利用油水稳定化和支持向量回归增强近红外光谱测定油中水分的方法

近红外光谱(NIRS)可以检测溶解于油中的水分含量,但油中水分较多时会散射而非吸收NIRS,从而引起较大误差。为此,筛选非离子型表面活性剂(Span-80)将含水油液稳定分散成小颗粒,利用其NIRS数据建立水分含量的支持向量回归模型。实验中油水稳定化将NIRS测定变压器油中水分含量的上限从传统的0.1%提升到1%(V/V),通过应用连续投影算法,在511个NIRS变量中筛选出15个有效变量(占原变量的2.9%),建立的支持向量回归模型对验证集的预测均方根误差为2.93%,相关系数为0.9944,相对分析误差为9.4732。     

纤连蛋白在石墨烯修饰二氧化钛表面吸附的计算机模拟

采用全原子分子动力学模拟方法研究了纤连蛋白(FN)在金红石表面、23%石墨烯覆盖率的金红石表面、92%石墨烯覆盖率的金红石表面、石墨表面的吸附行为.模拟结果表明:FN在金红石表面吸附不稳定.通过石墨烯修饰二氧化钛表面可降低金红石表面的亲水性;当表面含有石墨烯层时,FN都将稳定地吸附在表面上.在23%石墨烯覆盖率的金红石表面上,FN的特异性识别位点朝向溶液而有利于整合素识别.DSSP分析结果显示在40 ns的分子动力学模拟过程中,FN的七个β-折叠结构在所有体系中均没有发生太大变化.由于有石墨烯层存在,表面附近水分子层密度减小.FN的表面吸附能随着表面石墨烯覆盖率的增加而增大.石墨烯修饰能加强二氧化钛表面对蛋白质的吸附.本工作可以为移植体修饰生物材料设计与开发提供参考.     

Sequence-Dependent DNA Functionalization of Upconversion Nanoparticles and Their Programmable Assemblies

DNA-modified lanthanide-doped upconversion nanoparticles (DNA-UCNPs) that combine the functions of DNA and the optical features of UCNPs have shown great promise in a wide range of fields. However, challenges remain in precisely tethering and orienting the DNA strands on the UCNP surface. Herein, we systematically investigate the sequence dependence of DNAs in their interactions with UCNPs, and reveal that poly-cytosine (poly-C) has high affinity for the UCNP surface. A general approach to synthesize monodispersed DNA-UCNP conjugates is developed using poly-C-containing diblock DNA strands. The poly-C segment of the DNA strand binds to the surfaces of UCNPs and the second segment is oriented perpendicularly on the UCNP surface, making the DNA-UCNPs highly stable and monodispersed in aqueous solution. The dense layer of DNA on the UCNP surface enables the programmable assembly of UCNPs with other DNA-functionalized nanoparticles or DNA origamis through hybridization, resulting in the formation of well-organized complex structures.     

Metal–Sulfur Linkages Achieved by Organic Tethering of Ruthenium Nanocrystals for Enhanced Electrochemical Nitrogen Reduction

Inspired by the metal–sulfur (M-S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N₂ availability on a catalytic surface, which suppresses the hydrogen evolution reaction (HER) and improves the rate of NH₃ production. Ruthenium nanocrystals anchored on reduced graphene oxide (Ru/rGO) are modified with different aliphatic thiols to achieve M-S linkages. A high faradaic efficiency (11 %) with an improved NH₃ yield (50 μg h⁻¹ mg⁻¹) is achieved at −0.1 V vs. RHE in acidic conditions by using dodecanethiol. DFT calculations reveal intermediate N₂ adsorption and desorption of the product is achieved by electronic structure modification along with the suppression of the HER by surface modification. The modified catalyst shows excellent stability and recyclability for NH₃ production, as confirmed by rigorous control experiments including ¹⁵N isotope labeling experiments.     

顺铂前药接枝修饰硫代DNA及其自组装靶向纳米药物研究

选用具有良好生物相容性的硫代修饰嵌段核酸为载体,将其非硫代修饰部分设计为靶向MUC-1蛋白的核酸适配体序列,同时在其硫代修饰部分通过硫代磷酸酯基团（Phosphorothioate,PS）接枝修饰四价顺铂前药,制备了两亲性核酸-顺铂前药缀合物MUC-1/^PODNA-b-（^PSDNA-g-Pt）,并进一步自组装成类似球形核酸（Spherical nucleic acid,SNA）的含铂靶向纳米药物（MUC-1/Pt-SNAs）.结果表明,该纳米药物递送体系载药率高、形貌稳定、分散性好,能够高效靶向MUC-1蛋白过表达的MCF-7乳腺癌细胞,并在体内外实验中表现出优异的抗肿瘤效果和极低的毒副作用.     

红色荧光碳点的制备及其对过硫酸根的检测

以对苯二胺为碳源,乙醇为溶剂,采用溶剂热法合成红色荧光碳点(R-CDs)。 通过透射电子显微镜、紫外可见吸收光谱(UV-Vis)、红外光谱(FT-IR)、X射线光电子能谱(XPS)对其进行表征。 合成的R-CDs粒径约为(3.63±0.20) nm。 R-CDs的最大激发和发射波长分别为480和620 nm,具有激发波长独立性,光稳定性好。 基于静态猝灭,R-CDs的荧光可以被过硫酸根(S₂O₈^2-)有效猝灭。 在2.5~120 μmol/L范围内,S₂O₈^2-的浓度与R-CDs的荧光猝灭程度呈线性关系,相关系数(R²)为0.9970,检出限为1.2 μmol/L,具有良好的选择性和高灵敏度。 同时,该荧光传感体系可应用于自来水和湖水样品中S₂O₈^2-的检测。     

全固态钠离子电池硫系化合物电解质

全固态钠离子电池具有资源丰富、安全性高等优势,作为未来大规模储能的重要选择而成为近年来先进二次电池前沿研究热点。钠离子硫系化合物电解质室温离子电导率高、弹性模量高、容易冷压成型,能增强电极/电解质界面接触、减小界面阻抗、缓冲电极材料在充放电过程中的应力/应变,是全固态钠离子电池的研究重点。本文对钠离子硫系化合物固态电解质的结构及性质进行了总结,讨论了硫系化合物电解质的本征特性、与电极的界面稳定性,并介绍了硫系化合物全固态钠离子电池的研究现状,最后分析了硫系化合物电解质面临的挑战及今后的发展方向。     

Synthesis,Spectroscopic Properties,and Photodynamic Anticancer Activities of Novel Arginine-modified Silicon(Ⅳ) Phthalocyanines

We design and synthesize a series of novel silicon(IV)phthalocyanines(SiPcs,1a,2a,1b,and 2b)axially conjugated with arginine or arginine-containing oligopeptides(Arg-Arg,Cys-Arg,Cys-Arg-Arg)through ester or ether linkers to demonstrate the effects of substituents and coupling ways on the spectral behaviors and photodynamic activities.The ester-linked SiPcs(1a and 2a)show slight red-shift,higher fluorescence emission and singlet oxygen generation compared to the ether-linked analogues(1b and 2b)due to the stronger electron-withdrawing ability of the ester group,suggesting that electronic effect of the linkers plays an important role in their spectral properties.The introduction of arginine could effectively reduce the aggregation of phthalocyanine in aqueous solutions.With higher cellular uptake and plasma membrane localization ability,1b and 2b exhibit significantly higher photocytotoxicity against both HepG2 and Hela cells.Moreover,the in vivo fluorescence imaging suggests that 2b is the most specific toward H22 tumor-bearing ICR mice,and it shows efficient tumor growth inhibition with the tumor inhibition rate up to 93%.Thus,this work would provide a new reference for the development of phthalocyanine-based photosensitizers.     

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)†

A Cu(I)‐catalyzed three‐component reaction of terminal enynals/enynones, diazo compounds, and alkenes has been developed. With this method, a series of oxabicyclo[2.2.2]octanes were effectively synthesized in high yields under mild reaction conditions. This transformation is proposed to proceed through trapping of the cyclic vinyl‐o‐quinodimethanes (vinyl‐o‐QDMs) species, which were generated from terminal enynals/enynones and diazo compounds by alkenes. The obvious advantages of wide substrate scopes, mild reaction conditions, and high seteroselectivity and atom efficiency make this reaction highly appealing for construction of highly rigid [2.2.2]octane skeleton.     

全日制化学教育硕士的PCK水平调查研究*

以美国埃里克森学院PCK量化工具为研究基础设计调查问卷,选取离子反应第1课时的电离概念教学片断,以河北某高校学科教学(化学)专业37名教育硕士为研究对象,要求被试者在对视频片断进行观摩的基础上作答9个开放性问题。研究发现:全日制化学教育硕士PCK整体和各维度知识处于“基本的”水平,在教学内容知识维度表现最佳,在学生知识、教学策略知识维度稍差一些,在把握概念关系、调整教学策略等能力活动上的表现有待发展。针对研究发现,结合化学教育硕士的专业属性及培养过程中的问题,提出构建“教师专业学习共同体”,干预化学教育硕士PCK结构的改善;依托教学案例情境载体功能,帮助化学教育硕士进行PCK的深度建构;开展基于研究性反思的教学实践,促进化学教育硕士PCK螺旋式提升等3条建议。