Zn、Cd、Hg为什么分别比Cu、Ag、Au活泼?

在教学中经常遇到老师同学提出这个问题。初看起来,这的确是一个难以理解的问题。     

Optical Properties and Photo‐Oxidation of Tetraphenylethene‐Based Fluorophores

We report the optical properties of tetraphenylethene (TPE) and other TPE derivatives functionalised with an octyl group (TPE‐OCT) and polyethyleneglycol group (TPE‐PEG) in the side chain. We compared TPE‐OCT and TPE‐PEG with TPE in both organic solvents and under aqueous conditions. All materials exhibit aggregation‐induced emission, however, uncommonly, TPE‐PEG seems to aggregate in aqueous solution with enhanced photoluminescence quantum efficiency (PLQE) relative to that in organic solvents. All three materials can be photo‐oxidised in solution to their diphenylphenanthrene derivative by irradiation with UV light (at both ≈1 and ≈5 mW cm^?2), with a subsequent enhancement in PL efficiency. The electron‐donating ether group increases the rate of oxidation relative to bare TPE and also photo‐oxidation was shown to be solvent and concentration dependent. Finally, photo‐oxidation was also demonstrated in the aggregate state.     

Ultrasensitive aptamer-based bio bar code immunomagnetic separation and electrochemiluminescence method for the detection of protein

An ultrasensitive aptamer-based bio bar code immunomagnetic separation and electrochemiluminescence (IM-ECL) method for the detection of protein is developed. The target protein is captured by biotin-labeled aptamer (biotin probe) and [Ru(bpy)₃]²⁺ (TBR)-Au bio bar code-labeled aptamer (ECL nanoprobe), to form a double aptamer–protein sandwich complex. The complex is then immobilized on the streptavidin microbeads through biotin–streptavidin linkage and detected by ECL assay. The ECL signal of the target protein is amplified by the TBR-bio bar code DNAs. As an example, platelet-derived growth factor B-chain homodimer (PDGF-BB) was detected by the method. Experimental results show that the detection limit of the assay is 1 pM of PDGF-BB. A calibration curve with a linearity range from 1 pM to 10 nM is established, thus, make quantitative analysis possible. The method has been used to detect PDGF-BB in fetal calf serum with minimum background interference. Due to the wide availability of aptamer for numerous proteins, this aptamer-based bio bar code IM-ECL method holds great promise in protein detection.     

Preparation and optical properties of high-quality oriented of Al and Er co-doped ZnO thin films

High-quality c-axis oriented Al and Er co-doped ZnO films were prepared on the quartz glasses by sol?Cgel method. In order to obtain the optimal processing parameters for the growth of the oriented film, an L₁₆ (4⁵) orthogonal experimental design was chosen. The experimental results show the rank of 5-factors as follows: Er at.%?>?the number of coating layer?>?annealing temperature?>?Al at.%?>?the concentration of the sol. The Al and Er co-doped film prepared using the optimal parameters exhibits the preferential orientation along the c-axis perpendicular to the substrate surface. In addition, the structural, morphological and optical properties of the films were studied by X-ray diffraction, scanning electron microscopy, and UV?Cvisible spectrophotometer, respectively. The photoluminescence spectra were also used to characterize the luminescence properties of the samples. It is found that when ZnO was co-doped with 7?% Al and 1.5?% Er, the blue emission centered at 465?nm disappears and the green emission centered at 547?nm increases with a blue shift, resulted from the rapid reducing of the interstitial Zn defect, and increasing of the oxygen defects and vacancies caused by Al³⁺ and Er³⁺ dopants.     

Synthesis of mesoporous NiO nanosheet and its application on mercury (II) sensor

NiO nanosheets with uniformly distributed mesoporosity were successfully synthesized on a large scale by calcination of β-Ni(OH)₂ nanosheet precursor, which was simply prepared using 1,6-hexanediamine-assisted solution approach. The as-prepared mesoporous NiO nanosheets have been introduced for the first time for the sensing of mercury ions, which were found to be useful for selective electrochemical detection of Hg²⁺ with a linear range of 0.8 to 500?μM in pH?6.0 phosphate-buffered solutions, providing us another opportunity for exploring new electrochemical application of NiO nanomaterials.     

Synthesis of 4-amino-1,2,3,4-tetrahydropyridine derivatives by intramolecular nucleophilic addition of tertiary enamides to in-situ generated imines

The reactivity of stable tertiary enamides in nucleophilic addition reaction with various in-situ generated imines was explored. Under very mild conditions, formyl-bearing tertiary enamides reacted with both aromatic and aliphatic amines to form imine intermediates. In the absence or presence of p-toluenesulfonic acid as a catalyst, intramolecular nucleophilic addition of enamide to imine functionality proceeded effectively to produce diverse 4-amino-1,2,3,4-tetrahydropyridine derivatives in good to excellent yields.     

Promoted colorimetric response of spirooxazine derivative: a simple assay for sensitive mercury(II) detection

Research on Chemical Intermediates - A spirooxazine derivative 1,3-dihydro-1,3,3-trimethyl-spiro[2-H-indole-2-2′-[2H-1,4] oxazino [2,3-f] [1, 10] phenanthroline] (compound 1) was explored as...     

Advances in the Use of Cyclodextrins as Chiral Selectors in Capillary Electrokinetic Chromatography: Fundamentals and Applications

Capillary electrokinetic chromatography is generally recognized as a versatile and robust capillary electromigration technique for the separation of enantiomers. In this mode, one or more chiral selectors are added to the background electrolyte acting as pseudostationary phases. Within the various chiral selectors that have been applied to enantioseparations in capillary electrokinetic chromatography, cyclodextrins are by far the most often used selectors because of their versatility, structural variety and commercial availability. This is reflected in the large number of applications of cyclodextrins to analytical enantioseparations that have been reported between January 2012 and July 2016, the period of time covered by this review. Many of these applications cover aspects of life sciences such as drug analysis, bioanalysis or food analysis. Despite the large number of commercially available cyclodextrins, new derivatives have been developed in order to achieve altered enantioselectivities or to further broaden the application range. Cyclodextrins have also been used to demonstrate the validity of theoretical models of electromigration as well as complex formation equilibria in enantioseparations. Finally, recent studies for an understanding of the molecular basis of the chiral recognition between cyclodextrins and the analytes are discussed.

     

Catalytic Desymmetrizing Dehydrogenation of 4‐Substituted Cyclohexanones through Enamine Oxidation

A desymmetrizing dehydrogenation process catalyzed by a chiral primary amine is described herein. The reaction proceeds through the oxidation of a ketone enamine by IBX and enables the highly enantioselective desymmetrization of 4‐substituted cyclohexanones with the generation of chiral 4‐substituted cyclohexenones containing a remote γ‐stereocenter.     

Copper‐Catalyzed Enantioselective Arylative Desymmetrization of Prochiral Cyclopentenes with Diaryliodonium Salts

A copper‐catalyzed enantioselective arylative desymmetrization of prochiral cyclopentenes with diaryliodonium salts was developed. In the presence of a catalytic amount of a chiral copper–bisoxazoline complex, which was generated in situ, the reaction of 4‐substituted or 4,4‐disubstituted cyclopent‐1‐enes with diaryliodonium hexafluoroarsenates afforded the chiral arylated products in good yields with excellent enantioselectivity. A cyclohexyl‐containing Box ligand was essential for the high enantioselectivity. Transformation of the enantiomerically enriched adducts into other chiral building blocks is also documented.