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921.
922.
923.
Manuel A. Treto-Suárez Yoan Hidalgo-Rosa Eduardo Schott Ximena Zarate Dayan Páez-Hernández 《International journal of quantum chemistry》2020,120(3):e26083
The turn-on luminescent chemosensor [2-Hydroxy-1-naphthaldehyde-(2-pyridyl) hydrazone] (L), selective to Al3+ ions, was studied by means of density functional theory (DFT) and time-dependent-DFT quantum mechanics calculations. The UV-Vis absorption and the radiative channel from the adiabatic S1 excited state were assessed in order to elucidate the selective sensing mechanism of L to Al3+ ions. We found that twisted intramolecular charge transfer (TICT) and photoelectron transfer (PET), which alter the emissive state, are responsible for the luminescence quenching in L. After coordination with Al3+, the TICT is blocked, and PET is no longer possible. So, the emission of the coordination complex is activated, and a fluorescence effect enhanced by chelation is observed. For compounds with Zn2+ and Cd2+, the luminescence quenching is caused by PET, while for Ni2+, ligand to metal charge transfer is the prominent mechanism. To go into more detail, the metal-ligand interaction was analyzed via the Morokuma-Ziegler energy decomposition scheme and the natural orbital of chemical valence. 相似文献
924.
Two novel rhodamine-based polystyrene solid-phase fluorescence sensors PS-PA-I and PS-PA-II with different lengths of polyamines were synthesized for Hg(II) determination. The detection mechanism involving the Hg(II) chelation-induced spirocycle open of rhodamine was proposed with the aid of theoretical calculation. The stronger N-Hg bond and the longer polyamine chain in PS-PA-II led to a better selectivity, much higher and more quickly fluorescence response to Hg(II). 相似文献
925.
快速测量污染水中重金属元素含量对于监测野外突发污染至关重要.建立了使用以生物酶(DNA酶)为原理的便捷仪器快速测定污染水中铅(Pb)和镉(Cd)元素含量的方法.使用生物酶传感器对标准溶液进行测量,根据溶液推荐和测量浓度之间的线性关系对仪器进行校准后,可测量的质量浓度范围:Pb为2~100 μg/L,Cd为0.1~1.0 mg/L.仪器可以在3~5 min内方便快速完成重金属的现场测量,使用DNA酶可以快速获得污染水中的微量金属元素含量,有利于野外重金属污染的即时测量. 相似文献
926.
Dr. Joydev Hatai Dr. Christoph Hirschhäuser Prof. Dr. Carsten Schmuck Dr. Jochen Niemeyer 《ChemistryOpen》2020,9(7):786-792
A coumarin based probe for the efficient detection of hydrogen sulfide in aqueous medium is reported. The investigated coumarine-based derivative forms spherical nanoparticles in aqueous media. In presence of Pd2+, a metallosupramolecular coordination polymer is formed, which is accompanied by quenching of the coumarin emission at 390 nm. Its Pd2+ complex could be used as a probe for chemoselective detection of monohydrogensulfide (HS−). Presence of HS− leads to a'turn-on' fluorescence signal, resulting from decomplexation of Pd2+ from the metallosupramolecular probe. The probe was successfully applied for qualitative and quantitative detection of HS− in different sources of water directly collected from sea, river, tap and laboratory drain water, as well as in growth media for aquatic species. 相似文献
927.
Alexander V. Fejzagić Sebastian Myllek Fabian Hogenkamp Julian Greb Prof. Dr. Jörg Pietruszka Dr. Thomas Classen 《ChemistryOpen》2020,9(9):959-966
Screening for an interesting biocatalyst and its subsequent kinetic characterization depends on a reliable activity assay. In this work, a fluorometric assay based on the halogenation of 4-methyl-7-diethylamino-coumarin was established to monitor haloperoxidase-activity. Since haloperoxidases utilize hydrogen peroxide and halide ions to halogenate a broad range of substrates by releasing hypohalous acids, a direct quantification of haloperoxidase-activity remains difficult. With the system presented here, 3-bromo-4-methyl-7-diethylaminocoumarin is preferentially formed and monitored by fluorescence measurements. As starting material and product share similar spectroscopical properties, a two-dimensional calibration ap-proach was utilized to allow for quantification of each compound within a single measurement. To validate the system, the two-dimensional Michaelis-Menten kinetics of a vanadium-dependent chloroperoxidase from Curvularia inaequalis were recorded, yielding the first overall kinetic parameters for this enzyme. With limits of detection and quantification in the low μm range, this assay may provide a reliable alternative system for the quantification of haloperoxidase-activity. 相似文献
928.
Jayachandran Jayakumar Guganchandar Vedarethinam Huan‐Chang Hsiao Shang‐You Sun Shih‐Ching Chuang 《Angewandte Chemie (International ed. in English)》2020,59(2):689-694
Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C?H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2‐azobiaryls with alkenes to give orange‐red‐fluorescent cinnolino[2,3‐f]phenanthridin‐9‐ium salts and 15H‐cinnolino[2,3‐f]phenanthridin‐9‐ium‐10‐ide is proposed to involve ortho C?H olefination of the 2‐azobiaryl compound with the alkene, intramolecular aza‐Michael addition, concerted metalation–deprotonation (CMD), reductive elimination, and oxidation. 相似文献
929.
Jiancheng Rao Xinrui Liu Xuefei Li Liuqing Yang Lei Zhao Shumeng Wang Junqiao Ding Lixiang Wang 《Angewandte Chemie (International ed. in English)》2020,59(3):1320-1326
Based on a “TADF + Linker” strategy (TADF=thermally activated delayed fluorescence), demonstrated here is the successful construction of conjugated polymers that allow highly efficient delayed fluorescence. Small molecular TADF blocks are linked together using a methyl‐substituted phenylene linker to form polymers. With the growing number of methyl groups on the phenylene, the energy level of the local excited triplet state (3LEb) from the delocalized polymer backbone gradually increases, and finally surpasses the charge‐transfer triplet state (3CT). As a result, the diminished delayed fluorescence can be recovered for the tetramethyl phenylene containing polymer, revealing a record‐high external quantum efficiency (EQE) of 23.5 % (68.8 cd A?1, 60.0 lm W?1) and Commission Internationale de l′Eclairage (CIE) coordinates of (0.25, 0.52). Combined with an orange‐red TADF emitter, a bright white electroluminescence is also obtained with a peak EQE of 20.9 % (61.1 cd A?1, 56.4 lm W?1) and CIE coordinates of (0.36, 0.51). 相似文献
930.
Yang Li Yuan‐Yuan An Jian‐Zhong Fan Xiao‐Xu Liu Xin Li F. Ekkehardt Hahn Yao‐Yu Wang Ying‐Feng Han 《Angewandte Chemie (International ed. in English)》2020,59(25):10073-10080
A series of supramolecular assemblies of types [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4‐triazolium) salts H4‐L(PF6)4 and AgI ions, is described. The assembly type obtained dependends on the N‐wingtip substituents of H4‐L(PF6)4. Changes in the lengths of the N4‐wingtip substituents enables controlled formation of assemblies with either [Ag4( L )2](PF6)4 or [Ag8( L )4](PF6)8 stoichiometry. The molecular structures of selected [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4 assemblies were determined by X‐ray diffraction analyses. While H4‐ L (PF6)4 does not exhibit fluorescence in solution, their tetra‐NHC (NHC=N‐heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light‐induced, supramolecule‐to‐supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties. 相似文献