【特约专题】
介孔硅纳米载体应用于肿瘤治疗的研究进展
韩凯硕，任婷，李多，孙国辉，张娜，赵丽娇*，钟儒刚
(北京工业大学 环境与生命学部 环境与病毒肿瘤学北京市重点实验室，北京 100124)
摘要：化疗是临床上治疗恶性肿瘤的重要手段，但化疗药物毒副作用大、易产生耐药和生物相容性差等问题往往限制其治疗效果。纳米载体可使药物靶向作用于肿瘤部位，减少化疗药物对正常组织产生的毒副作用，从而提高治疗效果，近年来已成为癌症精准治疗领域中的研究热点。其中，介孔硅纳米粒子（Mesoporous silica nanoparticles，MSNs）作为一种无机纳米材料，具有比表面积大、孔径可调、孔体积大、生物相容性好和易于功能化修饰等优点，被广泛用于纳米递送系统的构建，尤其是集肿瘤靶向、治疗和成像等多种功能于一体的新型纳米递送系统。综述了近年来功能化MSNs递送载体应用于肿瘤靶向治疗、药物递送和肿瘤生物成像等方面的研究进展，为开发新型纳米递送系统以用于癌症治疗提供了参考。
关键词：介孔硅纳米载体；肿瘤靶向治疗；刺激响应；药物递送；生物成像
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0396
Progress in the Application of Mesoporous silica nanoparticles in tumor therapy HAN Kai-shuo, REN Ting, LI Duo, SUN Guo-hui, ZHANG Na, ZHAO Li-jiao*, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment & Life, Beijing University of Technology, Beijing 100124, China)
Abstract：Chemotherapy is an important method of treating malignant tumors in clinical practice, but its therapeutic effect is often limited by the problems of high systemic toxicity, susceptibility to drug resistance, and poor biocompatibility. Nanocarriers enable drugs to targetedly act on tumor sites and reduce the toxic side effects of chemotherapeutics on normal tissues, thus improving the therapeutic effect, which has become a hot research topic in the field of cancer precision therapy in recent years. Among them, mesoporous silica nanoparticles (MSNs), an inorganic nanomaterial, have the advantages of large specific surface area, adjustable pore size, large pore volume, favorable biocompatibility and easy functionalization modification. Therefore, MSNs have been widely used in the construction of nano-delivery systems, especially new nano-delivery systems that integrate multiple functions such as tumor targeting, therapy and imaging. The progress of functionalized MSNs delivery carriers developed in recent years for targeted tumor therapy, drug delivery and tumor bioimaging was summarized, which is expected to provide a reference for the development of novel nanodrug delivery systems for cancer therapy.
Key words：mesoporous silica nanoparticles; targeted tumor treatment; stimulus response; drug delivery; bioimaging
引用本文：韩凯硕，任婷，李多，等. 介孔硅纳米载体应用于肿瘤治疗的研究进展[J]. 化学试剂，2023，45（9）：1-10.
离子液[Bmim]BF4催化合成喹唑啉类化合物的研究
庞钰琪，应乐天，牟硕，马雪，陈雪柔，孙武积*，钟启迪*
（华北理工大学 药学院，河北 唐山 063000）
摘要：喹唑啉类化合物是一类重要的杂环骨架，广泛存在于各种具有生物药理活性的有机分子和生物碱中。报道了以醛类化合物和2-氨基二苯甲酮衍生物为底物，以乙酸铵为氮源，在[Bmim]BF4催化下合成喹唑啉类化合物的新方法。该方法无需使用有机溶剂，具有合成方法简单、反应产率高、底物范围广泛等优点，为喹唑啉类化合物的合成提供了新的思路。
关键词：喹唑啉；离子液；无溶剂；[Bmim]BF4；缩合环化
中图分类号：O622 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822 /j.cnki.hxsj.2023.0269
Synthesis of Quinazoline Compounds Catalyzed by Ionic Solution [Bmim]BF4 PANG Yu-qi, YING Le-tian, MU Shuo, MA Xue, CHEN Xue-rou, SUN Wu-ji*, ZHONG Qi-di* (School of Pharmacy, North China University of Science and Technology, Tangshan 063000, China)
Abstract：Quinazoline cyclic compounds are an essential heterocyclic framework and are widely found in a variety of organic molecules and alkaloids with biological pharmacological activity. A facile and selective method has been developed for the preparation of quinazoline compounds by the reaction of using aldehydes and 2-amino-diphenyl ketone derivatives as substrates and ammonium acetate as nitrogen source under the catalysis of [Bmim]BF4. The method has the advantages of solvent-free, simple synthesis method, high reaction yield and wide range of substrates, which provides a new idea for the synthesis of quinazoline compounds.
Key words：quinazoline; ionic liquid; solvent-free; [Bmim]BF4; condensation cyclization
引用本文：庞钰琪，应天乐，牟硕，等. Eu-2,5-二溴对苯二甲酸金属有机框架的合成及其对铀酰离子的荧光识别[J]. 化学试剂，2023，45（9）：11-18.
载亚硝基脲的多功能纳米载体的构建及其评价
韩凯硕，王小利，任婷，李多，孙国辉，张娜，赵丽娇*，钟儒刚
（北京工业大学 环境与生命学部 环境与病毒肿瘤学北京市重点实验室，北京 100124）
摘要：氯乙基亚硝基脲（CENUs）是临床上重要的抗肿瘤烷化剂，但因其水溶性差、毒副作用高以及肿瘤细胞内高表达的O6-烷基鸟嘌呤-DNA烷基转移酶介导的肿瘤细胞耐药性，降低了CENUs的抗癌效果。为了克服上述弊端，本研究合成了一种叶酸修饰抗耐药低氧激活纳米递送系统，用于CENUs的靶向递送。终产物及各中间体的结构经1HNMR、13CNMR、IR及HRMS确证，使用动态光散射（DLS）、紫外-可见分光光度计（UV-Vis）和透射电子显微镜（TEM）等方法表征纳米载体的理化性质及形貌，并利用高效液相色谱法（HPLC）测定纳米载体的包封率、载药量及其释药行为。此外，经细胞摄取、细胞毒性和划痕实验评价载药纳米载体的靶向性、低氧响应性和肿瘤细胞抑制能力。结果表明，该纳米载体具有合适的粒径、良好的安全性和优良的载药性能，可实现CENUs的靶向递送和低氧响应释放，能够有效抑制肿瘤细胞的增殖。
关键词：氯乙基亚硝基脲；纳米药物递送系统；耐药性；靶向性；低氧激活
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822 /j.cnki.hxsj.2023.0264
Construction and Evaluation of Multifunctional Nanocarriers Carrying Nitrosourea HAN Kai-shuo, WANG Xiao-li, REN Ting, LI Duo, SUN Guo-hui, ZHANG Na, ZHAO Li-jiao*, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment & Life, Beijing University of Technology, Beijing 100124, China)
Abstract：Chloroethylnitrosoureas (CENUs) are clinically vital antitumor alkylating agents, but the anticancer effect of CENUs is limited due to their poor water solubility, high toxicities and tumor cell resistance mediated by high expression of O6-alkylguanine-DNA alkyltransferase (AGT) in tumor cells. To overcome these drawbacks, this study synthesized a folate-modified anti-drug-resistant hypoxia-activated nano-delivery system for the targeted delivery of CENUs. The chemical structures of the end products and intermediates were confirmed by 1HNMR, 13CNMR, IR and HRMS. The physicochemical properties and morphology of nanocarriers were evaluated by dynamic light scattering (DLS), ultraviolet visible spectrophotometer (UV Vis), and transmission electron microscope (TEM). The encapsulation efficiency, drug loading and drug release behavior of nanocarriers were also determined by high performance liquid chromatography (HPLC). In addition, cell uptake, cytotoxicity and cell scratch experiments were utilized to evaluate the targeting, hypoxic responsiveness, and tumor cell inhibition of drug-loaded nanocarriers. The results demonstrated that the nanocarrier possesses suitable particle size, favorable safety and excellent drug loading performance, which can achieve targeted delivery and hypoxia responsive release of CENUs for effectively inhibiting the proliferation of tumor cells.
Key words：chloroethylnitrosoureas; nanodrug delivery systems; drug resistance; targeting; hypoxia activation
引用本文：韩凯硕, 李多, 王小利, 等. 载亚硝基脲的多功能纳米载体的构建及其评价[J]. 化学试剂, 2023, 45（9）：19-28.
硝基还原酶催化硝基咪唑还原机理的密度泛函理论研究
王圣博，王娇娇，任婷，孙国辉，张娜，赵丽娇*，钟儒刚
（北京工业大学 环境与生命学部 环境与病毒肿瘤学北京市重点实验室，北京 100124）
摘要：低氧是实体肿瘤的重要特征之一，靶向肿瘤低氧的抗肿瘤药物在临床上有广泛的应用。硝基咪唑具有低氧选择特性，在常氧环境下可稳定存在但在低氧环境下可经还原酶代谢发生还原反应，因而一些将硝基咪唑作为低氧响应基团的靶向性抗肿瘤前药近年来被研发并投入临床研究。采用密度泛函理论（Density functional theory，DFT）对硝基还原酶中辅酶还原性黄素单核苷酸（Reduced flavin mononucleotide，FMNH）介导的硝基咪唑还原机理进行了研究。结果表明，还原反应的优势途径为硝基咪唑首先经过第一次1e-/1H+转移，再通过一分子H2O作为质子转移通道接受来自FMNH的1e-/1H+生成亚硝基咪唑，后续再发生连续的四步1e-/1H+转移，最终生成氨基咪唑。上述结果可在新型抗肿瘤低氧激活前药的研发中作为理论参考。
关键词：硝基咪唑；密度泛函理论；低氧激活前药；还原机制；肿瘤低氧；硝基还原酶
中图分类号：O641 文献标识码：A 文章编号：0528-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0334
Reduction Mechanism of Nitroimidazole Catalyzed by Nitroreductase: A DFT Investigation WANG Sheng-bo, WANG Jiao-jiao, REN Ting, SUN Guo-hui, ZHANG Na, ZHAO Li-jiao*, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment & Life, Beijing University of Technology, Beijing 100124, China)
Abstract：Hypoxia is one of the significant characteristics of solid tumors, which has been applied as a target of antitumor drugs in clinic treatment of cancer. Nitroimidazole possesses hypoxia-selective properties and exists stably under normoxia but undergoes reductive reactions via reductase metabolism under hypoxia environment. In this study, density functional theory (DFT) was employed to investigate the reduction mechanism of nitroimidazole mediated by the coenzyme reduced flavin mononucleotide (FMNH) within nitroreductase. The results indicated that the dominant reaction pathway was that nitroimidazole underwent a first 1e-/1H+ transfer and then accepted 1e-/1H+ from FMNH through H2O as a proton transfer channel to generate nitrosoimidazole, followed by successive four steps of 1e-/1H+ transfer to yield aminoimidazole. The results above may serve as a theoretical reference in the development of novel hypoxia-activated antitumor prodrugs.
Key words：nitroimidazole; density functional theory; hypoxia-activated prodrugs; reduction mechanism; tumor hypoxia; nitroreductase
引用本文：王圣博, 王娇娇, 任婷, 等. 硝基还原酶催化硝基咪唑还原机理的密度泛函理论研究[J]. 化学试剂, 2023, 45（9）：29-37.
【综述与专论】
HKUST-1(Cu)及其复合材料吸附去除水体污染物的研究进展
李阳，王崇臣*
（北京建筑大学 建筑结构与环境修复功能材料北京市重点实验室，北京 100044）
摘要：金属有机框架及其复合材料因具有独特的结构和卓越的性能，在水处理研究领域得到广泛关注。HKUST-1(Cu)作为一种具有突出吸附性能的金属有机框架材料，近年已经成为吸附水体中有毒物质的研究热点。详细探讨HKUST-1(Cu)和相关复合材料的一般合成方法及其去除各类水体污染物的研究进展，目的是对于HKUST-1(Cu)和相关复合材料去除水体污染物的研究方向提供一个方便于理解的概述。根据HKUST-1(Cu)和相关复合材料的研究现状和进展，对其去除环境污染物方面的发展趋势做出展望。
关键词：HKUST-1(Cu)；复合材料；吸附；去除；水体污染物
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822 /j.cnki.hxsj.2023.0244
Research Progress of HKUST-1(Cu) and its Composite Materials for Adsorption and Removal to Water Pollutants Li Yang, WANG Chong-Chen* (Beijing Key Laboratory of Functional Materials for Building Structure and Environmental Restoration, Beijing University of Civil Engineering and Architecture, Beijing 100044, China)
Abstract：Metal-organic framework and its composites have been widely concerned in the water treatment due to their unique structure and excellent properties. As a sort of metal-organic framework with outstanding adsorption properties, HKUST-1(Cu) has become a hot spot for the adsorption to water toxic substances in recent years. Within this review paper, the general synthesis methods of HKUST-1(Cu) and its composites and the research progress on the removal of various pollutants in water were introduced, with the purpose of providing an easy-to-understand overview for the corresponding research direction. Finally, the development trend of HKUST-1(Cu) and its composites for removing environmental pollutants was prospected.
Key words：HKUST-1(Cu); composite material; adsorption; removal; water pollutant
引用本文：李阳, 王崇臣. HKUST-1(Cu)及其复合材料吸附去除水体污染物的研究进展[J]. 化学试剂, 2023, 45（9 ）：38-46 .
【生化与药用试剂】
多功能19F磁共振/CT成像及光热/化学联合治疗纳米平台用于肿瘤诊疗
李璐，刘怡萌，李楠楠，胡高飞*
（北京化工大学 化学学院，北京 100029）
摘要：开发具有多种成像模式指导的高效诊疗一体化纳米平台对于肿瘤精准诊断治疗和疗效评估具有广阔的应用前景同时也面临着巨大挑战。光热疗法（PTT）是一种特异性强副作用小的非侵入性癌症治疗方法，通过将Au与Cu7S4耦合制备而成的Cu7S4/Au异质结可以将吸收调节至808 nm的近红外窗口，使其具有优良的近红外光热效应，这有效避免了生物背景干扰，增大了组织穿透能力和深度，也减少了对正常组织的损伤。同时引入X射线衰减能力强的金赋予了异质结良好的CT成像功能。随后，利用油胺修饰的聚琥珀酰亚胺两亲高分子（PSIOAm）通过超声乳化实现对全氟冠醚（PFCE，作为氟源）、紫杉醇（PTX）以及Cu7S4/Au异质结纳米颗粒进行包封组装获得Cu7S4/Au-19F-PTX@PSI纳米复合探针，因而将19F磁共振（MRI）/CT成像和光热/化学药物联合治疗整合于一个纳米平台。19FMRI、CT及PTT模式相互匹配，均有利并奏效于深部肿瘤成像或治疗。体外和小鼠活体实验结果表明，该纳米探针具有良好的生物相容性和出色的19FMRI/CT及近红外光热成像能力，光热与化疗联合治疗显著抑制了实体肿瘤的生长。本研究所展示的多功能诊疗一体化纳米平台为构建新型高效纳米诊疗试剂提供了有益的设计思路和合成策略，有望在将来癌症诊断和治疗中发挥潜力。
关键词：多功能纳米复合探针；19F磁共振成像（MRI）；计算机断层扫描成像（CT）；光热/化学联合治疗；肿瘤
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0345
Multifunctional 19F MR/CT Imaging and Photothermo-/Chemo-therapy Nanoplatform for Tumor Diagnosis and Treatment LI Lu, LIU Yi-meng, LI Nan-nan, HU Gao-fei (School of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China)
Abstract: The development of multimodal imaging-guided integrated diagnosis and treatment nanoplatforms has broad application prospects for accurate tumor diagnosis, treatment and efficacy evaluations, but also faces great challenges. Photothermal therapy (PTT) is a non-invasive cancer treatment with strong specificity and less side effects. In this study, the Cu7S4/Au heterojunction prepared by coupling Au with Cu7S4 can adjust the absorption to a near-infrared window of 808 nm, thus exhibiting excellent near-infrared photothermal effect, which effectively avoids biological background interference, increases tissue penetration ability and depth, and reduces damage to normal tissues. Meanwhile, the introduction of Au with strong X-ray attenuation ability endowed the heterojunction with desired CT imaging function. Subsequently, the oleamine-modified polysuccinimide amphiphilic molecule (PSIOAm) was used to encapsulate and assemble perfluorocarboxane (PFCE, as the fluorine source), paclitaxel (PTX) and Cu7S4/Au heterojunction nanoparticles into Cu7S4/Au-19F-PTX@PSI nanocomposite probes, thus integrating 19F magnetic resonance imaging (MRI)/CT imaging and combined photothermo-/chemo-therapy into a nanoplatform. 19FMRI, CT and PTT modalities matched each other and were all beneficial and effective in deep-seated tumor imaging of treatment. In vitro and in vivo mouse experimental results showed that the nanoprobe had good biocompatibility and remarkable 19FMRI/CT and near-infrared photothermal imaging capabilities, and the combination of photothermo-/chemo-therapy significantly inhibited the growth of solid tumors. The multifunctional integrated nanoplatform demonstrated in this study will provide novel design and synthetic strategies for the construction of new and efficient diagnostic and therapeutic nanoreagents, which are expected to play a potential role in cancer diagnosis and treatment in the future.
Key words: multifunctional nanocomposite probes; 19F magnetic resonance imaging (MRI); computed tomography imaging (CT); combined photothermo-/chemo-therapy; tumors
引用本文：李璐, 刘怡萌, 李楠楠, 等. 多功能19F磁共振/CT成像及光热/化学联合治疗纳米平台用于肿瘤诊疗[J]. 化学试剂, 2023, 45(9): 47-55.
新型XO抑制剂的合成及其体外抑制作用探究
高静，李倩，苏虹霞，杨雨茹，唐世行，王月瑶，姜敏*
（陕西理工大学 化学与环境科学学院 陕西省催化基础与应用重点实验室，陕西 汉中 723000）
摘要：以乙酰氯和邻氨基苯甲酸为底物，采用活性基团拼接策略，“一锅法”反应合成了新型酰基硫脲（N-乙基-N’-2-羧基苯甲酰基硫脲）作为黄嘌呤氧化酶（XO）抑制剂，并对其进行结构和性能表征。通过体外酶催化法、荧光猝灭和分子对接评价了目标酰基硫脲的XO抑制活性。结果表明：目标抑制剂对XO显示了较好的抑制活性，该体系ΔH ＞ 0、ΔS ＞ 0且ΔG < 0，说明二者的结合过程是自发且焓增加的，推测疏水作用为其主要的驱动力。分子对接显示酰基硫脲能够插入XO的疏水空腔，通过疏水作用、氢键等与XO发生紧密结合，从而抑制了XO的催化活性。
关键词：酰基硫脲；黄嘌呤氧化酶抑制剂；荧光猝灭；分子对接
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822 /j.cnki.hxsj.2023.0343
Synthesis and Vitro Inhibition Investigation of A Novel XO Inhibitor GAO Jing, LI Qian, SU Hong-xia, YANG Yu-ru, TANG Shi-xing, WANG Yue-yao, JIANG Min* (Shaanxi Key Laboratory of Catalysis, School of Chemical and Environmental Sciences, Shaanxi University of Technology, Han Zhong 723000, China)
Abstract：Based on active groups splicing method, a novel acylthiourea (N-ethyl-N’-2-carboxybenzoyl thiourea) which acted as an efficient inhibitor of xanthine oxidase (XO), was synthesized by one-pot reaction, using acetyl chloride and o-aminobenzoic acid as substrates and its structure and properties were characterized. The XO inhibition activity in vitro of target acylthiourea was evaluated by enzyme catalysis, fluorescence quenching and molecular docking. The results showed that the target inhibitor exhibited good inhibitory activity against XO. ΔH > 0, ΔS > 0 and ΔG < 0 indicate that the binding process is spontaneous and the enthalpy increases, and it is speculated that hydrophobic action is the main driving force. Molecular docking shows that acylthiourea can insert into the hydrophobic cavity of XO and bind XO closely through hydrophobic action and hydrogen bonding, thus inhibiting the catalytic activity of XO.
Key words：acylthiourea; xanthine oxidase inhibitor; fluorescence quenching; molecular docking
引用本文：高静, 李倩, 苏虹霞, 等. 新型XO抑制剂的合成及其体外抑制作用探究[J]. 化学试剂, 2023, 45（9）：56-60.
【功能材料】
李傲a, c，王飞b, c，黄荣威b, c，游丹b, c，张义永*b, c，李雪*b, c，张英杰*b, c
（昆明理工大学 a.材料科学与工程学院；b.冶金与能源工程学院；c.国家地方锂离子电池及材料制备技术联合工程研究中心，云南 昆明 650093）
摘要：金属有机框架（MOF）是金属和有机配体组成的多孔材料，具有比表面积大、孔隙率高、催化效率强、稳定性好等优点，成为了改善储能器件性能的首选材料之一。MOF材料分为3大类：原始MOF、MOF复合材料及MOF衍生物材料。其中，MOF复合材料和MOF衍生物材料又有许多小分类：MOF金属氧化物、MOF金属硫化物、MOF硒化物、碳基MOF及双金属MOF等，根据各自的特点分别用于不同的储能器件中。综述了MOF材料应用于锂离子电池（LIBs）、锂硫电池（LSBs）、钠离子电池（SIBs）、超级电容器（SCs）以及其他储能器件中的现状并对未来MOF材料在储能器件中的应用展望。
关键词：原始MOF；MOF复合材料；MOF衍生物；储能器件；多功能改性
中图分类号: 文献标识码:A 文章编号: 0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0357
Application of Metal Organic Frame in Electrochemical Energy Storage system LI Aoa, c, WANG Feib, c, HUANG Rong-weib, c, YOU Danb, c, ZHANG Yi-yong*b, c, LI Xue*b, c, ZHANG Ying-jie*b, c (Kunming University of Science and Technology a. School of Materials Science and Engineering; b. School of Metallurgical and Energy Engineering;c. National local joint engineering research center for Lithium-ion Batteries and Materials Preparation Technology,Kunming 650093, PR China)
Abstract: Metal-organic frameworks (MOFs) is a novel type of materials composed of metal and organic ligands. It possesses the advantages of large specific surface area, high porosity, strong catalytic efficiency and superior stability, has become one of the preferred materials to improve the performance of energy storage devices. MOF materials are divided into three categories: pristine MOFs, MOF composites and MOF derivatives. Moreover, MOF composite materials and MOF derivatives can be divided into MOF metal oxides, MOF metal sulfides, MOF selenides, carbon-based MOFs and bimetallic MOFs, which are introduced in different energy storage devices according to their respective properties. The development of MOF materials for advanced lithium ion batteries (LIBs), lithium sulfur batteries (LSBs), sodium ion batteries (SIBs), supercapacitors (SCs) and other energy storage devices are summarized. Finally, the future application and prospect of MOF materials in energy storage devices is envisioned.
Key words: pristine MOFs; MOF composites; MOF derivatives; energy storage devices; multifunctional modification
引用本文：李傲，王飞，黄荣威，等. 金属有机框架在电化学储能体系中的应用[J]. 化学试剂, 2023, 45(9): 61-69.
Eu-2,5-二溴对苯二甲酸金属有机框架的合成及其对铀酰离子的荧光识别
张涨展
（宁波石化开发区热力有限公司，浙江 宁波 315200）
摘要：在溶剂热条件下，利用2,5-二溴对苯二甲酸与六水合硝酸铕合成得到一例新型稀土金属有机框架材料Eu(DBTA)1.5(DEA)(H2O)（H2DBTA = 2,5-二溴对苯二甲酸；DEA = N,N-二乙基乙酰胺），对其进行红外、热重、粉末衍射和光致发光等手段表征。晶体结构分析表明，Eu3+处于八配位的四方反棱柱中心，通过不同2,5-二溴对苯二甲酸根的桥联作用，形成二维层状结构。该MOF作为荧光探针对UO22+离子具有高选择性和灵敏性的检测能力，其检出限为6.2 ´ 10–5 mol/L。此外，通过PXRD、紫外光谱等手段系统地研究了响应过程中的荧光猝灭机制。
关键词：2,5-二溴对苯二甲酸；稀土金属有机框架；荧光探针；铀酰离子
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0103
Synthesis of Eu-2,5-Dibromo-Terephthalate Metal-Organic Framework and Its Fluorescence Recognition to Uranyl Ions ZHANG Zhang-zhan (Ningbo Petrochemical Development Zone Thermal Power Co., Ltd., Ningbo 315200, China)
Abstract: A new rare earth metal-organic framework Eu(DBTA)1.5(DEA)(H2O) (H2DBTA = 2,5-dibromoterephthalic acid; DEA = N,N-diethylacetamide) was synthesized using 2,5-dibromoterephthalic acid and europium nitrate hexahydrate under solvothermal method, and characterized by infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction and photoluminescence spectroscopy. Crystal structure analysis revealed that Eu3+ was in the center of a distorted square antiprism, and two-dimensional layer structure was formed by the bridging interaction of different 2,5-dibromoterephthalic acid moieties. This MOF exhibited high selectivity and sensitivity for UO22+ ions detection as a fluorescent probe with a detection limit of 6.2 ´ 10–5 mol/L. In addition, the fluorescence quenching mechanism in the response process was systematically investigated by PXRD and UV spectroscopy.
Key words: 2,5-dibromide-terephthalic acid; lanthanide organic framework; fluorescent probe; uranyl ions
引用本文：张涨展. Eu-2,5-二溴对苯二甲酸金属有机框架的合成及其对铀酰离子的荧光识别[J]. 化学试剂，2023，45（9）：70-75.
手性金属有机框架材料NH2-MIL-53(Al)-D-(+)-葡萄糖的液相色谱拆分性能研究
高顺秋，赖亚琳，蒋雪菲，普娜，袁黎明*
（云南师范大学 化学化工学院，云南 昆明 650500）
摘要：金属有机框架材料（MOFs）因其具有特殊的拓扑结构、规则的单元排列、特定的孔道形状及尺寸、孔道结构及性质可调、表面可修饰等特点，被广泛地应用于催化、分离和非线性光学等领域，其在手性分离分析领域也展现出其独特的应用价值。通过溶剂热法合成非手性MOFs (NH2-MIL-53(Al))，再用D-(+)-葡萄糖对其进行手性修饰，最终合成了手性MOFs (NH2-MIL-53(Al)-D-(+)-葡萄糖)。采用“网包法”制备了NH2-MIL-53(Al)-D-(+)-葡萄糖固定相用于高效液相色谱(HPLC)手性柱，对其拆分能力进行考察。实验结果表明：NH2-MIL-53(Al)-D-(+)-葡萄糖色谱柱拆分开了15种手性化合物和2种苯系位置异构体，其中共9个手性化合物和2种苯系位置异构体实现基线分离，且色谱柱具有良好的重复性，表明其分离效果良好。
关键词：金属有机框架材料；高效液相色谱；手性化合物；手性分离；手性固定相
中图分类号：O657. 7 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0361
Liquid Chromatographic Separation Performance of Chiral Metal-organic Framework Material NH2-MIL-53(Al)-D-(+)-glucose GAO Shun-qiu, LAI Ya-lin, JIANG Xue-fei, PU Na, YUAN Li-ming*(School of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China)
Abstract: Metal-organic frameworks (MOFs) are widely used in catalysis, separation and nonlinear optics due to their special topological structure, regular unit arrangement, specific pore shape and size, adjustable pore structure and properties, and surface modification. It also shows unique application value in the field of chiral separation and analysis. The chiral MOFs (NH2-MIL-53(Al)-D(+)-glucose) were obtained by grafting D-(+)-glucose onto achiral MOFs (NH2-MIL-53(Al)) synthesized by solvothermal method. The NH2-MIL-53(Al)-D-(+)-glucose stationary phase was prepared by “net-wrap method” for chiral column of high performance liquid chromatography (HPLC) , and its resolution ability was investigated. The experimental results exhibited that the NH2-MIL-53(Al)-D-(+)-glucose column had separated 15 chiral compounds and 2 benzene-based positional isomers. Among them, 9 chiral compounds and 2 benzene-based positional isomers achieved baseline separation, and the column had good repeatability, indicating that the separation effect was good.
Key words: metal-organic framework materials; high performance liquid chromatography; chiral compounds; chiral separation; chiral stationary phase
引用本文：高顺秋，赖亚琳，蒋雪菲，等. 手性金属有机框架材料NH2-MIL-53(Al)-D-(+)-葡萄糖的液相色谱拆分性能研究[J]. 化学试剂，2023，45（9）：76-82.
一种低pH响应的新型近红外菁类荧光探针
王筱楠，胡利明，孙国辉，郝振铭，杨静，莫善雁*
(北京工业大学 环境与生命学部 环境与病毒肿瘤学北京市重点实验室，北京 100124)
摘要：开发一种快速、准确的pH测定方法对研究生命体系内的理化环境具有着重要意义。以糠醛化合物为起始原料合成了两个水溶性良好的七甲川菁pH荧光探针I-1及I-2。光学性能研究表明，这两个探针都能在低pH条件发出较强的近红外荧光，最大发射波长分别为749、753 nm，且其荧光强度分别在pH为1.69～3.38、1.78～2.52时与pH值呈良好线性关系，pKa值分别为2.82、2.40，因此，可用于该范围内pH值的定量检测。它们对pH值的响应非常迅速、灵敏、可逆，并且响应前后荧光强度变化达20倍以上。另外，探针I-1及I-2在体外模拟胃液的低pH检测中同样显示出了良好的荧光响应以及稳定性。因此，探针I-1及I-2在低pH生物体系的pH值检测与荧光成像上具有较佳应用潜力。
关键词：pH；菁染料；近红外区；荧光探针；苯并噻唑
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0291
A Novel Heptamethine Cyanines Near-Infrared Fluorescent Probe for Low pH Monitoring WANG Xiao-nan, HU Li-ming, SUN Guo-hui, HAO Zhen-ming, YANG Jing, MO Shan-yan* (Beijing Key Laboratory of Environmental and Oncology, Faculty of Environment and Life, Beijing University of Technology, Beijing 100124)
Abstract: It is of great significance to develop a rapid and accurate pH detecting method for the study of physicochemical environment inside the living systems. In this article, we synthesized two water soluble heptamethine cyanine probes I-1 and I-2 from furfural derivatives. The investigation on their optical properties shows that both probes emit strong near-infrared fluorescence in low pH value environment. The maximum emission wavelengths of I-1 and I-2 are 749 nm and 753 nm, respectively. The fluorescent intensity of I-1 and I-2 are in good linear relationship with the pH value within the range of respectively 1.69～3.38 and 1.78～2.52, with the pKa value of 2.82 and 2.40, respectively. Thus, the probes can be employed for the quantitive detection of pH value in these range. The pH response of the probes is very rapid, sensitive and revisable. The fluorescence intensity changed more than 20 times before and after the response. Besides, the probe I-1 and I-2 also showed great fluorescence response and stability in simulate gastric low pH detection. Therefore, the probe I-1 and I-2 exihibit great potential for the application in detecting the pH value in low pH living systems.
Key words: pH; cyanines; near infrared; fluorescent probe; benzothiazole
引用本文：王筱楠，胡利明，孙国辉，等. 一种低pH响应的新型近红外菁类荧光探针[J]. 化学试剂, 2023, 45(9): 83-89.
木质素无卤素水相催化脱甲基反应及其利用
郑雨欣1, 吴可荆*2, 朱英明2, 吴剑3
（1. 四川大学 化学工程学院，四川 成都 610065；2. 四川大学 新能源与低碳技术研究院，四川 成都 610207; 3. 浙江臻泰能源科技有限公司，浙江 丽水 321404）
摘要：木质素脱甲基转化成多酚是其高值利用的重要途径。针对传统脱甲基反应的高卤素含量、高酸强度的缺点，以TiOSO4为前驱体在活性炭（AC）载体上一步法构筑了布朗斯特酸（B酸）和路易斯酸（L酸）共存的固体酸催化剂，在无卤素水相体系实现模型木质素的脱甲基反应。在300 ℃反应1 h可以获得48.5 %的产物收率，高的酸性位含量显著提高脱甲基反应活性，TiO2的表面团聚将降低单位酸性位的活性，B酸和L酸的协同作用促进了脱甲基反应的进行。真实木质素在该反应体系下同样可以进行脱甲基反应，提高木质素的酚羟基含量。将木质素用于聚氨酯表面改性，结合SiO2气相沉积提高聚氨酯阻燃性；结果表明，更多的酚羟基可以提高木质素在聚氨酯阻燃性能的作用。
关键词：木质素脱甲基；固体酸催化剂；酸性位；真实木质素；聚氨酯阻燃
中图分类号：TK6 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0320
Catalytic demethylation of lignin in halogen-free aqueous phase system and its utilization ZHENG Yu-xin1, WU Ke-jing*2, ZHU Ying-ming2, WU Jian3 (1. Sichuan University, School of Chemical Engineering, Chengdu 610065, China; 2. Sichuan University, Institute of New Energy and Low-Carbon Technology, Chengdu 610207, China)
Abstract: The demethylation of lignin into polyphenols is an important way for its high value utilization. In view of the shortcomings of traditional demethylation reactions, such as high halogen content and high acid strength, a solid acid catalyst with the coexistence of Bronsted acid (B acid) and Lewis acid (L acid) was constructed by one-step method on activated carbon (AC) carrier with TiOSO4 as precursor. The demethylation reaction of model lignin was achieved in halogen-free aqueous phase system. The yield of lignin was 48.5 % at 300 ℃ for 1 h. The high content of acid sites significantly improved the activity of the demethylation reaction. The surface agglomeration of TiO2 reduced the activity of unit acid sites. The synergistic effect of B acid and L acid promoted the demethylation reaction. Real lignin also undergo demethylation reaction under this reaction and increase the phenolic hydroxyl content of lignin. Lignin was used for surface modification of polyurethane, combined with SiO2 vapor deposition to improve the flame retardancy of polyurethane. Results showed that more phenolic hydroxyl groups could improve the flame retardancy of lignin in polyurethane.
Key words: lignin demethylation; solid acid catalyst; acid site; real lignin; polyurethane flame retardant
引用本文：郑雨欣, 吴可荆, 朱英明,等. 木质素无卤素水相催化脱甲基反应及其利用[J]. 化学试剂，2023，45（9）：90-96.
【分离提取技术】
基于红外辐射表面活性剂提取方式及Box-Behnken响应面试验优化当归中阿魏酸的提取工艺
刘珂*1，毕映燕2，李亚楠3，徐成1，何敏1，郭玉梅1，赵鑫1
（1. 兰州石化职业技术大学 应用化学工程学院，甘肃 兰州 730060；
2. 甘肃省中医院 药剂科，甘肃 兰州 730050；
3. 兰州大学第二医院 药剂科，甘肃 兰州 730030）
摘要：利用红外辐射表面活性剂提取方式结合Box-Behnken响应面试验优化当归中阿魏酸的提取工艺。选取提取剂浓度、液固比、提取时间、红外功率为考察因素，阿魏酸提取率为考察指标，单因素实验结合Box-Behnken响应面试验筛选提取当归中阿魏酸的最优组合条件。单因素实验结果表明：烷基多糖苷（APG1214）浓度10%（V/V）、液固比100:1、提取时间30 min、红外功率250 W，可得到最大阿魏酸提取率。响应面试验得出最优工艺条件为：APG1214浓度3.7%（V/V ）、液固比60.85:1（mL/g）、提取时间23.66 min、红外功率241.69 W，理论预测值为0.8010 mg/g，该条件下实际测得阿魏酸提取率为0.8054 mg/g。本研究通过响应面优化所得的阿魏酸理论预测值与实际测得值误差较小，仅为0.55%。通过响应面法优化的提取工艺绿色环保、简单可靠，为当归阿魏酸的高效提取和应用前景提供一定的理论基础。
关键词：红外辐射；表面活性剂；当归；阿魏酸；响应面法
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822 /j.cnki.hxsj.2023.0278
Optimizing the Extraction Process of Ferulic Acid in Angelica Sinensis Based on Infrared Radiation Surfactant Extraction Method and Box-Behnken Response Surface Test LIU Ke*1, BI Ying-yan2, LI Ya-nan3, XU Cheng1, HE Min1, GUO Yu-mei1, ZHAO Xin1 (1. College of Applied Chemical, Lanzhou Petrochemical University of Vocational Technology, Lanzhou 730060, China; 2. Department of Pharmacy, Gansu Provincial Hospital of TCM, Lanzhou 730050, China; 3. Department of Pharmacy, Lanzhou University Second Hospital, Lanzhou 730030, China)
Abstract：The extraction process of ferulic acid in Angelica was optimized by combining with Box-Behnken response surface test. The concentration of extraction agent, liquid-solid ratio, extraction time and infrared power were selected as the investigation factors, the extraction rate of ferulic acid was the investigation index, and the optimal combination conditions of the Box-Behnken response surface test were selected. The results of single factor experiment show that: APG1214 concentration was 10% (v/v), liquid-solid ratio was 100:1, extraction time was 30 min, infrared power was 250 W, the maximum extraction rate of ferulic acid can be obtained. The response surface test, the optimal process conditions are: APG1214 concentration was 3.7% (v/v), liquid-solid ratio was 60.85:1 (mL/g), extraction time was 23.66 min, and infrared power was 241.69 W, the theoretical predicted value is 0.8010 mg/g, and the actual measured extraction rate of ferulic acid is 0.8054 mg/g. In this study, the theoretical predicted value of ferulic acid and the actual measured value is only 0.55%. The extraction process optimized by the response surface method is green, simple and reliable, which provides a certain theoretical basis for the efficient extraction and application prospect of Angelica ferulic acid.
Key words：infrared emanation; surfactants; radix angelica sinensis; ferulic acid; response surface method
引用本文：刘珂，毕映燕，李亚楠，等. 基于红外辐射表面活性剂提取方式及Box-Behnken响应面试验优化当归中阿魏酸的提取工艺[J]. 化学试剂，2023, 45（9）：97-104.
【电化学和新能源】
焦磷酸铜光催化分解水产氢性能研究
覃彪*1，张影2，唐承性2
（1. 遵义师范学院 化学化工学院，贵州 遵义 563006；2. 遵义市产品质量检验检测院，贵州 遵义 563000）
摘要：以焦磷酸铜为催化剂，荧光素为光敏剂，三乙醇胺为牺牲剂，建立可见光照射下焦磷酸铜光催化分解水产氢体系。通过单因素试验和正交试验探究了不同的光敏剂用量、催化剂用量、牺牲剂用量等因素对焦磷酸铜光催化分解水产氢性能的影响。用气相色谱仪对其产氢量进行测定，结果表明在使用10 mg荧光素、2 mg焦磷酸铜、0.5 mL的三乙醇胺的实验条件下，焦磷酸铜的光催化分解水体系在反应20 h能产氢6.86 mL。以焦磷酸铜为催化剂建立光催化分解水产氢体系，实验操作简单，成本相对较低，稳定性较高。
关键词：焦磷酸铜；光催化；正交优化；产氢
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822 /j.cnki.hxsj.2023.0164
Study on Copper Pyrophosphate for Efficient Photocatalytic Hydrogen Evolution QIN Biao*1, ZHANG Ying2, TANG Cheng-Xing2 (1. The Department of Chemistry and Chemical Engineering, Zunyi Normal University, Zunyi 563006, China; 2. Zunyi Product Quality Inspection and Testing Institute, Zunyi 563000, China)
Abstract：With copper pyrophosphate as the catalyst, fluorescein as the photosensitizer and triethanolamine as the sacrificial agent, the photocatalytic system of copper pyrophosphate was established under visible light irradiation. The effects of different dosage of photosensitizer, catalyst and sacrificial agent on the photocatalytic water splitting were investigated by single factor test and orthogonal test. The hydrogen production was determined by gas chromatography, the results showed that using 10 mg fluorescein, 2 mg copper pyrophosphate and 0.5 mL of triethanolamine, the photocatalytic water splitting system of copper pyrophosphate can produce 6.86 mL of hydrogen in 20 h. Establishing a photocatalytic water splitting system with copper pyrophosphate as a catalyst, the experiment is simple, with relatively low cost and high stability.
Key words：copper pyrophosphate; photocatalysis; orthogonal optimization; hydrogen evolution
引用本文：覃彪，张影，唐承性. 焦磷酸铜光催化分解水产氢性能的研究[J]. 化学试剂，2023，45（9）：105-109.
微量氯离子对氧化钌析氧性能的影响
陈安阳1, 2，陶凯1，林贻超*2
（1. 宁波大学 材料科学与化学工程学院，浙江 宁波 315211；
2. 中国科学院 宁波材料技术与工程研究所，浙江 宁波 315201）
摘要：电解水制氢是目前最具潜力的绿氢制备技术。众所周知，电解液中含有大量氯离子会降低催化剂的活性和稳定性从而导致电解水效率下降。然而，目前的研究并未涉及微量氯离子（μg/L）对于催化剂性能的影响。借助于循环伏安扫描法、伏安线性扫描法、电化学阻抗谱等手段，仔细研究了微量氯离子在酸性介质中对二氧化钌（RuO2）析氧性能的影响，发现在含有极低浓度氯离子（μg/L）硫酸溶液中RuO2的析氧反应活性和稳定性均有小幅度下降。
关键词：电解水；二氧化钌；氯离子；电化学性能；析氧反应
中图分类号：O646.1 文献标志码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0274
Effect of Trace Chloride Ions on Ruthenium Oxide Oxygen Producing Performance CHEN An-yang1, 2, TAO Kai1, LIN Yi-chao*2 (1. School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China; 2. Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, China)
Abstract: Electrochemical water splitting is the most promising technology for the preparation of green hydrogen. It is well known that the presence of high levels of chloride ions in the electrolyte reduces the activity and stability of the catalyst, leading to a reduction in the efficiency of the water electrolysis. However, the effect of trace amounts of chloride ions (μg/L) on the performance of the catalyst has not been addressed in current studies. Cyclic voltammetry, linear scanning voltammetry and electrochemical impedance spectroscopy were used to investigate the effect of RuO2 on oxygen-evolution-reaction performance in acidic media containing trace amounts of chloride ions. We found a slight decrease in the OER activity and stability of RuO2 in sulphuric acid solutions containing very low concentrations of chloride ions (μg/L).
Key words: electrolysis water; ruthenium oxide; chloride ion; electrochemical characteristics; oxygen evolution reaction.
引用本文：陈安阳, 陶凯, 林贻超, 等. 微量氯离子对氧化钌析氧性能的影响[J]. 化学试剂，2023, 45(9):110-115.
