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941.
Katharina Zielke Ondřej Kováč Michael Winter Dr. Jiří Pospíšil Prof. Mario Waser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8163-8168
The first highly asymmetric catalytic synthesis of densely functionalized dihydrobenzofurans is reported, which starts from ortho-hydroxy-containing para-quinone methides. The reaction relies on an unprecedented formal [4+1]-annulation of these quinone methides with allenoates in the presence of a commercially available chiral phosphine catalyst. The chiral dihydrobenzofurans were obtained as single diastereomers in yields up to 90 % and with enantiomeric ratios up to 95:5. 相似文献
942.
Benjamin H. Strudwick Mark A. J. Koenis Hans J. Sanders Valentin P. Nicu Sander Woutersen Prof. Wybren Jan Buma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(54):12560-12566
Vibrational circular dichroism (VCD) studies are reported on a chiral compound in which a fullerene C60 moiety is used as an electron acceptor and local VCD amplifier for an alanine-based peptide chain. Four redox states are investigated in this study, of which three are reduced species that possess low-lying electronic states as confirmed by UV/Vis spectroelectrochemistry. VCD measurements in combination with (TD)DFT calculations are used to investigate (i) how the low-lying electronic states of the reduced species modulate the amplification of VCD signals, (ii) how this amplification depends on the distance between oscillator and amplifier, and (iii) how the spatial extent of the amplifier influences amplification. These results pave the way for further development of tailored molecular VCD amplifiers. 相似文献
943.
Prof. Dr. Yasuchika Hasegawa Takafumi Matsui Dr. Yuichi Kitagawa Dr. Takayuki Nakanishi Dr. Tomohiro Seki Prof. Dr. Hajime Ito Prof. Dr. Yuta Nakasaka Prof. Dr. Takao Masuda Prof. Dr. Koji Fushimi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12308-12315
Oxygen-sensitive and near-infrared (NIR) luminescent YbIII coordination polymers incorporating ligands based on pyrene derivatives were synthesized: YbIII–TBAPy and YbIII–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of YbIII–TIAPy has been evaluated by measuring its N2 adsorption isotherm. The NIR luminescence properties of YbIII–TBAPy and YbIII–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. YbIII–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent YbIII coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors. 相似文献
944.
Yinwu Li Jiahao Liu Dr. Xiao Huang Prof. Dr. Ling-Bo Qu Prof. Dr. Cunyuan Zhao Prof. Dr. Robert Langer Prof. Dr. Zhuofeng Ke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13785-13798
As a new type of bifunctional catalyst, the Lewis acid transition-metal (LA-TM) catalysts have been widely applied for hydrogen activation. This study presents a mechanistic framework to understand the LA-TM-catalyzed H2 activation through DFT studies. The mer(trans)-homolytic cleavage, the fac(cis)-homolytic cleavage, the synergetic heterolytic cleavage, and the dissociative heterolytic cleavage should be taken as general mechanisms for the field of LA-TM catalysis. Four typical LA-TM catalysts, the Z-type κ4-L3B-Rh complex tri(azaindolyl)borane-Rh, the X-type κ3-L2B-Co complex bis-phosphino-boryl (PBP)-Co, the η2-BC-type κ3-L2B-Pd complex diphosphine-borane (DPB)-Pd, and the Z-type κ2-LB-Pt complex (boryl)iminomethane (BIM)-Pt are selected as representative models to systematically illustrate their mechanistic features and explore the influencing factors on mechanistic variations. Our results indicate that the tri(azaindolyl)borane-Rh catalyst favors the synergetic heterolytic mechanism; the PBP-Co catalyst prefers the mer(trans)-homolytic mechanism; the DPB-Pd catalyst operates through the fac(cis)-homolytic mechanism, whereas the BIM-Pt catalyst tends to undergo the dissociative heterolytic mechanism. The mechanistic variations are determined by the coordination geometry, the LA-TM bonding nature, the electronic structure of the TM center, and the flexibility or steric effect of the LA ligands. The presented mechanistic framework should provide helpful guidelines for LA-TM catalyst design and reaction developments. 相似文献
945.
Zhen Wang Xiaodong Lian Ruiting Li Xinglei Tao Prof. Yapei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13811-13815
Photothermal materials (PTMs) have been intensively investigated in the fields of photothermal conversion. Superior to solid PTMs, liquid PTMs are leading the trends in satisfying the demands of high flexibility and easy recycling. Successful examples of liquid PTMs are mostly formulated by dispersing solid PTMs in solvents, but suffer from the problems of phase segregation and solvent pollution. In this work, a low-cost formulation is proposed, which involves an oxidative product of ethyl oleate by iodine. It is an intrinsic liquid PTM, preserving the fluidic nature as well as possessing considerable ability for photothermal conversion. In addition to understanding the mechanism of light absorption in the visible and even near infrared windows, two examples are presented to demonstrate the great potential of liquid PTMs in broad areas such as light sensing and energy storage. 相似文献
946.
Dr. Jiong Zhou Dr. Guocan Yu Yang Li Jie Shen Mengbin Wang Dr. Zhengtao Li Dr. Peifa Wei Prof. Dr. Jianbin Tang Prof. Dr. Feihe Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14447-14453
Cyanide is extremely hazardous to living organisms and the environment. Owing to its wide range of applications and high toxicity, the development of functional materials for cyanide detection and sensing is highly desirable. Host–guest complexation between bis(p-phenylene)-34-crown-10 H and N-methylacridinium salt G remarkably decreases the detection limit for cyanide anions compared with that of the guest itself. The [2]pseudorotaxane selectively recognizes the cyanide anion with high optical sensitivity as a result of the nucleophilic addition of the cyanide anion at the 9-position of G . The host–guest complexation is further incorporated into supramolecular materials for the visual detection of cyanide anions, especially the detection of cellular cyanide excretion with a detection limit of 0.6 μm . This supramolecular method provides an extremely distinct strategy for the visual detection of cyanide anions. 相似文献
947.
Dr. Yasunori Minami Prof. Dr. Tamejiro Hiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):391-399
Organo(trialkyl)silanes have several advantages, including high stability, low toxicity, good solubility, easy handling, and ready availability compared with heteroatom-substituted silanes. However, methods for the cross-coupling of organo(trialkyl)silanes are limited, most probably because of their exceeding robustness. Thus, a practical method for the cross-coupling of organo(trialkyl)silanes has been a long-standing challenging research target. This article discusses how aryl(trialkyl)silanes can be used in cross-coupling reactions. A pioneering example is CuII catalytic conditions with the use of electron-accepting aryl- or heteroaryl(triethyl)silanes and aryl iodides. The reaction forms biaryls or teraryls. This design concept can be extended to Pd/CuII-catalyzed cross-coupling polymerization reactions between such silanes and aryl bromides or chlorides and to CuI-catalyzed alkylation using alkyl halides. 相似文献
948.
Alexander Brand Prof. Dr. Werner Uhl 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1391-1404
Bicyclic phosphines with two annulated, electronically unsaturated five-membered heterocycles are available through facile routes. In most cases, their phosphorus atoms are bound to heteroatoms such as oxygen or nitrogen (PN3 or PN2O), whereas homoleptic coordination by three sp2-hybridized carbon atoms has been reported only recently. Steric strain causes unique reactivity. Oxidative addition of halogens, N−H or O−H bonds have afforded phosphoranes as valuable materials for secondary processes. Ring opening was identified as an important step for the understanding of these reactions and has been observed experimentally with a diphosphorus-based ring system. A PH2 derivative has been considered as a model system for small molecule activation, and hydrogen transfer to a diazo compound was observed experimentally. Several of these phosphines are excellent ligands for the coordination of transition-metal atoms. The very bulky PC3 compound has a basicity similar to that of PPh3 and may allow the synthesis of complexes with unusually low coordination numbers at the metal atoms. These phosphines found recently renewed interest as promising reagents in various secondary transformations such as the activation of σ-bonds or in coordination chemistry. 相似文献
949.
Jinchao Lou Xiaoyu Zhang Prof. Michael D. Best 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):20-25
Advancements in the field of liposomal drug carriers have culminated in greatly improved delivery properties. An important aspect of this work entails development of designer liposomes for release of contents triggered by environmental changes. The majority of these systems are driven by chemical reactions in the presence of different stimuli. However, a promising new paradigm instead focuses on molecular recognition events as the impetus for content release. In certain cases, these platforms exploit synthetic lipid switches designed to undergo conformational changes upon binding to target ions or molecules that perturb membrane assembly, thereby triggering cargo release. Examples of this approach reported thus far showcase how rational design of lipid switches can result in dramatic changes in lipid assembly properties. These strategies show great promise for opening up new pathophysiological stimuli that can be harnessed for programmed content release in drug delivery applications. 相似文献
950.
Xuan Hao Dr. Hongsen Zhang Dr. Qi Liu Dr. Jingyuan Liu Dr. Rongrong Chen Dr. Jing Yu Prof. Milin Zhang Peili Liu Prof. Jun Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):590-597
Enrichment of UVI is an urgent project for nuclear energy development. Herein, magnetic graphitic carbon nitride nanosheets were successfully prepared by in situ anchoring of pyrrhotite (Fe7S8) on the graphitic carbon nitride nanosheet (CNNS), which were used for capturing UVI. The structural characterizations of Fe7S8/CNNS-1 indicated that the CNNS could prevent the aggregation of Fe7S8 and the saturation magnetization was 4.69 emu g−1, which meant that it was easy to separate the adsorbent from the solution. Adsorption experiments were performed to investigate the sorption properties. The results disclosed that the sorption data conformed to the Langmuir isotherm model with the maximum adsorption capacity of 572.78 mg g−1 at 298 K. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that the main adsorption mechanism are as follows: UVI is adsorbed on the surface of Fe7S8/CNNS-1 through surface complexation initially, then it was reduced to insoluble UIV. Thereby, this work provided an efficient and easy to handle sorbent material for extraction of UVI. 相似文献