荧光可调控的碳量子点的电化学制备及性质研究

采用循环伏安法（Cyclic Voltammetry,CV）在碱性条件下电解石墨棒,得到水溶性的荧光碳量子点. 通过透射电子显微镜（TEM）、拉曼光谱（Raman spectrum）、原子力显微镜（AFM）对所制备的碳量子点进行形貌及结构表征,发现该碳量子点由1～4层石墨烯片层堆积形成,粒径在19 nm左右,厚度在1 nm左右. 通过荧光光谱（PL）、紫外可见吸收光谱（UV-vis）、傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）对所制备的碳量子点进行性质测定,发现该碳量子点在400和525 nm处有两个荧光发射峰,且通过控制扫描周数可以调节两个发射峰的相对强度,从而调控碳量子点的荧光颜色：随着扫描周数的增加,400 nm处发射峰的相对强度逐渐减小,而525 nm处发射峰的相对强度逐渐增大,两个荧光发射峰分别与碳量子点的π-π共轭体系和含氧官能团的n-π共轭体系有关.     

A hierarchical porous carbon membrane from polyacrylonitrile/polyvinylpyrrolidone blending membranes:Preparation,characterization and electrochemical capacitive performance

Novel hierarchical porous carbon membranes were fabricated through a simple carbonization procedure of well-defined blending polymer membrane precursors containing the source of carbon polyacrylonitrile （PAN） and an additive of polyvinylpyrrolidone （PVP）, which was prepared using phase inversion method. The as-fabricated materials were further used as the active electrode materials for supercapacitors. The effects of PVP concentration in the casting solution on structure feature and electrochemical capacitive performance of the as-prepared carbon membranes were also studied in detail. As the electrode material for supercapacitor, a high specific capacitance of 278.0 F/g could be attained at a current of 5 mA/cm2 and about 92.90% capacity retention could be maintained after 2000 charge/discharge cycles in 2 mol/L KOH solution with a PVP concentration of 0.3 wt% in the casting solution. The facile hierarchical pore structure preparation method and the good electrochemical capacitive performance make the prepared carbon membrane particularly promising for use in supercapacitor.     

Characterization of the Self-Assembly of Glutathione Stabilized Cadmium Selenide–Zinc Sulfide Quantum Dots with a Cyanine5-Labeled Peptide by Capillary Electrophoresis and Fluorescence

Capillary electrophoresis with fluorescence detection was used to characterize the self-assembly of cadmium selenide–zinc sulfide quantum dots and a cyanine5-labeled peptide (cyanine5-EAAAAAHHHHHH). The self-assembly was driven by metal-affinity forces to allow characterization by Förster resonance energy transfer. The Förster resonance energy transfer signal increased with the ratio of cyanine5-EAAAAAHHHHHH to quantum dots and reached a plateau at a ratio of 32:1. This method illustrates the application of quantum dot-based bioanalysis.     

Validation of Sun Exposure Reported Annually Against Interim Self‐report and Daily Sun Diaries

Data on personal sun exposure over a period exceeding the immediate past days or weeks are typically self‐reported in brief questionnaire items. The validity of such self‐reporting of longer term personal sun exposure, for example over a year, including detail on variation across seasons, has not previously been investigated. In a volunteer sample (n = 331) of Australian adults aged 18 years and over, we assessed the 12‐month reliability of sun exposure reported separately for each season, and its accuracy compared to a daily sun diary in the same season. Seasonal time outdoors displayed fair‐to‐good reliability between baseline and end of study (12 months), with responses showing higher agreement at lower levels of time outdoors. There was good agreement for ranking of individuals' time outdoors with the daily sun diary data, although the actual diary time outdoors was typically considerably lower than the self‐reported questionnaire data. Place of residence, education, being a smoker, day of the week (i.e. working day vs nonworking day) and working mainly outdoors were significant predictors of agreement. While participants overestimated their actual time outdoors, the self‐report questionnaire provided a valid ranking of long‐term sun exposure against others in the study that was reliable over time.     

A Re2O7 catalyzed cycloetherification of monoallylic diols

A Re₂O₇ catalyzed cycloetherification of monoallylic diols is described. The reaction features short reaction time, mild reaction conditions and exclusive E selectivity. A wide range of monoallylic alcohols with alkyl or aryl substituents on olefin smoothly undergo ring closure to deliver corresponding oxa-heterocycles. The reaction is also operationally simple and not sensitive to air and moisture.     

Effect of halogen bonding on supramolecular assembly and photophysical properties of diaryl oxalates

In order to determine the effect of halogen bonding on supramolecular assemblies and photophysical properties of diaryl oxalates, diaryl oxalate itself and its derivatives with fluorine, chlorine, bromine, and iodine substituents in the p-position of phenyl rings were studied and compared. Their single-crystal structures were studied by geometrical analysis and theoretical calculation. The study reveals that different halogen bonds are formed with respect to different halogen atoms, such as C…F and X…X (bromine and iodine atoms) interactions, and molecular stacking modes would be affected by halogen bonds directly. Comparative studies of photophysical properties in dilute solution and solid state indicate that halogen substitutions would not affect the emission processes of diaryl oxalates in dilute solution; this is not the case for their solid state. This work has demonstrated that halogen bonds play an important role in regulating structures and photophysical properties of diaryl oxalates.     

Synthesis,structure, and DNA-binding properties of manganese(II) and zinc(II) complexes with tris(<Emphasis Type="Italic">N</Emphasis>-methylbenzimidazol-2-ylmethyl)amine ligand

Tris(N-methylbenzimidazol-2-ylmethyl)amine (Mentb) and its two complexes, [Mn(Mentb)(DMF)(H₂O)](pic)₂ 1 and [Zn(Mentb)(pic)](pic) 2 (pic = picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single crystal X-ray diffraction revealed that the two complexes have different structures. In complex 1, the coordination sphere around Mn(II) is distorted octahedral, whereas in complex 2 the coordination sphere around Zn(II) is distorted trigonal bipyramidal. The DNA-binding properties of the free ligand and its two complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and its two complexes bind to DNA via an intercalation binding mode, and their binding affinity for DNA follows the order 1 > 2 > ligand.     

Fabrication of Predominantly Mn4+‐Doped TiO2 Nanoparticles under Equilibrium Conditions and Their Application as Visible‐Light Photocatalyts

The chemical state of a transition‐metal dopant in TiO₂ can intrinsically determine the performance of the doped material in applications such as photocatalysis and photovoltaics. In this study, manganese‐doped TiO₂ is fabricated by a near‐equilibrium process, in which the TiO₂ precursor powder precipitates from a hydrothermally obtained transparent mother solution. The doping level and subsequent thermal treatment influence the morphology and crystallization of the TiO₂ samples. FTIR spectroscopy and X‐ray photoelectron spectroscopy analyses indicate that the manganese dopant is substitutionally incorporated by replacing Ti⁴⁺ cations. The absorption band edge can be gradually shifted to 1.8 eV by increasing the nominal manganese content to 10 at %. Manganese atoms doped into the titanium lattice are associated with the dominant 4+ valence oxidation state, which introduces two curved, intermediate bands within the band gap and results in a significant enhancement in photoabsorption and the quantity of photogenerated hydroxyl radicals. Additionally, the high photocatalytic performance of manganese‐doped TiO₂ is also attributed to the low oxygen content, owing to the equilibrium fabrication conditions. This work provides an important strategy to control the chemical and defect states of dopants by using an equilibrium fabrication process.     

Simultaneous determination of ten organophosphate pesticide residues in fruits by gas chromatography coupled with magnetic separation

In this study, γ‐Fe₂O₃/chitosan magnetic microspheres were synthesized and evaluated by X‐ray diffraction, SEM, thermogravimetric analysis, and static and kinetic adsorption experiments. Results showed that the magnetic microspheres exhibited good adsorption ability, and offered fast kinetics for the adsorption of trichlorfon, methamidophos, malathion, methyl parathion, dimethoate, omethoate, phosphamidon, phorate, isocarbophos, and chlorpyrifos. Based on magnetic separation, a simple method of magnetic SPE coupled to GC for the simultaneous determination of ten trace organophosphate pesticide residues was developed. Under the optimal conditions, the enrichment factor for ten organophosphorus pesticides was 10.1–364.7 and linear range was 0.001–10.0 mg/L. The LOD (S/N = 3) of the method for the ten pesticides was 0.31–3.59 μg/kg. The RSD for three replicate extractions of spiked samples was between 2.5 and 6.3%. The pear and apple samples spiked with ten organophosphate pesticides at 20 and 200 μg/kg levels were extracted and determined by this method with good recoveries ranging from 79.9 to 98.7%. Moreover, the method has been successfully applied for the determination of the ten organophosphate pesticide residues in peach samples.