會(huì)員動(dòng)態(tài)
《分析試驗(yàn)室》2024年3月第43卷第3期中英文摘要
CRISPR-Cas12a信號(hào)放大策略與便攜式血糖儀耦合定量檢測(cè)黃曲霉毒素B1
尹會(huì)，劉素君，李楊，賀范祥，周媛媛，李娜，舒琴，喬文艷，史鎧*
（樂山師范學(xué)院新能源材料與化學(xué)學(xué)院，樂山 614000）
摘要：建立了CRISPR-Cas12a與便攜式血糖儀耦合定量檢測(cè)黃曲霉毒素B1（AFB1）的方法。體系中AFB1能夠激活Cas12a的反式切割活性，激活后的Cas12a切割電極上蔗糖酶修飾的發(fā)夾探針，使得蔗糖酶游離到電極表面的溶液中。蔗糖酶催化蔗糖產(chǎn)生可以被血糖儀監(jiān)測(cè)的響應(yīng)信號(hào)，進(jìn)而實(shí)現(xiàn)對(duì)AFB1的檢測(cè)。在濃度0.001~0.1 ng/mL范圍內(nèi)，AFB1濃度與血糖信號(hào)呈良好的線性關(guān)系，線性方程為S=3.5+229.1c，檢出限為0.3 pg/mL。該方法特異性強(qiáng)，適用于實(shí)際樣品中AFB1的檢測(cè)。
關(guān)鍵詞：CRISPR-Cas12a；血糖儀；黃曲霉毒素B1；便攜式定量檢測(cè)
中圖分類號(hào)：TS201.6 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0301-06
Quantitative detection of aflatoxin B1 by CRISPR-Cas12a signal amplification strategy coupled with portable glucose meter
YIN Hui，LIU Sujun，LI Yang，HE Fanxiang，ZHOU Yuanyuan，LI Na，SHU Qin，QIAO Wenyan，SHI Kai*
College of New Energy Materials and Chemistry，Leshan Normal University，Leshan 614000，China）
Abstract：A method for the quantitative detection of aflatoxin B1 （AFB1） by coupling CRISPR-Cas12a with a portable glucose meter was established. The presence of AFB1 in the system will activate the trans-cleavage activity of CRISPR-Cas12a to cleave the sucrase modified hairpin DNA on the electrode and release sucrase from the electrode surface into the solution. The released sucrase could catalyze sucrose to produce a response signal that can be monitored by the personal glucose meter to realize the detection of AFB1. The developed biosensor exhibited a good linear relationship in AFB1 concentration range of 0.001-0.1 ng/mL，along with the linear equation of S=3.5+229.1c，with the detection limit of 0.3 pg/mL. This method has highly specificity and can be used for the detection of AFB1 in actual samples.
Keywords：CRISPR-Cas12a；personal glucose meter；aflatoxin B1；portable quantitative detection
熒光偏振免疫法測(cè)定水產(chǎn)品中的丁香酚
王強(qiáng)，王旭峰，張英俠，黃珂*
（中國(guó)水產(chǎn)科學(xué)研究院南海水產(chǎn)研究所，農(nóng)業(yè)農(nóng)村部水產(chǎn)品加工重點(diǎn)實(shí)驗(yàn)室，廣州 510300）
摘要：將丁香酚（Eul）與丙烯酸甲酯進(jìn)行衍生化反應(yīng)，合成了一種新型的丁香酚半抗原4-（4羥基-3-甲氨基苯基）-丁-2-烯酸（Eul-Aca）。采用活性酯法將丁香酚半抗原與乙二胺異硫氰酸熒光素（EDF）偶聯(lián)，分別制備了同源和異源熒光示蹤物。通過比較不同示蹤物的抗體稀釋度和靈敏度，優(yōu)化反應(yīng)時(shí)間等檢測(cè)條件，建立了一種檢測(cè)水產(chǎn)品中丁香酚的熒光偏振免疫分析法（FPIA）。結(jié)果表明：異源示蹤物（Eul-Aca-EDF）具有更優(yōu)的檢測(cè)靈敏度，抗體稀釋度為1/200，反應(yīng)時(shí)間僅需5 min。該方法的半抑制濃度（IC50）為11.2 μg/L，檢測(cè)線性范圍為1.1~111.5 μg/L，檢出限（LOD）為0.24 μg/L。實(shí)際樣品中丁香酚的加標(biāo)回收率為80.6%~107.4%，相對(duì)標(biāo)準(zhǔn)偏差（RSD）<15%。FPIA檢測(cè)結(jié)果與氣相色譜-質(zhì)譜（GC-MS）法結(jié)果具有良好的一致性（r=0.993），適用于水產(chǎn)品中丁香酚的殘留檢測(cè)。
關(guān)鍵詞：熒光偏振免疫分析法；示蹤物；丁香酚；水產(chǎn)品
中圖分類號(hào)：O657.6 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0307-07
A fluorescence polarization immunoassay for the detection of eugenol residues in aquatic products
WANG Qiang，WANG Xufeng，ZHANG Yingxia，HUANG Ke*
South China Sea Fisheries Research Institute，Chinese Academy of Fishery Sciences，Key Laboratory of Aquatic Product Processing，Ministry of Agriculture and Rural Affairs，Guangzhou 510300，China）
Abstract：Eugenol was derivatized with methyl acrylate to obtain 4-（4-hydroxy-3-methamphenyl）-butyl-2-acrylic acid. The hapten was coupled to fluoresceinthiocarbamyl ethylenediamine （EDF） using the active ester method to produce homologous and heterologous tracers. The influence of tracer structures on assay parameters such as antibody dilution and incubation time were investigated. Furthermore，a fluorescence polarization immunoassay （FPIA） was developed to detect eugenol residues in aquatic products. The results showed that the heterologous tracer （Eul-Aca-EDF） exhibited higher sensitivity with an antibody titer of 1/200. The reaction time of FPIA was only 5 min. The detection limit of eugenol，the IC50 value，and the working range were 0.24，11.2 and 1.1-111.5 μg/L，respectively. The recoveries of spiked aquatic products were in the range of 80.6%-107.4%，with the relative standard deviations （RSDs） less than 15%. The FPIA also showed a good correlation to the GC-MS method （r=0.993）. Therefore，the developed FPIA exhibited potential practicality in the detection of eugenol residues in aquatic products.
Keywords：fluorescence polarization immunoassay；tracer；eugenol；aquatic product
一步法制備鐵氮摻雜碳點(diǎn)熒光探針用于測(cè)定丙酮酸
石曉冉1，趙慧1，張涵1，李群芳1，3，婁方明*1，2，3
（1. 湖北民族大學(xué)化學(xué)與環(huán)境工程學(xué)院，恩施 445000；2. 遵義醫(yī)科大學(xué)藥學(xué)院，遵義 563000；3. 風(fēng)濕性疾病發(fā)生與干預(yù)湖北省重點(diǎn)實(shí)驗(yàn)室，恩施 445000）
摘要：以鄰苯二甲酸為前體，三乙烯二胺為氮源，氯化血紅素為鐵源，采用一步微波法制備了熒光量子產(chǎn)率約20.8%的新型鐵氮摻雜碳點(diǎn)（Fe，N@CDs），并對(duì)其形貌、組成及發(fā)光性能進(jìn)行了研究。Fe，N@CDs在425 nm激發(fā)波長(zhǎng)下能夠發(fā)射出500 nm的綠色熒光。基于Fe，N@CDs的熒光猝滅作用，建立了對(duì)丙酮酸定量測(cè)定的方法。在50~350 μmol/L范圍內(nèi)，F(xiàn)e，N@CDs的熒光猝滅程度與丙酮酸濃度呈良好的線性關(guān)系，相關(guān)系數(shù)R2=0.998，檢出限（LOD）為16.7 μmol/L。該方法成功應(yīng)用于胎牛血清蛋白中丙酮酸含量的檢測(cè)，回收率范圍為99.3%~103.4%。
關(guān)鍵詞：鐵氮摻雜量子點(diǎn)；熒光；丙酮酸；一步微波法
中圖分類號(hào)：O657.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0314-08
One-step preparation of iron-nitrogen doped carbon dot fluorescent probe for the detection of pyruvic acid
SHI Xiaoran1，ZHAO Hui1，ZHANG Han1，LI Qunfang1，3，LOU Fangming*1，2，3
1. School of Chemistry and Environmental Engineering，Hubei University for Nationalities，Enshi 445000，China；2. School of Pharmacy，Zunyi Medical University，Zunyi 563000，China；3. Hubei Provincial Key Laboratory of Rheumatic Disease Occurrence and Intervention，Enshi 445000，China）
Abstract：The new iron-nitrogen doped carbon dots （Fe，N@CDs） with a fluorescence quantum yield of about 20.8% were prepared by a one-step microwave method using phthalic acid as the precursor，triethylenediamine as the nitrogen source，and heme chloride as the iron source. The morphology，composition，and luminescence properties of the prepared Fe，N@CDs were investigated. Fe，N@CDs are capable of emitting green fluorescence of 500 nm at an excitation wavelength of 425 nm. A method for the quantitative determination of pyruvate was developed based on the quenching effect of Fe，N@CDs. The quenching of Fe，N@CDs showed a good linear relationship with pyruvate concentration in the range of 50-350 μmol/L，with a correlation coefficient of R2=0.998. The limit of detection （LOD） was 16.7 μmol/L. This method was successfully applied to the determination of pyruvate in fetal bovine serum proteins with recoveries ranging from 99.3%to 103.4%.
Keywords：iron and nitrogen doped quantum dots；fluorescent；pyruvic acid；one-step microwave method
玉米苞衣熱解法制備碳點(diǎn)及熒光猝滅法測(cè)定Hg2+
王越，劉根起*，劉建勛，王剛，趙伶俐，劉莉莎，孫辰昕，馬曉燕
（西北工業(yè)大學(xué)化學(xué)與化工學(xué)院，西安 710129）
摘要：以農(nóng)業(yè)廢棄物玉米苞衣為碳源，采用一步熱解法制備熒光碳點(diǎn)（CDs），利用透射電子顯微鏡、紅外光譜、X射線光電子能譜、紫外-可見光譜和熒光光譜等對(duì)CDs的結(jié)構(gòu)和光學(xué)性能進(jìn)行了表征。結(jié)果表明，制備得到的CDs呈球形，粒徑約為5.5 nm，其表面富含羥基和羧基。CDs在紫外光照射下可以發(fā)出明亮的藍(lán)色熒光。Hg2+對(duì)CDs溶液的熒光具有顯著的猝滅作用，據(jù)此建立了檢測(cè)Hg2+的新體系。在0~4.0 μmol/L范圍內(nèi)，CDs溶液的熒光猝滅程度與Hg2+濃度呈良好的線性關(guān)系，檢出限為0.011 μmol/L。本方法適用于自來水和湖水水樣中Hg2+的測(cè)定。
關(guān)鍵詞：玉米苞衣；碳點(diǎn)；熱解法；汞離子；熒光猝滅法
中圖分類號(hào)：O657.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0322-06
Preparation of carbon dots by pyrolysis of maize bract and determination of Hg2+ by fluorescence quenching method
WANG Yue，LIU Genqi*，LIU Jianxun，WANG Gang，ZHAO Lingli，LIU Lisha，SUN Chenxin，MA Xiaoyan
School of Chemistry and Chemical Engineering，Northwestern Polytechnical University，Xi'an 710129，China）
Abstract：The fluorescent carbon dots （CDs） were prepared by one-step pyrolysis from agricultural waste maize bract. The structure and optical properties of the CDs were characterized by transmission electron microscopy，F(xiàn)ourier transform infrared，X-ray photoelectron spectroscopy，ultraviolet-visible spectrscopy and fluorescence spectroscopy. The results showed that the prepared CDs were spherical in shape with a particle size of about 5.5 nm，and their surface were rich in hydroxyl and carboxyl groups. CDs can emit bright blue fluorescence when exposed to ultraviolet light，and Hg2+ had a significant quenching effect on the fluorescence of CDs solution. Thus，a new method for detecting Hg2+ was established. In the range of 0-4.0 μmol/L，the fluorescence quenching degree of CDs solution showed a good linear relationship with the concentration of Hg2+，and the detection limit was 0.011 μmol/L. The proposed method can be used for the determination of Hg2+ in tap water and lake water samples.
Keywords：corn bract；carbon dots（CDs）；pyrolysis；mercury ions；fluorescence quenching method
基于三線態(tài)一三線態(tài)湮滅上轉(zhuǎn)換發(fā)光的比率型pH納米探針
許宗意1，陳碩然*1，2，王董煊1，李琳1，2，王筱梅1，2，葉常青*1，2
（1. 綠色印刷納米光子工程技術(shù)研究中心，蘇州科技大學(xué)材料科學(xué)與工程學(xué)院，蘇州 215009；2. 蘇州市新能源材料與低碳技術(shù)重點(diǎn)實(shí)驗(yàn)室，蘇州 215009）
摘要：通過將pH熒光探針分子異硫氰酸熒光素（FITC）引入三線態(tài)―三線態(tài)湮滅上轉(zhuǎn)換（TTA-UC）體系中，使TTA-UC的發(fā)射與FITC的吸收重疊，從而實(shí)現(xiàn)從TTA-UC到FITC的能量傳遞過程。TTA-UC由光敏劑四苯基四苯駢鉑（PtTPBP）和湮滅劑9，10-雙苯乙炔基蒽（BPEA）組成，可以實(shí)現(xiàn)“紅轉(zhuǎn)青”上轉(zhuǎn)換發(fā)光。將上述有機(jī)染料負(fù)載于兩親性嵌段共聚物Pluronic P123形成的納米膠束內(nèi)，能夠形成比率型上轉(zhuǎn)換納米探針，并應(yīng)用于水溶液中的pH檢測(cè)。光敏劑PtTPBP的磷光發(fā)射由于不受pH影響，可以作為構(gòu)建比率探針的內(nèi)參比信號(hào)。上轉(zhuǎn)換發(fā)射強(qiáng)度與光敏劑磷光發(fā)射強(qiáng)度之間的比率信號(hào)（I507/I770）在pH 5~8范圍內(nèi)呈良好線性。這種新型的比率型上轉(zhuǎn)換pH納米探針為制備基于TTA-UC的比率型檢測(cè)傳感體系提供了新的思路和視角。
關(guān)鍵詞：上轉(zhuǎn)換；三線態(tài)-三線態(tài)湮滅；比率型探針；pH檢測(cè)；納米膠束
中圖分類號(hào)：O657.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0328-07
Ratiometric pH nanoprobe based on triplet-triplet annihilation upconversion
XU Zongyi1，CHEN Shuoran*1，2，WANG Dongxuan1，LI Lin1，2，WANG Xiaomei1，2，YE Changqing*1，2
1. Research Center for Green Printing Nanophotonic Materials，School of Materials Science and Engineering，Suzhou University of Science and Technology，Suzhou 215009，China；2. Suzhou Key Laboratory for New Energy Materials and Low Carbon Technologies，Suzhou 215009，China）
Abstract：By introducing the pH fluorescent probe fluorescein isothiocyanate （FITC） into the triplet-triplet annihilation upconversion （TTA-UC） system，an energy transfer process from TTA-UC to FITC could be achieved when UC emission overlapped with FITC absorption. The TTA-UC system consisting of the sensitizer Pt-tetraphenyltetrabenzoporphyrin （PtTPBP） and the annihilator 9，10-bis（phenylethynyl）anthracene （BPEA） could achieve red-to-cyan upconversion luminescence. By encapsulating the above organic dyes in nanomicelles assembled by the amphiphilic block copolymer Pluronic P123，a ratiometric upconversion nanoprobe could be constructed and applied for pH detection in aqueous solution. Since the phosphorescence emission of the sensitizer PtTPBP was not affected by pH，it could be used as an internal reference signal for the ratiometric probe. The ratio signal （I507/I770） between UC emission intensity and phosphorescence emission intensity of the sensitizer showed a good linear relationship with pH in the range from 5 to 8. This novel ratiometric upconversion pH nanoprobe provides a new perspective for the construction of ratiometric sensing platforms based on TTA-UC.
Keywords：upconversion；triplet-triplet annihilation；ratiometric probe；pH detection；nanomicelle
Cu0-Fe3O4@殼聚糖微球的制備及其對(duì)染料污染物的催化氧化
李豪，趙鳳，沈忱思*
（東華大學(xué)環(huán)境科學(xué)與工程學(xué)院，上海201620）
摘要：采用Fe2+以及Cu2+與殼聚糖形成的雙金屬絡(luò)合物作為前驅(qū)體溶液，一步成球后通過水熱法制得Cu0-Fe3O4@殼聚糖微球。表征結(jié)果證明，Cu0以及Fe3O4均以納米尺寸均勻鑲嵌在殼聚糖微球中。當(dāng)此殼聚糖微球投加量為0.5 g/L，H2O2投加量為40 mmol/L時(shí)，對(duì)初始濃度為20 mg/L的活性紅73在60 min中內(nèi)的脫色效率可達(dá)99%，且在pH 3.0~9.0范圍內(nèi)均能維持較高的效率。納米Cu0在有氧條件下表面易形成Cu2O層，不僅能夠活化H2O2產(chǎn)生?OH，還可提供電子加快Fe（III）/Fe（II）之間的循環(huán)，使類芬頓反應(yīng)高效進(jìn)行。
關(guān)鍵詞：零價(jià)銅；四氧化三鐵；類芬頓催化劑；染料廢水
中圖分類號(hào)：X832 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0335-05
Preparation of Cu0-Fe3O4@chitosan microspheres and its catalytic oxidation of dye contaminants
LI Hao，ZHAO Feng，SHEN Chensi*
College of Environmental Science and Engineering，Donghua University，Shanghai 201620，China）
Abstract：Fe2+，Cu2+ and chitosan were used to form a bimetallic complex as precursor to prepare Cu0-Fe3O4@chitosan microspheres catalyst in one step by hydrothermal method. The characterization results showed that both Cu0 and Fe3O4 were uniformly embedded in chitosan microspheres. When the dosages of the catalysts and H2O2 were 0.5 g/L and 40 mmol/L，respectively，99% of C. I. Acid Red 73 at the initial concentration of 20 mg/L could be removed in 60 min. The catalyst could maintain high efficiency in the pH range of 3.0-9.0. Cu2O sphere can generate on the surface of Cu0 under aerobic condition，which not only activated H2O2 to produce ?OH，but also provided electrons to accelerate the cycle of Fe（III）/Fe（II），promoting the Fenton-like reactions.
Keywords：zero-valent copper；Fe3O4；Fenton-like catalyst；dye wastewater
多光譜法和分子對(duì)接模擬研究對(duì)羥基苯甲酸甲酯與乳鐵蛋白的相互作用
史夢(mèng)潔，李澤萌，陸勇睿，徐敏華，何進(jìn)鋒，林曉蓮，劉紅艷*，姜鐵民
（桂林理工大學(xué)化學(xué)與生物工程學(xué)院，桂林541006）
摘要：利用多光譜法和分子模擬法研究了天然人乳鐵蛋白（HLF）、重組人乳鐵蛋白（rHLF）和對(duì)羥基苯甲酸甲酯（MP）之間相互作用的機(jī)制。穩(wěn)態(tài)熒光光譜和時(shí)間分辨熒光光譜法發(fā)現(xiàn)MP與乳鐵蛋白的猝滅機(jī)理為靜態(tài)猝滅。熱力學(xué)分析計(jì)算得范德華力和氫鍵是乳鐵蛋白和MP之間的主要作用力。同步熒光光譜分析表明酪氨酸殘基和色氨酸殘基均參與了MP與乳鐵蛋白的作用過程；三維熒光光譜分析表明MP的加入引起peak 1和peak 2的峰強(qiáng)度降低。紫外-可見吸收光譜、傅里葉紅外光譜和圓二色譜則表明乳鐵蛋白的二級(jí)結(jié)構(gòu)發(fā)生變化。分子對(duì)接表明乳鐵蛋白與MP間主要通過氫鍵和疏水作用力相互作用，分子動(dòng)力學(xué)表明MP改變了HLF的二級(jí)結(jié)構(gòu)。研究還表明，rHLF與MP的反應(yīng)效果更加明顯。本研究為揭示MP在生物體內(nèi)的分布、代謝及毒理作用機(jī)制等提供參考，同時(shí)也可以為MP的生產(chǎn)應(yīng)用提供理論參考。
關(guān)鍵詞：乳鐵蛋白；對(duì)羥基苯甲酸甲酯；多光譜法；分子對(duì)接
中圖分類號(hào)：O657.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0340-09
Interaction between methyl paraben and lactoferrin studied by multispectral method and molecular docking simulation
SHI Mengjie，LI Zemeng，LU Yongrui，XU Minhua，HE Jinfeng，LIN Xiaolian，LIU Hongyan*，JIANG Tiemin
College of Chemistry and Bioengineering，Guilin University of Technology，Guilin 541006，China）
Abstract：The mechanism of interaction between natural human lactoferrin，recombinant human lactoferrin and methyl paraben （MP） was investigated using multispectral and molecular simulation methods. The quenching mechanism of MP with lactoferrin was found to be a static quenching by steady-state fluorescence spectroscopy and time-resolved fluorescence spectroscopy. Thermodynamic analysis calculated that van der Waals forces and hydrogen bonds were the main forces between lactoferrin and MP. Simultaneous fluorescence spectroscopy showed that both Tyrosine residues and Tryptophan residues involved in the interaction between MP and lactoferrin；three-dimensional fluorescence spectroscopy showed that the addition of MP caused a decrease in the peak intensities of peak 1 and peak 2. UV-vis absorption spectroscopy，F(xiàn)ourier infrared spectroscopy and circular dichroism indicated that the secondary structure of lactoferrin had changed. Molecular docking showed that lactoferrin interacted with MP mainly through hydrogen bonds and hydrophobic forces，and molecular dynamics indicated that MP changed the secondary structure of HLF. It was also shown that the reaction of rHLF with MP was more effective. The results of this study can provide a reference for revealing the distribution，metabolism and toxicological mechanism of MP in living organisms，as well as a theoretical reference for the production and application of MP.
Keywords：lactoferrin；methyl paraben；multispectral method；molecular docking
基于3，3'，5，5'-四甲基聯(lián)苯胺光熱法檢測(cè)維生素C
劉曉霞*，侯文雅，郭曉迪，張建剛，趙晉忠
（山西農(nóng)業(yè)大學(xué)基礎(chǔ)部，晉中 030801）
摘要：構(gòu)建了一種基于3，3'，5，5'-四甲基聯(lián)苯胺（TMB）的光熱效應(yīng)檢測(cè)飲料中維生素C含量的方法。TMB在木瓜蛋白酶催化作用下可與過氧化氫反應(yīng)，生成藍(lán)色的氧化態(tài)產(chǎn)物（ox-TMB）。由于ox-TMB具有強(qiáng)烈的光熱效應(yīng)，吸收808 nm近紅外光后可將其轉(zhuǎn)換為熱能，從而導(dǎo)致溶液溫度升高；維生素C存在時(shí)可以將一部分ox-TMB還原，導(dǎo)致溫度增量下降，且下降的溫度增量與維生素C的濃度在5.0~125 μmol/L范圍內(nèi)存在線性關(guān)系，檢出限為2.3 μmol/L。該方法僅用筆式數(shù)字溫度計(jì)作為信號(hào)讀取器，已成功用于市售飲料中維生素C的定量檢測(cè)。本文所提出的策略為開發(fā)低成本的生物和臨床診斷方法提供了一種新的思路。
關(guān)鍵詞：3，3'，5，5'-四甲基聯(lián)苯胺；光熱效應(yīng)；數(shù)字溫度計(jì)；維生素C
中圖分類號(hào)：O655 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0349-06
Determination of vitamin C based on the photothermal effect of 3，3'，5，5'-tetramethylbenzidine
LIU Xiaoxia*，HOU Wenya，GUO Xiaodi，ZHANG Jiangang，ZHAO Jinzhong
Department of Basic Teaching，Shanxi Agricultural University，Jinzhong 030801，China）
Abstract：A new method for the determination of vitamin C in beverages was developed based on the photothermal effect of 3，3'，5，5'-tetramethylbenzidine （TMB）. TMB can react with hydrogen peroxide in the presence of papain to form the blue oxidized product （ox-TMB），which exhibits a strong photothermal effect. The ox-TMB can adsorb 808 nm near-infrared light and transform the analysis signal into heat，leading to a rise in solution temperature. In the presence of vitamin C，a part of ox-TMB can be reduced to TMB，resulting in the decrease of temperature increment. There was a linear relationship between the concentration of vitamin C and the temperature increment in the concentration range of 5.0-125 μmol/L，with a limit of detection of 2.3 μmol/L. This method only uses an easily operated pen-style digital thermometer as the signal reader，and was successfully applied to the quantitative detection of vitamin C in commercial beverages. The proposed strategy may provide a new way for the development of low-cost biological and clinical diagnostic methods.
Keywords：3，3'，5，5'-tetramethylbenzidine；photothermal effect；digital thermometer；vitamin C
基于金屬有機(jī)骨架的分散固相萃取-高效液相色譜法測(cè)定麥冬等樣品中6種新煙堿類農(nóng)藥殘留
李娜，黃海智，俞曉平，葉子弘*
（中國(guó)計(jì)量大學(xué)生命科學(xué)學(xué)院，浙江省生物計(jì)量及檢驗(yàn)檢疫技術(shù)重點(diǎn)實(shí)驗(yàn)室，杭州 310018）
摘要：通過熱溶劑法合成了金屬有機(jī)骨架（MOF）材料NH2-MIL-101（Fe），并建立了基于NH2-MIL-101（Fe）的分散固相萃取-高效液相色譜（DSPE-HPLC）法，用于檢測(cè)麥冬等藥食同源樣品中6種新煙堿類農(nóng)藥（噻蟲嗪、噻蟲胺、吡蟲啉、氯噻啉、啶蟲脒、噻蟲啉）殘留。與MIL-53（Al）、多壁碳納米管（MWCNTs）、ZIF-8及MIL-53（Fe）等吸附劑相比，NH2-MIL-101（Fe）的吸附能力更好，回收率更高；與液相色譜-質(zhì)譜聯(lián)用（LC-MS）相比，HPLC在達(dá)到檢測(cè)要求的同時(shí)能降低檢測(cè)成本。利用場(chǎng)發(fā)射掃描電子顯微鏡（FESEM）和傅里葉變換紅外光譜（FT-IR）表征制備的NH2-MIL-101（Fe），對(duì)吸附劑的種類和用量、萃取溶劑體積、萃取時(shí)間、洗脫溶劑體積和萃取洗脫方式進(jìn)行優(yōu)化。結(jié)果表明，NH2-MIL-101（Fe）穩(wěn)定性高、選擇性好、能在水中快速分散。據(jù)此構(gòu)建的方法檢測(cè)6種新煙堿類農(nóng)藥，在0.01~2.5 mg/L濃度范圍內(nèi)線性關(guān)系良好（R2>0.9993），加標(biāo)樣品檢出限（LOD）為0.50~1.0 μg/L，平均回收率為93.8%~104.2%，相對(duì)標(biāo)準(zhǔn)偏差小于6.5%。本文建立的基于MOF的DSPE-HPLC方法可極大減少實(shí)際樣品中復(fù)雜基質(zhì)的干擾。
關(guān)鍵詞：新煙堿類農(nóng)藥；NH2-MIL-101（Fe）；分散固相萃取；高效液相色譜；吸附
中圖分類號(hào)：TS207.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0355-09
Determination of six neonicotinoid pesticide residues in Ophiopogonis samples by dispersed solid-phase extraction coupled with high-performance liquid chromatography based on metal-organic frameworks
LI Na，HUANG Haizhi，YU Xiaoping，YE Zihong*
Zhejiang Provincial Key Laboratory of Biometrology and Inspection & Quarantine，College of Life Science，China Jiliang University，Hangzhou 310018，China）
Abstract：Metal-organic framework （MOF） material NH2-MIL-101（Fe） was synthesized by thermal solvent method，and a dispersive solid-phase extraction coupled with high-performance liquid chromatography （DSPE-HPLC） method based on NH2-MIL-101（Fe） was established. It was used to detect the residues of six neonicotinoid pesticides （thiamethoxam，clothiandin，imidacloprid，imidaclothiz，acetamiprid，thiacloprid） in medicine and food homologous products of Ophiopogon. NH2-MIL-101（Fe） had better adsorption capacity and higher recoveries than the adsorbents MIL-53（Al），multi-walled carbon nanotubes（MWCNTs），ZIF-8，and MIL-53（Fe）. Compared with the liquid chromatography-mass spectrometry （LC-MS） method，HPLC method can not only meet the detection requirements，but also reduce the detection cost. NH2-MIL-101（Fe） was characterized by field emission scanning electron microscopy （FESEM） and Fourier transform infrared （FT-IR） spectroscopy. The conditions such as the amount and type of adsorbent，volume of extraction solvent，extraction time，volume of elution solvent，and extraction elution methods were optimized. The results showed that NH2-MIL-101（Fe） had high stability，good selectivity，and rapid dispersion in water. For the constructed method based on NH2-MIL-101（Fe），the six neonicotinoids had good linear relationships in the range of 0.01-2.5 mg/L（R2>0.9993），the limits of detection （LODs） of the spiked samples were 0.25-0.5 μg/kg，the average recoveries were 93.8%-104.2%，and the relative standard deviations were less than 6.5%. The proposed DSPE-HPLC method based on MOFs can greatly reduce the interference of complex matrix in real samples.
Keywords：neonicotinoid pesticides；NH2-MIL-101（Fe）；dispersed solid phase extraction；high performance liquid chromatography；adsorption
手持式拉曼光譜儀結(jié)合雙金屬Au@AgNPs聚集體檢測(cè)環(huán)境水中結(jié)晶紫
董錦汝1，馮紫臨1，沈雪怡1，王文璇1，王凱強(qiáng)*2
（1. 中國(guó)海洋大學(xué)海德學(xué)院，青島 266100；2. 中國(guó)海洋大學(xué)食品科學(xué)與工程學(xué)院，青島 266404）
摘要：構(gòu)建了一種基于手持式拉曼光譜儀，結(jié)合雙金屬銀包金粒子（Au@AgNPs）聚集體的現(xiàn)場(chǎng)快速檢測(cè)結(jié)晶紫的表面增強(qiáng)拉曼光譜（SERS）方法。首先制備了“核-殼”粒徑分別約為30 nm和6 nm的雙金屬銀包金粒子（Au@AgNPs），并以NaCl作為聚集劑，獲得了具有SERS活性的Au@AgNPs聚集體。結(jié)合激發(fā)光源785 nm的手持式拉曼光譜儀，實(shí)現(xiàn)了結(jié)晶紫的快速檢測(cè)。以結(jié)晶紫位于1621 cm-1處的特征峰進(jìn)行定量分析，方法檢出限為8.20 μg/L，對(duì)河水和湖水中結(jié)晶紫的加標(biāo)回收率為71.0%~128.4%。本文所構(gòu)建的方法可用于監(jiān)測(cè)結(jié)晶紫的非法使用。
關(guān)鍵詞：結(jié)晶紫；表面增強(qiáng)拉曼光譜；Au@AgNPs；環(huán)境水；手持拉曼光譜儀
中圖分類號(hào)：O657.31；X832 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0364-07
Detection of crystal violet in environmental water by a handheld Raman spectrometer combined with bimetallic Au@AgNPs aggregates
DONG Jinru1，F(xiàn)ENG Zilin1，SHEN Xueyi1，WANG Wenxuan1，WANG Kaiqiang*2
1. College of Haide，Ocean University of China，Qingdao 266100，China；2. College of Food Science and Engineering，Ocean University of China，Qingdao 266404，China）
Abstract：A surface-enhanced Raman spectroscopy （SERS） method for the rapid and in situ detection of crystal violet was developed based on a handheld Raman spectrometer combined with bimetallic silver coated gold particles （Au@AgNPs）. Firstly，the Au@AgNPs with core and shell sizes of about 30 nm and 6 nm respectively were prepared. Sodium chloride was used as an inducer to prepare Au@AgNPs aggregate substrates with SERS activity. In combination with a handheld Raman spectrometer with an excitation source of 785 nm，the rapid detection of crystal violet was achieved. Quantitative analysis was conducted through the characteristic peak of crystal violet at 1621 cm-1 accompanied by the detection limit of 8.20 μg/L and the recoveries of 71.0%-128.4%. The constructed SERS method can be applied to monitor the illegal use of crystal violet.
Keywords：crystal violet；surface-enhanced Raman spectroscopy；Au@AgNPs；environmental water；handheld Raman spectrometer
磁性核殼型Ni（II）印跡聚合物的制備及其吸附性能
鄧秀君1，李悅1，胡興亮2，陸茜1，孫婷1，張煒業(yè)1，何紅星*1
（1. 云南省金屬有機(jī)分子材料與器件重點(diǎn)實(shí)驗(yàn)室，昆明學(xué)院化學(xué)化工學(xué)院，昆明 650214；2. 昆明綠島環(huán)境科技有限公司，昆明 650228）
摘要：以2-丙烯酰胺-2-甲基-1-丙磺酸（AMPS）為功能單體，2-膦酸丁烷-1，2，4-三羧酸為配體，綠色溶劑水為致孔劑，利用表面印跡技術(shù)制備了一種新型磁性核殼型Ni（II）印跡聚合物。考察了溶液pH、吸附時(shí)間、Ni（II）初始濃度和溫度對(duì)印跡材料吸附性能的影響。利用傅立葉紅外光譜儀（FTIR）、X射線粉末衍射儀（XRD）、掃描電鏡（SEM）、熱重分析儀（TGA）和振動(dòng)樣品磁強(qiáng)計(jì)（VSM）對(duì)印跡聚合物的結(jié)構(gòu)、表面形貌、熱穩(wěn)定性和磁性能進(jìn)行了表征，并探究了印跡聚合物對(duì)Ni（II）的吸附機(jī)理。結(jié)果表明：磁性核殼型Ni（II）印跡聚合物在25 ℃，pH 6時(shí)吸附平衡時(shí)間為30 min，最大吸附量可達(dá)38.09 mg/g，吸附過程符合準(zhǔn)二級(jí)動(dòng)力學(xué)模型和Langmuir吸附等溫模型。吸附熱力學(xué)研究表明，印跡聚合物對(duì)Ni（II）的吸附是一個(gè)自發(fā)、吸熱、熵增的過程。印跡聚合物相較于非印跡聚合物展現(xiàn)出較好的選擇性，在Ni（II），Co（II），Cu（II）和Zn（II）的混合溶液中，對(duì)Ni（II）的分配系數(shù)達(dá)319.01 mL/g，證明該印跡聚合物具有選擇性吸附Ni（II）的能力。
關(guān)鍵詞：Ni（II）；表面印跡技術(shù)；磁性核殼；選擇性
中圖分類號(hào)：O657.31；X832 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0371-08
Preparation and adsorption properties of magnetic core-shell Ni（II） imprinted polymer
DENG Xiujun1，LI Yue1，HU Xingliang2，LU Xi1，SUN Ting1，ZHANG Weiye1，HE Hongxing*1
1. Yunnan Key Laboratory of Metal-Organic Molecular Materials and Device，School of Chemistry and Chemical Engineering，Kunming University，Kunming 650214，China；2. Kunming Lvdao Environmental Technology Co.，Ltd.，Kunming 650228，China）
Abstract：A novel magnetic core-shell Ni（II） imprinted polymer was prepared by surface imprinting technique using 2-acrylamide-2-methyl-1-propanesulfonate （AMPS） as functional monomer，2-phosphonobutane-1，2，4-tricarboxylic acid as ligand and green solvent water as porogen. Different conditions such as the solution pH，adsorption time，initial concentration of Ni（II），and temperature on the adsorption properties of the imprinted material were studied. The structure，stability，surface morphology，thermal stability and magnetic properties of imprinted polymers were characterized by Fourier transform infrared （FTIR） spectroscopy，X-ray diffraction （XRD），scanning electron microscopy （SEM），thermal analysis （TGA） and vibrating sample magnetometry （VSM），and the adsorption mechanism of imprinted polymers for Ni（II） was investigated. The results showed that the adsorption equilibrium time of the magnetic core-shellimprinted polymer was 30 min at 25 ℃ and pH 6，and the maximum adsorption capacity could reach 38.09 mg/g. The adsorption process could be well fitted bypseudo-second-order kinetic model and Langmuir adsorption isotherm model. The adsorption thermodynamic results showed that the adsorption of Ni（II） on the imprinted polymer was a spontaneous，endothermic and entropy-increasing process. Moreover，the imprinted polymer showed better selectivity compared with the non-imprinted polymer. In the mixed solution of Ni（II），Co（II），Cu（II） and Zn（II），the distribution coefficient of Ni（II） reached 319.01 mL/g，which proved that the imprinted polymer could selectively adsorb Ni（II）.
Keywords：Ni（II）；surface imprinting technology；magnetic core-shell；selectivity
一種三苯胺酰腙熒光探針的合成及其對(duì)Al3+的選擇性識(shí)別
王欣，薛蕾，曾姿涵，徐陽，張楊，王海濱*
（寧夏師范學(xué)院化學(xué)化工學(xué)院，固原 756000）
摘要：將4-二苯基氨基苯甲酰肼和2，4-二羥基苯甲醛結(jié)合，合成了一種新的三苯胺酰腙類熒光探針（N18），并利用核磁共振氫譜（1H NMR）、碳譜（13C NMR）和質(zhì)譜（MS）技術(shù)對(duì)其結(jié)構(gòu)進(jìn)行了表征。在二甲基亞砜（DMSO）/H2O溶液中對(duì)N18的光學(xué)性能進(jìn)行了測(cè)定。紫外-可見（UV-vis）吸收光譜和熒光發(fā)射光譜結(jié)果表明，N18對(duì)Al3+識(shí)別表現(xiàn)出高選擇性和高靈敏度，并且對(duì)其他金屬離子有較強(qiáng)的抗干擾能力。利用Job曲線和1H NMR測(cè)得N18與Al3+的結(jié)合比為1∶1，通過熒光滴定得到N18對(duì)Al3+的檢出限為4.9×10-8 mol/L，結(jié)合常數(shù)（Ka）為5.95×105 L/mol。探針N18可以檢測(cè)實(shí)際水樣中的Al3+，并且可以制備成試紙用于檢測(cè)Al3+，具有一定的應(yīng)用前景。
關(guān)鍵詞：熒光探針；三苯胺；酰腙；識(shí)別；Al3+
中圖分類號(hào)：O657.31 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0379-07
Synthesis of a triphenylamine acylhydrazone based fluorescent probe and its selective recognition for Al3+
WANG Xin，XUE Lei，ZENG Zihan，XU Yang，ZHANG Yang，WANG Haibin*
College of Chemistry and Chemical Engineering，Ningxia Normal University，Guyuan 756000，China）
Abstract：A novel triphenylamine acylhydrazone based fluorescent probe （N18） was synthesized from
4-（diphenylamino）benzohydrazide and 2，4-dihydroxybenzaldehyde，and the structure of N18 was characterized by 1H NMR，13C NMR and mass spectrometry （MS）. The optical performance of N18 was measured in dimethyl sulfoxide （DMSO）/H2O solution. According to the UV-vis absorption and fluorescence spectra results，N18 exhibited high selectivity and sensitivity towards Al3+，and had strong anti-interference ability to other metal ions. The binding ratio between N18 and Al3+ was obtained as 1∶1 by Job’ plot and 1H NMR. The detection limit was 4.9×10-8 mol/L and the binding constant （Ka） was 5.95×105 L/mol based on the fluorescence titration data. In addition，the probe N18can detect Al3+ in actual water sample and can be prepared into test papers for Al3+ detection，which has a good application prospect.
Keywords：fluorescent probe；triphenylamine；acylhydrazone；recognition；Al3+
氣相色譜-四極桿飛行時(shí)間質(zhì)譜快速篩查和確證農(nóng)藥制劑中51種非法添加化合物
黃培鑫，楊紅菊，李玲，黃寶勇*，于寒冰*
（北京市農(nóng)產(chǎn)品質(zhì)量安全中心，北京 100029）
摘要：建立了氣相色譜-四極桿飛行時(shí)間質(zhì)譜（GC-Q-TOF/MS）篩查農(nóng)藥制劑中51種非法添加化合物的方法。乳油等15種農(nóng)藥劑型被分為3組，經(jīng)丙酮溶解提取，GC-Q-TOF/MS測(cè)定，建立了51種化合物的一級(jí)精確質(zhì)量數(shù)據(jù)庫(kù)和二級(jí)碎片質(zhì)譜庫(kù)。結(jié)果表明，51種化合物在各自線性范圍內(nèi)線性關(guān)系良好，相關(guān)系數(shù)（R2）均大于0.99，檢出限（LODs）為0.04~0.2 mg/kg，0.5，1.0，5.0 mg/kg 3個(gè)濃度的加標(biāo)回收率為93.0%~105.2%，相對(duì)標(biāo)準(zhǔn)偏差（RSDs）為2.5%~7.8%。該方法適用于農(nóng)藥制劑中非法添加化合物的分析。
關(guān)鍵詞：氣相色譜-四極桿-飛行時(shí)間質(zhì)譜；農(nóng)藥制劑，快速篩查；非法添加
中圖分類號(hào)：O657.63；X839.2 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0386-08
Rapid screening and quantitative analysis of 51 illegally added compounds in pesticide preparations by gas chromatography-quadrupole time-of-flight mass spectrometry
HUANG Peixin，YANG Hongju，LI Ling，HUANG Baoyong*，YU Hanbing*
Beijing Center of Agricultural Products Quality and Safety，Beijing 100029，China）
Abstract：A method based on gas chromatography-quadrupole time-of-flight mass spectrometry （GC-Q-TOF/MS） was established to determine 51 illegally added compounds in pesticide preparations. Emulsifiable concentrate and other 14 pesticide formulations were divided into three groups，which were extracted by acetone and determined by GC-Q-TOF/MS. Thus，an accurate primary mass database and fragment ion database of 51 compounds were established. The experiment results revealed that all compounds showed good linear relationships in their corresponding concentration ranges，with the correlation coefficients （R2） above 0.99. The limits of detection （LODs） were 0.04-0.2 mg/kg. The recoveries at the three spiked levels of 0.5，1.0 and 5.0 mg/kg were 93.0%-105.2%，and the relative standard deviations （RSDs） ranged from 2.5% to 7.8%. This method is suitable for the determination of illegally added compounds in pesticide preparations.
Keywords：Gas chromatography-quadrupole time-of-flight mass spectrometry （GC-Q-TOF/MS）；pesticide preparations；rapid screening；illegal addition
磁性表面分子印跡聚合物的制備及對(duì)梓醇的選擇性吸附
秦兵1，張偉東2，李淑賢*1
（1. 佳木斯大學(xué)藥學(xué)院，佳木斯 154000；2. 吉林大學(xué)藥學(xué)院，長(zhǎng)春 130000）
摘要：以Fe3O4@SiO2磁性復(fù)合材料為載體，梓醇為模板分子，采用沉淀聚合法合成了新型磁性表面分子印跡聚合物。優(yōu)化了吸附條件，通過靜態(tài)與動(dòng)態(tài)吸附實(shí)驗(yàn)，考察了新型復(fù)合材料的吸附性能。結(jié)果表明，該材料對(duì)梓醇的最大吸附量為69.07 μg/mg，印跡因子為1.97，對(duì)梓醇有優(yōu)良的特異性識(shí)別能力。重復(fù)使用6次后，回收率仍在85%以上，重復(fù)利用性良好。基于此，結(jié)合磁固相萃取法，建立了應(yīng)用于地黃中梓醇富集和檢測(cè)的高效液相色譜法，梓醇回收率為89.5%~96.8%，相對(duì)標(biāo)準(zhǔn)偏差（RSD）≤2.0%，線性范圍為0.1~1.15 mg/mL，線性相關(guān)系數(shù)R2>0.9998，檢出限（LOD）為5.4 ng/mL。該新型磁性復(fù)合材料為天然產(chǎn)物中活性成分的富集和分析提供了一種新的預(yù)處理策略。
關(guān)鍵詞：磁性表面分子印跡聚合物；梓醇；HPLC；磁性材料
中圖分類號(hào)：O657.31；X832 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0394-08
Preparation of magnetic surface molecular imprinted polymer and its selective adsorption for catalpol
QIN Bing1，ZHANG Weidong2，LI Shuxian*1
1. College of Pharmacy，Jiamusi University，Jiamusi 154000，China；2. College of Pharmacy，Jilin University，Changchun 130000，China）
Abstract：A novel magnetic surface molecularly imprinted polymer was synthesized by precipitation polymerization using Fe3O4 and SiO2 magnetic composites as carriers and catalpol as template molecules. The adsorption conditions were optimized and the adsorption performance of the new composite material was investigated by static and dynamic adsorption experiments. The results showed that the maximum adsorption capacity of the material for catalpol was 69.07 μg/mg with the imprinted factor （IF） of 1.97，showing excellent specific recognition ability for catalpol. After 6 times of reuse，the recovery was still above 85%，showing good reuse performance. Combined with magnetic solid phase extraction，the high performance liquid chromatography method was established and successfully applied to enrich and determine catalpol in rehmannia glutinosa. The recoveries of catalpol were 89.5%-96.8%，with the relative standard deviations （RSDs） lower than 2%. The linear range was 0.1-1.15 mg/mL，with the correlation coefficient （R2） above 0.9998，and the limit of detection （LOD） of 5.4 ng/mL. The new composite magnetic material can provide a promising pretreatment strategy for the enrichment and analysis of active components in natural products.
Keywords：magnetic surface molecularly imprinted polymer；catalpol；HPLC；magnetic material
超高效合相色譜-質(zhì)譜法對(duì)甲卡西酮對(duì)映異構(gòu)體的手性分離和定量檢測(cè)
胡爽1，武磊1，黃鈺2，杜宇2，花鎮(zhèn)東*3
（1. 北京警察學(xué)院刑事科學(xué)技術(shù)系，北京 102202；2. 中國(guó)藥科大學(xué)藥學(xué)院，南京 210009；3. 公安部禁毒情報(bào)技術(shù)中心，北京 100193）
摘要：建立了超高效合相色譜-質(zhì)譜法（UPC2-MS）對(duì)甲卡西酮（MC）對(duì)映異構(gòu)體進(jìn)行手性分離和定量檢測(cè)。使用Acquity UPC2 Trefoil CEL2 （2.5 μm，3.0 mm×150 mm）手性色譜柱，以超臨界流體CO2為主要流動(dòng)相，含10 mmol/L甲酸銨和0.1%甲酸的異丙醇為改性劑進(jìn)行梯度洗脫，可以在13 min內(nèi)實(shí)現(xiàn)2個(gè)對(duì)映異構(gòu)體的基線分離。在三重四極桿質(zhì)譜多反應(yīng)監(jiān)測(cè)（MRM）模式下，2個(gè)對(duì)映異構(gòu)體的檢出限為0.5 ng/mL，定量限為1.0 ng/mL，在1~100 ng/mL質(zhì)量濃度范圍內(nèi)線性關(guān)系良好，線性相關(guān)系數(shù)（R2）≥0.999，10種常見毒品和藥品對(duì)檢測(cè)均無干擾。對(duì)實(shí)際繳獲毒品的檢測(cè)結(jié)果表明：直接作為毒品銷售的MC主要為外消旋體，而非法制造麻黃堿的地下窩點(diǎn)繳獲的MC以S構(gòu)型為主。
關(guān)鍵詞：超高效合相色譜-質(zhì)譜；甲卡西酮；對(duì)映異構(gòu)體；手性分離
中圖分類號(hào)：O656.2 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0402-07
Chiral separation and quantitative determination of methcathinone enantiomers by ultra-performance convergence chromatography-mass spectrometry
HU Shuang1，WU Lei1，HUANG Yu2，DU Yu2，HUA Zhendong*3
1. Department of Criminal Science and Technology，Beijing Police College，Beijing 102202，China；2. School of Pharmacy，China Pharmaceutical University，Nanjing 210009，China；3. Anti-drug Information Technology Center of the Ministry of Public Security，Beijing 100193，China）
Abstract：A chiral separation and quantification method for methcathinone （MC） enantiomers based on ultra-performance convergence chromatography-mass spectrometry （UPC2-MS） was developed. The baseline separation of two enantiomers could be achieved within 13 min under the conditions of acquity UPC2 Trefoil CEL2 （2.5 μm，3.0 mm×150 mm） as chiral column，supercritical fluid CO2 as primary mobile phase，isopropanol containing 10 mmol/L ammonium formate and 0.1% formic acid as the modifier for gradient elution. Under the multi reaction monitoring （MRM） mode of triple quadrupole mass spectrometry，the limits of detection were 0.5 ng/mL and the limits of quantification were 1.0 ng/mL for both enantiomers. There were great linear relationships in the concentration range of 1.0-100 ng/mL，and the correlation coefficients （R2） were not less than 0.999. 10 common drugs did not interfere with the determination of target substances. The seized drug samples were analyzed using this method，and the results showed that the methcathinone products seized in the market as drugs were mainly in racemic form，while that seized from illegal ephedrine manufacturing dens were mainly in S-configuration.
Keywords：ultra performance convergence chromatography-mass spectrometry；methcathinone；enantiomers；chiral separation
磁性功能介孔材料固相萃取-氣相色譜法測(cè)定水中的多氯聯(lián)苯
張利1，李莉2，張登耀2，張盛貴*1，陳自弟1
（1. 甘肅農(nóng)業(yè)大學(xué)食品科學(xué)與工程學(xué)院，蘭州 730070；2. 甘肅農(nóng)業(yè)大學(xué)理學(xué)院，蘭州 730070）
摘要：采用一鍋法合成Fe3O4納米粒子，并利用溶膠-凝膠法制備了SBA-15@Fe3O4磁性介孔復(fù)合材料。以介孔二氧化硅材料（SBA-15）的表面硅羥基為靶位，借助苯基三氯硅烷與硅羥基的硅烷化反應(yīng)將苯基基團(tuán)接枝到材料表面，得到苯基功能化磁性介孔材料Ph-SBA-15@Fe3O4，該材料有良好的疏水性，并保留了SBA-15的有序二維六方孔道結(jié)構(gòu)。將其用于磁性固相萃取（MSPE）吸附水樣中的多氯聯(lián)苯（PCBs），建立了氣相色譜-電子捕獲檢測(cè)法（GC-ECD）檢測(cè)PCBs。在優(yōu)化條件下，7種PCBs在0.025~50 μg/L范圍內(nèi)呈良好線性關(guān)系，線性相關(guān)系數(shù)（R2）均大于0.9999，方法回收率為89.8%~108%。該方法可用于實(shí)際水樣中痕量PCBs的高效快速檢測(cè)。
關(guān)鍵詞：磁性固相萃取（MSPE）；多氯聯(lián)苯（PCBs）；氣相色譜-電子捕獲檢測(cè)法（GC-ECD）
中圖分類號(hào)：O657.7 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0409-06
Determination of polychlorinated biphenyls in water by magnetic functional mesoporous materials solid phase extraction-gas chromatography
ZHANG Li1，LI Li2，ZHANG Dengyao2，ZHANG Shenggui*1，CHEN Zidi1
1. College of Food Science and Engineering，Gansu Agricultural University，Lanzhou 730070，China；2. College of Science，Gansu Agricultural University，Lanzhou 730070，China）
Abstract：Fe3O4 nanoparticles were synthesized by one pot method，and SBA-15@Fe3O4 magnetic mesoporous composites were synthesized by sol-gel method. Surface silicon hydroxyl groups of mesoporous silica material （SBA-15） served as target，Ph-SBA-15@Fe3O4 functional magnetic mesoporous material were obtained by grafting phenyl groups onto SBA-15@Fe3O4 surface via silylation reaction between phenyl trichlorosilane and silanol group. The material not only possessed good hydrophobicity，but also retained the ordered two-dimensional hexagonal pore-like structure of SBA-15. The material was used in magnetic solid-phase extraction （MSPE） pretreatment to adsorb polychlorinated biphenyls （PCBs） in water samples，and a gas chromatography method for the determination of PCBs was established. Under the optimized conditions，the seven PCBs exhibited good linear relationships in the range of 0.025-50 μg/L，the correlation coefficients （R2） were greater than 0.9999，and the recoveries were 89.8%-108%. The MSPE method could be applied to the determination of trace PCBs in real water samples.
Keywords：magnetic solid-phase extraction （MSPE）；polychlorinated biphenyls （PCBs）；gas chromatography-electron capture detection （GC-ECD）
高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定稻谷和糙米中的溴硝醇
王飛*，俞子萱，張靜
（天津海關(guān)動(dòng)植物與食品檢測(cè)中心，天津 300457）
摘要：建立了稻谷和糙米中溴硝醇的高效液相色譜-串聯(lián)質(zhì)譜檢測(cè)方法。樣品采用酸性乙腈提取，經(jīng)HLB固相萃取柱凈化，以Hypersil GOLD-C18柱分離，在負(fù)離子模式下采集數(shù)據(jù)，基質(zhì)外標(biāo)法定量。溴硝醇在電噴霧負(fù)離子模式下的母離子m/z 167.8，實(shí)際為溴硝醇發(fā)生反應(yīng)后的產(chǎn)物2-溴-2-硝基乙醇的分子離子峰。溴硝醇在0~5.0 μg/mL濃度范圍內(nèi)呈良好線性，線性相關(guān)系數(shù)大于0.99，平均回收率為86.2%~94.6%，相對(duì)標(biāo)準(zhǔn)偏差不超過13%。該方法適用于大批量糧谷樣品中溴硝醇的快速檢測(cè)。
關(guān)鍵詞：高效液相色譜-串聯(lián)質(zhì)譜；溴硝醇；稻谷；糙米
中圖分類號(hào)：O657.63 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0415-05
Determination of 2-bromo-2-nitropropane-1，3-diol residues in grain and unpolished rice by high performance liquid chromatography-tandem mass spectrometry
WANG Fei*，YU Zixuan，ZHANG Jing
Tianjin Customs Plants Animals and Foods Inspection Center，Tianjin 300457，China）
Abstract：A high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） method was established for the determination of 2-bromo-2-nitropropane-1，3-diol residues in grain and unpolished rice products. The acetonitrile solution containing formic acid and HLB solid phase extraction column were used for the extraction and purification of 2-bromo-2-nitropropane-1，3-diol，respectively，following separation via Hypersil GOLD-C18 column. The target analyte was detected in the negative ion mode using an electrospray ionization （ESI） source with external standard method. The parent ion m/z 167.8 of 2-bromo-2-nitropropane-1，3-diol was actually the molecular ion peak of 2-bromo-2-nitroethanol，which was the degraded product of reversible aldehyde alcohol reaction of 2-bromo-2-nitropropane-1，3-diol. The results showed that there was a good relationship with correlation coefficient above 0.99 in the concentration range of 0-5.0 μg/mL. Average recoveries for the residues were in the range of 86.2% to 94.6%，and the relative standard deviations （RSDs） was no more than 13% in grain and unpolished rice products. The developed method was suitable to determinate 2-bromo-2-nitropropane-1，3-diol residues in grain and unpolished rice.
Keywords：HPLC-MS/MS；2-bromo-2-nitropropane-1，3-diol；grain；unpolished rice
KED-ICP-MS法測(cè)定電子級(jí)丙二醇甲醚中的銀、鎘和鉛
萬曦1，劉涌2，鄭玉婷2，陳辰1，郭登峰*1
（1. 常州大學(xué)石油化工學(xué)院，常州 213164；2. 江蘇怡達(dá)化學(xué)股份有限公司，無錫 214441）
摘要：建立了電感耦合等離子體質(zhì)譜法（ICP-MS）測(cè)定電子級(jí)丙二醇甲醚中銀（Ag）、鎘（Cd）和鉛（Pb）含量的方法。樣品經(jīng)超純水稀釋后直接進(jìn)樣，采用標(biāo)準(zhǔn)加入法作為定量方法，選擇待測(cè)同位素為107Ag，111Cd，208Pb，并通過選擇檢測(cè)模式和碰撞/反應(yīng)池氣體流量有效消除質(zhì)譜干擾。結(jié)果表明，在碰撞模式下利用動(dòng)能歧視技術(shù)（KED），He流量為4 mL/min時(shí)，質(zhì)譜干擾消除效果最佳。該方法的線性范圍為0.2~5 μg/L，線性相關(guān)系數(shù)大于0.9995，各元素檢出限（LODs）為0.002~0.009 μg/L，加標(biāo)回收率為93.8%~104.2%，相對(duì)標(biāo)準(zhǔn)偏差（RSDs）小于9.5%。使用KED-ICP-MS法可以準(zhǔn)確測(cè)定電子級(jí)丙二醇甲醚中Ag，Cd和Pb的含量。
關(guān)鍵詞：電感耦合等離子體質(zhì)譜法（ICP-MS）；動(dòng)能歧視（KED）；標(biāo)準(zhǔn)加入法；電子級(jí)丙二醇甲醚；金屬元素銀、鎘和鉛
中圖分類號(hào)：TQ413.2 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0420-05
Determination of silver，cadmium and lead in electronic grade propylene glycol methyl ether by inductively coupled plasma mass spectrometry with kinetic energy discrimination
WAN Xi1，LIU Yong2，ZHENG Yuting2，CHEN Chen 1，GUO Dengfeng*1
1. Collage of Petrochemical Technology，Changzhou University，Changzhou 213164，China；2. Jiangsu Yida Chemical Co.，Ltd.，Wuxi 214441，China）
Abstract：A method for the determination of silver （Ag），cadmium （Cd） and lead （Pb） in electronicgrade propylene glycol methyl ether by inductively coupled plasma mass spectrometry with kinetic energy discrimination （KED-ICP-MS） was established. The sample was diluted with ultra-pure water and then injected directly. The quantitative method is the standard addition method. The isotopes to be measured were 107Ag，111Cd，208Pb，and the interference of the mass spectrum was effectively eliminated by selecting the detection mode and the gas flow rate in the collision/reaction cell. When the collision mode was used as the best detection mode，and the He flow of the collision gas was 4 mL/min，the best effect of mass spectrometry interference elimination could be obtained. The linear range of the method was 0.2-5 μg/L，the linear correlation coefficients were not less than 0.9995，and the limits of detection （LODs） were in the range of 0.002-0.009 μg/L. The spiked recoveries for each element ranged from 93.8% to 104.2%，and the relative standard deviations （RSDs） were less than 9.5%. The contents of Ag，Cd，and Pb in electronic grade propylene glycol methyl ether can be accurately determined by KED-ICP-MS.
Keywords：inductively coupled plasma mass spectrometry （ICP-MS）；kinetic energy discrimination （KED）；standard addition method；electronic grade propylene glycol methyl ether；metal elements of Ag，Cd，and Pb
基于5-氨基水楊酸的碳量子點(diǎn)用于測(cè)定高錳酸根
朱建濤*，溫翯，韓偉，車春霞，張峰，劉超偉
（中國(guó)石油天然氣股份有限公司蘭州化工研究中心，蘭州 730060）
摘要：采用簡(jiǎn)單的水熱法制備了以5-氨基水楊酸為前驅(qū)體的氮摻雜碳量子點(diǎn) （N-CQDs）。合成的N-CQDs呈球形，平均粒徑3.45 nm，表面含有豐富的功能基團(tuán)。在紫外燈照射下，N-CQDs發(fā)出綠色熒光，熒光量子產(chǎn)率為10.4%，最大激發(fā)和發(fā)射波長(zhǎng)分別為340 nm和502 nm。加入MnO4-后，N-CQDs的熒光強(qiáng)度呈濃度依賴性猝滅，基于此，構(gòu)建了靈敏的“開-關(guān)”型納米探針。通過考察紫外-可見吸收光譜、熒光壽命和Stern-Volmer常數(shù)，MnO4-猝滅N-CQDs熒光歸因于內(nèi)濾效應(yīng)和靜態(tài)猝滅。在優(yōu)化條件下，N-CQDs檢測(cè)MnO4-的線性范圍為0~14 μmol/L，檢出限（LOD）為0.14 μmol/L。N-CQDs對(duì)水中常見的其他陽離子和陰離子表現(xiàn)出優(yōu)良的選擇性和抗干擾能力。該方法已成功應(yīng)用于湖水中MnO4-的測(cè)定。
關(guān)鍵詞：氮摻雜碳量子點(diǎn)；高錳酸根；納米探針
中圖分類號(hào)：O657.31； X832 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0425-08
Carbon quantum dots based on 5-aminosalicylic acid for the determination of permanganate
ZHU Jiantao*，WEN He，HAN Wei，CHE Chunxia，ZHANG Feng，LIU Chaowei
Lanzhou Petrochemical Research Center，Petro China Company Limited，Lanzhou 730060，China）
Abstract：A simple hydrothermal method was used to prepare the nitrogen doped carbon quantum dots （N-CQDs） with 5-aminosalicylic acid as precursor. The synthesized N-CQDs were spherical with an average particle size of 3.45 nm and had abundant functional groups on the surface. N-CQDs emitted green fluorescence under ultraviolet irradiation with quantum yield of 10.4%，and the maximum excitation and emission wavelengths were 340 and 502 nm，respectively. Upon the addition of MnO4-，the fluorescence intensity of N-CQDs was quenched with a concentration-dependent manner. Based on this result，a sensitive “on-off” probe was constructed. Through examining UV-visible absorption spectrum，fluorescence lifetime and Stern-Volmer constant，the fluorescence quenching triggered by MnO4- was attributed to inner filter effect and static quenching. Under the optimized conditions，the linear detection range of MnO4- was 0-14 μmol/L，with the detection limit （LOD） of 0.14 μmol/L. N-CQDs showed excellent selectivity and anti-interference ability to other common cations and anions in water. The method has been successfully applied to the determination of MnO4- in lake water.
Keywords：nitrogen doped carbon quantum dots；permanganate；nanoprobe
基于核酸適配體的比色生物傳感器研究進(jìn)展
黃麗珊，胡奕津，范申，張紅艷*
（福建中醫(yī)藥大學(xué)藥學(xué)院，福州 350122）
摘要：核酸適配體因能與目標(biāo)物特異性結(jié)合而被用作生物識(shí)別元件，廣泛用于生物傳感器的研究。基于適配體的比色生物傳感器，因簡(jiǎn)便、經(jīng)濟(jì)且直觀可視等特點(diǎn)，在環(huán)境保護(hù)、醫(yī)療診斷和食品安全等領(lǐng)域備受青睞。隨著生物技術(shù)和納米技術(shù)的迅速發(fā)展，結(jié)合不同顯色途徑和信號(hào)放大方法，已建立了多種操作簡(jiǎn)便、特異性強(qiáng)、靈敏度高的基于適配體的比色傳感方法，為現(xiàn)場(chǎng)快速檢測(cè)技術(shù)的發(fā)展提供了新思路和新選擇。識(shí)別元件、信號(hào)探針及信號(hào)放大策略都是影響比色生物傳感器準(zhǔn)確性和靈敏度的重要因素，納米材料和放大策略的選擇及設(shè)計(jì)非常重要。本文主要基于酶催化和等離子體共振比色原理，介紹了近年來比色適配體傳感器的研究進(jìn)展，為高靈敏比色生物傳感器的研究和應(yīng)用提供參考。
關(guān)鍵詞：核酸適配體；比色生物傳感器；傳感模式；綜述
中圖分類號(hào)：Q503；TP212.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0433-10
Advance of aptamer-based colorimetric biosensor
HUANG Lishan，HU Yijin，F(xiàn)AN Shen，ZHANG Hongyan*
College of Pharmacy，F(xiàn)ujian University of Traditional Chinese Medicine，F(xiàn)uzhou 350122，China）
Abstract：Aptamers have been widely used as biological recognition elements of biosensor because of their specific binding to the targets. The colorimetric biosensors based on aptamers are popular in the fields of environmental protection，medical diagnosis and food safety due to their advantages of simplicity，economy and visualization. With the rapid development of biological technology and nano science technology，many colorimetric methods based on aptamers with easy operation，strong specificity and high sensitivity have been established by combining different color rendering pathways and signal amplification methods，providing new ideas and choices for the development of on-site rapid detection. Definitely，recognition elements，signal probes and signal amplification strategies are key factors that affect the accuracy and sensitivity of colorimetric biosensors. Therefore，it is very important to select and design them ingeniously. Accordingly，this paper will mainly introduce the advance of colorimetric sensors in recent years based on the two most common colorimetric principles of enzymatic catalysis and plasma resonance，providing a reference for the research and application of highly sensitive colorimetric biosensors.
Keywords：aptamer；colorimetric biosensor；sensing mode；review
全細(xì)胞生物傳感器用于檢測(cè)農(nóng)藥的研究進(jìn)展
楊瑞1，張紀(jì)媛1，唐博1，劉大喜1，2，馬小龍*1，2，崔建升*1，2
（1. 河北科技大學(xué)環(huán)境科學(xué)與工程學(xué)院，石家莊 050018；2. 河北省污染防治生物技術(shù)實(shí)驗(yàn)室，石家莊 050018）
摘要：農(nóng)藥殘留以多種形式存在于自然環(huán)境中，并通過遷移、生物積累等方式對(duì)各種環(huán)境基質(zhì)和人類健康造成不利影響。全細(xì)胞生物傳感器（WCBs）是一種新型的污染物分析裝置，因其操作簡(jiǎn)便、低成本、高靈敏度和選擇性好被廣泛應(yīng)用于環(huán)境監(jiān)測(cè)領(lǐng)域。本文綜述了近年來基于藻類、細(xì)菌和真菌的全細(xì)胞生物傳感器在檢測(cè)環(huán)境中各類農(nóng)藥的應(yīng)用進(jìn)展，并展望了全細(xì)胞生物傳感器未來的研究重點(diǎn)和發(fā)展趨勢(shì)。
關(guān)鍵詞：農(nóng)藥殘留；全細(xì)胞生物傳感器；光學(xué)測(cè)量；電信號(hào)測(cè)量；綜述
中圖分類號(hào)：TP212.3；O657 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1000-0720（2024）03-0443-12
Advances in pesticide detection using whole cell biosensors
YANG Rui1，ZHANG Jiyuan1，TANG Bo1，LIU Daxi1，2，MA Xiaolong*1，2，CUI Jiansheng1，2
1. College of Environmental Science and Engineering，Hebei University of Science and Technology，Shijiazhuang 050018，China；2. Pollution Prevention Biotechnology Laboratory of Hebei Province，Shijiazhuang 050018，China）
Abstract：Pesticide residues exist in natural environment in many forms，which have adverse effects on various environmental substrates and human health through migration and bioaccumulation. Whole-cell biosensors （WCBs） are a new type of pollutant analysis device that is widely applied in the field of environmental monitoring due to its ease of operation，low cost，high sensitivity，and good selectivity. Hence，this review summarized the recent progress in the application of WCBs based on algae，bacteria and fungi for the detection of various pesticides in the environment. The future research focus and development trend of WCBs were also prospected.
Keywords：pesticide residues；whole cell biosensors；optical measurement；electrical signal measurement；review
