The growth and dislocation characterization of Yb0.005Y0.848Lu0.147VO4 mixed laser crystal

A new mixed laser crystal, Yb_0.005Y_0.848Lu_0.147VO₄, has been successfully grown using the Czochralski method. An ICP‐OES was used to measure the concentrations of elements (Yb, Y, Lu, V) in the crystal, and the chemical formula was determined. X‐ray powder diffraction analysis shows that the crystal has ZrSiO₄ structure. A pair of edge dislocations with certain orientation was observed by the HREM, and the orientation was confirmed by the calibration of the diffraction spots. The formation mechanism of this type dislocation was given by analysis on structure and thermal expansion of crystal. The suggestion to avoid these dislocations was also given.     

Amberlyst‐15‐Catalyzed Novel Synthesis of Quinoline Derivatives in Ionic Liquid

In recent years, ionic liquids have attracted much attention as useful synthetic solvents. Compared with classical molecular solvents, the ionic liquids are environmentally benign reaction media. A variety of quinoline derivatives have been synthesized under ionic liquid conditions using Amberlyst‐15 as catalyst.     

Origin of the N-coordinated single-atom Ni sites in heterogeneous electrocatalysts for CO2 reduction reaction

Heterogeneous Ni–N–C single-atom catalysts (SACs) have attracted great research interest regarding their capability in facilitating the CO₂ reduction reaction (CO₂RR), with CO accounting for the major product. However, the fundamental nature of their active Ni sites remains controversial, since the typically proposed pyridinic-type Ni configurations are inactive, display low selectivity, and/or possess an unfavorable formation energy. Herein, we present a constant-potential first-principles and microkinetic model to study the CO₂RR at a solid–water interface, which shows that the electrode potential is crucial for governing CO₂ activation. A formation energy analysis on several NiN_xC_4−x (x = 1–4) moieties indicates that the predominant Ni moieties of Ni–N–C SACs are expected to have a formula of NiN₄. After determining the potential-dependent thermodynamic and kinetic energy of these Ni moieties, we discover that the energetically favorable pyrrolic-type NiN₄ moiety displays high activity for facilitating the selective CO₂RR over the competing H₂ evolution. Moreover, model polarization curves and Tafel analysis results exhibit reasonable agreement with existing experimental data. This work highlights the intrinsic tetrapyrrolic coordination of Ni for facilitating the CO₂RR and offers practical guidance for the rational improvement of SACs, and this model can be expanded to explore mechanisms of other electrocatalysis in aqueous solutions.

A constant-potential first-principles and microkinetic model is developed to uncover the nature of heterogeneous Ni–N–C catalysts. It highlights the crucial role of a pyrrolic-type NiN₄ moiety in electrochemical CO₂ reduction.     

Antioxidant Properties of Hydrogen Gas Attenuates Oxidative Stress in Airway Epithelial Cells

Oxidative stress plays a crucial role in the development of airway diseases. Recently, hydrogen (H₂) gas has been explored for its antioxidant properties. This study investigated the role of H₂ gas in oxidative stress-induced alveolar and bronchial airway injury, where A549 and NCI-H292 cells were stimulated with hydrogen peroxide (H₂O₂) and lipopolysaccharide (LPS) in vitro. Results show that time-dependent administration of 2% H₂ gas recovered the cells from oxidative stress. Various indicators including reactive oxygen species (ROS), nitric oxide (NO), antioxidant enzymes (catalase, glutathione peroxidase), intracellular calcium, and mitogen-activated protein kinase (MAPK) signaling pathway were examined to analyze the redox profile. The viability of A549 and NCI-H292 cells and the activity of antioxidant enzymes were reduced following induction by H₂O₂ and LPS but were later recovered using H₂ gas. Additionally, the levels of oxidative stress markers, including ROS and NO, were elevated upon induction but were attenuated after treatment with H₂ gas. Furthermore, H₂ gas suppressed oxidative stress-induced MAPK activation and maintained calcium homeostasis. This study suggests that H₂ gas can rescue airway epithelial cells from H₂O₂ and LPS-induced oxidative stress and may be a potential intervention for airway diseases.     

Cl–改性对Ag/Al2O3催化剂结构及其催化C3H6-SCR和H2/C3H6-SCR反应性能的影响

以烯烃为还原剂的NOx选择性催化还原(HC-SCR)是重要的环境催化反应之一.Ag/Al2O3催化剂(SA)因在HC-SCR反应中表现高活性、高N2选择性及中等H2O和SO2耐受性等优点,而被广泛研究.SA催化剂中存在不同的Ag物种,包括孤立Ag+离子,带部分正电荷Agnδ+团簇和金属态Agn0团簇.文献研究结果表明,SA催化剂中Agnδ+团簇是催化HC-SCR反应的活性Ag物种,而Ag物种类型与Ag的负载量密切相关.因此文献中研究SA催化HC-SCR反应的结构-性能关系主要是通过改变Ag负载量来开展的,最优Ag负载量约为1％～2％.本文以Cl–改性的γ-Al2O3作为载体,采用传统的浸渍法制备了Ag/Al2O3-Cl催化剂(SA-Cl),通过XRD、TEM、H2-TPR、UV-Vis DRS以及XPS对催化剂进行了结构表征,并结合C3H6-SCR和H2/C3H6-SCR活性测试,建立催化剂结构-催化性能关系;同时利用原位傅里叶变换红外光谱(DRIFTS)和在线同步辐射单光子电离质谱(SVUV-PIMS)研究了SA催化HC-SCR的反应机理.结构表征结果表明,在SA催化剂中,Ag负载量的提高主要是增加了Agn0物种,而在SA-Cl催化剂中,Ag负载量的提高主要是增加了Agnδ+物种,因此Cl?改性能促进SA催化剂中Agnδ+物种的形成.活性测试结果表明,在相同Ag负载量下,SA-Cl催化剂表现出比SA催化剂更好的HC-SCR催化性能.Cl?改性对SA催化剂中Ag物种的调控作用和HC-SCR催化性能的促进作用随Ag负载量的增加变得更为明显.原位DRIFTS结果表明,γ-Al2O3载体(Al位点)是NO氧化形成硝酸盐物种的主要活性位点;Agnδ+物种催化丙烯适度氧化主要生成乙酸盐类物种,可以还原表面硝酸盐物种;而Agn0催化丙烯过度氧化主要生成羧酸盐类物种,进而生成CO2,不能还原表面硝酸盐物种.由此可见,Agnδ+是催化HC-SCR反应的活性Ag物种,而Agn0是催化烃类完全氧化反应的活性Ag物种;Cl–改性能有效促进Agnδ+的形成,进而提高HC-SCR催化反应活性.在线SVUV-PIMS结果检测到H2/C3H6-SCR反应中存在气态中间物种丙烯腈(CH2=CHCN).–CN和–NCO物种被认为是HC-SCR反应的关键中间物种,能够直接与气相NO+O2反应生成N2.因此,CH2=CHCN的存在说明HC-SCR反应涉及到气相反应机理.基于SA和SA-Cl催化剂,进一步研究了H2对C3H6-SCR低温活性的促进作用.结果表明,H2的促进作用是通过作用于Agnδ+物种,而不是通过Agn0物种来实现的;H2的引入有利于低温下强吸附硝酸盐物种的脱附或分解以及中间体向–NCO和–CN物种的转化,从而提高HC-SCR低温催化活性.综上,基于Cl–改性的Ag/Al2O3-Cl催化剂,本文成功证实了Agnδ+物种是催化HC-SCR反应的活性Ag物种,并结合原位DRIFTS在线SVUV-PIMS谱分别鉴定了催化反应表面中间物种和气相中间物种.这些结果加深了对SA催化HC-SCR反应构-效关系和反应机理的基础理解.     

Dynamic Oxime-Urethane Bonds,a Versatile Unit of High Performance Self-healing Polymers for Diverse Applications

Oxime-urethane bond featuring with high reversibility even at room temperature and multiple reactivity is an emerging dynamic covalent bond, and has shown great potential for self-healing polymers, which are one of the most attractive development directions for next generation of polymeric materials. In this review, recent progresses on the oxime-urethane-based self-healing polymers, including their designs and applications in diverse fields such as biomedicine, flexible electronics, soft robots...     

Response surface methodology for the optimization of the ultrasonic-assisted rhamnolipid treatment of oily sludge

This study investigates the recovery of oily sludge using ultrasound-assisted rhamnolipids and uses oil recovery yield as an evaluation index. The Box–Behnken response surface method was employed to investigate the individual and interactive effects of four different operating factors: frequency, dosage, liquid–solid ratio, and stirring speed. The model optimization results showed that the order of degree of influence of these four factors is frequency > liquid–solid ratio > dosage > stirring speed. The mathematical model predicted the highest oil recovery yield as 92.27%, which was highly accurate (in the 95% confidence interval) as from the experimental results, the highest oil recovery yield was 89.95% under optimal reaction conditions (frequency = 25.58 kHz, dosage = 150.45 mg/L, liquid–solid ratio = 4.1:1 mL/g, and stirring speed = 407 rpm). Thus, the deviation from the prediction model was only 2.32%, indicating that this method provides a theoretical basis for the treatment of oily sludge and can be implemented for practical application in Huaidong in the Xinjiang Province.     

NMR Spectroscopy for Protein Higher Order Structure Similarity Assessment in Formulated Drug Products

Peptide and protein drug molecules fold into higher order structures (HOS) in formulation and these folded structures are often critical for drug efficacy and safety. Generic or biosimilar drug products (DPs) need to show similar HOS to the reference product. The solution NMR spectroscopy is a non-invasive, chemically and structurally specific analytical method that is ideal for characterizing protein therapeutics in formulation. However, only limited NMR studies have been performed directly on marketed DPs and questions remain on how to quantitively define similarity. Here, NMR spectra were collected on marketed peptide and protein DPs, including calcitonin-salmon, liraglutide, teriparatide, exenatide, insulin glargine and rituximab. The 1D ¹H spectral pattern readily revealed protein HOS heterogeneity, exchange and oligomerization in the different formulations. Principal component analysis (PCA) applied to two rituximab DPs showed consistent results with the previously demonstrated similarity metrics of Mahalanobis distance (D_M) of 3.3. The 2D ¹H-¹³C HSQC spectral comparison of insulin glargine DPs provided similarity metrics for chemical shift difference (Δδ) and methyl peak profile, i.e., 4 ppb for ¹H, 15 ppb for ¹³C and 98% peaks with equivalent peak height. Finally, 2D ¹H-¹⁵N sofast HMQC was demonstrated as a sensitive method for comparison of small protein HOS. The application of NMR procedures and chemometric analysis on therapeutic proteins offer quantitative similarity assessments of DPs with practically achievable similarity metrics.     

Matrix-Assisted DOSY for Analysis of Indole Alkaloid Mixtures

Diffusion-ordered spectroscopy (DOSY) is a powerful tool for investigating mixtures and identifying peaks of chemical components. However, similar diffusion coefficients of the components, particularly for complex mixtures that contain crowded resonances, limit resolution and restrict application of the DOSY technique. In this paper, matrix-assisted DOSY were used to explore whether the diffusion resolution of a complex model involving indole alkaloid mixtures can be realized. Furthermore, we investigated the influence of different factors on the separation effect. The results showed that the changes in diffusion coefficient differences were achieved more obviously when using sodium dodecyl sulfate (SDS) micelles as the matrix. In addition, we also found that increasing the concentration of SDS can improve the resolution of the DOSY spectrum. Finally, after investigating the influence factors and NMR conditions, we demonstrated the applications of the SDS-assisted DOSY on analyzing the total alkaloid extract of Alstonia Mairei, and the virtual separation of mixtures was achieved.     

Synthesis of sulfhydryl-functionalized polymers for the efficient adsorption of Pd2+ and Ag+ from aqueous solution

Herein, two sulfhydryl-functionalized polymers, namely, EDT-HCPS and TMPMP-HCPS, were synthesized according to the Friedel-Craft s alkylation and nucleophilic substitution, and they were used to adsorb Pd²⁺ and Ag⁺ from aqueous solution. The Friedel-Crafts alkylation offered the polymers with hyper-cross-linking frameworks composed of plentiful rigid methylene. The nucleophilic substitution brought abundant functional  SH groups (the sulfur contents were 12.6 and 9.4 wt%, respectively) to the polymers. The adsorption results showed that the capacities of Pd²⁺ and Ag⁺ on EDT-HCPS were larger than TMPMP-HCPS, and the higher quantities of functional  SH groups and the porosity played a beneficial role. The equilibrium data can be characterized by the Langmuir model, and the maximum capacities of Pd²⁺ and Ag⁺ on EDT-HCPS at 308 K were predicted to be 383.92 and 212.93 mg g⁻¹, respectively. The produced polymers represented superior adsorption selectivity, reproducibility, and reusability, demonstrating their excellent performance for the adsorption of Pd²⁺ and Ag⁺, and analysis of the adsorption mechanism demonstrated that the  SH groups played a major role due to the strong chemical complexation of the functional  SH with Pd²⁺/Ag⁺.