Nanoporous Surface High-Entropy Alloys as Highly Efficient Multisite Electrocatalysts for Nonacidic Hydrogen Evolution Reaction

Electrocatalytic hydrogen evolution in alkaline and neutral media offers the possibility of adopting platinum-free electrocatalysts for large-scale electrochemical production of pure hydrogen fuel, but most state-of-the-art electrocatalytic materials based on nonprecious transition metals operate at high overpotentials. Here, a monolithic nanoporous multielemental CuAlNiMoFe electrode with electroactive high-entropy CuNiMoFe surface is reported to hold great promise as cost-effective electrocatalyst for hydrogen evolution reaction (HER) in alkaline and neutral media. By virtue of a surface high-entropy alloy composed of dissimilar Cu, Ni, Mo, and Fe metals offering bifunctional electrocatalytic sites with enhanced kinetics for water dissociation and adsorption/desorption of reactive hydrogen intermediates, and hierarchical nanoporous Cu scaffold facilitating electron transfer/mass transport, the nanoporous CuAlNiMoFe electrode exhibits superior nonacidic HER electrocatalysis. It only takes overpotentials as low as ≈240 and ≈183 mV to reach current densities of ≈1840 and ≈100 mA cm⁻² in 1 m  KOH and pH 7 buffer electrolytes, respectively; ≈46- and ≈14-fold higher than those of ternary CuAlNi electrode with bimetallic Cu–Ni surface alloy. The outstanding electrocatalytic properties make nonprecious multielemental alloys attractive candidates as high-performance nonacidic HER electrocatalytic electrodes in water electrolysis.     

Enantioselective Self‐Assembly of Triangular Dy3 Clusters with Single‐Molecule Magnet Behavior

Three pairs of enantiopure chiral triangular Ln₃ clusters, [Ln₃L_{RRRRRR/SSSSSS}(μ₃‐OH)₂(H₂O)₂(SCN)₄]?xCH₃OH?yH₂O ( R ‐Dy₃ , Ln=Dy, x=6, y=0; S ‐Dy₃ , Ln=Dy, x=6, y=1; R ‐Ho₃ , Ln=Ho, x=6, y=1; S ‐Ho₃ , Ln=Ho, x=6, y=1; R ‐Er₃ , Ln=Er, x=6, y=0; S ‐Er₃ , Ln=Er, x=6, y=1), have been successfully synthesized by a rational enantioselective synthetic strategy. The core of triangular Ln₃ is bound in the central N₆O₃ of the macrocyclic ligand, and the coordination spheres of Ln ions are completed by four SCN^? anions and two H₂O molecules in axial positions of the macrocycle. The circular dichroism (CD) and vibrational circular dichroism (VCD) spectra of the enantiomers demonstrate that the chirality is successfully transferred from the ligands to the resulting Ln₃ clusters. Ac susceptibility measurements reveal that single‐molecule magnet behavior occurs for both enantiopure clusters of R ‐Dy₃ and S ‐Dy₃ . This work is one of the few examples of the successful design of a pair of triangular Dy₃ clusters showing simultaneously slow magnetic relaxation and optical activity, and this might open up new opportunities to develop novel multifunctional materials.     

基于神经网络的光伏发电功率预测不良数据处理的研究

光伏发电系统历史发电功率数据的真实可靠是光伏发电系统发电功率预测的基础,而在光伏发电系统运行或数据采集、测量、传输、转换等环节出现故障时会导致历史数据中含有不良数据。本论文提出采用小波分析中的信号奇异点检测法对不良数据进行剔除,并采用神经网络的时间序列预测模型对剔除后的数据进行重构,从而达到检测并消除不良数据的目的,为光伏发电系统发电功率预测提供能反应其变化规律的真实历史信息。     

Preparation,Characterization and Drug Release Behavior of 5-Fluorouracil Loaded Carboxylic Poly(ε-caprolactone) Nanoparticles

In this paper, 5-Fluorouracil (5-FU) loaded carboxylic poly(ε-caprolactone) nanoparticles have been prepared by emulsification/solvent evaporation o/w method, and the drug release behaviors of 5-FU were investigated. The novel carboxylic poly (ε-caprolactone) (P(CL-OPD)-mal) was synthesized via conjugation of maleic anhydride to sodium borohydride (NaBH₄) reduced poly(ε-caprolactone-co -4- carbonyl -ε-caprolactone) (P(CL-OPD)), while P(CL-OPD) was synthesized in bulk by ring-opening polymerization of ε-caprolactone and 4-carbonyl-ε-caprolactone (OPD) with stannous octoate as a catalyst. Their structures were confirmed by ¹HNMR, FT-IR and GPC. Dynamic light scattering (DLS), transmission electron microscopy (TEM), zeta potential measurements were used for nanoparticle characterization. TEM and DLS showed the nanoparticles were with spherical shape and uniform size distribution (mean diameter 70～100 nm), respectively. Zeta potential analysis revealed that the nanoparticles had an increased negative surface with the increase of carboxyl group concentration. UV spectroscopy was adopted to study the entrapment and release behaviour. The maximum 5-FU loading efficiency was 14.39% with the entrapment efficiency be 42%. In vitro release studies were performed in PBS at 37°C. Results of the study showed that the release behavior can be well-controlled, and the balanced release was up to 96 h. P(CL-OPD)-mal nanoparticles would provide increased benefit in biomedical and pharmaceutical applications.     

SPE–HPLC–MS/MS method for the trace analysis of tobacco‐specific N‐nitrosamines and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in rabbit plasma using tetraazacalix[2]arene[2]triazine‐modified silica as a sorbent

Tobacco‐specific N‐nitrosamines (TSNAs), including N′‐nitrosonornicotine, 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, N′‐nitrosoanatabine, and N′‐nitrosoanabasine, have been implicated as a source of carcinogenicity in tobacco and cigarette smoke. We present a rapid and effective method comprising SPE based on tetraazacalix[2]arene[2]triazine‐modified silica as sorbent and analysis with HPLC–MS/MS for the determination of TSNAs and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a metabolite of 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, in rabbit plasma. The linear dynamic ranges were 10–2000 pg/mL for NNAL and 4–2000 pg/mL for the four TSNAs with good correlation coefficients (>0.9965). The LODs were in the range of 0.9–3.7 pg/mL, and the LOQs were between 2.9 and 12.3 pg/mL. The accuracies of the method were also evaluated and found to be in the range of 90.1–113.3%. This method is promising to be applied to the preconcentration and determination of TSNAs and NNAL in smoke and human body fluids.     

Butterfly‐Shaped Pentanuclear Dysprosium Single‐Molecule Magnets

Two new “butterfly‐shaped” pentanuclear dysprosium(III) clusters, [Dy₅(μ₃‐OH)₃(opch)₆(H₂O)₃] ? 3 MeOH ? 9 H₂O ( 1 ) and [Dy₅(μ₃‐OH)₃(Hopch)₂(opch)₄(MeOH)(H₂O)₂] ? (ClO₄)₂ ? 6 MeOH ? 4 H₂O ( 2 ), which were based on the heterodonor‐chelating ligand o‐vanillin pyrazine acylhydrazone (H₂opch), have been successfully synthesized by applying different reaction conditions. Single‐crystal X‐ray diffraction analysis revealed that the butterfly‐shaped cores in both compounds were comparable. However, their magnetic properties were drastically different. Indeed, compound 1 showed dual slow‐relaxation processes with a transition between them that corresponded to energy gaps (Δ) of 8.1 and 37.9 K and pre‐exponential factors (τ₀) of 1.7×10^?5 and 9.7×10^?8 s for the low‐ and high‐temperature domains, respectively, whilst only a single relaxation process was noted for compound 2 (Δ=197 K, τ₀=3.2×10^?9 s). These significant disparities are most likely due to the versatile coordination of the H₂opch ligands with particular keto–enol tautomerism, which alters the strength of the local crystal field and, hence, the nature or direction of the easy axes of anisotropic dysprosium ions.     

The BIOREMA project—part 3: International interlaboratory comparison for bio-ethanol test methods

The main objective of the reference materials for biofuel specifications (BIOREMA) project is the development of two test materials (one bio-ethanol material and one biodiesel material) with well-established reference values. Of a series of three papers, this part describes the material preparation, homogeneity study, stability study, and characterisation of the bio-ethanol material. The test material thus obtained was used in an interlaboratory comparison (ILC) to assess current practices and comparability amongst laboratories providing bio-ethanol testing services. Only 13 participants provided data, resulting in a small dataset for evaluation. Further, it appeared that for a number of laboratories, there was not sufficient material for the determination of all requested parameters. In most cases, as far as the data permit, it can be concluded that the consensus values (based on participant’s results) are in good agreement with the reference or the BIOREMA values (obtained by NMIs participating in the project). For three parameters, namely ethanol content, water content, and density, there is good agreement between the reference and consensus values. For these parameters, the reproducibility standard deviation is close to, or even smaller than, the expanded uncertainty associated with the reference value. A number of parameters show very poor reproducibility, for example, pH_e, electrolytic conductivity, and acidity. The same applies to sodium and copper content, which are very low and therefore challenging parameters to measure accurately. The results of the ILC underpin the need for certified reference materials and demonstrate the requirement for more robust quality control to improve the precision and trueness of the results from testing laboratories.