or topologically protected states. Block copolymers offer a route to mesoscale periodic architectures, but their use as structure directing agents for metallic materials has not been fully realized. A versatile approach to mesostructured metals via bulk block copolymer self-assembly derived ceramic templates, is demonstrated. Molten indium is infiltrated into mesoporous, double gyroidal silicon nitride templates under high pressure to yield bulk, 3D periodic nanocomposites as free-standing monoliths which exhibit emergent quantum-scale phenomena. Vortices are artificially introduced when double gyroidal indium metal behaves as a type II superconductor, with evidence of strong pinning centers arrayed on the order of the double gyroid lattice size. Sample behavior is reproducible over months, showing high stability. High pressure infiltration of bulk block copolymer self-assembly based ceramic templates is an enabling tool for studying high-quality metals with previously inaccessible architectures, and paves the way for the emerging field of block-copolymer derived quantum metamaterials.     

Directed Evolution of a Cp*RhIII-Linked Biohybrid Catalyst Based on a Screening Platform with Affinity Purification

Directed evolution of Cp*Rh^III-linked nitrobindin (NB), a biohybrid catalyst, was performed based on an in vitro screening approach. A key aspect of this effort was the establishment of a high-throughput screening (HTS) platform that involves an affinity purification step employing a starch-agarose resin for a maltose binding protein (MBP) tag. The HTS platform enables efficient preparation of the purified MBP-tagged biohybrid catalysts in a 96-well format and eliminates background influence of the host E. coli cells. Three rounds of directed evolution and screening of more than 4000 clones yielded a Cp*Rh^III-linked NB(T98H/L100K/K127E) variant with a 4.9-fold enhanced activity for the cycloaddition of acetophenone oximes with alkynes. It is confirmed that this HTS platform for directed evolution provides an efficient strategy for generating highly active biohybrid catalysts incorporating a synthetic metal cofactor.     

Synthesis of the Antibiotic Precursor Thiazolyl‐7‐Aminocephalosporanic Acid in a Microstructured Flow System

The synthesis of thiazolyl‐7‐aminocephalosporanic acid, a pharmaceutical precursor of the β‐lactam antibiotic drug cefodizime, could be successfully realized in a continuous microstructured flow system. This was accomplished by changing the process window from batch, having a reaction temperature of 60 °C with a reaction time of 1 h, to a flow system at temperatures > 100 °C and reaction times of several minutes. The space‐time yield could be increased by a factor of 130.     

Plasmonic‐Induced Photon Recycling in Metal Halide Perovskite Solar Cells

Organic–inorganic metal halide perovskite solar cells have emerged in the past few years to promise highly efficient photovoltaic devices at low costs. Here, temperature‐sensitive core–shell Ag@TiO₂ nanoparticles are successfully incorporated into perovskite solar cells through a low‐temperature processing route, boosting the measured device efficiencies up to 16.3%. Experimental evidence is shown and a theoretical model is developed which predicts that the presence of highly polarizable nanoparticles enhances the radiative decay of excitons and increases the reabsorption of emitted radiation, representing a novel photon recycling scheme. The work elucidates the complicated subtle interactions between light and matter in plasmonic photovoltaic composites. Photonic and plasmonic schemes such as this may help to move highly efficient perovskite solar cells closer to the theoretical limiting efficiencies.     

Trans-Splicing Improvement by the Combined Application of Antisense Strategies

Spliceosome-mediated RNA trans-splicing has become an emergent tool for the repair of mutated pre-mRNAs in the treatment of genetic diseases. RNA trans-splicing molecules (RTMs) are designed to induce a specific trans-splicing reaction via a binding domain for a respective target pre-mRNA region. A previously established reporter-based screening system allows us to analyze the impact of various factors on the RTM trans-splicing efficiency in vitro. Using this system, we are further able to investigate the potential of antisense RNAs (AS RNAs), presuming to improve the trans-splicing efficiency of a selected RTM, specific for intron 102 of COL7A1. Mutations in the COL7A1 gene underlie the dystrophic subtype of the skin blistering disease epidermolysis bullosa (DEB). We have shown that co-transfections of the RTM and a selected AS RNA, interfering with competitive splicing elements on a COL7A1-minigene (COL7A1-MG), lead to a significant increase of the RNA trans-splicing efficiency. Thereby, accurate trans-splicing between the RTM and the COL7A1-MG is represented by the restoration of full-length green fluorescent protein GFP on mRNA and protein level. This mechanism can be crucial for the improvement of an RTM-mediated correction, especially in cases where a high trans-splicing efficiency is required.     

A Dynamic Combinatorial Approach for Identifying Side Groups that Stabilize DNA-Templated Supramolecular Self-Assemblies

DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.     

Effects of skim milk concentrate dry matter and spray drying air temperature on formation of capsules with varying particle size and the survival microbial cultures in a microcapsule matrix

The impact of total solid (TS) content in combination with the feed rate and air inlet temperature on the survival of Lactobacillus paracasei ssp. paracasei F19 after spray drying in a skim milk matrix has been investigated and correlated with the capsule size. Depending on the experimental conditions, the survival rates ranged from 64 to 0.2%. The higher the air inlet temperature, the lower was the survival rate and an inversely correlation between the TS content and particle size has been determined. These results clearly indicate that process stress analyses and product-related characteristics must not be regarded separately.