Micropatterning of Confined Surfaces with Polymer Brushes by Two-Photon-Initiated Reversible Addition-Fragmentation Chain-Transfer Polymerization.

Photopatterned polymer brushes provide a viable option to alter the surface properties of biosensors, substrates for tissue engineering, or microelectronic implants. Although the one-photon direct laser writing enables excellent control over pattern geometry, it has an inherently limited writing resolution caused by the used light source; moreover, no patterning of undercuts or channels is possible. This article describes the preparation of patterned polymer brushes on confined glass substrates using two-photon-initiated reversible addition-fragmentation chain-transfer (2PRAFT) polymerization of -acryloylmorpholine as a hydrophilic model monomer.

Structural tuning of tetrazole-BODIPY Ag(i) coordination compounds co-ligand addition and counterion variation.

The coordination properties of a previously described fluorescence active ligand (), consisting of a coordinating unit (1-tetrazol-1-yl) and a fluorophore (4,4-difluoro-4-bora-3,4-diaza--indacene (BODIPY) derivative) towards Ag(i) were investigated. Additionally, the influence of different anions (BF , PF , PFO , ClO , ReO and NO ) and a co-ligand (CHCN) on the crystal structure formation and intramolecular interactions of the Ag(i) coordination compounds was studied. Beside structural investigations single crystal X-ray diffraction, bulk characterization of the coordination compounds was conducted in both solution and solid-state, including NMR (H, B, F, P and C), ATR-IR, UV-vis and photoluminescence spectroscopy as well as PXRD.

Online Coupling High-Temperature Electrolysis with Carbonylation Reactions: A Powerful Method for Continuous Carbon Dioxide Utilization.

Despite being widely available, the broad utilization of CO for chemical production remains in its infancy. The difficulty of using CO as an important resource for the chemical industry lies in the high stability of the molecule and its associated inertia. In this work, we demonstrate how to overcome these limitations by utilizing a solid oxide electrolysis cell (SOEC) with an optimized cathode to produce dry CO through the high-temperature electrolysis of CO.

Bioinspired Synthesis of Alstoscholarinoids A and B.

Biomimetic synthesis can be an attractive approach to access complex natural products by addressing challenging structural features through cascade reactions, which are inferred through tangible biosynthetic hypotheses. In some instances, the originally proposed structure or biosynthetic path might be revised through synthesis. In this communication we report a short and efficient bioinspired synthesis of Alstoscholarinoids A and B, rearranged triterpenes from the tree.

Identification and Characterization of a Leoligin-Inspired Synthetic Lignan as a TGR5 Agonist.

The G-protein coupled bile acid receptor 1 (GPBAR1 or TGR5) is the major cell membrane receptor for bile acids regulating metabolic and immunological functions. Its pharmacological modulation has been shown to alleviate inflammatory diseases, such as type 2 diabetes and atherosclerosis. The naturally occurring lignan leoligin and structural analogues have shown anti-inflammatory effects in vitro.

Towards DFO*-Preliminary Results of a New Chelator for the Complexation of Actinium-225.

: Actinium-225 (Ac) has gained interest in nuclear medicine for use in targeted alpha therapy (TAT) for the treatment of cancer. However, the number of suitable chelators for the stable complexation of Ac is limited. The promising physical properties of Ac result in an increased demand for the radioisotope that is not matched by its current supply.

Discovery of the antifungal compound ilicicolin K through genetic activation of the ilicicolin biosynthetic pathway in Trichoderma reesei.

Background: Given the global rise in antimicrobial resistance, the discovery of novel antimicrobial agents and production processes thereof are of utmost importance. To this end we have activated the gene cluster encoding for the biosynthesis of the potent antifungal compound ilicicolin H in the fungus Trichoderma reesei. While the biosynthetic gene cluster (BGC) is silent under standard cultivation conditions, we achieved BGC activation by genetically overexpressing the transcription factor TriliR.

Photocatalytic Carbon Dioxide Reduction with Imidazolium-Based Ionic Liquids.

The growing urgency of addressing climate change caused by greenhouse gas emissions and dwindling fossil fuel supplies has heightened the need for effective strategies to capture and utilize carbon dioxide. Photocatalytic CO conversion, inspired by natural photosynthesis, presents a viable approach for transforming CO into useful C-C chemical intermediates for industrial purposes. However, the inherent stability of CO and the competing hydrogen evolution reaction (HER) introduce significant obstacles.

Enhanced catalytic activity of carbonate buffer for isomerization of D-galactose into D-tagatose.

D-tagatose (Tag) is a rare monosaccharide with health benefits. In this work, catalytic activity of CAPS (pH 10.4), carbonate (pH 10.

Significant Efficiency Enhancements in Non-Y Series Acceptors by the Addition of Outer Side Chains.

Most current highly efficient organic solar cells utilize small molecules like Y6 and its derivatives as electron acceptors in the photoactive layer. In this work, a small molecule acceptor, SC8-IT4F, is developed through outer side chain engineering on the terminal thiophene of a conjugated 6,12-dihydro-dithienoindeno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (IDTT) central core. Compared to the reference molecule C8-IT4F, which lacks outer side chains, SC8-IT4F displays notable differences in molecule geometry (as shown by simulations), thermal behavior, single-crystal packing, and film morphology.

Fabrication of nanoparticles with precisely controllable plasmonic properties as tools for biomedical applications.

Metal nanoparticles are established tools for biomedical applications due to their unique optical properties, primarily attributed to localized surface plasmon resonances. They show distinct optical characteristics, such as high extinction cross-sections and resonances at specific wavelengths, which are tunable across the wavelength spectrum by modifying the nanoparticle geometry. These attributes make metal nanoparticles highly valuable for sensing and imaging in biology and medicine.

The synthesis of higher-carbon sugar alcohols via indium-mediated acyloxyallylation as potential phase change materials.

Unlabelled: In recent years, sugar alcohols have gained significant attention as organic phase change materials (PCMs) for thermal energy storage due to their comparably high thermal storage densities up to 350 J/g. In a computational study, outstandingly high values of up to ~ 450-500 J/g have been postulated for specific higher-carbon sugar alcohols. These optimized structures feature an even number of carbon atoms in the backbone and a stereochemical configuration in which all hydroxyl groups are in an 1,3--relationship, as found in the natural hexitol d-mannitol.

The modulating role of uniaxial straining in the IL-1β and TGF-β mediated inflammatory response of human primary ligamentocytes.

Biomechanical (over-)stimulation, in addition to inflammatory and fibrotic stimuli, severely impacts the biology, contributing to the overall chronic nature of desmopathy. A major challenge has been the lack of representative two-dimensional (2D) models mimicking inflammatory processes in the presence of dynamic mechanical strain, both being crucial for ligament homeostasis. Physiological levels of strain exert anti-inflammatory effects, while excessive strain can facilitate inflammatory mechanisms.

Rapid 3D printing of unlayered, tough epoxy-alcohol resins with late gel points dual-color curing technology.

Additive manufacturing technologies and, in particular, vat photopolymerization promise complex structures that can be made in a fast and easy fashion for highly individualized products. While the technology has upheld this promise many times already, some polymers are still out of reach or at least problematic to print reliably. High-performance epoxide-based resins, which are regulated by chain transfer multifunctional alcohols, are a typical example of resins with late gel points, which require long irradiation times and high light intensities to print.

Decellularized Extracellular Matrix and Polyurethane Vascular Grafts Have Positive Effects on the Inflammatory and Pro-Thrombotic State of Aged Endothelial Cells.

In vitro assessment of small-diameter synthetic vascular grafts usually uses standard cell culture conditions with early-passage cells. However, these conduits are mainly implanted in elderly patients and are subject to complex cellular interactions influenced by age and inflammation. Understanding these factors is central to the development of vascular grafts tailored to the specific needs of patients.

Modeling early phenotypes of Parkinson's disease by age-induced midbrain-striatum assembloids.

Parkinson's disease, an aging-associated neurodegenerative disorder, is characterised by nigrostriatal pathway dysfunction caused by the gradual loss of dopaminergic neurons in the substantia nigra pars compacta of the midbrain. Human in vitro models are enabling the study of the dopaminergic neurons' loss, but not the dysregulation within the dopaminergic network in the nigrostriatal pathway. Additionally, these models do not incorporate aging characteristics which potentially contribute to the development of Parkinson's disease.

Palladium-Catalyzed Ortho Alkoxylation of Oxazoline Derivatives: An Avenue to Reach Meta-Substituted Electron-Rich Arenes Exploiting Oxazoline as a Removeable Directing Group.

An efficient and highly regioselective palladium-catalyzed oxazoline-directed alkoxylation is reported. The reaction proceeds under air and mild temperatures (60 °C). A series of alcohols can be used as alkoxylating agents and concomitantly act as reaction solvents, whereas primary and secondary alcohols are tolerated.

Proton transfer induced excited-state aromaticity gain for chromophores with maximal Stokes shifts.

Excited state aromaticity (ESA) offers a fascinating route for driving photophysical and photochemical processes but is challenging to harness fully due to its inherent association with unstable antiaromatic ground states. Here, we propose to circumvent this problem the introduction of a new class of photophysical processes, the generation of ESA an excited-state intramolecular proton transfer. We select twelve candidate molecules based on the cyclobutadiene and pentalene scaffolds and investigate their ground and excited state properties using computation.

Harnessing nature's catalysts: Advances in enzymatic alkene cleavage.

Double bonds are prevalent in various substrates and renewable feedstocks, and their cleavage typically necessitates harsh reaction conditions involving high temperatures, organic solvents, and hazardous catalysts such as heavy metals or ozone. This review explores the sustainable enzymatic alternatives developed by nature for alkene cleavage. It provides a comprehensive overview of alkene-cleaving enzymes, detailing their mechanisms, substrate specificities, and applications.

Thiol-Acrylate polyHIPEs via Facile Layer-by-Layer Photopolymerization.

A highly reactive thiol-ene high internal phase emulsion based on the monomers 1,6-hexanediol diacrylate and tris 2-(3-mercaptopropionyloxy)ethyl isocyanurate was developed for the purpose of light-driven additive manufacturing, resulting in highly porous customizable poly(high internal phase emulsion) materials. The formulation was specifically designed to facilitate short irradiation times and low amounts of photoinitiator. Furthermore, the developed emulsion does not rely on employing harmful solvents to make scale-up and industrial applications feasible.

L-Cysteine-Catalysed Hydration of Activated Alkynes.

Hydration reactions consist of the introduction of a molecule of water into a chemical compound and are particularly useful to transform alkynes into carbonyls, which are strategic intermediates in the synthesis of a plethora of compounds. Herein we demonstrate that L-cysteine can catalyse the hydration of activated alkynes in a very effective and fully regioselective manner to access important building blocks in synthetic chemistry such as β-ketosulfones, amides and esters, in aqueous media. The mild reaction conditions facilitated the integration with enzyme catalysis to access chiral β-hydroxy sulfones from the corresponding alkynes in a one-pot cascade process in good yields and excellent enantiomeric ratios.