氮硫共掺杂碳量子点对胃液pH值的精确检测

doi:10.7503/cjcu20200133

摘要/Abstract

摘要：

以水杨酸和硫脲为原料, 通过水热法一步合成水溶性好、稳定性强、量子产率高(36.23%)、呈蓝光的氮硫共掺杂碳量子点(N,S-CQDs). 在302 nm波长激发下, N,S-CQDs在发射波长409 nm处的荧光强度与pH值(在2.01~5.11范围内)线性关系良好, 相关系数为0.9931, 可原位、实时检测胃液内pH值在Δ0.01范围内的变化. 可用于胃癌早期诊断和新生儿健康防护. 400 μg/mL N,S-CQDs孵育铜绿微囊藻细胞48 h, 存活率82.8%, 其可作为人体胃细胞荧光探针, 经人体排泄进入水环境, 对淡水浮游生物毒性低, 环境友好.

关键词: 碳量子点, 掺杂, pH值, 胃液, 荧光探针

Abstract:

Nitrogen-sulfur co-doped carbon quantum dots with blue light, good water solubility, strong stability and high quantum yield(36.23%), were synthesized by one-step hydrothermal method, using salicylic acid and thiourea as raw materials. Under the excitation of 302 nm, there is a good linear relationship between the fluorescence intensity and the pH value in the range of 2.01—5.11 at the emission wavelength of 409 nm, and the correlation coefficient is 0.9931. The change of pH value in gastric juice can be detected in situ and in real time. In view of the fact that the pH value of gastric juice is closely related to the diagnosis of gastric cancer and neonatal monitoring, N,S-CQDs are expected to contribute to the early diagnosis of gastric cancer and neonatal health protection. N,S-CQDs have low cytotoxicity and good biocompatibility. When microcystis aeruginosa cells as phytoplankton model are incubated with 400 μg/mL of N,S-CQDs for 48 h, their survival ratesare 82.8%, indicating that N,S-CQDs could be used as a environmental-friendly fluorescent probe for human gastric cells.

Key words: Carbon quantum dots, Doping, pH value, Gastric juice, Fluorescent probe

中图分类号:

O655

黄加玲,刘凤娇,王婷婷,刘翠娥,郑凤英,王振红,李顺兴. 氮硫共掺杂碳量子点对胃液pH值的精确检测[J]. 高等学校化学学报, 2020, 41(7): 1513-1520.

HUANG Jialing,LIU Fengjiao,WANG Tingting,LIU Cuie,ZHENG Fengying,WANG Zhenhong,LI Shunxing. Nitrogen and Sulfur co-Doped Carbon Quantum Dots for Accurate Detection of pH in Gastric Juice^†[J]. Chemical Journal of Chinese Universities, 2020, 41(7): 1513-1520.

图/表 11

Fig.1 HRTEM images(A, C), size distribution(B) and XRD pattern(D) of N,S-CQDs

Fig.2 FTIR spectrum of N,S-CQDs

Fig.3 XPS spectra of C1s(A), N1s(B), O1s(C) and S2p(D) of N,S-CQDs

Fig.4 UV-Vis absorption spectrum and fluorescence spectra of N,S-CQDs(A) and fluorescence spectroscopy of N,S-CQDs with different excitation wavelengths(B) Insets in (A) are photos of N,S-CQDs irradiated by natural light(left) and 300 nm UV light(right).

Fig.5 Effects of NaCl concentration(A), irradiation time(B), storage time(C) and cycle number(D) on the fluorescence intensity of N,S-CQDs

Fig.6 Survival rate of Microcystis aeruginosa cells cultured in N,S-CQDs with different concentrations for 0, 24 and 48 h

Fig.7 Effect of different metal ions on the fluorescence intensity of N,S-CQDs a. Blank; b. Na+; c. K+; d. Fe3+; e. Mn2+; f. Cd2+; g. Ca2+; h. Pb2+; i. Zn2+; j. Hg+; k. Co2+; l. Mg2+; m. Ni2+.

Fig.8 Fluorescence emission spectra of N,S-CQDs with different concentrations of Fe(Ⅲ)(A) and the linear relationship between(F0-F)/F0 and Fe(Ⅲ) concentration(B)

Fig.9 Influence of pH value on the fluorescence intensity of N,S-CQDs in gastric juice(A) and the linear relationship between FL intensity at 409 nm and pH value(B) pH: a. 2.01; b. 2.26; c. 2.53; d. 2.76; e. 3.00; f. 3.26; g. 3.53; h. 3.77; i. 3.99; j. 4.20; k. 4.54; l. 5.11.

Fig.10 Zeta potential of N,S-CQDs

Table 1 pH Detection with carbon quantum dot-based fluorescent probes

Carbon quantum dots	Raw material	Linear range	Quantum yield(%)	Sample	Ref.
dCDs	o-Phenylenediamine phosphoric acid	1.5—5.0	10.34	E. coli	[23]
DECDs	o-Phenylenediamine polyethylene glycol oxalic acid	2.2—4.0	4.72(integrating sphere)	pH test papers	[39]
N,S-CDs	Ammoniumpersulfate, glucose, ethylenediamine	3.0—10.0	10.34	HePG2 cells	[22]
N-OGQDs	CA, L-DOPA	4—8	18.0		[40]
S-doped carbon dots	Waste frying oil, sulfuric acid	3.0—9.0	3.66	Helacells	[41]
N,S-CQDs	L-cysteine NH₃·H₂O	5.5—7.0	17.2	Silk fiber	[21]
N,S-QDs	Salicylic acid, thiourea	2.01—5.11	36.23	Human gastric juice	This work

参考文献 41

[1]	Tang G., Hart R., Sholzberg M., Brezden-Masley C., Eur. J. Gastroenterol. Hepatol., 2018, 30(12), 1497—1501 doi: 10.1097/MEG.0000000000001251 URL pmid: 30179903
[2]	Xu Z. J., Lin S. R., Zhou L. Y., Ding S. G., Li Y., Geng Q. M., Chin. J. Gastroenter., 2004, 9(4), 213—216
	( 徐志洁, 林三仁, 周丽雅, 丁士刚, 李渊, 耿秋明. 胃肠病学, 2004, 9(4), 213—216)
[3]	Pi Y. J., You Y., Hao Q. Y., Chinese Nursing Research, 2015, 29(12C), 4578—4580
	( 皮玉菊, 游勇, 郝群英. 护理研究, 2015, 29(12C), 4578—4580)
[4]	Li Z. H., Wang D. H., Chin. J. Perinat. Med., 2013, 16(12), 722—724
	( 李正红, 王丹华. 中华围产医学杂志, 2013, 16(12), 722—724)
[5]	Hu X. M., ., Chin. J. Prac. Nurs., 2013, 29(027), 50—51
	( 胡小梅. 中国实用护理杂志, 2013, 29(027), 50—51)
[6]	Sun L. X., Jia J., Li F. F., Systems Medicine, 2017, 2(1), 146—148
	( 孙丽霞, 贾静, 李方方. 系统医学, 2017, 2(1), 146—148)
[7]	Chen J., Zhang Y. N., Hao Q. Y., J. Kunming Med. Univ., 2015, 36(10), 118—120
	( 陈军, 张燕妮, 郝群英. 昆明医科大学学报, 2015, 36(10), 118—120)
[8]	Li H., Kang Z., Liu Y., Lee S. T., J. Mater. Chem., 2012, 22(46), 24230—24253 doi: 10.1039/c2jm34690g URL
[9]	Krishna A. S., Radhakumary C., Antony M., Sreenivasan K., J. Mater. Chem. B, 2014, 2(48), 8626—8632 URL pmid: 32262221
[10]	Li H., Liu R., Kong W., Liu J., Liu Y., Zhou L., Zhang X., Lee S. T., Kang Z., Nanoscale, 2014, 6(2), 867—873 URL pmid: 24270880
[11]	Liu Y., Wu P., Mater. Interfaces, 2013, 5(8), 3362—3369
[12]	Zhang Y., Chan K. F., Wang B., Chiu P. W. Y., Zhang L., Sens. Actuators B, 2018, 271, 128—136
[13]	Wang R., Wang X., Sun Y., Sens. Actuators B, 2017, 241, 73—79
[14]	Kong B., Zhu A., Ding C., Zhao X., Li B., Tian Y., Adv. Mater., 2012, 24(43), 5844—5848 URL pmid: 22933395
[15]	Atchudan R., Edison T. N. J. I., Aseer K. R., Perumal S., Karthik N., Lee Y. R., Biosens. Bioelectron., 2018, 99, 303—311 doi: 10.1016/j.bios.2017.07.076 URL
[16]	Li L. S., Jiao X. Y., Zhang Y., Cheng C., Huang K., Xu L., Sens. Actuators B, 2018, 268, 84—92 doi: 10.1016/j.snb.2018.03.189 URL
[17]	Tao H., Yang K., Ma Z., Wan J., Zhang Y., Kang Z., Liu Z., Small, 2012, 8(2), 281—290 URL pmid: 22095931
[18]	Yang K., Gong H., Shi X., Wan J., Zhang Y., Liu Z., Biomaterials, 2013, 34(11), 2787—2795 URL pmid: 23340196
[19]	Guo Y., Cao F., Li Y., Sens. Actuators B, 2018, 255, 1105—1111 doi: 10.1016/j.snb.2017.08.104 URL
[20]	Tang D., Liu J., Wu X., Liu R., Han X., Han Y., Huang H., Liu Y., Kang Z., Mater. Interfaces, 2014, 6(10), 7918—7925
[21]	Song Z., Quan F., Xu Y., Liu M., Cui L., Liu J., Carbon, 2016, 104, 169—178 doi: 10.1016/j.carbon.2016.04.003 URL
[22]	Zhuang Q., Si X., Li L., Zeng H., Ding Y., Talanta, 2020, 208, 119780 URL pmid: 31816740
[23]	Song W., Duan W., Liu Y., Ye Z., Chen Y., Chen H., Qi S., Wu J., Liu D., Xiao L., Anal. Chem., 2017, 89(24), 13626—13633
[24]	Wang Z. H., Zhang H. P., Luo Z. X., Environmental Science, 2016, 37(7), 2570—2576
	( 王振红, 张汉鹏, 罗专溪. 环境科学, 2016, 37(7), 2570—2576)
[25]	Lin L. X., Li S. X., Zheng F. Y., Chinese J. Anal. Chem., 2010, 38(6), 823—827
	( 林路秀, 李顺兴, 郑凤英. 分析化学, 2010, 38(6), 823—827)
[26]	Ding H., Wei J. S., Xiong H. M., Nanoscale, 2014, 6(22), 13817—13823 URL pmid: 25297983
[27]	Li Y., Liu F., Cai J., Huang X., Lin L., Lin Y., Yang H., Li S., Microchem. J., 2019, 147, 1038—1047 doi: 10.1016/j.microc.2019.04.015 URL
[28]	Wu C. W., Wei Y. Y., Chi C. W., Lui W. Y., P'eng F. K., Chung C., Dig. Dis. Sci., 1996, 41(1), 119—125 URL pmid: 8565743
[29]	Lu W., Qin X., Liu S., Chang G., Zhang Y., Luo Y., Asiri A. M., Al-Youbi A. O., Sun X., Anal. Chem., 2012, 84(12), 5351—5357 URL pmid: 22681704
[30]	Dong Y., Pang H., Yang H. B., Guo C., Shao J., Chi Y., Li C. M., Yu T., Angew. Chem. Int. Ed., 2013, 52(30), 7800—7804
[31]	Choi Y., Kang B., Lee J., Kim S., Kim G. T., Kang H., Lee B. R., Kim H., Shim S. H., Lee G., Chem. Mater., 2016, 28(19), 6840—6847
[32]	Joseph J., Anappara A. A., PCCP, 2017, 19(23), 15137—15144 URL pmid: 28561114
[33]	Liu W., Diao H., Chang H., Wang H., Li T., Wei W., Sens. Actuators B, 2017, 241, 190—198
[34]	Meng A., Xu Q., Zhao K., Li Z., Liang J., Li Q., Sens. Actuators B, 2018, 255, 657—665
[35]	Lin Y., Li Y. H., Yang H., Huang H. P., Li L., Li S. X., Chinese J. Anal. Chem., 2019, 47(5), 748—755
	( 林烨, 李跃海, 杨辉, 黄虹浦, 李琳, 李顺兴. 分析化学, 2019, 47(5), 748—755)
[36]	Huang H., Li C. G., Shi Z., Feng S. H., Chem. J. Chinese Universities, 2019, 40(8), 1579—1585
	( 黄贺, 李春光, 施展, 冯守华. 高等学校化学学报, 2019, 40(8), 1579—1585)
[37]	Kimura I., Yamana M., Gastroenterol. Jpn., 1969, 4(2), 127—127
[38]	Xu Y., Chen Y. H., Ding L., Chem. J. Chinese Universities, 2018, 39(7), 1420—1426
	( 徐源, 陈艳华, 丁兰. 高等学校化学学报, 2018, 39(7), 1420—1426)
[39]	Xia C., Cao M., Xia J., Zhou G., Jiang D., Zhang D., Wang J., Li H., J. Mater. Chem. C, 2019, 7(9), 2563—2569
[40]	Shi B., Zhang L., Lan C., Zhao J., Su Y., Zhao S., Talanta, 2015, 142, 131—139 URL pmid: 26003702
[41]	Hu Y., Yang J., Tian J., Jia L., Yu J. S., Carbon, 2014, 77, 775—782

相关文章 15

[1]	赵国庆, 袁钊, 王连, 郭卓. 磷化镍/氮硫双掺杂石墨烯复合材料的制备及电催化析氢性能[J]. 高等学校化学学报, 2020, 41(7): 1575-1581.
[2]	祝玉鑫, 欧阳杰, 宋艳华, 唐盛, 崔言娟. 硼碘共掺杂氮化碳的制备及光解水制氢性能[J]. 高等学校化学学报, 2020, 41(7): 1645-1652.
[3]	熊俊宇, 王姗姗, 许颜清, 胡长文. 原子级分散Fe-N-C温和条件下选择性氧化催化特性[J]. 高等学校化学学报, 2020, 41(6): 1262-1268.
[4]	程时富,胡皓,陈必华,吴海虹,高国华,何鸣元. 双离子液体基多孔炭的制备与电化学性能[J]. 高等学校化学学报, 2020, 41(5): 1048-1057.
[5]	王霞, 刘彦吉, 贾永锋, 吉磊, 胡全丽, 段莉梅, 刘景海. 含氮多孔纳米碳纤维的制备及对锂硫电池容量的提高[J]. 高等学校化学学报, 2020, 41(4): 829-837.
[6]	赵鹏,张晋腾,林艳红. Mg-ZnO复合物的紫外光催化效率及协同作用研究[J]. 高等学校化学学报, 2020, 41(3): 538-547.
[7]	韩洪晶,葛芹,陈彦广,王海英,赵宏志,王怡真,张亚男,邓冀童,宋华,张梅. Ca₁_-xPr_xFeO₃催化热解甘蔗渣木质素制备酚类化合物[J]. 高等学校化学学报, 2020, 41(2): 331-340.
[8]	赵艳锋,孙效龙,胡绍争,王辉,王菲,李萍. 氧掺杂对V_N-g-C₃N₄催化剂光催化固氮性能的影响[J]. 高等学校化学学报, 2020, 41(1): 132-139.
[9]	王金金, 戚少龙, 杜建时, 杨清彪, 宋岩, 李耀先. 苯并噻唑类荧光探针的合成及对N₂H₄·H₂O和HS $O 3 -$ 的检测性能[J]. 高等学校化学学报, 2019, 40(7): 1397-1404.
[10]	董向阳, 牛晓青, 魏济时, 熊焕明. 一步水热法制备铜掺杂纳米碳点及其在白光器件中的应用[J]. 高等学校化学学报, 2019, 40(6): 1288-1292.
[11]	马东玮, 田润赛, 刘振江, 冯源源, 丁泓宇, 冯季军. Na掺杂Li_2-_xNa_xMnSiO₄/C正极材料的微波辅助合成与电化学性能[J]. 高等学校化学学报, 2019, 40(6): 1280-1287.
[12]	刘欢欢, 袁龙, 刘景海, 侯长民, 冯守华. 铁掺杂钐镓石榴石Sm₃Ga_5-_xFe_xO₁₂(x=1,2,3,4)可逆热致变色材料的合成与表征[J]. 高等学校化学学报, 2019, 40(4): 652-658.
[13]	张勇,申城,幸志荣,陈归柒,卢资,侯志兵,陈雪梅. 可视化检测次氯酸的苯并咪唑类荧光增强型探针[J]. 高等学校化学学报, 2019, 40(12): 2480-2485.
[14]	张莹莹,黄译文,赵冰,王丽艳,宋波. Cr ³⁺比色荧光探针的合成及细胞成像应用[J]. 高等学校化学学报, 2019, 40(12): 2486-2493.
[15]	段玉珍,朱金玉,郭俊明,向明武,刘晓芳,白红丽,苏长伟. 尖晶石型锰酸锂正极材料LiNi_0.01Co_0.03Mn_1.96O₄的合成及电化学性能[J]. 高等学校化学学报, 2019, 40(12): 2574-2582.