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This research is performed on a selection of archaeological glass finds with corresponding soil samples, excavated on the site of the High Medieval castle Cucagna in Friuli/Northern Italy. In the frame of understanding medieval glass technology and the chemical–physical conditions that influenced the state of preservation of the glass finds, this study uses a multi-analytical line-up of methods to characterize the composition of the glass and basic parameters of the soil including texture, mineralogical composition, pH, redox potential (Eh) and electric conductivity (EC). The results show that glass corrosion in soil not only depends on acidity, alkalinity or glass composition but also on the texture of the soil, measurable as grain-size distribution, and the mineralogical composition. The compositional groups of the glassware from Cucagna indicate the use of various raw material sources, pointing to Northern and Central Italian glass workshops with primary or secondary glass production.

Fungal unspecific peroxygenases (UPOs) have gained substantial attention for their versatile oxyfunctionalization chemistry paired with impressive catalytic capabilities. A major drawback, however, remains their sensitivity towards their co‐substrate hydrogen peroxide, necessitating the use of smart in situ hydrogen peroxide generation methods to enable efficient catalysis setups. Herein, we introduce flavin‐containing protein photosensitizers as a new general tool for light‐controlled in situ hydrogen peroxide production. By genetically fusing flavin binding fluorescent proteins and UPOs, we have created two virtually self‐sufficient photo‐enzymes (PhotUPO). Subsequent testing of a versatile substrate panel with the two divergent PhotUPOs revealed two stereoselective conversions. The catalytic performance of the fusion protein was optimized through enzyme and substrate loading variation, enabling up to 24300 turnover numbers (TONs) for the sulfoxidation of methyl phenyl sulfide. The PhotUPO concept was upscaled to a 100 mg substrate preparative scale, enabling the extraction of enantiomerically pure alcohol products. [ABSTRACT FROM AUTHOR]

An induction‐based energy harvesting (EH) device was presented. It converted part of the rotational energy of magnetic stirrers back into electrical energy, making it accessible for electrochemical transformations. After rectification, the induced AC voltage was optionally provided as a constant voltage or constant current whereby the available voltage could directly be adjusted by the stirring rate of the reaction. The comparability of the results with reactions carried out with commercial power supplies has been demonstrated on six different late‐stage functionalization, including methylation, carboxylation, trifluoromethylation, imidation, hydrolysis, and keto‐olefin coupling. Therefore, the described EH device is a low‐cost, resource‐efficient alternative to a commercial electrochemical set‐up and enables laboratories without specialized equipment to perform electrochemical reactions. [ABSTRACT FROM AUTHOR]

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Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single‐electron transfer (SET) reactions in a much greener way and broadens the redox window of possible transformations. Herein, the most recent contributions are reviewed, demonstrating exciting new opportunities, namely, the combination of PEC with other reactivity paradigms (hydrogen‐atom transfer, radical polar crossover, energy transfer sensitization), scalability up to multigram scale, novel selectivities in SET super‐oxidations/reductions and the importance of precomplexation to temporally enable excited radical ion catalysis. [ABSTRACT FROM AUTHOR]

We report a novel example of electro‐mediated photoredox catalysis (e‐PRC) in the reductive cleavage of C(sp3)−O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E‐selective and can be made Z‐selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide‐type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity‐determining C(sp3)−O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch‐type reductions. [ABSTRACT FROM AUTHOR]

Anisotropic fiber-reinforced composites are used in lightweight construction, which is of great industrial relevance. During mold filling of fiber suspensions, the microstructural evolution of the local fiber arrangement and orientation distribution is determined by the local velocity gradient. Based on the Folgar–Tucker equation, which describes the evolution of the second-order fiber orientation tensor in terms of the velocity gradient, the present study addresses selected states of deformation rates that can locally occur in complex flow fields. For such homogeneous flows, exact solutions for the asymptotic fiber orientation states are derived and discussed based on the quadratic closure. In contrast to the existing literature, the derived exact solutions take into account the fiber-fiber interaction. The analysis of the asymptotic solutions relying upon the common quadratic closure shows disadvantages with respect to the predicted material symmetry, namely, the anisotropy is overestimated for strong fiber-fiber interaction. This motivates us to suggest a novel normalized fully symmetric quadratic closure. Two versions of this new closure are derived regarding the prediction of anisotropic properties and the fiber orientation evolution. The fiber orientation states determined with the new closure approach show an improved prediction of anisotropy in both effective viscous and elastic composite behaviors. In addition, the symmetrized quadratic closure has a simple structure that reduces the effort in numerical implementation compared to more elaborated closure schemes. [ABSTRACT FROM AUTHOR]

This research is performed on a selection of archaeological glass finds with corresponding soil samples, excavated on the site of the High Medieval castle Cucagna in Friuli/Northern Italy. In the frame of understanding medieval glass technology and the chemical–physical conditions that influenced the state of preservation of the glass finds, this study uses a multi-analytical line-up of methods to characterize the composition of the glass and basic parameters of the soil including texture, mineralogical composition, pH, redox potential (Eh) and electric conductivity (EC). The results show that glass corrosion in soil not only depends on acidity, alkalinity or glass composition but also on the texture of the soil, measurable as grain-size distribution, and the mineralogical composition. The compositional groups of the glassware from Cucagna indicate the use of various raw material sources, pointing to Northern and Central Italian glass workshops with primary or secondary glass production. [ABSTRACT FROM AUTHOR]

This research is performed on a selection of archaeological glass finds with corresponding soil samples, excavated on the site of the High Medieval castle Cucagna in Friuli/Northern Italy. In the frame of understanding medieval glass technology and the chemical–physical conditions that influenced the state of preservation of the glass finds, this study uses a multi-analytical line-up of methods to characterize the composition of the glass and basic parameters of the soil including texture, mineralogical composition, pH, redox potential (Eh) and electric conductivity (EC). The results show that glass corrosion in soil not only depends on acidity, alkalinity or glass composition but also on the texture of the soil, measurable as grain-size distribution, and the mineralogical composition. The compositional groups of the glassware from Cucagna indicate the use of various raw material sources, pointing to Northern and Central Italian glass workshops with primary or secondary glass production. [ABSTRACT FROM AUTHOR]

A homogeneous, redox-neutral photo fragmentation of diol derivatives was developed. Under photo/hydrogen atom transfer (HAT) dual catalysis, diol derivatives such as lignin model compounds and diol monoesters undergo selective β C(sp3)–O bond cleavage to afford ketones, phenols and acids effectively. [ABSTRACT FROM AUTHOR]

More information can be found in the Research Article by T. A. Karl, M. Seidl and B. König. Electrochemistry, Energy harvesting, Late-stage functionalization, Radicals, Self-sustaining Keywords: Electrochemistry; Energy harvesting; Late-stage functionalization; Radicals; Self-sustaining EN Electrochemistry Energy harvesting Late-stage functionalization Radicals Self-sustaining 1 1 1 02/03/23 20230201 NES 230201 B The Front Cover b illustrates an induction-based energy harvesting (EH) device that converts part of the rotational energy of magnetic stirrers back into electrical energy, making it accessible for electrochemical transformations. [Extracted from the article]

Keywords: Elektrophotokatalyse; Photoelektrochemie; Photoredoxkatalyse; Vorassemblierung; Wasserstoffatomtransfer DE Elektrophotokatalyse Photoelektrochemie Photoredoxkatalyse Vorassemblierung Wasserstoffatomtransfer 1 1 1 03/11/22 20220314 NES 220314 B Molekulare Photoelektrochemie b , nur einen Katzensprung entfernt, entwickelt sich zu einem vielseitigen Werkzeug für die Synthese und selektive Funktionalisierung komplexer Moleküle. Die molekulare Photoelektrochemie erlaubt den Zugang zu einem breiteren Spektrum umweltfreundlicher Einelektronentransfer-Chemie. In ihrem Aufsatz (e202107811) beleuchten Joshua Barham et al. aufregende synthetische Möglichkeiten, mechanistische Einblicke und sich fortentwickelnde Reaktorplattformen, welche das Screening und die Skalierbarkeit von Reaktionen ermöglichen. [Extracted from the article]

Keywords: electrophotocatalysis; hydrogen atom transfer; photoelectrochemistry; photoredox catalysis; preassembly EN electrophotocatalysis hydrogen atom transfer photoelectrochemistry photoredox catalysis preassembly 1 1 1 03/11/22 20220314 NES 220314 B Molecular photoelectrochemistry b , allowing access to a broader window of single electron transfer chemistry in a greener way, is a rapidly expanding toolbox for synthesis and selective functionalizations of complex molecules. Inside Cover: Synthetic Molecular Photoelectrochemistry: New Frontiers in Synthetic Applications, Mechanistic Insights and Scalability (Angew. Electrophotocatalysis, hydrogen atom transfer, photoelectrochemistry, photoredox catalysis, preassembly. [Extracted from the article]

Fungal unspecific peroxygenases (UPOs) have gained substantial attention for their versatile oxyfunctionalization chemistry paired with impressive catalytic capabilities. A major drawback, however, remains their sensitivity towards their co-substrate hydrogen peroxide, necessitating the use of smart in situ hydrogen peroxide generation methods to enable efficient catalysis setups. Herein, we introduce flavin-containing protein photosensitizers as a new general tool for light-controlled in situ hydrogen peroxide production. By genetically fusing flavin binding fluorescent proteins and UPOs, we have created two virtually self-sufficient photo-enzymes (PhotUPO). Subsequent testing of a versatile substrate panel with the two divergent PhotUPOs revealed two stereoselective conversions. The catalytic performance of the fusion protein was optimized through enzyme and substrate loading variation, enabling up to 24300 turnover numbers (TONs) for the sulfoxidation of methyl phenyl sulfide. The PhotUPO concept was upscaled to a 100 mg substrate preparative scale, enabling the extraction of enantiomerically pure alcohol products., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single-electron transfer (SET) reactions in a much greener way and broadens the redox window of possible transformations. Herein, the most recent contributions are reviewed, demonstrating exciting new opportunities, namely, the combination of PEC with other reactivity paradigms (hydrogen-atom transfer, radical polar crossover, energy transfer sensitization), scalability up to multigram scale, novel selectivities in SET super-oxidations/reductions and the importance of precomplexation to temporally enable excited radical ion catalysis., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp 3 )-O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp 3 )-O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A broadly applicable method for the trifluoromethylthiolation of methylene C(sp 3 )-H, methine C(sp 3 )-H, α-oxygen C(sp 3 )-H, and formyl C(sp 2 )-H bonds is presented using the decatungstate anion as the sole catalyst. By adjusting the substrate ratio and reaction concentration, this method was applied to 40 examples in good regioselectivities, including the derivatization of natural products. Furthermore, SCF 3 -drug analogues were synthesized by subsequent functionalization of the SCF 3 products, highlighting the importance of this photocatalyzed C-H functionalization.