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951.
Valentina Ferraro;Clara R. Adam;Aleksandra Vranic;Stefan Bräse; 《Advanced functional materials》2024,34(20):2302157
The possibility of exploiting visible light to induce polymerizations is extremely appealing from a technological point of view as it improves the sustainability of the overall process. To achieve this objective, it is necessary to employ single- or multicomponent systems containing a photoinitiator, and in some cases, a photosensitizer in combination. Due to their long-lived excited states and reversible redox properties, transition metal complexes are a valid choice to be applied in photoinitiating systems, often exhibiting enhanced conversions compared to purely organic compounds. This review presents an overview of the transition metal complexes exploited in photopolymerization reactions. Particular attention will be devoted to recent applications in 3D printing, highlighting the possible challenges that need to be faced to achieve highly efficient and more sustainable processes. 相似文献
952.
Yong Ryun Kim Oskar J. Sandberg Stefan Zeiske Gregory Burwell Drew B. Riley Paul Meredith Ardalan Armin 《Advanced functional materials》2023,33(16):2300147
Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been one of the most established hole transport layers (HTL) in organic solar cells (OSCs) for several decades. However, the presence of PSS− ions is known to deteriorate device performance via a number of mechanisms including diffusion to the HTL-active layer interface and unwanted local chemical reactions. In this study, it is shown that PSS− ions can also result in local p-doping in the high efficiency donor:non-fullerene acceptor blends – resulting in photocurrent loss. To address these issues, a facile and effective approach is reported to improve the OSC performance through a two-component hole transport layer (HTL) consisting of a self-assembled monolayer of 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) and PEDOT:PSS. The power conversion efficiency (PCE) of 17.1% using devices with PEDOT:PSS HTL improved to 17.7% when the PEDOT:PSS/2PACz two-component HTL is used. The improved performance is attributed to the overlaid 2PACz layer preventing the formation of an intermixed p-doped PSS− ion rich region (≈5–10 nm) at the bulk heterojunction-HTL contact interface, resulting in decreased recombination losses and improved stability. Moreover, the 2PACz monolayer is also found to reduce electrical shunts that ultimately yield improved performance in large area devices with PCE enhanced from 12.3% to 13.3% in 1 cm2 cells. 相似文献
953.
Yixuan Jia Christoph A. Spiegel Alexander Welle Stefan Heißler Elaheh Sedghamiz Modan Liu Wolfgang Wenzel Maximilian Hackner Joachim P. Spatz Manuel Tsotsalas Eva Blasco 《Advanced functional materials》2023,33(39):2207826
Manufacturing programmable materials, whose mechanical properties can be adapted on demand, is highly desired for their application in areas ranging from robotics, to biomedicine, or microfluidics. Herein, the inclusion of dynamic and living bonds, such as alkoxyamines, in a printable formulation suitable for two-photon 3D laser printing is exploited. On one hand, taking advantage of the dynamic covalent character of alkoxyamines, the nitroxide exchange reaction is investigated. As a consequence, a reduction of the Young´s Modulus by 50%, is measured by nanoindentation. On the other hand, due to its “living” characteristic, the chain extension becomes possible via nitroxide mediated polymerization. In particular, living nitroxide mediated polymerization of styrene results not only in a dramatic increase of the volume (≈8 times) of the 3D printed microstructure but also an increase of the Young's Modulus by two orders of magnitude (from 14 MPa to 2.7 GPa), while maintaining the shape including fine structural details. Thus, the approach introduces a new dimension by enabling to create microstructures with dynamically tunable size and mechanical properties. 相似文献
954.
Prof. Dr. Oleksandr O. Grygorenko Prof. Dr. Rostyslav D. Lampeka Prof. Dr. Valentyn A. Chebanov Prof. Dr. Maksym V. Kovalenko Prof. Dr. Stefan Wuttke 《Chemical record (New York, N.Y.)》2024,24(2):e202400008
In this special issue, we highlight recent advances in chemical research by scientists in Ukraine, as well as by their compatriots and collaborators outside the country. Besides spotlighting their contributions, we see our task in fostering global partnerships and multi-, inter-, and trans-disciplinary collaborations, including much-needed co-funded projects and initiatives. The three decades of the renewed Ukraine independence have seen rather limited integration of Ukrainian (chemical) science into global research communities.[1] At the same time, the recent surge of collaborative science initiatives between European Union (EU) and Ukraine echoes the unfolding steps towards Ukraine's full research participation to the Horizon Europe Program. This recently implemented step opens enormous possibilities for Ukrainian researchers to apply for diverse EU research grants. Moreover, a number of journal special issues and collections were launched to highlight Ukrainian chemistry (i. e., by Chemistry of Heterocyclic Compounds[2] and ChemistrySelect[3]). Other scientific initiatives include ‘European Chemistry School for Ukrainians’[4] and ‘Kharkiv Chemical Seminar’[5] as voluntary projects aimed at engaging Ukrainian scientists into European and international chemical research. 相似文献
955.
Dr. Fabian Schmidt Dr. Saner Poplata Dr. Danny Morris Dr. Stefan Burger M.Sc. Markus Hegelmann Prof. Dr. Jason B. Love Dr. Mirza Cokoja 《ChemCatChem》2024,16(6):e202301482
The development of inexpensive and effective catalysts for the epoxidation of olefins to epoxides, which are key commodities for the chemical industry, is a continuing challenge. In this context, we present a supramolecular solution with the development of new host-guest assemblies of sulfate ions and amidoammonium receptor cations that, for the first time, are shown to act as catalysts for olefin epoxidation by hydrogen peroxide under biphasic conditions. Analysis of the reaction mechanism shows that the reactive and oxidizing peroxymonosulfate is formed in the organic phase. Furthermore, a variety of readily available precursors may be used to form the supramolecular ion pairs (SIPs), which is enabling a large-scale synthesis of the catalysts while maintaining catalytic control and effectiveness. 相似文献
956.
Raphaël Robidas Dominik L. Reinhard Prof. Stefan M. Huber Prof. Claude Y. Legault 《Chemphyschem》2023,24(1):e202200634
Cyclic diaryliodonium compounds like iodolium derivatives have increasingly found use as noncovalent Lewis acids in the last years. They are more stable toward nucleophilic substitution than acyclic systems and are markedly more Lewis acidic. Herein, this higher Lewis acidity is analyzed and explained via quantum-chemical calculations and energy decomposition analyses. Its key origin is the change in energy levels and hybridization of iodine's orbitals, leading to both more favorable electrostatic interaction and better charge transfer. Both of the latter seem to contribute in similar fashion, while hydrogen bonding as well as steric repulsion with the phenyl rings play at best a minor role. In comparison to iodolium, bromolium and chlorolium are less Lewis acidic the lighter the halogen, which is predominantly based on less favorable charge-transfer interactions. 相似文献
957.
Prof. Qi Lei Yaqian Sun Junda Huang Wei Liu Xiaolong Zhan Wenxiang Yin Sishi Guo Dr. Anna Sinelshchikova Prof. C. Jeffrey Brinker Prof. Zhiyuan He Prof. Jimin Guo Prof. Stefan Wuttke Prof. Wei Zhu 《Angewandte Chemie (International ed. in English)》2023,62(22):e202217374
To increase the red blood cell (RBC) cryopreservation efficiency by metal–organic frameworks (MOFs), a dimensional reduction approach has been proposed. Namely, 3D MOF nanoparticles are progressively reduced to 2D ultra-thin metal–organic layers (MOLs). We found that 2D MOLs are beneficial for enhanced interactions of the interfacial hydrogen-bonded water network and increased utilization of inner ordered structures, due to the higher surface-to-volume ratio. Specifically, a series of hafnium (Hf)-based 2D MOLs with different thicknesses (monolayer to stacked multilayers) and densities of hydrogen bonding sites have been synthesized. Both ice recrystallization inhibition activity (IRI) and RBCs cryopreservation assay confirm the pronounced better IRI activity and excellent cell recovery efficiency (up to ≈63 % at a very low concentration of 0.7 mg mL−1) of thin-layered Hf-MOLs compared to their 3D counterparts, thereby verifying the dimensional reduction strategy to improved cryoprotectant behaviors. 相似文献
958.
Stefan van Rootselaar Evert Peterse Dr. Daniel Blanco-Ania Prof. Dr. Floris P. J. T. Rutjes 《European journal of organic chemistry》2023,26(22):e202300053
Piperidine alkaloids are members of the alkaloid family that is characterized by the presence of a six-membered nitrogen-containing heterocycle. Piperidine alkaloids are found mainly in plants and often exhibit interesting biological and pharmacological activities. Despite the accumulation of these natural products in plants, relatively low quantities of alkaloids are produced in absolute terms and thus synthesis of alkaloids and derivatives thereof remains relevant to identify targets for drug discovery. Throughout the years, researchers have come up with a myriad of methods to synthesize piperidine derivatives. This review describes methods that employ stereoselective Mannich reactions to create the core of piperidine alkaloids. Asymmetric induction in the Mannich reaction has been achieved by a range of methods that have been divided into three conceptual approaches: (1) chiral pool-based (internal asymmetric induction), (2) chiral auxiliary-based (relayed asymmetric induction) and (3) asymmetric catalysis-based (external asymmetric induction). Of each approach, we describe the reaction mechanism and rationalize the stereochemical outcome of the Mannich products. 相似文献
959.
Dr. Zahid Hassan Prof. Dr. Stefan Bräse 《Angewandte Chemie (International ed. in English)》2023,62(16):e202214996
960.
Jimin Song Dr. Xiaojuan Yu Dr. Alexei Nefedov Dr. Peter G. Weidler Dr. Sylvian Grosjean Prof. Dr. Stefan Bräse Dr. Yuemin Wang Prof. Dr. Christof Wöll 《Angewandte Chemie (International ed. in English)》2023,62(34):e202306155
Studies on reactions in solutions are often hampered by solvent effects. In addition, detailed investigation on kinetics is limited to the small temperature regime where the solvent is liquid. Here, we report the in situ spectroscopic observation of UV-induced photochemical reactions of aryl azides within a crystalline matrix in vacuum. The matrices are formed by attaching the reactive moieties to ditopic linkers, which are then assembled to yield metal–organic frameworks (MOFs) and surface-mounted MOFs (SURMOFs). These porous, crystalline frameworks are then used as model systems to study azide-related chemical processes under ultrahigh vacuum (UHV) conditions, where solvent effects can be safely excluded and in a large temperature regime. Infrared reflection absorption spectroscopy (IRRAS) allowed us to monitor the photoreaction of azide in SURMOFs precisely. The in situ IRRAS data, in conjunction with XRD, MS, and XPS, reveal that illumination with UV light first leads to forming a nitrene intermediate. In the second step, an intramolecular rearrangement occurs, yielding an indoloindole derivative. These findings unveil a novel pathway for precisely studying azide-related chemical transformations. Reference experiments carried out for solvent-loaded SURMOFs reveal a huge diversity of other reaction schemes, thus highlighting the need for model systems studied under UHV conditions. 相似文献