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91.
Water-soluble triplet sensitizer with permethyl-β-cyclodextrin(PMCD) grafting on a Schiff-base Pt(Ⅱ)complex(Pt-2),in which PMCD unit serves as a host for binding the acceptors and the Schiff-base Pt(Ⅱ)complex serves as a triplet sensitizer,was synthesized to investigate the effect of supramolecular complexation and assembly on the triplet-triplet annihilation upconversion emission in water.9,10-Diphenylanthracence(DPA) carboxylate(A-1) and its dimer(A-2) in which two DPA carboxylate were covalently linked with an alkyl chain were synthesized as triplet acceptors which also play a role of guest molecules for PMCD.A-1 and A-2 showed high affinity with PMCD,and A-2 can readily aggregate in water and form micron sized assemblies due to the hydrophobic effect and π-π stacking of anthracene core in A-2.The efficiency of TTA-UC was demonstrated to be enhanced by a synergistic effect of host-guest complexation of Pt-2 with A-2 and the self-aggregation of the acceptor A-2,which facilitated the energy transfer and energy fusion among donor and acceptor. 相似文献
92.
Congcong Pei Dr. Chao Liu Dr. You Wang Dan Cheng Rongxin Li Weikang Shu Chaoqi Zhang Wenli Hu Dr. Aihua Jin Dr. Yannan Yang Prof. Jingjing Wan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):10923-10927
High-throughput metabolic analysis is of significance in diagnostics, while tedious sample pretreatment has largely hindered its clinic application. Herein, we designed FeOOH@ZIF-8 composites with enhanced ionization efficiency and size-exclusion effect for laser desorption/ionization mass spectrometry (LDI-MS)-based metabolic diagnosis of gynecological cancers. The FeOOH@ZIF-8-assisted LDI-MS achieved rapid, sensitive, and selective metabolic fingerprints of the native serum without any enrichment or purification. Further analysis of extracted serum metabolic fingerprints successfully discriminated patients with gynecological cancers (GCs) from healthy controls and also differentiated three major subtypes of GCs. Given the low cost, high-throughput, and easy operation, our approach brings a new dimension to disease analysis and classification. 相似文献
93.
Xu Liu Ruoyu Liu Jiaxing Qiu Prof. Dr. Xu Cheng Prof. Dr. Guigen Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(33):14066-14071
We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O2 evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral. 相似文献
94.
The halogen-bonded complexes between H2Te/Me2Te and the dihalogen molecules XY (XY = F2, Cl2, Br2, I2, ClF, ClBr, BrF, BrCl, BrI, IF, ICl, IBr) have been studied to investigate the dependence of its strength and nature on the halogen donor X and its adjoining atom Y, as well as the methyl groups in the electron donor. The interaction energy varies between −1.7 and − 43.5 kcal/mol, indicating that the Te atom in H2Te/Me2Te has a strong affinity for the dihalogen molecules. For the H2Te-XY complex, the halogen bond is stronger for the heavier halogen donor X atom and the strong electron-withdrawing group Y. However, for Me2Te-XY, the halogen bond is stronger for the lighter halogen donor X atom. The H2Te/Me2Te-F2 complex has the largest interaction energy, although the σ-hole on F2 is the smallest in magnitude. In most of the complexes, the electrostatic and polarization contributions to the binding strength are similar in magnitude. However, for H2Te/Me2Te-F2, the polarization contribution is much larger than the electrostatic contribution, with a significant contribution from charge transfer. 相似文献
95.
A novel metal–organic framework material {[N(C2H5)3][Zn2(ptmda)2(μ2-H2O)]·(H2O)0.5}n { GUT-3 ; H2ptmda is 4,4′-([p-tolylazanediyl]bis [methylene])dibenzoic acid} was successfully synthesized using the hydrothermal method and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. GUT-3 has a two-dimensional network based on dinuclear [Zn2(ptmda)2(μ2-H2O)]− building units which formed an eightfold interpenetration network in GUT-3 molecules. Hirshfeld surface analysis revealed that H–H, C–H, and O–H bonds accounted for the majority of intermolecular interactions. Moreover, the interactions between GUT-3 and As(V) – the form of As(V) is AsO43− – were analyzed in aqueous solutions in a batch system to study the effect of pH, concentration, adsorbent dose, adsorption time, adsorption temperature, and shaking speed. The kinetic and isotherm data of arsenic adsorption on GUT-3 were accurately modeled by pseudo-second-order, Langmuir (qm = 33.91 mg/g), and Freundlich models. The Box–Behnken response surface method was used to optimize the adsorption conditions of As(V) from the simulated arsenic-contaminated wastewater. The effect of various experimental parameters and optimal experimental conditions was ascertained using the quadratic model. 相似文献
96.
97.
Zixin Chen Dr. Min Chen Dr. Yunfeng Cheng Prof. Toshiyuki Kowada Dr. Jinghang Xie Dr. Xianchuang Zheng Prof. Jianghong Rao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(8):3298-3305
The condensation reaction between 6-hydroxy-2-cyanobenzothiazole (CBT) and cysteine has been shown for various applications such as site-specific protein labelling and in vivo cancer imaging. This report further expands the substrate scope of this reaction by varying the substituents on aromatic nitriles and amino thiols and testing their reactivity and ability to form nanoparticles for cell imaging. The structure–activity relationship study leads to the identification of the minimum structural requirement for the macrocyclization and assembly process in forming nanoparticles. One of the scaffolds made of 2-pyrimidinecarbonitrile and cysteine joined by a benzyl linker was applied to design fluorescent probes for imaging caspase-3/7 and β-galactosidase activity in live cells. These results demonstrate the generality of this system for imaging hydrolytic enzymes. 相似文献
98.
Pei-Ming Cheng Dr. Li-Xuan Cai Shao-Chuan Li Shao-Jun Hu Dan-Ni Yan Dr. Li-Peng Zhou Prof. Qing-Fu Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23775-23779
We report here a guest-reaction-induced mitosis-like host transformation from a known Pd4L2 cage 1 to a conjoined Pd6L3 twin-cage 2 featuring two separate cavities. The encapsulation of 1-hydroxymethyl-2-naphthol ( G1 ), a known ortho-quinone methide (o-QMs) precursor, within the hydrophobic cavity of cage 1 is found crucial to realize the cage to twin-cage conversion. Confined G1 molecules within the nanocavity undergo self-coupling dimerization reaction to form 2,2′-dihydroxy-1,1′-dinaphthylmethane ( G2 ) which then triggers the cage to twin-cage mitosis. The same conversion also proceeds, in a much faster rate, via the direct templation of G2 , confirming the induced-fit transformation mechanism. The structure of the ( G2 )2⊂ 2 host–guest complex has been established by X-ray crystallographic study, where cis- to trans- conformational switch on one bridging ligand is revealed. 相似文献
99.
A series of novel diaroylhydrazone aluminum complexes have been synthesized and well-defined structurally, and their catalytic performance in the polymerization of ε-caprolactone and lactides have also been evaluated. Complexes [(L1–4)2AlMe] ( 1 – 4 ) {[L1 = (3,5-tBu2–2-OMe-C6H2)CH=NNCOC6H5], [L2 = (3,5-tBu2–2-OMe-C6H2)CH=NNCO(C6H4–4-OCH3)], [L3 = (3,5-tBu2–2-OMe-C6H2)CH=NNCO(C6H4–4-Br)] and [L4 = (2-OMe-C6H4)CH=NNCO(C6H4–4-tBu)]} were prepared through treatment of AlMe3 with the corresponding proligands L1–4H in molar ratios of 1: 1 or 1: 2. Chemical structures of all the complexes were well-defined by elemental analysis, NMR spectra as well as single-crystal X-ray study. Complexes [(L1–4)2AlMe] ( 1 – 4 ) in this work represent the first examples of aluminum complexes of aroylhydrazone ligands with crystallographic characterization. Specifically, they are all in monomeric form with a penta-coordinated aluminum center, including two approximately co-planar five-membered metallacycles with aluminum. Introduced bulky tert-butyl substituents in aroylhydrazone ligands could affect the geometry around the central metal which is a distorted square-based pyramid in complexes 1 – 3 while being a trigonal bipyramidal in complex 4 , thus affecting their catalytic behaviors. The complexes can successfully catalyze the ring-opening polymerization of ε-caprolactone and L-lactide under mild conditions without any activator. In addition, complexes 1 – 4 could also polymerize rac-lactide, affording atactic polylactides with high conversions and good controllability in relatively short reaction time. 相似文献
100.