2026年48（2）中英文摘要
【特約專稿】
光誘導(dǎo)三氯化鈰催化構(gòu)建碳-碳鍵的研究進(jìn)展
莊元?jiǎng)P，安江振，李昊聰，孫凱，李祥飛，侯立芬*，於兵*
（鄭州大學(xué)化學(xué)學(xué)院，河南鄭州 450001）
摘要：可見光誘導(dǎo)的三氯化鈰（CeCl3）催化作為一種綠色合成策略，因其反應(yīng)條件溫和、原子經(jīng)濟(jì)性高，且環(huán)境友好，近年來在碳?碳鍵構(gòu)筑領(lǐng)域受到廣泛關(guān)注。CeCl3憑借其優(yōu)異的光反應(yīng)活性與獨(dú)特的配體?金屬電荷轉(zhuǎn)移（LMCT）特性，為惰性化學(xué)鍵的活化提供了新途徑。綜述了近年來可見光驅(qū)動(dòng)下CeCl3催化構(gòu)建碳?碳鍵的研究進(jìn)展，總結(jié)了C?H鍵直接官能團(tuán)化、醇的脫羥基轉(zhuǎn)化以及羧酸的脫羧偶聯(lián)3類代表性反應(yīng)。在C?H鍵官能團(tuán)化中，CeCl3通過LMCT過程實(shí)現(xiàn)惰性C?H鍵的活化，避免了預(yù)官能團(tuán)化步驟；醇的脫羥基轉(zhuǎn)化，利用光催化下烷氧自由基的β切斷，生成相應(yīng)的烷基自由基；羧酸的脫羧偶聯(lián)則通過可見光誘導(dǎo)CeCl3催化脫羧反應(yīng)，進(jìn)而發(fā)生后續(xù)偶聯(lián)。這些反應(yīng)體系均表現(xiàn)出良好的底物普適性和官能團(tuán)兼容性，為復(fù)雜有機(jī)分子的合成提供了新策略。CeCl3作為一種廉價(jià)、儲(chǔ)量豐富的稀土催化劑，在光催化有機(jī)合成領(lǐng)域展現(xiàn)出廣闊的應(yīng)用前景，其獨(dú)特的LMCT活化機(jī)制為發(fā)展綠色、高效的合成方法提供了重要思路，在藥物合成和材料科學(xué)等領(lǐng)域具有重要應(yīng)用價(jià)值。
關(guān)鍵詞：可見光誘導(dǎo)；三氯化鈰；碳碳鍵；官能團(tuán)化；烷基化；配體到金屬電荷轉(zhuǎn)移
中圖分類號(hào)：O65 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0001-08
DOI: 10.13822/j.cnki.hxsj.2025.0305
Recent Advances in Light-Induced CeCl3-Catalyzed C?C Bond Construction ZHUANG Yuan-kai, AN Jiang-zhen, LI Hao-cong, SUN Kai, LI Xiang-fei, HOU Li-fen*, YU Bing* (College of Chemistry, Zhengzhou University, Zhengzhou 450001, China)
Abstract: Visible light-induced cerium(III) chloride (CeCl3) catalysis has emerged as a green synthetic strategy, attracting significant attention in carbon-carbon bond formation due to its mild reaction conditions, high atom economy, and environmental friendliness. Unlike typical metal-to-ligand charge transfer (MLCT)-type catalysts, CeCl3 undergoes ligand-to-metal charge transfer (LMCT), in which electrons are transferred from a ligand's π orbital to the metal's d orbital, or from the metal-ligand σ orbital to the metal's d orbital. This LMCT process plays a crucial role in redox photoreactions: ligand-derived radical species such as chlorine radicals (Cl?) exhibit extremely high reactivity and can activate C?H bonds through hydrogen atom transfer (HAT), expanding the scope of photocatalysis transformation in organic synthesis. The unique LMCT properties of the Ce element arises from its 4f electron configuration([Xe]4f15d16s2). The 4f orbital is located in the inner shell and shielded by the outer 5s and 5p orbitals, giving the 4f electron high localization. This configuration facilitates facile Ce3?/Ce4? redox cycling, providing an ideal pathway for LMCT processes. Leveraging its excellent photoreactivity and unique ligand-to-metal charge transfer properties, CeCl3 offers a novel approach to activating inert chemical bonds. This review summarizes recent advances in visible-light-driven CeCl3-catalyzed carbon-carbon bond construction, focusing on three representative reaction types: direct C?H functionalization, dehydroxylative transformations of alcohols, and decarboxylative coupling of carboxylic acids. In C?H functionalization, CeCl3 activates inert C?H bonds via LMCT processes, eliminating the need for pre-functionalization. In dehydroxylative transformations, photocatalytic β-scission of alkoxy radicals generates corresponding alkyl radicals. In decarboxylative coupling, visible-light-induced CeCl3-catalyzed decarboxylation, followed by subsequent coupling. These reaction systems exhibit broad substrate scope and excellent functional group compatibility, providing new strategies for the synthesis of complex organic molecules. As an inexpensive and abundant rare-earth catalyst, CeCl3 demonstrates promising potential in photocatalytic organic synthesis. Its unique LMCT activation mechanism offers valuable insights for developing green and efficient synthetic methodologies, with significant applications in pharmaceutical synthesis and materials science.
Key words: visible-light-induced; cerium(III) chloride; carbon-carbon bond; functionalization; alkylation; ligand-to-metal charge transfer
天然活性小分子在胰腺癌治療中的研究進(jìn)展
李昊洋，趙潤(rùn)麗，劉夢(mèng)祥，孟麟，趙雨，韓超*
（中國(guó)藥科大學(xué)中藥學(xué)院，江蘇南京 210000）
摘要：胰腺癌起病隱匿、進(jìn)展迅速、轉(zhuǎn)移早且耐藥性顯著，患者總體預(yù)后極差，現(xiàn)有以吉西他濱為基礎(chǔ)的治療方案療效有限，亟需開發(fā)新的治療策略。天然產(chǎn)物來源的活性小分子因結(jié)構(gòu)多樣、作用靶點(diǎn)廣泛，在胰腺癌防治研究中展現(xiàn)出重要潛力。系統(tǒng)檢索并整理近年來國(guó)內(nèi)外相關(guān)文獻(xiàn)，按化學(xué)結(jié)構(gòu)及來源將天然活性小分子分為生物堿、黃酮、萜類、皂苷以及微生物和海洋來源化合物，重點(diǎn)綜述其在胰腺癌中的體內(nèi)外藥理活性及作用機(jī)制。研究表明，天然活性小分子可通過多途徑、多靶點(diǎn)協(xié)同發(fā)揮抗腫瘤作用：一是抑制腫瘤細(xì)胞增殖并誘導(dǎo)凋亡，主要通過阻斷 PI3K/AKT、MAPK、NF-κB 等信號(hào)通路；二是抑制遷移和侵襲，調(diào)控 EMT 進(jìn)程及 FAK/ERK 等信號(hào)軸；三是逆轉(zhuǎn)化療耐藥并抑制癌干性，下調(diào) CD44、ALDH1 等干細(xì)胞相關(guān)標(biāo)志物，提高吉西他濱等藥物的敏感性；四是抑制血管生成并改善腫瘤免疫微環(huán)境。此外，部分天然活性小分子通過結(jié)構(gòu)修飾或納米遞送體系顯著改善了體內(nèi)穩(wěn)定性與生物利用度。綜上，天然活性小分子具有多通路協(xié)同抗胰腺癌的獨(dú)特優(yōu)勢(shì)，未來應(yīng)結(jié)合多組學(xué)分析、網(wǎng)絡(luò)藥理學(xué)及先進(jìn)遞送技術(shù)，進(jìn)一步明確關(guān)鍵作用靶點(diǎn)，推動(dòng)其向臨床轉(zhuǎn)化應(yīng)用。
關(guān)鍵詞：胰腺癌；天然活性小分子；抗腫瘤機(jī)制；腫瘤轉(zhuǎn)移；耐藥性；腫瘤微環(huán)境
中圖分類號(hào)：O629 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0009-09
DOI：10.13822/j.cnki.hxsj.2025.0276
Research Progress on Natural Active Small Molecules in the Treatment of Pancreatic Cancer Li Hao-yang, Zhao Run-li, Liu Meng-xiang, Meng Lin, Zhao Yu, Han Chao* (School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing 210000, China)
Abstract: Pancreatic cancer is characterized by an insidious onset, rapid progression, early metastasis, and pronounced chemoresistance, resulting in an extremely poor prognosis. Current therapeutic strategies, mainly based on gemcitabine, provide limited clinical benefit, highlighting the urgent need for novel treatment approaches. Natural product-derived bioactive small molecules, with their structural diversity and multi-target properties, have attracted increasing attention in pancreatic cancer research. In this review, recent studies were systematically retrieved and summarized. According to chemical structure and biological origin, natural bioactive small molecules are classified into alkaloids, flavonoids, terpenoids, saponins, as well as compounds derived from microorganisms and marine organisms. Their pharmacological activities and underlying mechanisms against pancreatic cancer in vitro and in vivo are comprehensively discussed. Accumulating evidence indicates that these compounds exert anti-pancreatic cancer effects through multiple pathways: (1) inhibiting cell proliferation and inducing apoptosis by blocking the PI3K/AKT, MAPK, NF-κB, and related signaling pathways; (2) suppressing migration and invasion by regulating epithelial?mesenchymal transition (EMT) and FAK/ERK signaling; (3) reversing chemoresistance and attenuating cancer stemness by downregulating stem cell-associated markers such as CD44 and ALDH1, thereby enhancing sensitivity to gemcitabine; and (4) inhibiting angiogenesis and modulating the tumor microenvironment. Furthermore, structural modification and nano-delivery systems have been shown to significantly improve the in vivo efficacy and bioavailability of certain compounds. Overall, natural bioactive small molecules exhibit great potential as multi-pathway therapeutic agents against pancreatic cancer. Future studies integrating multi-omics, network pharmacology, and advanced delivery technologies are warranted to identify key targets and promote clinical translation.
Keywords: pancreatic cancer; natural bioactive small molecules; antitumor mechanisms; metastasis; chemoresistance; tumor microenvironment
有機(jī)小分子催化不對(duì)稱Aldol反應(yīng)的研究進(jìn)展
王宇1,2，羅倩婷1,2，何華鋒*1,2，秦緒隆*1,2
（1. 山東第一醫(yī)科大學(xué)（山東省科學(xué)院） 藥學(xué)院（藥物研究所），山東 濟(jì)南 271016；
2. 濟(jì)寧醫(yī)學(xué)院 藥學(xué)院，山東 日照 276826）
摘要：不對(duì)稱催化已發(fā)展成為有機(jī)合成中一種極具影響力的手段，為構(gòu)建復(fù)雜手性分子提供了多樣而高效的轉(zhuǎn)化路徑。按照催化劑來源和特征，可將不對(duì)稱催化大致分為酶催化、過渡金屬催化和有機(jī)小分子催化3大類。其中，有機(jī)小分子催化劑具有分子量小、結(jié)構(gòu)可設(shè)計(jì)性強(qiáng)、穩(wěn)定性高以及環(huán)境友好等優(yōu)勢(shì)，能夠在溫和條件下高效構(gòu)建具有挑戰(zhàn)性的手性碳?碳鍵，在可持續(xù)合成領(lǐng)域展現(xiàn)出獨(dú)特價(jià)值。不對(duì)稱Aldol反應(yīng)作為構(gòu)建β-羥基羰基化合物的經(jīng)典方法，廣泛用于天然產(chǎn)物、藥物分子及功能材料前體的合成。按照有機(jī)小分子催化劑骨架類型對(duì)近幾年（主要集中于2022年至今）有機(jī)小分子催化不對(duì)稱Aldol反應(yīng)的研究進(jìn)展進(jìn)行系統(tǒng)梳理，重點(diǎn)歸納了氨基酸及其衍生物、含硫脲結(jié)構(gòu)有機(jī)催化劑以及其他類型有機(jī)小分子催化劑在不對(duì)稱Aldol反應(yīng)中的應(yīng)用。針對(duì)代表性工作，從催化劑設(shè)計(jì)理念、反應(yīng)性能（收率、對(duì)映選擇性及底物適用性）、反應(yīng)介質(zhì)綠色化以及催化劑可回收利用等方面進(jìn)行總結(jié)與評(píng)述，并對(duì)存在的挑戰(zhàn)與發(fā)展方向進(jìn)行展望，以期為相關(guān)領(lǐng)域的深入研究提供參考與啟示。
關(guān)鍵字：不對(duì)稱催化；不對(duì)稱Aldol反應(yīng)；有機(jī)小分子催化劑；氨基酸；硫脲
中圖分類號(hào): O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0018-12
DOI：10.13822/j.cnki.hxsj.2025.0235
Recent Advances in Organocatalytic Asymmetric Aldol Reactions WANG Yu1,2, LUO Qian-Ting1,2, HE Hua-Feng*1,2, Qin Xu-Long*1,2(1. School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 271016, China; 2. School of Pharmacy, Jining Medical University, Rizhao 276826, China)
Abstract: Asymmetric catalysis has become a highly impactful strategy in organic synthesis, providing efficient and versatile tools for the construction of complex chiral molecules. According to catalyst origin and characteristics, asymmetric catalysis can be categorized into three major categories: enzymatic catalysis, transition-metal catalysis, and small-molecule organocatalysis. Among them, organocatalysts based on small organic molecules have attracted substantial attention due to their low molecular weight, high structural tunability, excellent stability, and environmentally friendly nature. They are particularly powerful for enabling the efficient formation of challenging chiral C?C bonds under mild conditions, thereby playing a key role in sustainable synthesis.. The asymmetric aldol reaction, a classical transformation for the synthesis of β-hydroxy carbonyl compounds, has become a powerful platform for the preparation of natural products, pharmaceuticals, and functional materials. In this review, we summarize recent advances (primarily from 2022 to the present) in small-molecule organocatalytic asymmetric aldol reactions, organized by catalyst structural classes. Emphasis is placed on amino acids and their derivatives, thiourea-based hydrogen-bonding organocatalysts, and other small organic catalysts including macrocycles, porous organic cages, covalent organic frameworks, and nanostructured systems. Representative studies are discussed with respect to catalyst design concepts, reaction efficiency and stereocontrol (yields, enantioselectivity, and diastereoselectivity), green reaction media, and catalyst recyclability. Challenges and future perspectives are also highlighted, aiming to offer insights and guidance for continued progress in organocatalytic asymmetric Aldol chemistry.
Keywords: asymmetric catalysis; aldol reaction; organocatalysts; amino acids; thiourea
【綜述與專論】
含蒽大環(huán)化合物的合成及其功能研究進(jìn)展
陳南英1，羅金榮2，黃春游1，陳志林1，盧遠(yuǎn)輝1，陶萍芳*1，黃國(guó)保*1
(1.玉林師范學(xué)院 a, 化學(xué)與食品科學(xué)學(xué)院, b. 廣西農(nóng)產(chǎn)資源化學(xué)與生物技術(shù)重點(diǎn)實(shí)驗(yàn)室, c 廣西高校桂東南特色農(nóng)產(chǎn)資源高效利用重點(diǎn)實(shí)驗(yàn)室, d. 電功能材料廣西高校工程研究中心，廣西 玉林 537000;
2. 玉林市檢驗(yàn)檢測(cè)研究院，廣西 玉林 537000)
摘要：超分子化學(xué)作為一門新興的熱點(diǎn)交叉學(xué)科，其發(fā)展總是伴隨著新型大環(huán)化合物的合成和應(yīng)用而前進(jìn)。含蒽大環(huán)化合物因其結(jié)合了蒽的優(yōu)異光物理性質(zhì)和可調(diào)的大環(huán)空腔，已成為超分子化學(xué)和材料科學(xué)的前沿領(lǐng)域。通過精妙的分子設(shè)計(jì)，研究人員已經(jīng)開發(fā)出多種合成策略，并探索了其在分子識(shí)別、刺激響應(yīng)材料、光電器件和復(fù)雜組裝體等方面的廣泛應(yīng)用。蒽是一種經(jīng)典的芳香烴，因其具有較大的疏水剛性平面和較強(qiáng)的富電子共軛體系，使其較高的熒光量子產(chǎn)率，納秒水平的熒光壽命，高分辨的吸收以及良好的化學(xué)穩(wěn)定性。使其在有機(jī)合成，藥物分析以及細(xì)胞成像領(lǐng)域中展現(xiàn)出優(yōu)越的應(yīng)用前景。將蒽單元引入到大環(huán)化合物的骨架中，可以結(jié)合大環(huán)的主客體化學(xué)和蒽的功能特性，創(chuàng)造出具有獨(dú)特光學(xué)、電子和識(shí)別性能的新型功能材料。綜述了最近十年含蒽大環(huán)化合物的合成方法及其在分子識(shí)別和超分子催化中的最新研究進(jìn)展。以蒽為“砌塊”，深入挖掘蒽在大環(huán)結(jié)構(gòu)中所扮演的不可替代的角色，重點(diǎn)強(qiáng)調(diào)蒽在大環(huán)動(dòng)態(tài)化學(xué)中的獨(dú)特性，及其剛性平面在穩(wěn)定特定主客體復(fù)合物中的關(guān)鍵作用，為今后此類大環(huán)化合物的合成及應(yīng)用提供參考。
關(guān)鍵詞：蒽; 大環(huán)化合物; 合成; 功能性; 分子識(shí)別
中圖分類號(hào)：O626 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0030-11
DOI：10.13822/j.cnki.hxsj.2025.0248
Recent Progress on the Synthesis and Function of Macrocyclic Compounds Based on Anthracene CHEN Nan-ying 1, LUO Jin-rong 2, HUANG Chun-you1, CHEN Zhi-lin1, LU Yuan-hui1, TAO Ping-fang*1, HUANG Guo-bao* 1(1a. Yulin Normal University, 1b. Guangxi Key Laboratory of Agricultural Resources Chemistry and Biotechnology, 1c. Guangxi Colleges and Universities Key Laboratory of Efficient Utilization of Special Resources in Southeast Guangxi, 1d. University Engineering Research Center of Electrical Functional Materials, Yulin 537000, China;2. Yulin Municipal Inspection and Testing Research Institute, Yulin 537000, China)
Abstract：Supramolecular chemistry, as an emerging and interdisciplinary field of great interest, has always advanced in tandem with the synthesis and application of novel macrocycles. Anthracene-incorporated macrocyclic compounds, which combine the excellent photophysical properties of anthracene with tunable macrocyclic cavities, have become a frontier in supramolecular chemistry and materials science. Through sophisticated molecular design, researchers have developed diverse synthetic strategies and explored their broad applications in molecular recognition, stimuli-responsive materials, optoelectronic devices, and complex assemblies. Anthracene, a classic aromatic hydrocarbon, possesses a large, rigid, hydrophobic plane and a strong electron-rich conjugated system. These features endow it with a high fluorescence quantum yield, a nanosecond-scale fluorescence lifetime, well-resolved absorption spectra, and good chemical stability, making it highly promising for applications in organic synthesis, pharmaceutical analysis, and cellular imaging. Introducing anthracene units into macrocyclic frameworks effectively merges the host?guest chemistry of macrocycles with the functional characteristics of anthracene, leading to the creation of novel functional materials with unique optical, electronic, and recognition properties. This review summarizes the synthetic methods developed over the past decade (2015-2025) for anthracene-based macrocycles and recent advances in molecular recognition and supramolecular catalysis. By treating anthracene as a fundamental building block, we delve into its irreplaceable role in macrocyclic architectures, emphasizing its unique contribution to dynamic macrocyclic chemistry and the key function of its rigid plane in stabilizing specific host?guest complexes, thereby providing valuable insights for the future synthesis and application of such macrocyclic compounds.
Key words：anthracene; macrocyclic compounds; synthesis; functional properties; molecular recognition
【電化學(xué)與新能源】
石墨烯/Si/SiOx納米復(fù)合材料的制備與電化學(xué)性能研究
何方方1，毛艷華*2
（1. 河南應(yīng)用技術(shù)職業(yè)學(xué)院 河南開封 475000；2. 河南醫(yī)藥健康技師學(xué)院 河南 開封 475000）
摘要：研究探索了一種新的制備石墨烯/Si/SiOx（G/Si/SiOx）納米復(fù)合材料的策略。采用改進(jìn)的Hummers法制備氧化石墨烯（GO）懸浮液；通過原位溶膠-凝膠法，以三乙氧基硅烷為硅源，在酸性條件下與GO反應(yīng)制備HSQ/GO前驅(qū)體，隨后在H2/Ar的混合氣體環(huán)境下進(jìn)行熱還原處理。研究團(tuán)隊(duì)對(duì)這種納米復(fù)合材料的合成機(jī)制、晶體結(jié)構(gòu)與電化學(xué)性質(zhì)進(jìn)行了詳細(xì)的分析。所制備的復(fù)合材料擁有特殊的納米級(jí)結(jié)構(gòu)，不僅能夠有效應(yīng)對(duì)Si納米粒子在充放電循環(huán)中的體積膨脹問題，而且還為電子提供了快速的傳輸路徑。循環(huán)伏安測(cè)試顯示，G/Si/SiOx-2電極的氧化還原峰間距更小，極化程度更低，且循環(huán)過程中峰形更穩(wěn)定，體現(xiàn)出良好的電化學(xué)可逆性。當(dāng)這種復(fù)合材料被用作鋰離子電池的負(fù)極材料時(shí)，它表現(xiàn)出了高首次可逆容量、出色的倍率性能以及持久的循環(huán)穩(wěn)定性的特點(diǎn)，這些都是其卓越的儲(chǔ)鋰能力的體現(xiàn)。研究成功制備了結(jié)構(gòu)與性能協(xié)同優(yōu)化的G/Si/SiOx納米復(fù)合材料，其核心優(yōu)勢(shì)源于各組分的協(xié)同作用，石墨烯作為導(dǎo)電骨架與體積緩沖層，不僅提供了連續(xù)的電子傳輸通道，還有效緩解了 Si 充放電過程中的體積膨脹。此項(xiàng)研究不僅為石墨烯增強(qiáng)的納米金屬材料在能源存儲(chǔ)領(lǐng)域的運(yùn)用提供了堅(jiān)實(shí)的理論與實(shí)驗(yàn)基礎(chǔ)，同時(shí)也為開發(fā)新一代具有高性能的鋰離子電池負(fù)極材料開辟了新的研究途徑和視角。
關(guān)鍵詞：石墨烯；納米復(fù)合材料；制備；電化學(xué)性能；鋰離子電池
中圖分類號(hào)：O69 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0041-08
DOI: 10.13822/j.cnki.hxsj.2025.0237
Preparation and Electrochemical Properties of Graphene/Si/SiOx Nanocomposites He Fang-fang1, Mao Yan-hua*2（1. Henan Technical Institute , Kaifeng 475000, China; 2. Henan Technician College of Medical and Health, Kaifeng 475000）
Abstract：A new strategy for preparing graphene/Si/SiOx (G/Si/SiOx) nanocomposites is explored. A graphene oxide (GO) suspension was prepared using an improved Hummers method; an HSQ/GO precursor was prepared via an in situ sol?gel method, with triethoxysilane as the silicon source reacting with GO under acidic conditions, and was subsequently thermally reduced in an H2/Ar mixed gas environment. The research team conducted a detailed analysis of the synthesis mechanism, crystal structure, and electrochemical properties of this nanocomposite material. The prepared composite material has a unique nanoscale structure, which not only effectively addresses the volume expansion problem of Si nanoparticles during charge-discharge cycles, but also provides fast electron transmission path. Cyclic voltammetry tests showed that the oxidation-reduction peak spacing and polarization degree of the G/Si/SiOx-2 electrode were smaller, and the peak shape was more stable during the cycling process, demonstrating good electrochemical reversibility. When this composite material was used as the negative electrode material for lithium-ion batteries, it exhibited high initial reversible capacity, excellent rate performance, and long-term cycling stability, all of which reflect its outstanding lithium storage capacity. A G/Si/SiOx nanocomposite material with synergistically optimized structure and performance was successfully prepared. Its core advantage lies in the synergistic effect of its component. Graphene, as a conductive skeleton and volume buffer layer, not only provides a continuous electron transfer channel, but also effectively alleviates the volume expansion of Si during charge-discharge processes. This study not only provides a solid theoretical and experimental foundation for the application of graphene reinforced nanometal materials in the field of energy storage, but also opens up new research avenues and perspectives for the development of a next-generation of high-performance lithium-ion battery negative electrode materials.
Key words: graphene; nanocomposite materials; preparation; electrochemical performance; lithium-ion battery
【化學(xué)品與環(huán)境】
固相萃取-高效液相色譜-串聯(lián)質(zhì)譜聯(lián)用法測(cè)定飲用水中17種氟喹諾酮類抗生素
李勝生*，高緒安，林慶文
(安徽省地質(zhì)實(shí)驗(yàn)研究所，安徽 合肥 230001)
摘要：建立了固相萃取-高效液相色譜-串聯(lián)質(zhì)譜聯(lián)用法（SPE-HPLC-MS/MS）同時(shí)測(cè)定飲用水中17種氟喹諾酮類抗生素的分析方法。水樣經(jīng)0.45 μm濾膜過濾后，采用HLB固相萃取柱富集，V（甲酸）：V（甲醇）=1:1000溶液洗脫，氮吹濃縮后進(jìn)行HPLC-MS/MS分析。色譜分離采用BEH C18柱（100 mm×2.1 mm，2.7 μm），以0.1%甲酸水溶液-甲醇為流動(dòng)相進(jìn)行梯度洗脫，質(zhì)譜采用電噴霧正離子源（ESI+）和多反應(yīng)監(jiān)測(cè)（MRM）模式。通過系統(tǒng)優(yōu)化色譜條件和質(zhì)譜參數(shù)，獲得了最佳的分離效果和檢測(cè)靈敏度。結(jié)果表明，17種目標(biāo)化合物在0.5~200 μg/L范圍內(nèi)線性關(guān)系良好（r2>0.995），檢出限為0.08~0.35 ng/L，定量限為0.25~1.15 ng/L。在低、中、高 3個(gè)加標(biāo)水平下，方法回收率為82.3%~108.5%，日內(nèi)和日間相對(duì)標(biāo)準(zhǔn)偏差（RSD）分別小于6.2%和8.7%。方法成功應(yīng)用于50份實(shí)際飲用水樣品的檢測(cè)，檢出率為18%，為飲用水中氟喹諾酮類抗生素的監(jiān)測(cè)和風(fēng)險(xiǎn)評(píng)估提供了可靠的技術(shù)支撐。
關(guān)鍵詞： 氟喹諾酮類抗生素；固相萃??；高效液相色譜-串聯(lián)質(zhì)譜；飲用水；痕量檢測(cè)
中圖分類號(hào)：O657 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0049-09
DOI：10.13822/j.cnki.hxsj.2025.0242
Determination of 17 Fluoroquinolone Antibiotics in Drinking Water by Solid Phase Extraction-High Performance Liquid Chromatography-Tandem Mass Spectrometry LI Sheng-sheng*, GAO Xu-an, Lin Qing-wen (Anhui Institute of Geological Experiment, Hefei 230001, China)
Abstract: A solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry (SPE-HPLC-MS/ MS) method was developed for simultaneous determination of 17 fluoroquinolone antibiotics in drinking water. Water samples were filtered through 0.45 μm membrane, enriched using an HLB solid phase extraction cartridge, eluted with V(formic acid):V(methanol)=1:1000 solution, concentrated by nitrogen, and analyzed by HPLC-MS/MS. Chromatographic separation was performed on a BEH C18 column (100 mm×2.1 mm, 2.7 μm) with gradient elution with 0.1% formic acid aqueous solution and methanol as mobile phases. Mass spectrometry detection employed electrospray positive ionization (ESI+) and multiple reaction monitoring (MRM) mode. Systematic optimization of chromatographic conditions (mobile phase composition, column temperature, flow rate) and mass spectrometry parameters (desolvation temperature, capillary voltage, cone voltage) achieved optimal separation and detection sensitivity. The results showed that all 17 target compounds exhibited good linearity in the range of 0.5-200 μg/L (r2>0.995), with detection limits of 0.08-0.35 ng/L and quantification limits of 0.25-1.15 ng/L. Method recoveries at low, medium and high spiking levels ranged from 82.3% to 108.5%, with intra-day and inter-day relative standard deviations (RSDs) below 6.2% and 8.7%, respectively. The method was applied to 50 actual drinking water samples with a detection rate of 18%, primarily detecting norfloxacin, ciprofloxacin and enrofloxacin. This method provides reliable technical support for monitoring and risk assessment of fluoroquinolone antibiotics in drinking water.
Keywords: fluoroquinolone antibiotics; solid phase extraction; HPLC-MS/MS; drinking water; trace detection
QuEChERS-超高相液相色譜-串聯(lián)質(zhì)譜法測(cè)定果蔬中38種農(nóng)藥殘留
李增明，馬春光*，李玉環(huán)*，甘瑛琳，楊增亮
（西寧市疾病預(yù)防控制中心 青海西寧 810000）
摘要：建立了一種同時(shí)快速測(cè)定果蔬中38種農(nóng)藥殘留的分析方法，即基于QuEChERS的分散固相萃取結(jié)合超高效液相色譜-串聯(lián)質(zhì)譜（UPLC-MS/MS）測(cè)定。該方法以氨基化多壁碳納米管作為核心凈化材料。蔬菜水果樣品經(jīng)過均質(zhì)用10 mL乙腈震蕩提取10 min，離心提取上清液后用改進(jìn)的QuEChERS（氨基化多壁碳納米管為凈化試劑）凈化方法凈化，經(jīng)濃縮定容后的提取液，采用 Waters ACQUITY UPLC BEH C18 色譜柱進(jìn)行分離，在電噴霧正離子 (ESI+) 模式與多反應(yīng)監(jiān)測(cè) (MRM) 條件下進(jìn)行電離與信號(hào)采集，并基于基質(zhì)匹配標(biāo)準(zhǔn)曲線外標(biāo)法進(jìn)行定量。結(jié)果表明：38種農(nóng)藥殘留在1~300 μg/kg的線性范圍內(nèi)有良好線性關(guān)系（R2>0.991）。方法的檢出限為0.001~0.003 mg/kg，定量限為0.003~0.009 mg/kg?？瞻准訕?biāo)樣品在20、50 和100 μg/ kg 3個(gè)濃度水平時(shí)，38種農(nóng)藥殘留平均回收率為63.3%~108.1%，相對(duì)標(biāo)準(zhǔn)偏差為1.20%~14.0%（n=8）。該方法快捷、重現(xiàn)性好、準(zhǔn)確度高，適合對(duì)果蔬中的多種農(nóng)藥痕量殘留進(jìn)行高效富集與靈敏檢測(cè)。
關(guān)鍵詞：農(nóng)藥殘留；QuEChERS；超高效液相色譜質(zhì)譜聯(lián)用；氨基化多壁碳納米管；果蔬
中圖分類號(hào)：O65 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283(2026)02-0058-08
DOI：10.13822/j.cnki.hxsj.2025.0240
Determination of 38 Pesticide Residues in Fruits and Vegetables by QuEChERS-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry LI Zeng-Ming, MA Chun-guang*, LI Yu-huan*, GAN Ying-ling, YANG Zeng-liang (Xining Center for Disease Control and Prevention, Xining 810000, China)
Abstract: This study established a rapid analytical method for the simultaneous determination of 38 pesticide residues in fruits and vegetables. The method is based on a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) dispersive solid-phase extraction (d-SPE) cleanup procedure coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Aminated multi-walled carbon nanotubes (NH?-MWCNTs) were employed as the primary purification material. Homogenized samples were extracted with 10 mL of acetonitrile by vortexing for 10 min. The supernatant, obtained after centrifugation, was purified using the improved QuEChERS method with NH?-MWCNTs. The purified extract was concentrated and reconstituted before separation on a Waters ACQUITY UPLC BEH C18 column. Detection was performed under electrospray ionization positive mode (ESI+) with multiple reaction monitoring (MRM). Quantification was achieved using a matrix-matched standard calibration curve with external standard method. The results demonstrated good linearity for all 38 pesticides in the range of 1-300 μg/kg (R2 > 0.991). The limits of detection (LOD) and quantification (LOQ) ranged from 0.001 to 0.003 mg/kg and 0.003 to 0.009 mg/kg, respectively. For blank samples spiked at three concentration levels (20, 50, and 100 μg/kg), the average recoveries for the 38 pesticides ranged from 63.3% to 108.1%, with relative standard deviations (RSD, n=8) between 1.20% and 14.0%. In conclusion, the developed method is rapid, reproducible, and accurate, suitable for the efficient enrichment and sensitive detection of multiple trace pesticide residues in fruits and vegetables.
Key words: pesticide residue; QuEChERS; ultra-performance liquid chromatography-mass spectrometry; aminated multi-walled carbon nanotubes; fruits and vegetables
【分析與測(cè)試】
衍生-HPLC法同時(shí)檢測(cè)反應(yīng)液中丙酮酸和丙酮酸乙酯的含量
董明燕，王艷，趙磊，馮棋?，高愛紅，岳濤*
（青島科技大學(xué)山東化工研究院，山東濟(jì)南 250014）
摘要：建立了衍生-高效液相色譜（HPLC）法同時(shí)測(cè)定丙酮酸反應(yīng)液中丙酮酸和丙酮酸乙酯含量的分析方法。用抗壞血酸（VC）淬滅樣品溶液中過氧化氫，用2,4-二硝基苯肼（DNPH）衍生丙酮酸和丙酮酸乙酯，并考察了淬滅劑（VC）、鹽酸溶液、衍生溶液、衍生溫度與時(shí)間等因素對(duì)衍生試驗(yàn)的影響。優(yōu)化后的色譜條件為：以C18柱為分析柱，以0.1%磷酸溶液和乙腈為流動(dòng)相，梯度洗脫方式，檢測(cè)波長(zhǎng)為360 nm，以外標(biāo)法定量。結(jié)果表明：丙酮酸和丙酮酸乙酯衍生物的色譜峰與其它色譜峰的分離度＞2.0，衍生劑、雜質(zhì)與溶劑均不干擾目標(biāo)物測(cè)定，方法的專屬性良好；在4.50~45.00 mg/L濃度范圍內(nèi)，丙酮酸和丙酮酸乙酯衍生物線性關(guān)系良好，相關(guān)系數(shù)＞0.9990；檢出限分別為0.00336和0.00387 mg/L，定量限分別為0.0112和0.0129 mg/L；3批次樣品的精密度檢測(cè)結(jié)果的相對(duì)標(biāo)準(zhǔn)偏差（RSD）值均小于1.5%（n=6），加標(biāo)回收率范圍分別為99.79%~101.31%與98.93%~99.45%；在室溫下放置下48 h，丙酮酸與丙酮酸乙酯衍生物的峰面積的RSD＜1.0%，樣品溶液穩(wěn)定性良好。建立的方法前處理操作簡(jiǎn)單，檢測(cè)速度快與準(zhǔn)確度高，可用于丙酮酸制備過程中各階段反應(yīng)情況的反應(yīng)監(jiān)控和產(chǎn)率評(píng)估，為工藝優(yōu)化與生產(chǎn)提供數(shù)據(jù)支撐。
關(guān)鍵詞：丙酮酸乙酯；丙酮酸；2,4-二硝基苯肼（DNPH）；衍生-HPLC法；抗壞血酸
中圖分類號(hào)：O65 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0066-07
DOI：10.13822/j.cnki.hxsj.2025.0241
Simultaneous Detection of Pyruvate and Ethyl PyruvateContent by Derivatization -HPLC DONG Ming-yan, WANG Yan, ZHAO Lei, FENG Qi-yun, GAO Ai-hong, YUE Tao*(Shandong Chemical Technology Academy, Qingdao University of Science & Technology, Jinan 250014, China)
Abstract：The derivatization HPLC method was established for the simultaneous detection of pyruvate and ethyl pyruvate in a pyruvate reaction solution. Hydrogen peroxide in the sample solution was quenched with ascorbic acid (VC). Pyruvate and ethyl pyruvate were derived with 2,4-dinitrophenylhydrazine (DNPH). The effects of the quenching agent (VC), hydrochloric acid concentration, derivatization reagent, derivatization temperature, and time on the derivatization reaction were investigated. The optimized chromatographic conditions were as following: a C18 column was used with 0.1% phosphoric acid solution and acetonitrile as the mobile phase under gradient elution. The detection wavelength was set at 360 nm, and quantification was performed using external standard method. The results showed that the chromatographic peaks of pyruvate and ethyl pyruvate derivatives were well separated from adjacent impurities with a resolution greater than 2.0. The derivatization reagent, impurities, and solvents did not interfere with the determination of the target compounds, indicating good specificity. Within the concentration range of 4.50~45.00 mg/L, good linear relationships were obtained for both pyruvate and ethyl pyruvate derivatives, with correlation coefficients greater than 0.9990. The detection limits were 0.00336 and 0.00387 mg/L, respectively, and the quantification limits were 0.0112 mg/L and 0.0129 mg/L, respectively. The relative standard deviation (RSD) values obtained from precision test results of three batches of samples were all less than 1.5% (n=6). The spiked recovery rates ranged from 99.79% to 101.31% for pyruvate and from 98.93% to 99.45% for ethyl pyruvate. After being placed at room temperature for 48 hours, the RSD of the peak area of pyruvate and ethyl pyruvate derivatives were less than 1.0%, indicating good stability of the sample solutions. This method features simple pretreatment, rapid analysis and high accuracy. It is suitable for reaction monitoring and yield evaluation at different stages of the pyruvate preparation process, providing reliable data support for process optimization and production.
Key words：ethyl pyruvate; pyruvic acid; 2, 4-dinitrophenylhydrazine (DNPH); derivatization -HPLC method; ascorbic acid
均一黃芪多糖APS-1a的制備與結(jié)構(gòu)表征
武延慧，雷子瑩，張瑜，趙生婷，王嘉蕾，韓毅麗*，賀潤(rùn)麗*
（山西中醫(yī)藥大學(xué)中藥食品工程學(xué)院，晉中 030619）
摘要：從黃芪中制備具有潛在免疫調(diào)節(jié)活性的均一多糖組分，并系統(tǒng)解析其結(jié)構(gòu)特征。采用透析法初步分離低分子量組分，依次利用離子交換纖維素（DEAE-52）、葡聚糖凝膠G-50（Sephadex G-50）柱分級(jí)純化具有潛在增強(qiáng)免疫活性的黃芪多糖。采用凝膠滲透色譜-多角度激光光散射聯(lián)用技術(shù)（GPC-MALLS）測(cè)定其分子量與溶液構(gòu)象；通過離子色譜分析其單糖組成；利用傅里葉變換紅外光譜（FT-IR）和核磁共振波譜（NMR）解析其糖苷鍵類型與官能團(tuán)修飾；并借助掃描電子顯微鏡（SEM）觀察其微觀形貌。結(jié)果表明，分離純化得到一個(gè)重均分子量為3.38 kDa、聚合物分散性指數(shù)（PDI）為1.18、純度為99.3%的多糖組分APS-1a，核心結(jié)構(gòu)為β-糖苷鍵連接的葡萄糖和半乳糖組成的吡喃多糖骨架，并帶有O-乙?；揎?/span>。溶液構(gòu)象分析顯示其在溶液中以柔性無規(guī)線團(tuán)形態(tài)存在，而固態(tài)下可觀察到自組裝形成的聚集體。進(jìn)一步確認(rèn)了具有潛在增強(qiáng)免疫活性黃芪多糖的結(jié)構(gòu)特征，為深入研究黃芪多糖的免疫活性構(gòu)效關(guān)系提供了理想的模型分子及相關(guān)制劑開發(fā)奠定了堅(jiān)實(shí)的物質(zhì)基礎(chǔ)與技術(shù)支持。
關(guān)鍵詞：黃芪；均一多糖；純化；結(jié)構(gòu)表征；自組裝
中圖分類號(hào)：O629 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0073-08
DOI：10.13822/j.cnki.hxsj.2025.0285
Preparation and Structural Characterization of Uniform Astragalus Polysaccharide APS-1a
WU Yan-hui, LEI Zi-ying, ZHANG Yu, ZHAO Sheng-ting, WANG Jia-lei, Han Yi-li*,HE Run-li* (School of Traditional Chinese Medicine Food Engineering, Shanxi University of Chinese Medicine, Jinzhong 030619, China)
Abstract: This study aimed to prepare a homogeneous Astragalus membranaceus polysaccharide fraction from Astragalus membranaceus with potential immunomodulatory activity and to systematically characterize its structural properties. The crude Astragalus membranaceus polysaccharides were initially extracted and subjected to dialysis for the preliminary isolation of low-molecular-weight components. Subsequently, a sequential purification strategy was employed, involving ion-exchange chromatography on a DEAE-52 cellulose column followed by size-exclusion chromatography on a Sephadex G-50 gel column, to obtain the target Astragalus membranaceus polysaccharide fraction. The molecular weight parameters and solution conformation were precisely determined using gel permeation chromatography coupled with multi-angle laser light scattering (GPC-MALLS). The monosaccharide composition was quantified through high-performance ion chromatography. Detailed structural insights into glycosidic linkage types and functional group modifications were acquired by Fourier transform infrared spectroscopy (FT-IR) and comprehensive nuclear magnetic resonance (NMR) spectroscopy, including 1H and 13C NMR. Furthermore, the morphological features in the solid state were examined using scanning electron microscopy (SEM). The results demonstrated the successful isolation of a polysaccharide fraction, designated APS-1a. It was characterized by a weight-average molecular weight (Mw) of 3.38 kDa, a narrow polymer dispersity index (PDI) of 1.18, and a high purity of 99.3%. Structural analysis revealed that APS-1a possesses a core backbone composed of β-glycosidically linked glucose and galactopyranose residues. Notably, the structure was found to be modified with O-acetyl groups. Conformational analysis in solution indicated that APS-1a adopts a flexible random coil architecture. In contrast, SEM observations revealed its tendency to form self-assembled supramolecular aggregates in the dried, solid state. In conclusion, these findings further clarify the structural features of the Astragalus membranaceus polysaccharide with potential immunoenhancing activity, providing an ideal model molecule for in-depth investigation of the structure-activity relationship of Astragalus membranaceus Polysaccharide and laying a solid material foundation and technical support for the development of related formulations.
Key words: Astragalus membranaceus; homogeneous polysaccharide; purification; structural characterization; self-assembly
【標(biāo)準(zhǔn)物質(zhì)與標(biāo)準(zhǔn)品】
空氣中二氧化碳同位素標(biāo)準(zhǔn)物質(zhì)研制
陳歡歡*，逯海，邢騰，任同祥，蔡瑋，趙博
（中國(guó)計(jì)量科學(xué)研究院，北京 100029)
摘要：實(shí)施節(jié)能減排政策和計(jì)算碳匯需要區(qū)分不同來源的二氧化碳，碳同位素測(cè)定已成為追溯二氧化碳來源的重要手段。高準(zhǔn)確度的二氧化碳同位素標(biāo)準(zhǔn)物質(zhì)可用于校正測(cè)量?jī)x器，是保證二氧化碳測(cè)量結(jié)果準(zhǔn)確性和可比性的物質(zhì)基礎(chǔ)。這篇文章主要介紹了空氣中二氧化碳同位素標(biāo)準(zhǔn)物質(zhì)的研制過程。該氣體同位素標(biāo)準(zhǔn)物質(zhì)采用重量法制備，分裝于380 mL的鋁合金氣瓶中，瓶?jī)?nèi)壓力為5.0 MPa。對(duì)所研制的氣體同位素標(biāo)準(zhǔn)物質(zhì)進(jìn)行均勻性檢驗(yàn)，方差檢驗(yàn)證實(shí)該標(biāo)準(zhǔn)物質(zhì)均勻性良好。對(duì)該標(biāo)準(zhǔn)物質(zhì)進(jìn)行隨時(shí)間和壓力變化的穩(wěn)定性檢驗(yàn)。分別在不同的氣瓶壓力條件下和12個(gè)月內(nèi)進(jìn)行量值考察，標(biāo)準(zhǔn)物質(zhì)量值在統(tǒng)計(jì)學(xué)上沒有明顯變化，穩(wěn)定性良好。通過GasBench Ⅱ-連續(xù)流穩(wěn)定同位素質(zhì)譜儀聯(lián)用分析法（GasBench Ⅱ-IRMS）進(jìn)行定值，標(biāo)準(zhǔn)值的不確定度重復(fù)考慮了均勻性評(píng)估、穩(wěn)定性評(píng)估、定值過程等。最終，空氣中二氧化碳同位素標(biāo)準(zhǔn)物質(zhì)量值為δ13C為-20.926 ‰，不確定度為0.256 ‰（k=2）。所研制的二氧化碳同位素標(biāo)準(zhǔn)物質(zhì)可以為空氣中二氧化碳中碳同位素的檢測(cè)提供量值溯源標(biāo)準(zhǔn)，為“雙碳”戰(zhàn)略提供計(jì)量基礎(chǔ)和技術(shù)支撐。
關(guān)鍵詞：碳同位素；氣體標(biāo)準(zhǔn)物質(zhì)；二氧化碳；同位素質(zhì)譜法；碳計(jì)量
中圖分類號(hào)：TB99；O659 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0081-07
DOI: 10.13822/j.cnki.hxsj.2025.0146
Development of Carbon Dioxide Isotope Reference Material in Air CHEN Huan-huan*, LU Hai, XING Teng, REN Tong-xiang, CAI Wei, ZHAO Bo (National Institute of Metrology, Beijing 100029, China)
Abstract: The implementation of energy conservation and emission reduction policies, as well as carbon sink calculations, necessitate the classification of carbon dioxide emissions by their respective sources. Carbon isotope analysis has emerged as a critical method for tracing carbon dioxide sources. High-accuracy carbon dioxide isotopic reference materials serve as a critical foundation for calibrating measurement instruments and for the accuracy and comparability of carbon dioxide measurements. This study describes the development of reference materials for carbon dioxide isotopes in air. A gas-isotope reference material was developed using a gravimetric method. It was then divided into 380 mL aluminum alloy cylinders pressurized to 5.0 MPa. The homogeneity of the gas-isotope materials was tested: the F-value of the variance test was lower than the critical value, indicating that the reference material exhibited satisfactory homogeneity. The stabilities of the gas isotopes were also tested by measuring the quantity of gas isotope material at different cylinder pressures over a 12 month period, during which no statistically significant change was observed, indicating that the reference material exhibited excellent stability. The GasBench II-IRMS system was used to accurately quantify the reference material. The uncertainty of the reference material value incorporates comprehensive considerations of the homogeneity assessment, stability evaluation, and quantification process. Ultimately, the carbon isotope ratio (δ13C) in the carbon dioxide isotope reference material was -20.926 ‰ and the expanded uncertainty was 0.256 ‰ (k = 2). Carbon dioxide isotope reference materials establish metrological traceability standards for the detection of carbon isotopes in atmospheric carbon dioxide and provide the metrological foundation and technical support for the implementation of the "dual carbon" strategy.
Key words：carbon isotopes; gas reference material; carbon dioxide; isotope mass spectrometry; carbon metering
【合成與應(yīng)用】
氮雜環(huán)卡賓配合物的合成及其對(duì)芳（雜）基酯與芳（雜）硼酸Suzuki偶聯(lián)反應(yīng)的催化研究
羅茜佩，黃菲東，劉豐收，梁營(yíng)*
（廣東藥科大學(xué)醫(yī)藥化工學(xué)院，廣東中山 528458）
摘要：設(shè)計(jì)并合成了一種新型大位阻氮雜環(huán)卡賓鈀配合物C1，并將其成功應(yīng)用于（雜）芳基酯與（雜）芳硼酸的 Suzuki 偶聯(lián)反應(yīng)。該配合物通過構(gòu)建芳胺對(duì)位具有大位阻的配位環(huán)境，有效穩(wěn)定了反應(yīng)過程中關(guān)鍵的鈀活性物種，從而顯著提升了催化體系的反應(yīng)活性與穩(wěn)定性。在優(yōu)化的溫和反應(yīng)條件下（0.5 mol% 配合物C1、2.0 mmol K?PO?、4 mL V(THF):V(H?O)=1:3 混合溶劑，80 ℃，4 h），該催化體系表現(xiàn)出優(yōu)異的反應(yīng)效率和良好的操作兼容性。多種具有不同電子效應(yīng)和空間位阻特征的芳基酯底物，包括電子給體和電子吸收基取代的底物，均可與多種芳基或雜芳基硼酸順利發(fā)生交叉偶聯(lián)反應(yīng)，高效合成一系列二芳基酮及雜環(huán)芳基酮化合物，最高分離產(chǎn)率可達(dá) 98%。該體系在雜環(huán)?雜環(huán)偶聯(lián)反應(yīng)中同樣保持較高反應(yīng)活性，有效克服了傳統(tǒng)催化體系中常見的反應(yīng)效率不足和副反應(yīng)較多等問題。上述結(jié)果表明，該大位阻氮雜環(huán)卡賓鈀催化體系為惰性酯類底物的高效轉(zhuǎn)化提供了一種切實(shí)可行的催化策略，并為結(jié)構(gòu)多樣、功能化酮類分子的構(gòu)建提供了具有應(yīng)用潛力的合成新方法。
關(guān)鍵詞：氮雜環(huán)卡賓鈀配合物；Suzuki-Miyaura偶聯(lián)；芳基酯；雜環(huán)硼酸；二芳基酮
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0088-09
DOI：10.13822/j.cnki.hxsj.2025.0274
Synthesis of Nitrogen-Heterocyclic Carbene Complexes and Catalytic Study on the Suzuki Coupling Reaction of (Hetero) Aryl Esters and (Hetero) Arylboronic Acids LUO Qian-pei, Huang Fei-dong, LIU Feng-shou, LIANG Ying* (School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, ZhongShan 528458, China)
Abstract: A sterically demanding N-heterocyclic carbene palladium complex C1 was designed, synthesized and successfully applied to the Suzuki cross-coupling of (hetero)aryl esters with (hetero)aryl boronic acids. The catalyst features a highly congested coordination environment introduced by para-substituted arylamine moieties, which stabilizes key palladium species during the catalytic cycle,, thereby significantly enhancing both catalytic activity and stability. Under optimized mild reaction conditions (0.5 mol% complex C1, 2.0 mmol K3PO4, 4 mL V(THF):V(H?O)=1:3, 80 °C, 4 h), the catalytic system demonstrates efficient conversion and operational compatibility.. A wide range of aryl ester substrates bearing diverse electronic properties and steric profiles, including both electron-donating and electron-withdrawing substituents, readily undergo cross-coupling with various aryl and heteroaryl boronic acids to afford a series of diaryl ketones and heteroaryl ketones in high yields, with isolated yields of up to 98%. The catalytic system also maintains high activity in heteroaryl-heteroaryl coupling, overcoming common limitations of conventional catalytic systems such as low reactivity and competitive side reactions. These results demonstrate that the sterically demanding NHC-palladium catalyst provides a practical and efficient strategy for activating inert ester substrates and offers a valuable synthetic approach for the construction of structurally diverse and functionalized ketone compounds.
Keywords: N-heterocyclic carbene palladium complex; Suzuki-Miyaura coupling; aryl ester; (hetero)aryl boronic acid; biaryl ketone
香豆素類新型三重態(tài)光敏劑的合成
馬潔*1, 李瑩瑩1, 趙方銘1, 侯玉琦2, 尹彥冰1, 何錫鳳1
（1. 齊齊哈爾大學(xué) 化學(xué)與化學(xué)工程學(xué)院，黑龍江 齊齊哈爾 161006；
2. 大連理工大學(xué) 化工學(xué)院，遼寧 大連 116024）
摘要：三重態(tài)光敏劑被廣泛地應(yīng)用于光催化、光動(dòng)力治療等領(lǐng)域而備受關(guān)注。但是現(xiàn)有光敏劑獲得三重態(tài)的方式還存在一定的局限性，如：三重態(tài)的產(chǎn)生有賴于重原子效應(yīng)、引入具有高效系間竄越能力的自旋轉(zhuǎn)換單元或者利用電荷復(fù)合過程促進(jìn)系間竄越產(chǎn)生機(jī)理，獲得不含重原子的三重態(tài)光敏劑等。在激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移過程中，能夠通過系間竄越獲得cis-酮式結(jié)構(gòu)的三重激發(fā)態(tài)。將具有強(qiáng)可見光吸收能力的吸光團(tuán)，與傳統(tǒng)的具有cis-酮式三重激發(fā)態(tài)的染料結(jié)合，利用其光物理過程中產(chǎn)生的三重態(tài)，設(shè)計(jì)合成不含重原子的有機(jī)三重態(tài)光敏劑。通過共軛和非共軛兩種連接方式，制備了香豆素和2-(2-羥基苯基)苯并噻唑（HBT）的新型染料（B-1~B-4）。B-1在甲苯中出現(xiàn)雙發(fā)射，斯托克斯位移達(dá)到131 nm，這是激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移（ESIPT）的典型特征。其中，在B-1和B-4中均觀察到了三重激發(fā)態(tài)（τT = 20.1和50.8 μs），通過1,3-二苯基異苯并呋喃（DPBF）的光氧化反應(yīng)，證明了B-1和B-4均具有光敏化能力，且B-1的敏化能力高于B-4。
關(guān)鍵詞：香豆素；2-(2-羥基苯基)苯并噻唑；激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移；三重激發(fā)態(tài)
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：0258-3283（2026）02-0097-07
DOI：10.13822/j.cnki.hxsj.2025.0297
Synthesis of Novel Triplet Photosensitizers based on Coumarin MA Jie*1, LI Ying-ying1, ZHAO Fang-ming1, HOU Yu-qi2, YIN Yan-bing1, HE Xi-feng1 ( 1.College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China; 2. College of Chemical Engineering, Dalian University of Technology, Dalian 116024, China )
Abstract: Much attention has been focused on triplet photosensitizers due to their wide applications in photocatalysis and photodynamic therapy. However, conventional photosensitizers have some limitations in obtaining triplet excited state, which usually rely on the heavy atoms or the incorporation of spin converters with highly efficient intersystem crossing ability. In addition, spin?orbit charge-transfer intersystem crossing (SOCT-ISC) is an important strategy to acquire heavy atom-free triplet photosensitizers. Previous studies has shown that cis-ketone triplet exited states can be excited in the process of excited state intramolecular proton transfer (ESIPT). Therefore, by combining chromophores with strong visible-light absorption and traditional dyes capable of forming cis-ketone triplet excited states, heavy-atom-free organic triplet photosensitizers can be designed. The dyes of coumarin conjugated or non-conjugated with 2-(2-hydroxyphenyl)benzothiazole (HBT) (B-1-B-4) were prepared. B-1 showed dual emission in toluene and its Stokes shift was up to 131 nm, which is a typical characteristics of excited state intramolecular proton transfer. The triplet excited states were observed for B-1 and B-4 (tT = 20.1 ms and 50.8 μs, respectively). The photosensitizing abilities of B-1 and B-4 were confirmed by 1,3-diphenylisobenzofuran (DPBF) photooxidation experiments, demonstrating that B-1 exhibited higher photosensitizing efficiency compared to B-4.
Key words：coumarin; 2-(2-hydroxyphenyl)benzothiazole; excited state intramolecular proton transfer; triplet excited state
