双金属MOFs及其衍生物在电化学储能领域中的应用

双金属有机骨架及其衍生物一方面具有单金属有机骨架孔道丰富、比表面积大、结构可调、活性位点丰富等特点,另一方面具有双组分与多孔结构之间的协同效应,因而受到了研究人员的密切关注,在储能、催化、分离、传感器、医药、气体存储等领域广泛应用。和单金属MOFs类似,双金属MOFs的导电性不佳、结构易坍塌,这极大地限制了其在电化学储能中的应用。通过对双金属MOFs进行热处理,易得到分布均匀的多孔碳@双金属氧化物/硫化物/磷化物/硒化物等衍生物,不仅保持了独特的多孔结构,而且提高了材料的导电性和结构稳定性,有利于在电化学储能中的应用。因此,本文从双金属MOFs中的主要金属离子入手,综述了双金属MOFs及其衍生物用于超级电容器、锂离子电池、钠离子电池、金属空气电池等电化学储能器件的最新应用进展。在此基础上,总结了双金属MOFs在电化学储能应用中的优势,并对其制备、作用机理和后处理研究提出了建议。     

MOF衍生的分层多孔三维N-CoPx/Ni2P大电流密度下加速析氢

氢气(H2)具有能量密度高、环境友好等优点,是一种很有前景的清洁能源载体.目前,电催化水裂解大规模制氢被认为是一种理想可行的方法.析氢反应(HER)涉及多个步骤,首先形成吸附的氢(Volmer步骤),然后是脱附步骤(Heyrovsky步骤)或两个相邻的吸附氢形成H2(Tafel步骤).与酸性介质相比,碱性介质中的HER...     

Microgels as drug carriers for sonopharmacology

The ultrasound-induced cleavage of covalent and non-covalent bonds to activate drugs (sonopharmacology) is a promising concept to gain control over the action of active pharmaceutical ingredients by an external trigger. Previously, linear polymer architectures bearing drug payloads were exploited for drug release by using the principles of polymer mechanochemistry. In this work, the carrier design is altered by the polymer topology to improve the ultrasound-triggered release of covalently anchored drugs from polymer scaffolds. We use microgels crosslinked by mechanoresponsive disulfides and copolymerized with Diels-Alder adducts of furylated payload molecules and acetylenedicarboxylate. Force-induced thiol formation induces a Michael-type addition liberating the payload from the microgels. The use of microgels significantly reduces sonication times compared to linear polymer chains and shields the cargo efficiently from non-triggered activation using ultrasound that produces inertial cavitation at a frequency of 20 kHz as model condition.     

Direct synthesis of hyperbranched ethene oligomers and ethene-MA co-oligomers using iminopyridyl systems with weak neighboring group interactions

The synthesis of hyper-branched ethene oligomers through catalytic insertion reactions with late transition metal catalysts is unique in its synthetic and practical scope. In this study, a series of iminopyridyl Ni(II) and Pd(II) complexes with electron-rich distal aryl motifs were synthesized and characterized. These complexes were very efficient in ethene oligomerization and co-oligomerization with methyl acrylate (MA). Hyperbranched ethene oligomers with different microstructures were generated using different metal species in ethene oligomerization. More importantly, hyperbranched ethene-MA co-oligomers with varying incorporation ratios were generated via ethene and MA co-oligomerization using the Pd(II) complexes. Most notably, weak neighboring group interactions of distal aryl motifs in the nickel system are more effective in influencing the microstructure of ethene oligomers than the corresponding palladium system.     

Surface hydrophobization of cotton via laccase-mediated polydopamine deposition and dodecyl gallate grafting

Natural fibers containing components with phenolic hydroxyl groups, such as jute, wool, and silk, can be directly modified by laccase-catalyzed grafting. However, cellulosic fibers like cotton cannot be functionalized in this manner. In this work, we developed a facile two-step method to graft polymers on cotton fabric via laccase catalysis. First, polydopamine (PDA) coating was deposited on the surface of the cotton fabrics via catalysis of laccase/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) system. Then, the newly formed PDA coating acted as the secondary reaction platform for subsequent laccase-mediated grafting of hydrophobic monomer dodecyl gallate (DG). The oxidation of dopamine (DA) catalyzed with the laccase/TEMPO system was investigated using UV–visible (UV–vis) spectroscopy. The scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results verified that the PDA was coated on the surface of cotton fibers. Fourier transform infrared (FTIR) spectra indicated that the PDA-coated cotton was successfully grafted with DG (DG-PDA-cotton). According to the weighting method, the grafting percentage was about 1.06%. The hydrophobicity of the DG-PDA-cotton fabrics was greatly improved with a contact angle of 133°. Also, the grafted cotton fabrics show repellency of water-soluble stains like coffee, milk, and tea. This study provides a new strategy for surface modification of cotton by laccase-mediated grafting, which offers the references for the green fabrication of cotton fabrics with improved functionalization.     

Detection of bleomycin based on N and S co-doped graphene quantum dots as a fluorescence probeEI北大核心CSCD

N and S co-doped graphene quantum dotsNS-GQDswith excellent fluorescence properties were synthesized by hydrothermal method using citrate and thiourea as ingredientsand were characterized. The fluorescence signal was notably reduced in the presence of single stranded DNAssDNAsince ssDNA can adsorb on the surface of NS-GQDs through p-p stacking interaction. Whereas a significantly restored fluorescence signal was observed in the presence of bleomycinowing to the irreversible cleavage of ssDNA by bleomycin with Fe2+ as cofactor. Thusa fluorescence sensor for bleomycin detection was developed. The linear range was from 1.8 to 1200 nmol/L and the detection limit was 0.25 nmol/L. The method was used to detect bleomycin content in human serum samples with satisfactory results. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Effects of Coverage,Water, and Defects on Catechol/TiO2 Interface

Catechol adsorbed on TiO₂ is one of the simplest models to explore the relevant properties of dye-sensitized solar cells. However, the effects of water and defects on the electronic levels and the excitonic properties of the catechol/TiO₂ interface have been rarely explored. Here, we investigate four catechol/TiO₂ interfaces aiming to study the influence of coverage, water, and defects on the electronic levels and the excitonic properties of the catechol/TiO₂ interface through the first-principles many-body Green's function theory. We find that the adsorption of catechol on the rutile (110) surface increases the energies of both the TiO₂ valence band maximum and conduction band minimum by approximately 0.7 eV. The increasing coverage and the presence of water can reduce the optical absorption of charge-transfer excitons with maximum oscillator strength. Regarding the reduced hydroxylated TiO₂ substrate, the conduction band minimum decreases greatly, resulting in a sub-bandgap of 2.51 eV. The exciton distributions in the four investigated interfaces can spread across several unit cells, especially for the hydroxylated TiO₂ substrate. Although the hydroxylated TiO₂ substrate leads to a lower open-circuit voltage, it may increase the separation between photogenerated electrons and holes and may therefore be beneficial for improving the photovoltaic efficiency by controlling its concentration. Our results may provide guidance for the design of highly efficient solar cells in future.     

热力学数据对1, 3-丁二烯燃烧特性的影响

基于G4方法, 计算了1,^{3-丁二烯框架燃烧反应机理中102个物种的热力学数据, 并考察了振动非谐性、 频率校正因子以及受阻内转动对结果的影响. 结果表明, 考虑振动非谐性或采用不同的频率校正因子, 对热力学数据的影响不大; 考虑内转动后, 对热力学数据有较大影响. 而且考虑内转动后, 得到的热力学数据与实验热力学数据吻合得更好. 用所得热力学数据模拟了1,3-丁二烯的绝热燃烧温度以及点火延迟时间, 结果显示, 要得到可靠的绝热火焰温度, 对小分子(如CO和CO₂等)的热力学数据需要采用实验结果. 将用所得热力学数据模拟得到的点火延迟时间, 与机理本身的热力学数据所得点火延迟时间进行对比, 二者差别显著, 表明所得热力学数据主要通过改变一些反应的逆反应速率常数来影响点火延迟时间. 进一步确定了用所得热力学数据对点火延迟时间有显著影响的一些物种.}     

Polymyxin B Combined with Minocycline: A Potentially Effective Combination against blaOXA-23-harboring CRAB in In Vitro PK/PD Model

Polymyxin-based combination therapy is commonly used to treat carbapenem-resistant Acinetobacter baumannii (CRAB) infections. In the present study, the bactericidal effect of polymyxin B and minocycline combination was tested in three CRAB strains containing bla_OXA-23 by the checkerboard assay and in vitro dynamic pharmacokinetics/pharmacodynamics (PK/PD) model. The combination showed synergistic or partial synergistic effect (fractional inhibitory concentration index ≤0.56) on the tested strains in checkboard assays. The antibacterial activity was enhanced in the combination group compared with either monotherapy in in vitro PK/PD model. The combination regimen (simultaneous infusion of 0.75 mg/kg polymyxin B and 100 mg minocycline via 2 h infusion) reduced bacterial colony counts by 0.9–3.5 log₁₀ colony forming units per milliliter (CFU/mL) compared with either drug alone at 24 h. In conclusion, 0.75 mg/kg polymyxin B combined with 100 mg minocycline via 2 h infusion could be a promising treatment option for CRAB bloodstream infections.     

三氯化钕异丙醇络合物的晶体结构和分子结构

本文报导了X射线衍射法确定的三氯化钕异丙醇络合物[NdCl₃·(CH₃CHOHCH₃)₃]₂的晶体结构。在晶体中每二个钕离子通过二个氯离子形成的氯桥相联,组成一个双核稀土络合物分子。其中每个Nd离子是七配位的。