2026年48（1）中英文摘要
【特約專題】
電化學免疫傳感器在腫瘤早診中的研究進展
趙靜1,2，鄺俊瑋1，郭子政1，尹磊1，王振宇*1,2
(1.大連理工大學 化工海洋與生命學院,遼寧 盤錦 124221；2.艾美誡信生物制藥有限公司,遼寧 大連 116600)
摘要：腫瘤早期診斷是提高患者生存率和改善預后的關鍵,但傳統方法存在檢出滯后、操作復雜等局限。電化學免疫傳感器結合免疫反應的特異性與電化學檢測的高靈敏性,為腫瘤標志物的痕量檢測(常低至皮摩爾-飛摩爾級)提供了新策略。系統梳理其在腫瘤早期診斷中的技術原理、信號放大策略及臨床應用,旨在推動臨床轉化。分析生物識別元件(如抗體、適配體)與信號轉導機制(無標記型如電化學阻抗譜、標記型如酶標記和納米材料標記),信號放大策略(酶催化級聯、納米材料介導、磁珠富集等)及納米材料創新應用(碳基材料如石墨烯/碳納米管、金屬基材料如鈀納米粒子/鐵氧化物、二維材料如MXene/二硫化鉬)。結果顯示,該類傳感器具有快速響應、低成本、易于微型化等優勢,在多癌種診斷中進展顯著,部分對肝癌、乳腺癌、結直腸癌等標志物的檢測限已達飛摩爾級,顯著提升早期診斷的靈敏度與特異性。但其仍面臨生物污染、穩定性不足及臨床驗證匱乏等挑戰,需深入研究以促進實際應用。
關鍵詞：電化學免疫傳感器；腫瘤早期診斷；腫瘤標志物；納米材料；信號放大
中圖分類號：O657 文獻標識碼：A 文章編號：0258-3283(2026)01-0001-11
DOI：10.13822/j.cnki.hxsj.2025.0239
Research Progress of Electrochemical Immunosensors in Early Diagnosis of Tumors ZHAO Jing1, 2, KUANG Jun-wei1,GUO Zi-zheng1, YIN Lei1, WANG Zhen-yu*1, 2 (1. School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin 124221, China；2. AIM Honesty Biopharmaceutical Co., Ltd.?, Dalian 116600, China)
Abstract: Early diagnosis of tumors is crucial for improving patient survival rates and prognosis,but traditional methods suffer from limitations such as delayed detection and complex procedures.Electrochemical immunosensors,which integrate the specificity of immune reactions with the high sensitivity of electrochemical detection,provide a promising strategy for trace detection of tumor markers (often as low as picomolar to femtomolar levels).This review systematically summarized the underlying principles,signal amplification strategies,and clinical applications of electrochemical immunosensors in early tumor diagnosis,aiming to promote clinical translation.In this review,biorecognition elements (e.g.,antibodies and aptamers) and signal transduction mechanisms (label-free methods such as electrochemical impedance spectroscopy,and labeled methods such as enzyme or nanomaterial labeling) were discussed in detail.Signal amplification strategies (e.g.,enzymatic catalytic cascades,nanomaterial-mediated methods,magnetic bead enrichment) were reviewed alongside innovative applications of nanomaterials,including carbon-based materials (e.g.,graphene,carbon nanotubes),metal-based materials (e.g.,palladium nanoparticles,iron oxides),and two-dimensional materials (e.g.,MXene/molybdenum disulfide).Results showed that such sensors have advantages including rapid response,low cost,and easy miniaturization,and have made significant progress in the diagnosis of multiple cancer types.For example,detection limits for biomarkers of liver,breast,and colorectal cancer have reached the femtomolar level,significantly improving the sensitivity and specificity of early diagnosis.However,challenges such as biofouling,limited stability,and insufficient clinical validation remain.Continued research is required to enhance their robustness and accelerate clinical implementation.
Key words：electrochemical immunosensor; early tumor diagnosis; tumor marker; nanomaterial; signal amplification
植物對新污染物的吸收與代謝研究進展
周豪，周慶華*
（浙江工業大學環境學院，浙江杭州 310014）
摘要：新污染物在環境多介質中的廣泛檢出已成為全球關注的焦點。植物作為生態系統的初級生產者,能夠從環境介質中吸收這些污染物,并通過食物鏈傳遞對生態系統和人類健康構成風險。現有報道主要關注新污染物的植物吸收或植物代謝單一過程,且對相關影響因素的系統闡述較為缺乏。基于此,系統綜述了植物對新污染物的吸收與代謝過程及其影響因素,旨在深入解析新污染物在植物中的歸趨行為。植物主要通過根吸收(被動擴散/主動轉運)和葉吸收(氣孔/角質層滲透)途徑吸收新污染物。植物吸收過程受植物特性(種類、根系分泌物、通道蛋白表達等)、污染物理化性質(極性、疏水性、分子大小等)及環境因素(土壤有機質、pH、溫度等)影響。新污染物進入植物體后,在代謝酶介導下發生代謝轉化反應,包括:Ⅰ相代謝(氧化、還原、水解、裂解等)、Ⅱ相代謝(與葡萄糖苷、谷胱甘肽、氨基酸等綴合)和Ⅲ相代謝(液泡或細胞壁隔離固定),最終生成水溶性更高、毒性更低的物質。植物代謝過程受植物特性(代謝酶、內源性物質等)和污染物化學結構(官能團類型、分子大小、空間構型等)影響。
關鍵詞：新污染物；植物吸收；植物代謝；理化性質；環境因素
中圖分類號：Q945.78、O6-1 文獻標識碼：A 文章編號：0258-3283(2026)01-0012-09
DOI：10.13822/j.cnki.hxsj.2025.0217
Advances in the Uptake and Metabolism of Emerging Contaminants in Plants ZHOU Hao，ZHOU Qing-hua*（College of Environment, Zhejiang University of Technology, Hangzhou 310014, China）
Abstract: The widespread occurrence of emerging contaminants (ECs) in multiple environmental media has become a global environmental concern.As primary producers in ecosystem,plants can absorb ECs from the surrounding environments and transfer them through the food chain,thereby posing potential risks to both ecosystems and human health.Previous studies have predominantly focused on either the uptake or the metabolism of ECs in plants,with limited systematic discussion of the influencing factors.Hence,this study comprehensively reviewed the uptake and metabolic processes of ECs in plants,as well as key factors affecting these processes,to provide a good understanding of the fate of ECs in plants.ECs are primarily taken up by roots (via passive diffusion or active transport) and leaves (via stomatal penetration or cuticular absorption).Plant uptake is influenced by plant traits (e.g.,species,root exudates,and channel protein expression),physicochemical properties of ECs (e.g.,polarity,hydrophobicity,and molecular size),and environmental factors (e.g.,soil organic matter,pH,and temperature).Once entering plants,ECs undergo enzyme-mediated metabolic transformations,including Phase Ⅰ metabolism (e.g.,oxidation,reduction,hydrolysis,and cleavage),Phase Ⅱ metabolism (conjugation with glucose,glutathione,amino acids),and Phase Ⅲ metabolism (compartmentalization in vacuoles or integration into cell walls).These processes convert ECs into more water-soluble and less toxic compounds.The metabolism process is affected by plant characteristics (e.g.,metabolic enzymes and endogenous substances) and the chemical structure of ECs (e.g.,functional groups,molecular size,and spatial configuration).
Key words: emerging contaminants; plant uptake; plant metabolism; physicochemical properties; environmental factors
用于識別抗腫瘤新藥A166的化學功能材料的開發
孫夢婷，王冬*，董林毅*
（天津醫科大學腫瘤醫院國家惡性腫瘤臨床醫學研究中心天津市惡性腫瘤臨床醫學研究中心天津市腫瘤防治重點實驗室，天津 300060）
摘要：A166 是一種靶向 HER2 的 ADC藥物，主要針對HER2陽性乳腺癌及其他HER2表達的實體瘤。用藥后的臨床藥物檢測對于臨床指導用藥來說至關重要，不僅可以優化給藥方案，以提高療效、減少毒副作用，還可以減少耐藥情況的產生。目前臨床血藥濃度監測（TDM）的主要方法包括免疫分析法、色譜法（如高效液相色譜法HPLC）以及新興的床旁檢測技術（如質譜法）。但是存在對操作人員要求高、價格昂貴、設備維護、步驟繁瑣等缺點。為了解決A166血液濃度監測的問題，創新性地提出了將硼酸與修飾羅丹明6G熒光素負載氧化石墨烯（HR6GGO）與硼酸親和導向表面印跡磁性納米顆粒（MIP-A166）相結合，用于藥物A166在體內的血藥濃度監測。經硼酸修飾并負載大量羅丹明6G熒光素的HR6GGO材料，可通過硼酸親和作用選擇性標記A166，實現熒光信號放大與輸出。成功制備了HRBGO和MIP-A166，通過實驗優化，得到的MIP-A166-HRBGO策略對A166的檢測具有超高靈敏度和優越的特異性。MIP-A166則借助硼酸親和分子印跡識別機制，對模板藥物表現出特異性選擇能力。MIP-A166偶聯HR6GG0的夾心檢測策略依托雙重硼酸親和協同作用，展現出普適性應用潛力，為臨床藥物監測以及指導用藥提供幫助。
關鍵詞：分子印跡聚合物；血藥濃度監測；A166；單抗藥物；雙硼酸親和協同作用
中圖分類號：O65 文獻標識碼：A 文章編號：0258-3283(2026)01-0021-07
DOI：10.13822/j.cnki.hxsj.2025.0199
Development of Chemical Functional Materials for Identifying New Antitumor Drug A166 SUN Meng-ting, WANG Dong*, DONG Lin-yi* (Tianjin Key Laboratory of Cancer Prevention and Therapy, Tianjin’s Clinical Research Center for Cancer, National Clinical Research Center for Cancer, Tianjin Medical University Cancer Institute & Hospital, Tianjin 300060, China)
Abstract: A166 is an ADC drug targeting HER2,mainly used for the treatment of HER2-positive breast cancer and other solid tumors expressing HER2.Clinical drug monitoring after administration is crucial for clinical medication guidance,as it can optimize the dosing regiments to enhance efficacy,minimize side effects,and reduce the development of drug resistance.Currently,the main methods for therapeutic drug monitoring (TDM) include immunoassay methods,chromatography methods (such as high-performance liquid chromatography HPLC),and emerging point-of-care technologies (such as mass spectrometry).However,these methods have several drawbacks,including the need for highly trained operators,high cost,equipment maintenance,and complex procedures.To address the challenge of monitoring A166 blood concentration,a novel strategy was proposed by combining boronic acid-modified rhodamine 6G-functionalized graphene oxide (HR6GGO) with a boronic acid-affinity molecularly imprinted magnetic nanoparticle (MIP-A166).The HR6GGO material,modified with borate and loaded with a large amount of rhodamine 6G fluorescent dye,can selectively label A166 through boronic acid affinity,achieving fluorescence signal amplification and output.HRBGO and MIP-A166 were successfully prepared and the MIP-A166-HRBGO strategy achieved extremely high sensitivity and excellent specificity for the detection of A166 after experimental optimization.MIP-A166 utilizes the boronic acid affinity molecular imprinting recognition mechanism,showing specific selectivity for the template drug.The sandwich detection strategy,based on the coupling of MIP-A166 with HR6GGO,relies the dual boronic acid affinity synergism,demonstrating board application potential and providing a promising tool for clinical drug monitoring and medication guidance.
Key words: molecularly imprinted polymer; serum concentration monitoring; A166; monoclonal antibody drugs; diboronic acid affinity cooperative effect
【功能材料】
構建高催化活性的BiVO4@Ag復合材料
蔡旭鵬，王月榮，蔡依辰，洪先健，郭少波，郭小華，季曉暉*
(陜西理工大學 化學與環境科學學院，陜西 漢中 723000)
摘要：針對釩酸鉍(BiVO4)光催化劑存在的載流子復合率高、表面反應動力學遲緩等問題,以球形BiVO4為基底,通過3種不同光化學還原方法(直接還原法、銀氨配合物-還原法、溴化鉀調控還原法)構建BiVO4@Ag-6%復合材料,系統探究不同負載方式對材料微觀結構及光催化性能的影響。利用透射電子顯微鏡(TEM)、X射線光電子能譜(XPS)、X射線衍射(XRD)、紫外-可見漫反射光譜(UV-Vis DRS)以及電化學測試等對復合材料的結構和性質進行了系統表征。實驗結果表明,通過溴化鉀調控還原法制備的目標材料具有較好催化活性。這是由于利用AgBr配合物緩釋Ag+機制,顯著優化了Ag納米顆粒(Ag NPs)的分散度及界面結合強度,其光催化降解Cr6+和羅丹明B(RhB)的活性最佳(Cr6+在20 min內完全降解,RhB降解效率較純BiVO4提升明顯)。結合表征分析,其優異性能歸因于Ag NPs的等離子體共振效應(SPR)和肖特基勢壘的協同作用,能夠有效抑制載流子復合,并加速界面電荷傳輸。
關鍵詞：BiVO4；銀納米顆粒（Ag NPs）；光催化降解；等離子體共振效應（SPR）；降解率
中圖分類號：O611.4 文獻標識碼：A 文章編號：0258-3283(2026)01-0028-08
DOI：10.13822/j.cnki.hxsj.2025.0253
Synthesis of Highly Active BiVO?@Ag Composites with Enhanced Catalytic Performance CAI Xu-peng, WANG Yue-rong, CAI Yi-chen, HONG Xian-jian, GUO Shao-bo, GUO Xiao-hua, JI Xiao-hui*( School of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong 723000, China)
Abstract：This study addressed the issues of high carrier recombination rates and sluggish surface reaction kinetics in bismuth vanadate (BiVO4) photocatalysts.Using spherical BiVO4 as the substrate,BiVO4@Ag-6% composite materials were constructed via three distinct photochemical reduction methods (direct reduction,silver-ammonia complex reduction,and potassium bromide-mediated reduction).The effects of different loading methods on the microstructure and photocatalytic performance of the materials were systematically investigated.The structure and properties of the composite materials were systematically characterized using transmission electron microscopy (TEM),X-ray photoelectron spectroscopy (XPS),X-ray diffraction (XRD),ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS),and electrochemical measurements.Experimental results indicated that the target material prepared via the potassium bromide-controlled reduction method exhibits superior catalytic activity.The AgBr complex-mediated Ag+ release mechanism significantly optimizes the dispersion and interfacial bonding strength of Ag nanoparticles (Ag NPs),resulting in optimal photocatalytic degradation activity for Cr6+ and Rhodamine B (RhB) with complete Cr6+ degradation within 20 min and a markedly enhanced RhB degradation efficiency compared to pure BiVO4.Characterization analysis attributes this superior performance to the synergistic effects of surface plasmon resonance (SPR) and the Schottky barrier in Ag NPs,which effectively suppressed carrier recombination and accelerate interfacial charge transport.
Key words：BiVO?; silver nanoparticles (Ag NPs); photocatalytic degradation; surface plasmon resonance (SPR)；degradation rate
基于便攜式熒光試紙條的水體抗生素比率熒光檢測方法研究
李鳳蘭*a，黃碧妃a，林澤彪a，黃文杰b
(福建警察學院 a.刑事科學技術系，b.偵查系，福州 福建 350007)
摘要：通過開發一種高靈敏、高選擇性的新方法,以應對水環境中抗生素污染對生態環境和人類健康造成的危害。采用一步法合成沸石咪唑酯-8(ZIF-8)材料,通過FT-IR、XRD、SEM、TEM、XPS等多種表征技術對其結構進行系統分析,構建基于比率熒光的左氧氟沙星(LFX)檢測傳感器。在ZIF-8濃度為25 μg/mL、pH為7.0、反應時間為5 min的最佳反應條件下,所制備傳感器對LFX的線性檢測范圍為1～80 μmol/L,檢出限達0.29 μmol/L;實際水樣檢測回收率98.27%～101.90%,RSD≤2.99%,與HPLC結果吻合良好;開發的智能手機便攜式試紙傳感器可實現10～100 μmol/L范圍內的實時檢測。該研究為ZIF-8基熒光傳感器的設計提供了新思路,建立了環境水體中痕量抗生素污染物的快速檢測新方法。
關鍵詞：ZIF-8；比率型；熒光傳感器；左氧氟沙星；熒光試紙
中圖分類號：O65 文獻標識碼：A 文章編號：0258-3283(2026)01-0036-07
DOI：10.13822/j.cnki.hxsj.2025.0214
Research on a Ratiometric Fluorescence Detection Method for Antibiotics in Water Based on Portable Fluorescent Test Strips Li Feng-lan*a, Huang Bi-feia, Lin Ze-biaoa, Huang Wen-jieb (a.Department of Criminal Science and Technology, b.Department of Criminal Investigation, Fujian Police College, Fuzhou, Fujian 350007, China)
Abstract： This study aims to develop a novel,highly sensitive and selective method to address the ecological and human health risks posed by antibiotic pollution in aquatic environments.Zeolitic imidazolate framework-8 (ZIF-8) was synthesized via a one-step method and systematically characterized using FT-IR,XRD,SEM,TEM,and XPS.A ratiometric fluorescence sensor was then constructed for the detection of levofloxacin (LFX).Under optimal conditions (ZIF-8 concentration:25 μg/mL,pH 7.0,reaction time:5 min),the sensor exhibited a linear detection range of 1～80 μmol/L for LFX,with a detection limit of 0.29 μmol/L.The recovery rate in real water samples was from 98.27% to 101.9%,with RSD≤2.99%,showing good agreement with HPLC results.Additionally,a smartphone-based portable test strip sensor was developed,enabling real-time detection in the range of 10～100 μmol/L.This study provides a new approach for designing ZIF-8-based fluorescence sensors and establishes a rapid detection method for trace antibiotic pollutants in environmental water.
Key words：ZIF-8; Ratiometric; Fluorescence sensor; Levofloxacin (LFX); Fluorescent test strip
【化學品與環境】
尿素-Na2CO3協同改性生物炭的表面自由基調控機制及PMS活化效能
馬紫朝*，董剛，劉伯渠，盧新生
（甘肅民族師范學院化學與生命科學學院，甘肅合作 747000）
摘要：為解決水體中難降解有機污染物的處理問題,治理環境污染,以苯胺為模型污染物,采用尿素與碳酸鈉共摻雜協同改性玉米芯生物炭,探究其表面自由基調控機制及過氧單硫酸鹽活化效能。實驗通過不同氮源、尿素摻量、碳酸鈉摻量及熱解溫度等條件的調控,制備改性生物炭,并對其自由基生成、苯胺去除效果、官能團及元素含量等進行分析。30%尿素的摻入對應的持久性自由基濃度為5.339×109 spins/g,顯著高于其他氮源。尿素摻量30%、碳酸鈉摻量40%時,持久性自由基濃度最高,苯胺去除效果最佳;持久性自由基濃度與苯胺去除效果為正相關。同時,熱解溫度從300 ℃上升至 900 ℃,生物炭C的含量從6.983%上升至53.256%,H含量上升后下降至1.169%,O含量下降至20.065%,N含量上升后下降,峰值為7.142%,金屬元素富集,其中Fe含量富集至9 258.477 mg/kg;此外改性生物炭的官能團逐漸減少,含氧官能團下降。持久性自由基、改性生物炭添加量是影響苯胺去除效果的關鍵因素,適當條件下最佳去除率可達97.6%。此外,500 ℃熱解溫度下制備的改性生物炭具有適中的孔隙結構和穩定的表面官能團,重復使用性能良好。尿素-碳酸鈉協同改性生物炭可有效調控表面自由基,顯著提升持久性自由基的活化效能,為難降解有機污染物的高效處理提供了新思路。
關鍵詞：有機污染物；生物炭；過氧單硫酸鹽；自由基；環境治理
中圖分類號：O69 文獻標識碼：A 文章編號：0258-3283(2026)01-0043-09
DOI：10.13822/j.cnki.hxsj.2025.0229
Surface Radical Regulation Mechanism and PMS Activation Efficiency of Urea-Na2CO3 Synergistically Modified Biochar MA Zi-chao*, DONG Gang, Liu Bo-qu, LU Xin-sheng(College of Chemistry and Life Sciences, Gansu Minzu Normal University, Cooperation, Hezuo 747000)
Abstract： To address the issue of treating refractory organic pollutants in water and to control environmental pollution,this study used aniline as a model pollutant and investigated the co-doping and synergistic modification of corn cob biochar with urea and sodium carbonate.The surface free radical regulation mechanism and the activation efficiency of peroxymonosulfate were explored.Modified biochar was prepared by varying nitrogen sources,urea dosage,sodium carbonate dosage and pyrolysis temperature,and analyzed for free radical generation,aniline removal efficiency,functional groups,and elemental composition.Incorporation of 30% urea resulted in a persistent free radical concentration of 5.339×109 spins/g,significantly higher than other nitrogen sources.When urea and sodium carbonate contents were 30% and 40%,respectively,the persistent free radical concentration and aniline removal efficiency were maximized,showing a positive correlation.As pyrolysis temperature increased from 300 to 900 ℃,the carbon content of biochar increased from 6.983% to 53.256%,hydrogen content initially increased and then decreased to 1.169%,oxygen content decreased to 20.065%,and nitrogen content peaked at 7.142%.Metal elements were enriched,with Fe concentration reaching 9 258.477 mg/kg.Functional groups in the modified biochar gradually decreased,especially oxygen-containing functional groups.Persistent free radicals and biochar the dosage were key factors affecting aniline removal,achieving an optimal removal rate of 97.6% under optimal conditions.Moreover,biochar prepared at 500 ℃ exhibited a moderate pore structure,stable surface functional groups,and good reusability.Urea-sodium carbonate synergistic modification effectively regulates surface free radicals,significantly enhance their activation efficiency,providing a new idea for the efficient treatment of refractory organic pollutants.
Key words：Organic pollutants; Biochar; Peroxymonosulfate; Free radicals; Environmental remediation
固定化漆酶纖維素納米晶復合水凝膠的制備及其除污性能的研究
舒士倡*,閆宏濤
(寧夏大學新華學院 工程與應用科學系，寧夏 銀川 750021)
摘要：水污染已經成為當今環境治理中的難題,不僅造成了巨大的經濟損失,更是危害到了人類的生產生活。其中難降解的酚類具有化學需氧量高、毒性大、穩定性強等特點,而且對微生物具有抑制作用,使得廢水處理過程具有挑戰性。采用傳統均相反應所用催化劑存在催化活性低、易產生污泥、不可重復使用等缺點。水凝膠具有獨特三維網狀結構,對廢水中污染物具有高去除率、高循環率,廣泛應用在廢水處理。而生物酶催化處理法具有催化效能高、反應條件溫和、對廢水質量及設備情況要求較低、可以重復使用等優點,使其在污水處理具有顯著優勢。因此,通過聚合反應將漆酶引入水凝膠三維網絡結構,通過纖維素納米晶調控水凝膠的滲透性能及力學性能,從而制備一種非均相水凝膠催化劑。研究各組分對水凝膠性能的影響,并分析漆酶纖維素納米晶水凝膠對4種典型有機酚類有機化合物的降解效率,并總結相關技術參數,為指導水凝膠基非均相催化劑提供技術指導。
關鍵詞：纖維素納米晶；水凝膠；固定化酶；有機酚降解；除污性能
中圖分類號：O69 文獻標識碼：A 文章編號：0258-3283(2026)01-0052-06
DOI：10.13822/j.cnki.hxsj.2025.0275
Preparation of Immobilized Laccase Cellulose Nanocrystal Composite Hydrogels and Their Decontamination Properties SHU Shi-chang, YAN Hong-tao (Department of Engineering and Applied Sciences, Xinhua College of Ningxia University, Yinchuan 750021, China)
Abstract：Water pollution has become a major challenge in contemporary environmental management,causing not only significant economic losses but also posing threats to human production and daily life.Among various pollutants,recalcitrant phenolic compounds are particular problematic due to their high chemical oxygen demand,high toxicity,and chemical stability.Furthermore,their inhibitory effects on microbial activity future increase the difficulty of wastewater treatment.Traditional homogeneous catalysts suffer from drawbacks such as low catalytic activity,sludge generation,and non-reusability.Hydrogels,featuring unique three-dimensional network structures,demonstrate high pollutant removal efficiency and excellent recyclability,and thus have been widely used in wastewater treatment.Enzymatic catalytic treatment methods,characterized by high catalytic efficiency,mild reaction conditions,low requirements for wastewater quality and equipment,and reusability,also provide significant advantages in wastewater treatment.In this work,laccase was incorporated into a three-dimensional network structure of hydrogels via polymerization reactions.By introducing cellulose nanocrystals to modulate the permeability and mechanical properties of the hydrogels,a heterogeneous hydrogel catalyst is prepared.The study investigated the effects of various components on hydrogel properties and analyzed the degradation efficiency of laccase-cellulose nanocrystal hydrogel toward four typical organic phenolic compounds.It summarized relevant technical parameters to provide guidance for hydrogel-based heterogeneous catalysts.
Key words：cellulose nanocrystals; hydrogels; immobilized enzymes; degradation of organic phenols; pollution removal performance
【分析與測試】
聚乙烯醇-碘法在線測定表面處理槽液中硼酸含量
馬艷子1，何?1，唐俊榕2，王亞齊2，王巖1，趙美萍*1
(1. 北京大學化學與分子工程學院化學國家級實驗教學示范中心，北京 100871；2. 上海飛機制造有限公司，上海 201324)
摘要：為實現金屬表面處理槽液中常量硼酸的在線快速檢測，開發了一種基于反應動力學與原位光譜分析的新型測定方法。該方法系統研究了硼酸存在下聚乙烯醇（PVA）與碘三負離子（I3-）之間的顯色反應動力學過程。通過調控反應物濃度、介質組成與溫度等條件，并監測溶液吸收光譜隨時間的變化，發現體系中固有的硫酸與鈉離子對PVA-I3-顯色反應具有顯著促進作用，且低溫條件更有利于反應進行?；谏鲜霭l現，將反應溫度精確控制于20 °C，并優化介質中硫酸濃度與靜電環境，在抑制槽液背景干擾的同時，顯著加快了依賴于硼酸濃度的PVA-I3-顯色反應速率。該方法在反應開始后120 s即可獲得可用于定量分析的響應信號，在0 ~ 9 mmol/L硼酸濃度范圍內線性關系良好，檢出限為0.34 mmol/L。實際樣品檢測的相對誤差＜1%，表明該方法具有良好的準確性與實用價值。進一步集成高精度注射泵、多通道閥與自動流路系統，構建了全自動在線檢測裝置。該裝置可在45 min內完成校準與樣品檢測全過程，無需前處理步驟，適用于工業現場對槽液硼酸含量的實時監測與閉環控制。
關鍵詞：硼酸；表面處理槽液；聚乙烯醇-碘；光纖光譜；原位快速檢測
中圖分類號：O65 文獻標識碼：A 文章編號：0258-3283(2026)01-0058-08
DOI：10.13822/j.cnki.hxsj.2025.0262
Polyvinyl Alcohol-Iodine Method for Online Determination of Boric Acid in Surface Treatment Bath MA Yan-zi1b, He Peng1b, TANG Jun-rong2, WANG Ya-qi2, WANG Yan1b, ZHAO Mei-ping*1a (National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 2. Shanghai Aircraft Manufacturing Co., Ltd., Shanghai 201324, China)
Abstract：A novel method based on reaction kinetics and in-situ spectroscopic analysis was developed for the online rapid detection of boric acid in metal surface treatment bath solutions. This method systematically investigated the kinetic behavior of the chromogenic reaction between polyvinyl alcohol (PVA) and triiodide ions (I3-) in the presence of boric acid. By adjusting parameters such as reactant concentration, medium composition, and temperature, and monitoring the temporal changes in the solution absorption spectrum, it was found that the inherent sulfuric acid and sodium ions in the system significantly promote the PVA-I3- chromogenic reaction, with lower temperatures being more favorable for the reaction to proceed. Based on these findings, the reaction temperature was precisely controlled at 20 °C, and the sulfuric acid concentration and electrostatic environment in the reaction medium were optimized. This approach significantly accelerated the boric acid concentration-dependent PVA-I3- chromogenic reaction while effectively suppressing interference from background components in the bath solution. A reliable analytical signal suitable for quantification was obtained within 120 s after reaction initiation. The method demonstrated a good linear relationship within the boric acid concentration range of 0-9 mmol/L, with a detection limit of 0.34 mmol/L. The relative error of actual sample testing was less than 1%, indicating good accuracy and practical utility. Furthermore, a fully automated online detection system was built by integrating high-precision syringe pumps, multi-port valves, and an automated flow path system. This setup completed the entire calibration and sample detection process within 45 minutes without any pre-treatment steps, making it applicable for real-time monitoring and closed-loop control of boric acid concentration in industrial settings.
Key words：boric acid; surface treatment bath; polyvinyl alcohol-iodine; optical fiber spectrum; in-situ rapid quantitative detection
16種嗅味物質在環境水中的穩定性及樣品保存試驗研究
郭愛華*，王瑋，王晨，李?遙?溫雅
（北京市西城區疾病預防控制中心，北京 100120）
摘要：了解環境水中16種嗅味物質的穩定性和樣品最佳保存條件,以提高檢測結果準確性?？疾?/span>16種嗅味化合物在兩種不同基質(地表水和自來水)環境水中的穩定時間,以及常見采樣容器(棕色硬質玻璃容器、棕色聚乙烯容器)、保存溫度(20～25 ℃常溫、0～4 ℃冷藏)和常用保存劑(抗壞血酸、鹽酸溶液、硫代硫酸鈉)對水樣中目標物穩定性的影響,采用固相微萃取-氣相色譜-串聯質譜法對水樣中嗅味化合物進行檢測。各嗅味物質隨時間的延長濃度降低,萜類(2-MIB、GSM)、吡嗪類(IPMP、IBMP)在環境水中的穩定性優于酮類(β-ionone)、醛類(β-cyclocitral、2,4-HD、2,6-ND)和芳香雜環類(indole);水樣采集后應置于磨口硬質棕色玻璃瓶0～4 ℃保存,聚乙烯塑料瓶存在MTBE和2,6-dichlorphenol污染溶出風險,相較于常溫保存,0～4 ℃保存可緩解待測物損失速度;地表水中2,4-HD、2,6-ND、β-ionone、indole穩定性較差,自來水中2,4-HD、2,6-ND穩定性較差,其他化合物在無添加保存劑時,可保存24 h;地表水中2,4-HD、2,6-ND、β-ionone應添加鹽酸保存,indole應添加抗壞血酸保存并當天測定,自來水中2,4-HD添加抗壞血酸后可保存24 h。水樣中嗅味物質的穩定性不同,應根據其在不同基質水樣中穩定性的差異,采用相應保存方法,確保檢測結果的準確。
關鍵詞：環境水；嗅味化合物；穩定性；樣品保存；固相微萃取-氣相色譜-串聯質譜法
中圖分類號：O69 文獻標識碼：A 文章編號：0258-3283(2026)01-0066-10
DOI：10.13822/j.cnki.hxsj.2025.0226
Study on the Stability and Sample Preservation of 16 Odor Substances in Environmental Water GUO Ai-hua，WANG Wei，WANG Chen，LI Kun，WEN Ya (Xicheng District Center for Disease Control and Prevention, Beijing 100120,China)
Abstract： To understand the stability of 16 odorous substances in environmental water and determine optimal preservation conditions,this study investigated their stability in two different matrices (surface water and tap water),as well as the effects of common sampling containers (brown hard glass and brown polyethylene),storage temperatures (20～25 ℃ at room temperature or 0～4 ℃ refrigerated),and commonly used preservatives (ascorbic acid,hydrochloric acid solution,and sodium thiosulfate).Odorous compounds in water samples were detected by solid-phase microextraction-gas chromatography-tandem mass spectrometry.Concentrations of all compounds decreased over time.Terpenoids (2-MIB,GSM) and pyrazines (IPMP,IBMP) were more stable in environmental water than ketones (β-ionone),aldehydes (β-cyclocitral,2,4-HD,2,6-ND),and aromatic heterocycles (indole).After collection,water samples should be stored in ground-mouthed hard brown glass bottles at 0～4 ℃.Polyethylene containers pose a risk of contamination from MTBE and 2,6-dichlorphenol.Compared with room temperature storage,refrigeration slows the loss of target compounds.The stability of 2,4-HD,2,6-ND,β-ionone,and indole was relatively poor in surface water,while 2,4-HD and 2,6-ND were less stable in tap water.Other compounds remained stable for up to 24 h without preservatives.In surface water,2,4-HD,2,6-ND and β-ionone should be stored with hydrochloric acid,and indole with ascorbic acid,with same-day analysis recommended.In tap water,2,4-HD can be preserved for 24 hours with ascorbic acid.The stability of odorous compounds varies by compound and matrix.Therefore,appropriate preservation methods should be applied to ensure accurate measurements.
Key words：environmental water；odorous compounds；stability；sample preservation；SPME-GC-MS/MS
【合成與應用】
以酯鍵鏈接的甾體羥肟酸化合物的合成及體外抗腫瘤活性
周濤，劉欽洲，周卉，甘春芳*
（南寧師范大學化學與材料學院廣西天然高分子化學與物理重點實驗室，廣西南寧 530001）
摘要：分別以膽固醇、去氫表雄酮及孕烯醇酮為原料,通過縮合與水解反應對甾體母核進行結構修飾,并與甾核綴合,設計并合成了一系列通過酯鍵連接的甾體-羥肟酸新型化合物。采用分步合成策略構建甾體與羥肟酸結構片段,并運用分子雜交方法將兩部分綴合,成功制備出多個以酯鍵相連的甾體-羥肟酸綴合物,同時對實驗條件進行了系統優化。在體外抗腫瘤活性篩選中,以SAHA為陽性對照,采用MTT法評估目標化合物的抑制活性。結果顯示,N-[(三苯甲基)氨基]-4-氧代丁酸甲酯(4a)和甲基N-[(三苯甲基)氨基]-4-氧代戊酸酯(4b)對SKOV-3腫瘤細胞的增殖抑制效果優于其他測試細胞系。其中,化合物4a對多種腫瘤細胞均表現出一定的抑制活性,尤其對T47D細胞的IC50值為9.23 μmol/L;而化合物4b對HeLa細胞株顯示出更強的抑制能力,IC50值低至8.58 μmol/L。進一步通過分子對接研究探討其作用機制,發現化合物4a可通過多種疏水相互作用表現出更優的結合親和力,而化合物4b則通過與鋅離子結合,在催化抑制方面展現出更高潛力,為開發高效抗腫瘤藥物前體化合物提供了新的策略與研究方向。
關鍵詞：甾體；羥肟酸；抗腫瘤藥物；合成；分子對接
中圖分類號：O621.3 文獻標識碼：A 文章編號：0258-3283(2026)01-0076-10
DOI：10.13822/j.cnki.hxsj.2025.0246
Synthesis and In-Vitro Antitumor Screening of Ester-Linked Steroid-Hydroxamic Acid Conjugates ZHOU Tao,LIU Qin-zhou,ZHOU Hui,GAN Chun-fang*（Guangxi Key Laboratory of Natural Polymer Chemistry and Physics,School of Chemistry and Materials,Nanning Normal University,Nanning 530001,China）
Abstract：In this study,cholesterol,dehydroepiandrosterone,and pregnenolone were used as starting materials to design and synthesize a series of novel steroidal-hydroxamic acid conjugates linked via ester bonds.Structural modification of the steroidal core was achieved through condensation and hydrolysis reactions,followed by conjugation with hydroxamic acid fragments.A stepwise synthetic strategy was employed to construct the steroidal and hydroxamic acid fragments,which were subsequently conjugated using a molecular hybridization approach.Multiple steroid-hydroxamic acid conjugates with ester linkages were successfully prepared,and the reaction conditions were systematically optimized.For in vitro antitumor activity screening,the MTT assay was performed with SAHA as a positive control.The results indicated that compounds Methyl N-(tritylamino)-4-oxobutanoate (4a) and Methyl N-(tritylamino)-4-oxopentanoate (4b) exhibited superior antiproliferative activity against SKOV-3 tumor cells compared to other tested cell lines.Compound 4a showed moderate inhibitory activity against several tumor cell lines,with an IC50 value of 9.23 μmol/L against T47D cells,whereas compound 4b demonstrated enhanced potency against the HeLa cell line,achieving an IC50 value as low as 8.58 μmol/L.Molecular docking studies were conducted to further explore the mechanism of action.Compound 4a displayed superior binding affinity through diverse hydrophobic interactions,while 4b exhibited greater potential in catalytic inhibition by coordinating with zinc ions.This research provides a new strategy and direction for the future development of highly effective antitumor drug precursor compounds.
Key words：steroid;hydroxamic acid;antitumor agent;synthesis;molecular docking
可見光誘導氧摻雜氮化碳催化芐基碳氧化合成酮
趙波，谷嘉寧，潘揚，金甲婧，尚積禎，穆兵*
(湖州師范學院生命科學學院，浙江湖州 313000 )
摘要：芳基酮骨架廣泛存在于藥物和功能材料中,發展其高效、綠色的合成方法具有重要意義。近年來,以廉價易得的烷基芳烴為原料,通過可見光催化實現芐基碳的直接氧化,為芳基酮的綠色合成提供了新思路。以三聚氰胺為前驅體,通過高溫煅燒、熱剝離、熱氧化制備了氧摻雜氮化碳(O-g-C3N4)。在室溫下,以二苯甲烷(Ⅰa)為模板底物、O-g-C3N4為光催化劑,探究溶劑、催化劑用量、反應時間、光源、反應氛圍對二苯甲酮(Ⅱa)產率的影響,篩選最優的反應體系為:在室溫、紫光照射、氧氣氛圍下,以CH3CN/H2O(3 mL/3 mL)為溶劑、15 mg O-g-C3N4、反應時間為24 h。在篩選最佳的反應條件下,進行底物拓展,以31%～96%產率得到19種芳香酮類化合物,并通過 1HNMR、13CNMR、MS對其結構進行表征,與目標化合物的結構一致。研究結果表明,該反應體系對芳烴、雜環芳烴芐基碳的氧化均展現較好的底物適用性,并推斷芐基碳氧化合成芳香酮可能為單電子轉移自由基反應歷程。此外,O-g-C3N4光催化劑經5次循環利用,氧化產物的產率變化不明顯,表明O-g-C3N4具有良好的穩定性以及實際應用性。
關鍵詞：光催化；氧摻雜氮化碳；芐基碳的氧化；綠色合成；芳香酮的合成
中圖分類號：O62 文獻標識碼：A 文章編號：0258-3283(2026)01-0086-10
DOI：10.13822/j.cnki.hxsj.2025.0223
Visible Light-Induced Oxygen-Doped Graphitic Carbon Nitride Catalyzed Oxidation of Benzyl Carbons to Ketones ZHAO Bo, GU Ja-ning, PAN Yang, JIN Jia-jing, SHANG Ji-zhen, MU Bing* (College of Life Sciences, Huzhou University, Huzhou 313000, China)
Abstract：ryl ketone scaffolds are widely found in pharmaceuticals and functional materials,making the development of efficient and green synthetic methods highly significant.Recently,visible light-mediated direct oxidation of benzylic C―H bonds in readily available alkylarenes has provided a novel approach to the green synthesis of aryl ketones.In this paper,oxygen-doped graphitic carbon nitride (O-g-C3N4) was prepared using melamine as the precursor via high-temperature calcination,thermal exfoliation and oxidation.At room temperature,diphenylmethane (Ⅰa) was used as a model substrate and O-g-C3N4 as the photocatalyst to systematically investigate the effects of solvent,catalyst loading,reaction time,light source,and reaction temperature on the yield of benzophenone (Ⅱa).The optimized reaction system was identified as follows:CH3CN/H2O (3 mL/3 mL) as solvent,15 mg of O-g-C3N4,24 h reaction time,room temperature,purple light irradiation,and an oxygen atmosphere.Under the optimized conditions,a broad range of alkylarenes were oxidized to afford 19 aromatic ketones in isolated yields ranging from 31% to 96%.The structures of all products were identified by 1HNMR,13CNMR,and MS,and were consistent with the target compounds.The results demonstrate that this reaction system exhibits good substrate tolerance towards arenes and heteroarenes.Control experiments suggest that the oxidation of benzylic carbons proceeds via a radical-mediated single-electron transfer mechanism.Moreover,the catalyst could be reused for five cycles without significant loss of activity,demonstrating the excellent stability and practical applicability of O-g-C3N4.
Key words：photocatalysis; oxygen doped graphitic carbon nitride; oxidation of benzyl carbon; green synthesis; synthesis of aromatic ketone
嘧啶-5-甲醛的新合成工藝
王宇，黃鴻坤，凌春，嚴兆華*
(南昌大學 化學化工學院，江西 南昌 330031)
摘要：嘧啶-5-甲醛(1)是合成新型介離子類殺蟲劑三氟苯嘧啶的一種原料。報道了嘧啶-5-甲醛的一種新型合成方法。以4,6-二羥基嘧啶(3)為原料,通過Vilsmeier反應首先合成得到了中間體4,6-二氯嘧啶-5-甲醛(2)。中間體化合物2隨后在酸催化下和乙醇反應生成相應的縮醛保護產物4,6-二氯-5-(二乙氧基甲基)嘧啶(5c)。化合物5c在鈀碳催化下和氫氣反應脫去兩個氯原子生成了5-(二乙氧基甲基)嘧啶(4c)。最后化合物4c在濃硫酸作用下脫去醛保護基順利地合成得到了目標產物嘧啶-5-甲醛。4步反應的總產率為75%。詳細地考察了不同的縮醛保護基對反應的影響。當使用乙二醇代替乙醇作為化合物2的保護基時,4步反應總產率僅為5%;當使用甲醇代替乙醇作為化合物2的保護基時,4步反應總產率是36%。這些實驗結果表明,使用乙醇作為化合物2的保護基,4步反應總產率最高。開發的新型合成方法適合于工業化生產。
關鍵詞：嘧啶-5-甲醛；4,6-二羥基嘧啶；合成；保護基；還原
中圖分類號：O62 文獻標識碼：A 文章編號：0258-3283(2026)01-0094-05
DOI：10.13822/j.cnki.hxsj.2025.0258
A Novel Synthetic Method of Pyrimidine-5-carbaldehyde WANG Yu, HUANG Hong-kun, LING Chun, YAN Zhaohua*(College of Chemistry and Chemical Engineering, Nanchang University, Nanchang 330031, China)
Abstract: Pyrimidine-5-carbaldehyde (compound 1) is one of the key starting materials for the synthesis of the novel mesoionic insecticide triflumezopyrim.A novel synthetic method of pyrimidine-5-carbaldehyde is reported.Using 4,6-dihydroxypyrimidine (compound 3) as the starting material,4,6-dichloropyrimidine-5-carbaldehyde (compound 2) was first prepared through the Vilsmeier reaction.The intermediate compound 2 then reacted with ethanol under acid catalysis to form the corresponding acetal-protected product 4,6-dichloro-5-(diethoxymethyl)pyrimidine (compound 5c).Compound 5c was subsequently reduced by H2 under the catalysis of Pd/C,removing the two chlorine atoms to yield 5-(diethoxymethyl)pyrimidine (compound 4c).Finally,compound 4c was converted to the target product pyrimidine-5-carbaldehyde via deprotection with concentrated H2SO4.The overall yield of the four-step reaction was 75%.The effects of different acetal protecting group on the reaction were systematically investigated.When ethylene glycol was used instead of ethanol as the protecting group for intermediate compound 2,the overall yield of the four-step reaction was only 5%;when methanol was used,the yield was 36%.These results indicate that using ethanol as the protecting group for compound 2 provides the highest total yield.The developed protocol was suitable for industrial-scale production.
Key words：pyrimidine-5-carbaldehyde; 4,6-dihydroxypyrimidine; synthesis; protecting group; reduction
1,4-二羰基化合物合成吡咯和喹喔啉的研究
韋琳素，韋美玲，雷祿*
(百色學院 a. 化學與環境工程學院，b. 廣西城市水環境重點實驗室，廣西 百色 533000)
摘要：吡咯是重要的雜環化合物,它不僅存在于生物藥理活性的分子骨架中,還被用于制備電致發光器件導電功能材料。利用布朗斯特酸或路易斯酸等酸催化劑催化伯胺與1,4-二羰基前體反應制備,通過Paal-Knorr反應構建吡咯被認為是最具有吸引力和有效的策略之一。為構建結構新穎的吡咯稠環化合物,在合成吲哚的基礎上,發展多取代吡咯化合物的多樣性的合成。研究吡咯苯胺與二羰基化合物在酸性條件下的反應,構建結構新穎的吡咯和吡咯稠環衍生物,以拓展含氮雜環衍生物的高效合成。以鄰吡咯苯胺和1,4-二羰基化合物(2,5-己二酮)或1,4-酮酯為原料,在一水合對甲苯磺酸存在下進行反應,優化反應條件,如溶劑、反應溫度、催化劑用量等反應條件,以中等的產率得到吡咯和吡咯稠環化合物。所得產物均通過 1HNMR、13CNMR、HRMS進行了表征,新化合物通過單晶X-ray衍射,確定吡咯和吡咯稠環化合物的相對構型。通過控制實驗,提出可能反應的機理,對反應中間體進行核磁二維譜確認。發展了一種一水合對甲苯磺酸催化鄰吡咯苯胺和1,4-二羰基化合物串聯反應的方法,以高化學選擇性和區域選擇性得到目標化合物,并闡明了二羰基化合物結構對產物選擇性的影響。該方法條件溫和、收率高,為含氮雜環化合物的合成提供了新策略。
鍵詞：吡咯稠環；1,4-二羰基化合物；分子內環化；串聯反應
中圖分類號：O62 文獻標識碼：A 文章編號：0258-3283(2026)01-0099-08
DOI：10.13822/j.cnki.hxsj.2025.0243
Research on the Synthesis of Pyrroles and Quinoxalines from 1,4-Dicarbonyl Compounds WEI Lin-su, WEI Mei-ling, LEI Lu*( a. School of Chemical and Environmental Science Engineering, b. Guangxi Key Laboratory of Urban Water Environment, Baise University, Baise 533000, China)
Abstract: Pyrrole is an important heterocyclic compound that not only appears in molecular frameworks with biological and pharmacological activities but is also used in the preparation of conductive functional materials for electroluminescent devices.Among the various synthetic strategies,the Paal-Knorr reaction,using Br?nsted acids or Lewis acids to catalyze the reaction between primary amines and 1,4-dicarbonyl precursors,is regarded as one of the most attractive and efficient approach for constructing pyrrole frameworks.To access structurally novel pyrrole-fused ring systems,diverse synthetic routes toward polysubstituted pyrroles has been developed based on the methodologies used for indole construction.This study investigates the reaction of pyrrolylaniline with dicarbonyl compounds under acidic conditions to construct novel pyrrole and pyrrole-fused derivatives,thereby expanding the efficient synthesis of nitrogen-containing heterocyclic derivatives.Using ortho-pyrrolylaniline and 1,4-dicarbonyl compounds (2,5-hexanedione) or 1,4-ketoesters as starting materials,the reactions were carried out in the presence of p-toluenesulfonic acid monohydrate.Optimization of the reaction conditions,including solvent,reaction temperature,and catalyst loading,afforded pyrrole and pyrrole-fused ring compounds in moderate yields.All products were characterized by 1HNMR,13CNMR,and HRMS,while the relative configurations of the new compounds were determined by single-crystal X-ray diffraction.Based on control experiments,a plausible reaction mechanism was proposed,and the reaction intermediates were confirmed by two-dimensional NMR spectroscopy.This work established a p-toluenesulfonic acid monohydrate-catalyzed tandem reaction between ortho-pyrrolylaniline and 1,4-dicarbonyl compounds,delivering target products with high chemoselectivity and regioselectivity.The influence of the structure of the dicarbonyl compounds on product selectivity was also elucidated,providing a new strategy for the synthesis of nitrogen-containing heterocyclic compounds.
Key words：pyrrole-fused rings; 1,4-dicarbonyl compounds; intramolecular cyclization; tandem reaction
