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131.
In this paper, the Ni/Al hybrid open-cell foams are characterized on different hierarchical levels by means of experiments and numerical modeling from the atomic to the microscale. In this case, it is possible to compare the elastic-plastic behavior at different scales in order to attain a deeper understanding of the multiscale properties of the Ni/Al hybrid foams. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
132.
Dr. Carolin Müller Alexander Schwab Dr. Nicholas M. Randell Dr. Stephan Kupfer Prof. Benjamin Dietzek-Ivanšić Dr. Murielle Chavarot-Kerlidou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202103882
The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy)2Ru( oxim-dppqp )]2+ ( Ru ), storing two electrons coupled to two protons on the π-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy)2Ru(dppz)]2+ and [(bpy)2Ru( oxo-dppqp )]2+ complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states. 相似文献
133.
Christian Balischewski Dr. Biswajit Bhattacharyya Dr. Eric Sperlich Dr. Christina Günter Alkit Beqiraj Prof. Dr. Tillmann Klamroth Dr. Karsten Behrens Stefan Mies Alexandra Kelling Susanne Lubahn Lea Holtzheimer Anne Nitschke Prof. Dr. Andreas Taubert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202201068
Fifteen N-butylpyridinium salts – five monometallic [C4Py]2[MBr4] and ten bimetallic [C4Py]2[M0.5aM0.5bBr4] (M=Co, Cu, Mn, Ni, Zn) – were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10−5 and 10−6 S cm−1. At elevated temperatures, the conductivities reach up to 10−4 S cm−1 at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs. 相似文献
134.
Dr. Yile Wu Zhao Zhao Dr. Ting Chen Jingjie Tan Dr. Zheng-Wang Qu Prof. Dr. Stefan Grimme Prof. Dr. Yufen Zhao Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(25):e202200666
The germylene species (CH{(CMe)(2,6-iPr2C6H3N)}2)GePCO 1 is shown to react with the Lewis acids (E(C6F5)3 E=B, Al). Nonetheless, 1 participates in FLP chemistry with electron deficient alkynes or olefins, acting as an intramolecular FLP. In contrast, in the presence of B(C6F5)3 and an electron rich alkyne, 1 behaves as Ge-based nucleophile to effect intermolecular FLP addition to the alkyne. This reactivity demonstrates that the reaction pathway is controlled by the nature of the electrophile and nucleophile generated in solution, as revealed by extensive DFT calculations. 相似文献
135.
Jannik Brückmann Dr. Carolin Müller Tamar Maisuradze Dr. Alexander K. Mengele Dr. Djawed Nauroozi Sven Fauth Andreas Gruber Prof. Dr. Stefanie Gräfe Prof. Dr. Kerstin Leopold Dr. Stephan Kupfer Prof. Dr. Benjamin Dietzek-Ivanšić Prof. Dr. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202200766
The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)3]2+ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD+ to NADH was achieved, highlighting the potential of this system for photocatalytic applications. 相似文献
136.
Christopher J. Major Dr. Zheng-Wang Qu Prof. Dr. Stefan Grimme Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202200698
The known boranes (R(Me3Si)N)2BF (R=Me3Si 1 , tBu 2 , C6F5 3 , o-tol 4 , Mes 5 , Dipp 6 ) and borinium salts (R(Me3Si)N)2B][B(C6F5)4] (R=Me3Si 7 , tBu 8 ) are prepared and fully characterized. Compound 7 is shown to react with phosphines to generate [R3PSiMe3]+ and [R3PH]+ (R=Me, tBu). Efforts to generate related borinium cations via fluoride abstraction from (R(Me3Si)N)2BF (R=C6F5 3 , o-tol 4 , Mes 5 ) gave complex mixtures suggesting multiple reaction pathways. However for R=Dipp 6 , the species [(μ-F)(SiMe2N(Dipp))2BMe][B(C6F5)4] was isolated as the major product, indicating methyl abstraction from silicon and F/Me exchange on boron. These observations together with state-of-the-art DFT mechanistic studies reveal that the trimethylsilyl-substituents do not behave as ancillary subsitutents but rather act as sources of proton, SiMe3 and methyl groups. 相似文献
137.
Dr. Anna R. Ziefuss Michael Willeke Matthias Miertz Dr. Alexander Heinemann Dr. Christoph Rehbock Prof. Dr. Stephan Barcikowski 《Chemphyschem》2022,23(10):e202200033
Noble metal alloy nanoclusters (NCs) are interesting systems as the properties of two or more elements can be combined in one particle, leading to interesting fluorescence phenomena. However, previous studies have been exclusively performed on ligand-capped NCs from wet chemical synthesis. This makes it difficult to differentiate to which extent the fluorescence is affected by ligand-induced effects or the elemental composition of the metal core. In this work, we used laser fragmentation in liquids (LFL) to fabricate colloidal gold-rich bi-metallic AuPt NCs in the absence of organic ligands and demonstrate the suitability of this technique to produce molar fraction series of 1nm alloy NC. We found that photoluminescence of ligand-free NCs is not a phenomenon limited to Au. However, even minute amounts of Pt atoms in the AuPt NCs lead to quenching and red-shift of the fluorescence, which may be attributed to the altered surface charge density. 相似文献
138.
Patrick M. TomHon Dr. Suyong Han Dr. Sören Lehmkuhl Prof. Stephan Appelt Prof. Eduard Y. Chekmenev Prof. Milad Abolhasani Prof. Thomas Theis 《Chemphyschem》2021,22(24):2526-2534
We introduce a Spin Transfer Automated Reactor (STAR) that produces continuous parahydrogen induced polarization (PHIP), which is stable for hours to days. We use the PHIP variant called signal amplification by reversible exchange (SABRE), which is particularly well suited to produce continuous hyperpolarization. The STAR is operated in conjunction with benchtop (1.1 T) and high field (9.4 T) NMR magnets, highlighting the versatility of this system to operate with any NMR or MRI system. The STAR uses semipermeable membranes to efficiently deliver parahydrogen into solutions at nano to milli Tesla fields, which enables 1H, 13C, and 15N hyperpolarization on a large range of substrates including drugs and metabolites. The unique features of the STAR are leveraged for important applications, including continuous hyperpolarization of metabolites, desirable for examining steady-state metabolism in vivo, as well as for continuous RASER signals suitable for the investigation of new physics. 相似文献
139.
Stephan Wasielewski Eduard Rott Ralf Minke Heidrun Steinmetz 《Molecules (Basel, Switzerland)》2021,26(1)
Sludge water (SW) arising from the dewatering of anaerobic digested sludge causes high back loads of ammonium, leading to high stress (inhibition of the activity of microorganisms by an oversupply of nitrogen compounds (substrate inhibition)) for wastewater treatment plants (WWTP). On the other hand, ammonium is a valuable resource to substitute ammonia from the energy intensive Haber-Bosch process for fertilizer production. Within this work, it was investigated to what extent and under which conditions Carpathian clinoptilolite powder (CCP 20) can be used to remove ammonium from SW and to recover it. Two different SW, originating from municipal WWTPs were investigated (SW1: c0 = 967 mg/L NH4-N, municipal wastewater; SW2: c0 = 718–927 mg/L NH4-N, large industrial wastewater share). The highest loading was achieved at 307 K with 16.1 mg/g (SW1) and 15.3 mg/g (SW2) at 295 K. Kinetic studies with different specific dosages (0.05 gCLI/mgNH4-N), temperatures (283–307 K) and pre-loaded CCP 20 (0–11.4 mg/g) were conducted. At a higher temperature a higher load was achieved. Already after 30 min contact time, regardless of the sludge water, a high load up to 7.15 mg/g at 307 K was reached, achieving equilibrium after 120 min. Pre-loaded sorbent could be further loaded with ammonium when it was recontacted with the SW. 相似文献
140.
Low water vapor and air permeability is a persistent challenge in wearable and on-skin electronics, as it reduces wearing comfort, and leads to skin irritation and inflammation in the long term. To tackle this issue, Zheng and coworkers designed a stretchable conductor based on an elastomeric fiber mat coated by liquid metal. After simple activation via stretching, the flexible conductor was endowed with excellent permeability, good stretchability, exceptional electrical stability, and good biocompatibility, ascribed to the mesh-like structure and the vertically buckled structure of the liquid metal. Based on the intriguing properties of the material, it was employed in a multi-functional wearable device, able to detect the heartbeat and sweat while serving as a heating device. The corresponding research has been published in Nature Materials and can be accessed at https://doi.org/10.1038/s41563-020-00902-3. 相似文献