梯度共聚物接枝纳米粒子的合成及其力学性能

通过RAFT聚合制备了3种不同序列(无规、嵌段及梯度)的丙烯酸正丁酯(BA)/甲基丙烯酸甲酯(MMA)二元共聚物(PBA-r-PMMA、PBA-b-PMMA、PBA-g-PMMA),以及2种含可交联侧链的聚甲基丙烯酸酰氧基丙基三乙氧基硅烷(PTEPM)的三元共聚物PTEPM-b-(PBA-g-PMMA)和PTEPM-b-(PBA-r-PMMA),三元共聚物中PBA/PMMA分别为无规和梯度结构.这5个共聚物中PBA/PMMA段具有相近的分子量和组分比.三元共聚物通过共组装及交联后得到球状的共聚物接枝纳米粒子NP-(PBA-g-PMMA)和NP-g-(PBA-rPMMA). DSC结果表明NP-(PBA-g-PMMA)和PBA-g-PMMA具有较宽的玻璃化转变温度区间(～130℃),证明成功合成了梯度共聚物和接枝梯度共聚物的纳米粒子.通过DMA测试和变温拉伸测试发现,在升温过程中梯度结构二元共聚物及其对应的纳米复合材料力学性能呈现渐进式变化,而无规或嵌段对应物力学性能呈现突变,原因是前者具有较宽的玻璃化转变过程.由于无机内核的作用,NP-(PBA-g-PMMA)和NP-(PBA-r-PM...     

H2S在B16N16及M@B16N16(M=K,Na,Cl,F)纳米笼催化剂上的分解机理研究

采用密度泛函理论研究了B₁₆N₁₆及M@B₁₆N₁₆(M=K,Na, Cl, F)纳米笼催化剂的稳定性及H₂S在催化剂上的分解机理.结果表明,Na和F掺杂有利于提高B₁₆N₁₆稳定性,而K和Cl掺杂则降低了B₁₆N₁₆的稳定性.H₂S在催化剂上的降解按H₂S→HS+H→S+H₂方式进行,第二步为反应的速率控制步.动力学研究表明H₂S在B₁₆N₁₆笼上第一步分解的活化能为0.60eV,第二步分解的活化能为2.01eV. Na和K的掺入对H₂S降解有利,而F和Cl的掺入则对H₂S降解不利.特别是Na@B₁₆N₁₆纳米笼不但展现出良好的稳定性,而且能将速控步能垒从2.01降低至1....     

泡沫镍铁合金自支撑NiFeOOH纳米片的制备及析氧性能研究

电催化析氧反应(OER)是电解水制氢的重要半电池反应。然而,OER的缓慢动力学仍需研究高效的电催化剂。在非贵金属催化剂中,NiFe基材料是OER催化剂研究热点。本文通过食人鱼溶液简单一步浸渍刻蚀法将不同Fe含量的泡沫NiFe合金进行氧化,制备了表面具有纳米片形貌的NiFeOOH自支撑电催化剂,并深入研究其电催化析氧性能。通过SEM、XRD、XPS等对电催化剂的形貌结构及成分进行表征,证实了三维多孔基底上NiFeOOH纳米片结构的形成。由于高价镍、铁物种的存在以及二维纳米片结构的生成,NiFeOOH/NF的析氧性能大幅度提高,在10 mA?cm-2的电流密度下过电位仅155.68 mV,Tafel斜率为 88.2 mV?dec-1。这为研制高效、耐用的自支撑非贵金属电极提供了新思路。     

基于MoS2纳米花的表面离子印迹材料的制备及性能

以镉离子做模板离子,以多巴胺为功能单体和交联剂,通过多巴胺的自聚合反应,在二硫化钼(MoS₂)纳米花的表面形成一薄层镉离子印迹聚合物。通过扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FT-IR)、X射线粉末衍射仪(XRD)、热重分析仪(TGA)以及比表面和孔径分布分析等表征了离子印迹材料(IIM)的形貌和结构,确证了印迹聚合层的生成。平衡吸附实验结果表明,由于IIM的印迹位点位于MoS₂纳米花的表面,可接触性好,因而IIM对镉离子结合速度快,吸附25 min即可达到平衡。同时,该印迹材料具有很好的印迹效果(印迹因子为6.877),对镉离子有很强的特异性识别能力,特异性结合量为518.1μmol/g。Scatchard模型分析表明印迹材料的结合位点对镉离子的亲和力不是均一的,可以分为高亲和力和低亲和力两部分。吸附等温模型分析表明,印迹材料对镉离子的吸附行为符合Langmuir吸附等温模型,由该模型可以计算出其对镉离子的最大吸附量为1081.0μmol/g。本研究为制备对重金属离子具有高选择性吸附能力的印迹材料提供了一种简单、可靠的方法。     

Preparation and application of novel polymer nanoparticles in the detection of copper ion and cysteineEI北大核心CSCD

A novel amphiphilic copolymer,dipropenoxystyrene anthracene and acrylic acid copolymer（BASA-AA） was designed and synthesized based on divinyl anthracene. The polymer self-assembled rapidly in water to create polymer nanoparticles（BASA-AA NPs）with a uniform size of 45 nm,no dye leakage,and great brightness（Φ= 36%）. Because of the enormous number of carboxyl groups on the surface of the particles,it can disperse extremely well in water,and can be used for the rapid detection of copper ion and cysteine（Cys）in pure water, with the limit of detection of 45 nmol/L. The fluorescent intensity of the nanoparticles will be greatly reduced after the introduction of copper ion,realizing the detection of copper ion with high selectivity and sensitivity. A composite probe made of BASA-AA NPs and copper ion can detect Cys in the range of 0.1-10 µμmol/L,with the detection limit of 84 nmol/L,due to the high binding capacity of the sulfhydryl group and copper ion. The method is simple and rapid in material synthesis and preparation,and shows high selectivity and sensitivity in pure water. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

CoMn@NC催化5-羟甲基糠醛常压氧化为2, 5-呋喃二甲酸二甲酯

Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co₃Mn₂@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―N_x (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN⁻ ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.     

胍胶压裂液体系有机硼交联剂合成研究进展

胍胶压裂液是目前压裂作业中应用最多的工作液,但存在胍胶用量高、残渣量大、储层伤害严重的问题。有机硼交联剂因交联性能优异、延迟交联易调控、压裂液破胶彻底、可降低胍胶用量、减少胍胶残渣对储层的伤害,是目前胍胶压裂液体系交联剂的主要研究方向。文章介绍了胍胶压裂液体系有机硼交联剂的研究进展,探讨了有机硼交联剂的交联作用机理,重点总结了有机硼交联剂的合成研究情况,在此基础上对今后发展方向进行了展望。从合成研究情况来看,有机硼交联剂主要有多种配体复合制备、长链多头极性有机胺硼制备、纳米交联剂制备三种方式,在降低胍胶用量、提高压裂液携砂性能方面表现优异。今后研究中应以提高交联效率为关键,长链多头极性结构是主要研究方向,有机配体的优选和反应设计将是研究的核心问题。     

基于中空多孔金纳米/石墨烯复合纳米材料的葡萄糖氧化酶直接电化学及其生物传感研究

采用溶液相牺牲模板法制备中空多孔金纳米粒子（HPAuNPs）,并将该材料与还原氧化石墨烯（rGO）复合,用于葡萄糖氧化酶（GOx）在玻碳电极（GCE）表面的有效固定,构建GOx/HPAuNPs/rGO/GCE传感界面。利用扫描和透射电镜、X射线光电子能谱、X射线衍射谱、红外光谱及电化学等方法对材料的形貌与结构,GOx的固定化过程,以及传感器的直接电化学和电催化性能进行表征。结果表明,HPAuNPs和rGO的协同作用能有效促进GOx与电极之间的直接电子转移（DET）。基于GOx/HPAuNPs/rGO/GCE对葡萄糖的良好电催化性能,该方法有效实现了对葡萄糖的高灵敏度检测,其电流响应的线性范围为0.05～7.0 mmol/L,检出限（S/N=3）为16μmol/L。该传感器具有良好的选择性、重现性及稳定性,对实际样品血清中血糖的测定结果令人满意,回收率为98.0%～103%,相对标准偏差不大于5.0%。     

CRISPR/Cas9基因编辑非病毒递送系统

规律间隔成簇短回文重复序列及相关蛋白9(CRISPR/Cas9)系统的基因编辑技术为哺乳细胞基因组的精准修饰与编辑研究提供了高效、快捷的工具,但其化学生物学应用依然面临着CRISPR基因编辑工具Cas9蛋白和g RNA的细胞及活体递送等问题.近年来,研究人员通过开发多种非病毒递送载体,实现了编码CRISPR/Cas9基因编辑工具的DNA和信使RNA(mRNA)以及Cas9/gRNA核糖核蛋白(RNP)复合物的递送,并应用于靶基因的化学修饰与编辑调控.本文主要概述了近期CRISPR/Cas9基因编辑递送的研究进展,并对其化学生物学应用前景进行了展望.     

CoO纳米颗粒/石墨烯纳米纤维复合材料的制备及电化学性能

用石墨烯和Co(CH₃COO)₂·4H₂O作为原料,利用超声辅助法合成了锂离子电池的负极材料CoO纳米颗粒/中空石墨烯纳米纤维复合物.采用X射线衍射(XRD)确定材料的物相组成,采用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察材料的表面形貌和微观结构,采用X射线光电子能谱(XPS)确定材料的价态结构.采用循环伏安、恒电流充放电和交流阻抗谱表征材料的电化学性能.结果显示,在100 mA/g的电流密度下,循环了160次后,可逆容量仍超过800 mA/g,库仑效率保持在99%以上.该材料优异的电化学性能主要归因于石墨烯的中空纤维结构,中空内部可以容纳电解液,能直接将离子输送到颗粒表面,实现了离子的快速传输;二维中空纤维搭建成三维网络结构,实现了三维电子传导网络.