Facile synthesis of ultra-long Cu microdendrites for the electrochemical detection of glucose

Ultra-long Cu microdendrites (MDs) were prepared by one-step electrodeposition on a glassy carbon electrode. The results demonstrated that the reduction potential, pH, and temperature of the electrolysis solution, as well as the amount of Cu²⁺ and citrate ions, play important roles in the formation of the Cu MDs. Notably, the X-ray diffraction experiments confirmed that the aggregations of the Cu nanocrystals preferred to grow along (111) direction. In addition, the resulting Cu MDs-modified electrode showed good electrochemical performance as a non-enzyme glucose sensor in alkaline media.     

Solid-state MAS NMR studies of Brønsted acid sites in zeolite H-Mordenite

(17)O-(1)H double resonance NMR spectroscopy was used to study the local structure of zeolite H-Mordenite. Different contact times were used in cross-polarization magic angle spinning (CPMAS) NMR, CP rotational-echo double resonance (CP-REDOR) NMR, and heteronuclear correlation (HETCOR) NMR spectroscopy to distinguish between Br?nsted acid sites with different O-H distances. The accessibility of the various Br?nsted acid sites was quantified by adsorbing the basic probe molecule trimethylphosphine in known amounts. On the basis of these experiments, locations of different Br?nsted acid sites in H-Mordenite (H-MOR) were proposed. The use of (17)O chemical shift correlations to help assign sites is discussed.     

一种基于光谱分析的二元不完全重叠色谱峰的分离解析方法

基于二极管阵列检测器获得的色谱-光谱数据,建立了一种二元不完全重叠液相色谱峰的解析方法: 色谱数据经过去噪、归一化处理后,计算各时间点的光谱差异并进行系统聚类分析,提取特征光谱后,利用非负最小二乘法对色谱-光谱矩阵进行解析,得到基于特征光谱的流出曲线,进而得到分离后的色谱峰。将解析结果和纯标样的色谱峰进行比较,解析后的光谱图和纯标样的光谱图无显著差异,保留时间相差小于0.01 min。实验结果表明,该方法在二元不完全重叠液相色谱峰的解析方面能取得良好的效果。     

Enhanced indirect fluorescence detection of p-nitrophenol, 2,4-dinitrophenol and trinitrophenol by micellar electrokinetic capillary chromatography with in-column optical-fiber LED-induced fluorescence detection

Enhanced indirect fluorescence detection with in-column optical-fiber LED-induced fluorescence (LED-IF) detection has been developed for the simultaneous separation and determination of p-nitrophenol, 2,4-dinitrophenol and trinitrophenol. The instrumental set-up is simple, cost-effective and the detection method is stable. Different experimental parameters have been studied. The optimum conditions were determined as: running buffer (pH 9.1) composed of 10 mM borate, 80 mM sodium dodecylsulfate and 0.18 μM fluorescein (as a background reagent); applied voltage of 15 kV; working temperature of 25.0 °C. The limits of detection (S/N = 3) were 11, 18 and 16 μM for p-nitrophenol, 2,4-dinitrophenol and trinitrophenol, respectively. The nitrophenols were completely separated in 13 min and the number of theoretical plates for p-nitrophenol, 2,4-dinitrophenol and trinitrophenol were 8.1 × 10(6), 6.5 × 10(6) and 8.4 × 10(6), respectively. The RSDs (n = 6) for the migration time and the peak area were better than 0.85 and 0.91%, respectively. Our proposed method possesses the advantages of rapidness and good separation efficiency.     

Oxidative Dehydrogenative Silylation‐Alkenation Reaction of Alkyl Aromatics with Silanes

A Cu(OAc)₂/DDQ/DTBP/Py system catalyzed oxidative dehydrogenative silylation‐alkenation tandem reaction of readily available alkyl aromatic compounds with silanes was established. A variety of functionalized alkenyl organosilicon compounds were provided in good to high yields with a total β‐(E) selectivity. The control experiments revealed that the transformation might proceed through a radical pathway.     

Two-Coordinate Copper(I)/NHC Complexes: Dual Emission Properties and Ultralong Room-Temperature Phosphorescence

As a kind of photoluminescent material, Cu^I complexes have many advantages such as adjustable emission, variable structures, and low cost, attracting attention in many fields. In this work, two novel two-coordinate Cu^I-N-heterocyclic carbene complexes were synthesized, and they exhibit unique dual emission properties, fluorescence and phosphorescence. The crystal structure, packing mode, and photophysical properties under different conditions were systematically studied, proving the emissive mechanism to be the locally excited state of the carbazole group. Based on this mechanism, ultralong room-temperature phosphorescence (RTP) with a lifetime of 140 ms is achieved by selective deuteration of the carbazole group. These results deepen the understanding of the luminescence mechanism and design strategy for two-coordinate Cu^I complexes, and prove their potential in applications as ultralong RTP materials.     

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr,iPr or iBu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu₃₀H₁₈{S₂P(OnPr)₂}₁₂] ( 1_H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1_H reveals an unprecedented central Cu₁₂ hollow icosahedron. Six faces of this icosahedron are capped by Cu₃ triangles, the whole Cu₃₀ core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S₆ symmetry. The locations of the 18 hydrides in 1_H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ₃-H, interstitial μ₄-H (seesaw) and μ₅-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the ¹H NMR spectrum of 1_H are in line with their coordination environment in the solid state, retaining the S₆ symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu₃₀H₁₈{Se₂P(OR)₂}₁₂] ( 2_H : R=iPr 3_H : R=iBu) were synthesized from their sulfur relative 1_H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1_H – 3_H . In addition, the reaction of 1_H with [Pd(PPh₃)₂Cl₂] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu₁₄H₂{S₂P(OnPr)₂}₆(C≡CR)₆] ( 4 : R=Ph; 5 : R = C₆H₄F).     

ZnO-rich CdS-ZIF-8 catalyst for enhanced visible-light photocatalytic degradation of methylene blue

CdS-ZIF-8 photocatalyst was prepared by introducing a ZnO-rich zeolitic imidazolate framework-8 (ZIF-8) during synthesis of CdS by a facile solvothermal method, using ZnO-rich ZIF-8 and cadmium acetate [Cd(Ac)₂] as support and CdS precursor, respectively. The introduction of ZnO-rich ZIF-8 and the photodegradation performance of the catalyst for methylene blue (MB) organic dye were systemically investigated. The CdS-ZIF-8 catalysts were also characterized using X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy, N₂ adsorption–desorption measurements, Fourier-transform infrared (FT-IR) spectroscopy, ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy (DRS), and photoluminescence spectroscopy. The results indicated that CdS-ZIF-8 contained ZIF-8, CdS, and ZnO phases. The CdS in CdS-ZIF-8 catalysts exhibited smaller particle size compared with pure CdS. Furthermore, compared with pure CdS, CdS-ZIF-8-30 with introduction of ZnO-rich ZIF-8 exhibited higher surface area (77.3 m²/g) and pore volume (0.103 cm³/g). EDX and FT-IR results suggested that a CdS/ZnO heterostructure was formed, which effectively reduced recombination of photogenerated electron–hole pairs. Radical trapping experimental data and band edge position analysis revealed that Z-scheme behavior also played a role in the system. Relying on the combined effect of their structure, the photodegradation efficiency of all the CdS-ZIF-8 catalysts was obviously superior to that of pure CdS for degradation of MB under visible-light irradiation. Photodegradation results illustrated that CdS-ZIF-8 with introduction of 30 mg ZnO-rich ZIF-8 (denoted as CdS-ZIF-8-30) exhibited optimal photodegradation activity.     

Efficient approach to allylated quinolines via palladium-catalyzed cyclization–allylation of 1-azido-2-(2-propynyl) benzenes with allyl methyl carbonate

The palladium-catalyzed cyclization–allylation reaction of ortho-azido propynylbenzenes 1 and allyl methyl carbonate 2d gives the corresponding allylated quinolines in moderate to good yields. The reaction of 1-azido-2-(2-propynyl)benzene 1a proceeds smoothly with 10 mol % Pd(PPh₃)₄ and 5 equiv K₃PO₄ or NaOAc in DMF at 100 °C to afford 3,4-diallylquinoline 3a in 69% yield in the case of R² = H and 3-allylquinoline 4 in 67% yield in the case of R² ≠ H.     

Preparation of superhydrophobic composite paper mulching film

To study the influence of different concentrations of zinc oxide (ZnO)/silicon dioxide (SiO₂) composite coating on hydrophobic property and mechanical stability of paper mulch film, three kinds of ZnO/SiO₂ composite coating paper mulch films (2%, 4%, 6%) with different coating substance contents were prepared by brush coating method. Through particle size analysis, contact angle, rolling angle and mechanical stability test, combined with scanning electron microscope, three-dimensional morphology and roughness measuring instrument, the optimal concentration of ZnO/SiO₂ composite coated paper mulch film was screened out. Through acid-base salt corrosion test, silver mirror reaction and surface self-cleaning, the optimal concentration of composite coated paper mulch film was compared with the original paper mulch film to prove its excellent chemical stability and hydrophobicity. The results show that the paper mulch film with 4% coating material has excellent hydrophobicity and mechanical stability, can effectively reduce the surface roughness of paper mulch film, and has remarkable effects in resisting acid, alkali and salt and self-cleaning.