@article{37936, author = {{Pelucchi, Emanuele and Fagas, Giorgos and Aharonovich, Igor and Englund, Dirk and Figueroa, Eden and Gong, Qihuang and Hannes, Hübel and Liu, Jin and Lu, Chao-Yang and Matsuda, Nobuyuki and Pan, Jian-Wei and Schreck, Florian and Sciarrino, Fabio and Silberhorn, Christine and Wang, Jianwei and Jöns, Klaus}}, issn = {{2522-5820}}, journal = {{Nature Reviews Physics}}, keywords = {{General Physics and Astronomy}}, number = {{3}}, pages = {{194--208}}, publisher = {{Springer Science and Business Media LLC}}, title = {{{The potential and global outlook of integrated photonics for quantum technologies}}}, doi = {{10.1038/s42254-021-00398-z}}, volume = {{4}}, year = {{2021}}, } @article{41002, abstract = {{Homogeneous catalysts immobilized on metal oxides often have different catalytic properties than in homogeneous solution. This can be either activating or deactivating and is often attributed to interactions of catalyst species with the metal oxide surface. However, few studies have ever demonstrated the effect that close associations of active sites with surfaces have on the catalytic activity. In this paper, we immobilize H2Ru(PPh3)2(Ph2P)2N–C3H6–Si(OEt)3 (3) on SiO2, Al2O3, and ZnO and interrogate the relationship to the surface using IR, MAS NMR, 1H–31P HETCOR, and XAS spectroscopies. We found that while there are close contacts between the P atoms of the complex and all three metal oxide surfaces, the Ru–H bond only reacts with oxygen bridges on SiO2 and Al2O3, forming new Ru–O bonds. In contrast, complex 3 stays intact on ZnO. Comparison of the catalytic activities of our immobilized species for CO2 hydrogenation to ethyl formate showed that Lewis acidic metal oxides activate, rather than deactivate, complex 3 in the order Al2O3 > ZnO > SiO2. The Lewis acidic sites on the metal oxide surfaces most likely increase the productivity by increasing the rate of esterification of formate intermediates.}}, author = {{Nguyen, Hoang-Huy and Li, Zheng and Enenkel, Toni and Hildebrand, Joachim and Bauer, Matthias and Dyballa, Michael and Estes, Deven P.}}, issn = {{1932-7447}}, journal = {{The Journal of Physical Chemistry C}}, keywords = {{Surfaces, Coatings and Films, Physical and Theoretical Chemistry, General Energy, Electronic, Optical and Magnetic Materials}}, number = {{27}}, pages = {{14627--14635}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Probing the Interactions of Immobilized Ruthenium Dihydride Complexes with Metal Oxide Surfaces by MAS NMR: Effects on CO2 Hydrogenation}}}, doi = {{10.1021/acs.jpcc.1c02074}}, volume = {{125}}, year = {{2021}}, } @article{40998, abstract = {{Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as heterogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in α,ω-diene ring-closing metathesis reactions, leading to increased macrocyclization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous olefin metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O=1.35) of up to 51 % compared to the homogeneous catalyst (MMC:O=0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement.}}, author = {{Emmerling, Sebastian T. and Ziegler, Felix and Fischer, Felix R. and Schoch, Roland and Bauer, Matthias and Plietker, Bernd and Buchmeiser, Michael R. and Lotsch, Bettina V.}}, issn = {{0947-6539}}, journal = {{Chemistry – A European Journal}}, keywords = {{General Chemistry, Catalysis, Organic Chemistry}}, number = {{8}}, publisher = {{Wiley}}, title = {{{Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity}}}, doi = {{10.1002/chem.202104108}}, volume = {{28}}, year = {{2021}}, } @article{41003, abstract = {{Combining strong σ-donating N-heterocyclic carbene ligands and π-accepting pyridine ligands with a high octahedricity in rigid iron(II) complexes increases the 3MLCT lifetime from 0.15 ps in the prototypical [Fe(tpy)2]2+ complex to 9.2 ps in [Fe(dpmi)2]2+12+. The tripodal CNN ligand dpmi (di(pyridine-2-yl)(3-methylimidazol-2-yl)methane) forms six-membered chelate rings with the iron(II) centre leading to close to 90° bite angles and enhanced iron-ligand orbital overlap}}, author = {{Reuter, Thomas and Kruse, Ayla and Schoch, Roland and Lochbrunner, Stefan and Bauer, Matthias and Heinze, Katja}}, issn = {{1359-7345}}, journal = {{Chemical Communications}}, keywords = {{Materials Chemistry, Metals and Alloys, Surfaces, Coatings and Films, General Chemistry, Ceramics and Composites, Electronic, Optical and Magnetic Materials, Catalysis}}, number = {{61}}, pages = {{7541--7544}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Higher MLCT lifetime of carbene iron(ii) complexes by chelate ring expansion}}}, doi = {{10.1039/d1cc02173g}}, volume = {{57}}, year = {{2021}}, } @article{40997, abstract = {{On transition metals such as iron rests lots of hope to replace precious metal catalysts in the field of photochemistry for a more sustainable future. Indeed, significant progress has been made in recent years in terms of lifetime extension and emerging applications in catalysis. For this reason, recent synthetic strategies of new photoactive iron compounds, which have proved to show particularly promising properties, are reviewed here. The lifetime of the excited state serves as a key parameter for comparison with the standard ruthenium complex, [Ru(bpy)3]2+, to discuss the potential and performance of the iron complexes. This approach is complemented by a more holistic examination of the sustainability of such a substitution strategy in order to answer the question: when or at which point can we assume that iron represents a more sustainable alternative for noble metals in photochemical applications?}}, author = {{Dierks, Philipp and Vukadinovic, Yannik and Bauer, Matthias}}, issn = {{2052-1553}}, journal = {{Inorganic Chemistry Frontiers}}, keywords = {{Inorganic Chemistry}}, number = {{2}}, pages = {{206--220}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Photoactive iron complexes: more sustainable, but still a challenge}}}, doi = {{10.1039/d1qi01112j}}, volume = {{9}}, year = {{2021}}, } @article{41000, abstract = {{Metal-catalyzed C−H activations are environmentally and economically attractive synthetic strategies for the construction of functional molecules as they obviate the need for pre-functionalized substrates and minimize waste generation. Great challenges reside in the control of selectivities, the utilization of unbiased hydrocarbons, and the operation of atom-economical dehydrocoupling mechanisms. An especially mild borylation of benzylic CH bonds was developed with the ligand-free pre-catalyst Co[N(SiMe3)2]2 and the bench-stable and inexpensive borylation reagent B2pin2 that produces H2 as the only by-product. A full set of kinetic, spectroscopic, and preparative mechanistic studies are indicative of a tandem catalysis mechanism of CH-borylation and dehydrocoupling via molecular CoI catalysts.}}, author = {{Ghosh, Pradip and Schoch, Roland and Bauer, Matthias and Jacobi von Wangelin, Axel}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{1}}, publisher = {{Wiley}}, title = {{{Selective Benzylic CH‐Borylations by Tandem Cobalt Catalysis}}}, doi = {{10.1002/anie.202110821}}, volume = {{61}}, year = {{2021}}, } @article{41013, abstract = {{Within this article, it is shown that an electrochemical defluorination and additional fluorination of Ruddlesden–Popper-type La2NiO3F2 is possible within all-solid-state fluoride-ion batteries. Structural changes within the reduced and oxidized phases have been examined by X-ray diffraction studies at different states of charging and discharging. The synthesis of the oxidized phase La2NiO3F2+x proved to be successful by structural analysis using both X-ray powder diffraction and automated electron diffraction tomography techniques. The structural reversibility on re-fluorinating and re-defluorinating is also demonstrated. Moreover, the influence of different sequences of consecutive reduction and oxidation steps on the formed phases has been investigated. The observed structural changes have been compared to changes in phases obtained via other topochemical modification approaches such as hydride-based reduction and oxidative fluorination using F2 gas, highlighting the potential of such electrochemical reactions as alternative synthesis routes. Furthermore, the electrochemical routes represent safe and controllable synthesis approaches for novel phases, which cannot be synthesized via other topochemical methods. Additionally, side reactions, occurring alongside the desired electrochemical reactions, have been addressed and the cycling performance has been studied.}}, author = {{Wissel, Kerstin and Schoch, Roland and Vogel, Tobias and Donzelli, Manuel and Matveeva, Galina and Kolb, Ute and Bauer, Matthias and Slater, Peter R. and Clemens, Oliver}}, issn = {{0897-4756}}, journal = {{Chemistry of Materials}}, keywords = {{Materials Chemistry, General Chemical Engineering, General Chemistry}}, number = {{2}}, pages = {{499--512}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Electrochemical Reduction and Oxidation of Ruddlesden–Popper-Type La2NiO3F2 within Fluoride-Ion Batteries}}}, doi = {{10.1021/acs.chemmater.0c01762}}, volume = {{33}}, year = {{2021}}, } @article{41010, abstract = {{We present the η3-coordination of the 2-phosphaethynthiolate anion in the complex (PN)2La(SCP) (2) [PN=N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate-bridged (PN)2La(μ-1,3-SCN)2La(PN)2 (3) and azide-bridged (PN)2La(μ-1,3-N3)2La(PN)2 (4) complexes indicates that the [SCP]− coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*-orbital of the [SCP]− ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP]− anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]− ligand to form the first CAAC stabilized group 15–group 16 fulminate-type complexes (PN)2La{SPC(RCAAC)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP-to-SPC isomerization is proposed based on DFT calculations.}}, author = {{Watt, Fabian A. and Burkhardt, Lukas and Schoch, Roland and Mitzinger, Stefan and Bauer, Matthias and Weigend, Florian and Goicoechea, Jose M. and Tambornino, Frank and Hohloch, Stephan}}, issn = {{1433-7851}}, journal = {{Angewandte Chemie International Edition}}, keywords = {{General Chemistry, Catalysis}}, number = {{17}}, pages = {{9534--9539}}, publisher = {{Wiley}}, title = {{{η 3 ‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**}}}, doi = {{10.1002/anie.202100559}}, volume = {{60}}, year = {{2021}}, } @article{41012, abstract = {{Here we explore the electronic structure of the diiron complex [(dppf)Fe(CO)3]0/+ [10/+; dppf = 1,1′-bis(diphenylphosphino)ferrocene] in two oxidation states by an advanced multitechnique experimental approach. A combination of magnetic circular dichroism, X-ray absorption and emission, high-frequency electron paramagnetic resonance (EPR), and Mössbauer spectroscopies is used to establish that oxidation of 10 occurs on the carbonyl iron ion, resulting in a low-spin iron(I) ion. It is shown that an unequivocal result is obtained by combining several methods. Compound 1+ displays slow spin dynamics, which is used here to study its geometric structure by means of pulsed EPR methods. Surprisingly, these data show an association of the tetrakis[3,5-bis(trifluoromethylphenyl)]borate counterion with 1+.}}, author = {{Winkler, Mario and Schnierle, Marc and Ehrlich, Felix and Mehnert, Kim-Isabelle and Hunger, David and Sheveleva, Alena M. and Burkhardt, Lukas and Bauer, Matthias and Tuna, Floriana and Ringenberg, Mark R. and van Slageren, Joris}}, issn = {{0020-1669}}, journal = {{Inorganic Chemistry}}, keywords = {{Inorganic Chemistry, Physical and Theoretical Chemistry}}, number = {{5}}, pages = {{2856--2865}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Electronic Structure of a Diiron Complex: A Multitechnique Experimental Study of [(dppf)Fe(CO) 3]+/0}}}, doi = {{10.1021/acs.inorgchem.0c03259}}, volume = {{60}}, year = {{2021}}, } @article{41011, abstract = {{The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe4, Fe6, and Fe7 nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles.}}, author = {{Chakraborty, Uttam and Bügel, Patrick and Fritsch, Lorena and Weigend, Florian and Bauer, Matthias and Jacobi von Wangelin, Axel}}, issn = {{2191-1363}}, journal = {{ChemistryOpen}}, keywords = {{General Chemistry}}, number = {{2}}, pages = {{265--271}}, publisher = {{Wiley}}, title = {{{Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles}}}, doi = {{10.1002/open.202000307}}, volume = {{10}}, year = {{2021}}, } @article{22770, author = {{Gil López, Jano and Santandrea, Matteo and Roland, Ganaël and Brecht, Benjamin and Eigner, Christof and Ricken, Raimund and Quiring, Viktor and Silberhorn, Christine}}, issn = {{1367-2630}}, journal = {{New Journal of Physics}}, title = {{{Improved non-linear devices for quantum applications}}}, doi = {{10.1088/1367-2630/ac09fd}}, year = {{2021}}, } @article{26410, author = {{Gil López, Jano and Teo, Yong Siah and De, Syamsundar and Brecht, Benjamin and Jeong, Hyunseok and Silberhorn, Christine and Sánchez-Soto, Luis L.}}, issn = {{2334-2536}}, journal = {{Optica}}, title = {{{Universal compressive tomography in the time-frequency domain}}}, doi = {{10.1364/optica.427645}}, year = {{2021}}, } @article{30119, abstract = {{Abstract Background Subjective Memory Complaints (SMC) in elderly people due to preclinical Alzheimer’s Disease may be associated with dysregulation of the Kynurenine Pathway (KP), with an increase in neurotoxic metabolites that affect cognition. Golf is a challenging sport with high demands on motor, sensory, and cognitive abilities, which might bear the potential to attenuate the pathological changes of preclinical AD. This trial investigated the feasibility of learning to play golf for elderly with cognitive problems and its effects on cognitive functions and the KP. Methods In a 22-week single-blinded randomized controlled trial, elderly people with SMC were allocated to the golf (n = 25, 180 min training/week) or control group (n = 21). Primary outcomes were feasibility (golf exam, adherence, adverse events) and general cognitive function (Alzheimer’s Disease Assessment Scale). Secondary outcomes include specific cognitive functions (Response Inhibition, Corsi Block Tapping Test, Trail Making Test), KP metabolites and physical performance (6-Minute-Walk-Test). Baseline-adjusted Analysis-of-Covariance was conducted for each outcome. Results 42 participants were analyzed. All participants that underwent the golf exam after the intervention passed it (20/23). Attendance rate of the golf intervention was 75 %. No adverse events or drop-outs related to the intervention occurred. A significant time*group interaction (p = 0.012, F = 7.050, Cohen’s d = 0.89) was found for correct responses on the Response Inhibition task, but not for ADAS-Cog. Moreover, a significant time*group interaction for Quinolinic acid to Tryptophan ratios (p = 0.022, F = 5.769, Cohen’s d = 0.84) in favor of the golf group was observed. An uncorrected negative correlation between attendance rate and delta Quinolinic acid to Kynurenic acid ratios in the golf group (p = 0.039, r=-0.443) was found as well. Conclusions The findings indicate that learning golf is feasible and safe for elderly people with cognitive problems. Preliminary results suggest positive effects on attention and the KP. To explore the whole potential of golfing and its effect on cognitive decline, a larger cohort should be studied over a longer period with higher cardiovascular demands. Trial registration The trial was retrospectively registered (2nd July 2018) at the German Clinical Trials Register (DRKS00014921). }}, author = {{Stroehlein, Julia K. and Vieluf, Solveig and Zimmer, Philipp and Schenk, Alexander and Oberste, Max and Gölz, Christian Johannes and van den Bongard, Franziska and Reinsberger, Claus}}, issn = {{1471-2377}}, journal = {{BMC Neurology}}, keywords = {{Clinical Neurology, General Medicine}}, number = {{1}}, publisher = {{Springer Science and Business Media LLC}}, title = {{{Learning to play golf for elderly people with subjective memory complaints: feasibility of a single‐blinded randomized pilot trial}}}, doi = {{10.1186/s12883-021-02186-9}}, volume = {{21}}, year = {{2021}}, } @article{31702, author = {{Vieluf, S and Hasija, Tanuj and Schreier, PJ and El Atrache, R and Hammond, S and Mohammadpour Touserkani, F and Sarkis, RA and Loddenkemper, T and Reinsberger, Claus}}, issn = {{1525-5050}}, journal = {{Epilepsy Behav}}, pages = {{108321}}, title = {{{Generalized tonic-clonic seizures are accompanied by changes of interrelations within the autonomic nervous system.}}}, volume = {{124}}, year = {{2021}}, } @article{30115, abstract = {{AbstractCardiorespiratory fitness was found to influence age-related changes of resting state brain network organization. However, the influence on dedifferentiated involvement of wider and more unspecialized brain regions during task completion is barely understood. We analyzed EEG data recorded during rest and different tasks (sensory, motor, cognitive) with dynamic mode decomposition, which accounts for topological characteristics as well as temporal dynamics of brain networks. As a main feature the dominant spatio-temporal EEG pattern was extracted in multiple frequency bands per participant. To deduce a pattern’s stability, we calculated its proportion of total variance among all activation patterns over time for each task. By comparing fit (N = 15) and less fit older adults (N = 16) characterized by their performance on a 6-min walking test, we found signs of a lower task specificity of the obtained network features for the less fit compared to the fit group. This was indicated by fewer significant differences between tasks in the theta and high beta frequency band in the less fit group. Repeated measures ANOVA revealed that a significantly lower proportion of total variance can be explained by the main pattern in high beta frequency range for the less fit compared to the fit group [F(1,29) = 12.572, p = .001, partial η2 = .300]. Our results indicate that the dedifferentiation in task-related brain activation is lower in fit compared to less fit older adults. Thus, our study supports the idea that cardiorespiratory fitness influences task-related brain network organization in different task domains.}}, author = {{Gölz, Christian Johannes and Mora, Karin and Stroehlein, Julia Kristin and Haase, Franziska Katharina and Dellnitz, Michael and Reinsberger, Claus and Vieluf, Solveig}}, issn = {{1871-4080}}, journal = {{Cognitive Neurodynamics}}, keywords = {{Cognitive Neuroscience}}, number = {{5}}, pages = {{847--859}}, publisher = {{Springer Science and Business Media LLC}}, title = {{{Electrophysiological signatures of dedifferentiation differ between fit and less fit older adults}}}, doi = {{10.1007/s11571-020-09656-9}}, volume = {{15}}, year = {{2021}}, } @article{30114, author = {{Gölz, Christian Johannes and Mora, K. and Rudisch, J. and Gaidai, Roman and Reuter, E. and Godde, B. and Reinsberger, Claus and Voelcker-Rehage, C. and Vieluf, S.}}, issn = {{0893-6080}}, journal = {{Neural Networks}}, keywords = {{Artificial Intelligence, Cognitive Neuroscience}}, pages = {{363--374}}, publisher = {{Elsevier BV}}, title = {{{Classification of visuomotor tasks based on electroencephalographic data depends on age-related differences in brain activity patterns}}}, doi = {{10.1016/j.neunet.2021.04.029}}, volume = {{142}}, year = {{2021}}, } @article{35326, abstract = {{Thermostable compartmentalized sodium-water sites through intercalated γ-aminopropyl-dimethyl-ethoxy silane in synthetic hectorite.}}, author = {{Keil, Waldemar and Zhao, Kai and Oswald, Arthur and Bremser, Wolfgang and Schmidt, Claudia and Hintze-Bruening, Horst}}, issn = {{1463-9076}}, journal = {{Physical Chemistry Chemical Physics}}, keywords = {{Physical and Theoretical Chemistry, General Physics and Astronomy}}, number = {{1}}, pages = {{477--487}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Thermostable water reservoirs in the interlayer space of a sodium hectorite clay through the intercalation of γ-aminopropyl(dimethyl)ethoxysilane in toluene}}}, doi = {{10.1039/d1cp03321b}}, volume = {{24}}, year = {{2021}}, } @article{41817, abstract = {{Pseudo isocyanine chloride monomers equilibrate with H-oligomers and, separated by a threshold, with H-oligomers and fiber-like J-aggregates. The mechanism and thermodynamics of J-aggregate formation is interpreted with the concept of chain growth.}}, author = {{Hämisch, Benjamin and Huber, Klaus}}, issn = {{1744-683X}}, journal = {{Soft Matter}}, keywords = {{Condensed Matter Physics, General Chemistry}}, number = {{35}}, pages = {{8140--8152}}, publisher = {{Royal Society of Chemistry (RSC)}}, title = {{{Mechanism and equilibrium thermodynamics of H- and J-aggregate formation from pseudo isocyanine chloride in water}}}, doi = {{10.1039/d1sm00979f}}, volume = {{17}}, year = {{2021}}, } @article{41818, author = {{Hense, Dominik and Büngeler, Anne and Kollmann, Fabian and Hanke, Marcel and Orive, Alejandro and Keller, Adrian and Grundmeier, Guido and Huber, Klaus and Strube, Oliver I.}}, issn = {{1525-7797}}, journal = {{Biomacromolecules}}, keywords = {{Materials Chemistry, Polymers and Plastics, Biomaterials, Bioengineering}}, number = {{10}}, pages = {{4084--4094}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Self-Assembled Fibrinogen Hydro- and Aerogels with Fibrin-like 3D Structures}}}, doi = {{10.1021/acs.biomac.1c00489}}, volume = {{22}}, year = {{2021}}, } @article{41816, author = {{Wagner, Maximilian and Krieger, Anja and Minameyer, Martin and Hämisch, Benjamin and Huber, Klaus and Drewello, Thomas and Gröhn, Franziska}}, issn = {{0024-9297}}, journal = {{Macromolecules}}, keywords = {{Materials Chemistry, Inorganic Chemistry, Polymers and Plastics, Organic Chemistry}}, number = {{6}}, pages = {{2899--2911}}, publisher = {{American Chemical Society (ACS)}}, title = {{{Multiresponsive Polymer Nanoparticles Based on Disulfide Bonds}}}, doi = {{10.1021/acs.macromol.1c00299}}, volume = {{54}}, year = {{2021}}, }