By using an asymmetric ligand with triazole and imidazole groups, three Keggin-based complexes were obtained, [Cu(HMET)4(H2O)2](PMo12O40)2·2H2O (1), [Cu3(HMET)4Cl2(H2O)2(XM12O40)2]·4H2O (X?=?Si, M?=?W 2, X?=?Ge, M?=?Mo 3) (MET?=?4-(2-imidazol-1-yl-ethyl)-4H-[1,3,4]triazole). Complex 1 contains discrete Keggin anions and mono-nuclear [Cu(MET)4(H2O)2]2+ clusters. Complexes 2 and 3 are isostructural with tri-nuclear Cu clusters linked by Keggin anions to construct a 1D chain. The 1- to 3-CPEs show electrocatalytic properties and can also act as nitrite amperometric sensors. Complexes 1–3 exhibit photocatalytic activities for degradation of MB. Complexes 1–?3 own fluorescence sensing properties for detecting Hg2+ ions.
Graphical abstract
By using an asymmetric ligand three POM-based complexes were constructed. The 1– to 3–CPEs exhibit good electrocatalytic activities and can be used as nitrite amperometric sensors. The title complexes show good photocatalytic activities for degradation of MB. Moreover, complexes 1–3 can act as fluorescence sensors to selectively detect Hg2+.
Cobalt-free Li-rich layered oxides(LLOs)such as Li1.2Mn0.6Ni0.2O2 have attracted extensive atten-tion owing to their high specific capacity and low cost.Nonethe... 相似文献
The key to type 1 copper (T1Cu) function lies in the fine tuning of the CuII/I reduction potential (E°′T1Cu) to match those of its redox partners, enabling efficient electron transfer in a wide range of biological systems. While the secondary coordination sphere (SCS) effects have been used to tune E°′T1Cu in azurin over a wide range, these principles are yet to be generalized to other T1Cu-containing proteins to tune catalytic properties. To this end, we have examined the effects of Y229F, V290N and S292F mutations around the T1Cu of small laccase (SLAC) from Streptomyces coelicolor to match the high E°′T1Cu of fungal laccases. Using ultraviolet-visible absorption and electron paramagnetic resonance spectroscopies, together with X-ray crystallography and redox titrations, we have probed the influence of SCS mutations on the T1Cu and corresponding E°′T1Cu. While minimal and small E°′T1Cu increases are observed in Y229F- and S292F-SLAC, the V290N mutant exhibits a major E°′T1Cu increase. Moreover, the influence of these mutations on E°′T1Cu is additive, culminating in a triple mutant Y229F/V290N/S292F-SLAC with the highest E°′T1Cu of 556 mV vs. SHE reported to date. Further activity assays indicate that all mutants retain oxygen reduction reaction activity, and display improved catalytic efficiencies (kcat/KM) relative to WT-SLAC. 相似文献
Over the recent decades, due to the special electronic characteristics and diverse reactivities, N-heterocyclic carbene (NHC) has received significant interest in organocatalyzed reactions. The formation of Breslow intermediates by NHC can convert into acyl anion equivalent, enolates, homoenolate, acyl azolium, and vinyl enolate etc., and the cycloaddition reactions of these species has attracted lots of attention. In this review, we focus on the summry of the development of NHC-activation of carbonyl carbon (or imine carbon) in situ, α-, β-, γ-, and beyond, and the cycloaddition reaction of these species. 相似文献
The development of PtIV prodrugs that are reduced into the therapeutically active PtII species within the tumor microenvironment has received much research interest. In order to provide spatial and temporal control over the treatment, there is a high demand for the development of compounds that could be selectively activated upon irradiation. Despite recent progress, the majority of PtIV complexes are excited with ultraviolet or blue light, limiting the use of such compounds to superficial application. To overcome this limitation, herein, the first example of PtIV prodrug nanoparticles that could be reduced with deeply penetrating ultrasound radiation is reported, enabling the treatment of deep-seated or large tumors. The nanoparticles were found to selectively accumulate inside a mouse colon carcinoma tumor upon intravenous injection and were able to eradicate the tumor upon exposure to ultrasound radiation. 相似文献
Flexible batteries based on gel electrolytes with high safety are promising power solutions for wearable electronics but suffer from vulnerable electrode-electrolyte interfaces especially upon complex deformations, leading to irreversible capacity loss or even battery collapse. Here, a supramolecular sol-gel transition electrolyte (SGTE) that can dynamically accommodate deformations and repair electrode-electrolyte interfaces through its controllable rewetting at low temperatures is designed. Mediated by the micellization of polypropylene oxide blocks in Pluronic and host-guest interactions between α-cyclodextrin (α-CD) and polyethylene oxide blocks, the high ionic conductivity and compatibility with various salts of SGTE afford resettable electrode-electrolyte interfaces and thus constructions of a series of highly durable, flexible aqueous zinc batteries. The design of this novel gel electrolyte provides new insights for the development of flexible batteries. 相似文献
Oxygen reduction reaction (ORR) is vital for clean and renewable energy technologies, which require no fossil fuel but catalysts. Platinum (Pt) is the best-known catalyst for ORR. However, its high cost and scarcity have severely hindered renewable energy devices (e.g., fuel cells) for large-scale applications. Recent breakthroughs in carbon-based metal-free electrochemical catalysts (C-MFECs) show great potential for earth-abundant carbon materials as low-cost metal-free electrocatalysts towards ORR in acidic media. This article provides a focused, but critical review on C-MFECs for ORR in acidic media with an emphasis on advances in the structure design and synthesis, fundamental understanding of the structure-property relationship and electrocatalytic mechanisms, and their applications in proton exchange membrane fuel cells. Current challenges and future perspectives in this emerging field are also discussed. 相似文献
AbstractThree novel dammarane-type saponins, 2α,3β,12β,20(S),24(S)-pentahydroxydammar-25-ene-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-glucopyranoside (1, namely gypenoside J1), 2α,3β,12β,20(S),25-pentahydroxydammar-23-ene-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-glucopyranoside (2, namely gypenoside J2) and 2α,3β,12β,20(S)-tetrahydroxydammar-25-en-24-one-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside (3, namely gypenoside J3) along with one known gypenoside (gypenoside LVII) were isolated from the aerial parts of G. pentaphyllum using various chromatographic methods. Their structures were elucidated on the basis of IR, 1D- (1H and 13C), 2D-NMR spectroscopy (HSQC, HMBC and COSY), and mass spectrometry (ESI-MS/MS). Their activity was tested using CCK-8 assay. These four compounds showed little anti-cancer activity with IC50 values more than 100?μM against four types of human cancer lines. The effects of them against H2O2-induced oxidative stress in human neuroblastoma SH-SY5Y cells were evaluated and they all showed potential neuroprotective effects with 3.64–18.16% higher cell viability than the H2O2-induced model group. 相似文献
A new ion-exchange adsorbent (IEA) derived from Fe(3)O(4)/SiO(2)-GPTMS-DEAE with paramagnetic properties was prepared. Fe(3)O(4) nanoparticles were firstly prepared in water-in-oil microemulsion. The magnetic Fe(3)O(4) particles were modified in situ by hydrolysis and condensation reactions with tetraethoxysilane (TEOS) to form the core-shell Fe(3)O(4)/SiO(2). The modified particles were further treated by 3-glycidoxypropyltrimethoxysilane (GPTMS) to form Fe(3)O(4)/SiO(2)-GPTMS nanoparticles. Fe(3)O(4)/SiO(2)-GPTMS-DEAE nanoparticles (IEA) were finally obtained through the condensation reaction between the Cl of diethylaminoethyl chloride-HCl (DEAE) and the epoxy groups of GPTMS in the Fe(3)O(4)/SiO(2)-GPTMS. The obtained IEA has features of paramagnetic and ion exchange properties because of the Fe(3)O(4) nanoparticles and protonated organic amine in the sample. The intermediates and final product obtained in the synthesis process were characterized. The separation result of genomic DNA from blood indicated that Fe(3)O(4)/SiO(2)-GPTMS-DEAE nanoparticles have outstanding advantages in operation, selectivity, and capacity. 相似文献