Citation: HUANG Yanjie, LIAN Chao, ZHOU Jinyan, HUANG Zichen, KANG Xiaohong, HUANG Zhenyu, LI Xiaojing, CHEN Lin, GUAN Yan. Investigation of Excitation-, pH-, Metal Ion-, Temperature-, and Polarity-Dependent Fluorescence of Carbon Dots Derived from Silkworm Excrement[J]. Acta Physico-Chimica Sinica, ;2019, 35(11): 1267-1275. doi: 10.3866/PKU.WHXB201812053 shu

Investigation of Excitation-, pH-, Metal Ion-, Temperature-, and Polarity-Dependent Fluorescence of Carbon Dots Derived from Silkworm Excrement

1.
Guangdong Provincial Key Laboratory of Modern Geometric and Mechanical Metrology Technology, Guangdong Provincial Institute of Metrology, Guangzhou 510405, P. R. China
2.
Department of Chemistry, School of Science, Beijing Jiaotong University, Beijing 100044, P. R. China
3.
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Corresponding author: HUANG Yanjie, yjhuang@scm.com.cn GUAN Yan, yanguan@pku.edu.cn
Received Date: 30 December 2018
Revised Date: 22 February 2019
Accepted Date: 25 February 2019
Available Online: 4 November 2019
Fund Project: The project was supported by the National Natural Science Foundation of China (21204001), Technical Project of Guangdong Science and Technology Department, China (2017A040405034) and the Technical Project of Guangdong Provincial Bureau of Quality and Technical Supervision, China (2018ZJ02)

As a new fluorescent nanomaterial, carbon dots (CDs) have many advantages, such as uniform particle size distribution, good light stability, adjustable excitation-emission wavelength, and surface modification. Moreover, one of the fascinating characters of CDs is that they are considered to be low-toxic and eco-friendly alternatives in chemical and biological analyses. They have exhibited broad application prospects in the fields of analysis, detection, and bioimaging. Silkworm excrement is dried and easily available. A large number of hydroxyl and carboxyl compounds in silkworm excrement can be used as ideal starting materials for the preparation of CDs. Also, compounds containing nitrogen and sulfur in silkworm excrement can be used as nitrogen and sulfur sources; thus, when used in the preparation of CDs, silkworm excrement can impart many more unique properties to CDs. Nitrogen-containing CDs prepared by microwave synthesis have an average hydration diameter of 4.86 nm. Elemental analysis data show that the prepared CDs contained 59.84% carbon, 5.46% nitrogen, and 2.32% sulfur. XPS spectra reveals sulfur (2p), carbon (1s), nitrogen (1s), and oxygen (1s) in CDs. FTIR data demonstrate that the prepared CDs may contain hydroxyl, amino, carbonyl, sulfonic, ester, and ether functional groups as well as carbon-nitrogen structures. The XRD pattern of the CDs has a broader peak of the amorphous carbon phase at approximately 2θ = 24.6°, and only D bands (at ~1400 cm^-1) can be obviously detected in the Raman spectra of CDs. The intensity of fluorescence emission peak of CDs increases first and then decreases with the increase in excitation wavelength. The maximum intensity of fluorescence emission shifts gradually with the red shift of the excitation wavelength, and the relationship between excitation and emission wavelengths is exponential. In the pH ranging from 2.18 to 10.24, the fluorescence emission intensity of CDs decreases gradually with the increase in pH, and the maximum fluorescence emission intensity shifts gradually with the increase in pH. There is a linear relationship between pH and maximum emission wavelength. The fluorescence emission intensity of CDs decreases gradually with the increase in metal ion concentration. Under neutral conditions, CDs can selectively detect Cu²⁺. Under acidic conditions, CDs can detect Cu²⁺, Fe³⁺, Al³⁺, Ni²⁺, and Fe²⁺ separately without interference from other ions. There is a Stern-Volmer linear relationship between metal ion concentration and fluorescence intensity. The intensity of the fluorescence emission peak of CDs decreases with the increase in temperature, which may be due to the non-radiative transition process caused by molecular thermal motion. There is a linear relationship between temperature and fluorescence intensity. The maximum fluorescence emission intensity of CDs gradually shifts with the increase in polarity of the dispersed solvents. There is a linear relationship between fluorescence intensity and empirical constant E_T of solvent polarity. Compared with the reported CDs prepared from natural products, silkworm-excrement-based CDs have abundant surface groups although they do not have an obvious crystal structure, which makes them have excellent response to various environmental factors (pH, temperature, ion concentration, temperature, solvent polarity, etc.) in a wide range. Above all, the fluorescence property changes with multiple environmental parameters will facilitate a broad application of silkworm-excrement-based CDs in biodetection and imaging.
- Carbon dots,
- Silkworm excrement,
- Nano-materials,
- Fluorescence,
- Sensing
1. [1]
  Wang, R.; Lu, K. Q.; Tang, Z. R.; Xu, Y. J. J. Mater. Chem. A 2017, 5 (8), 3717. doi: 10.1039/C6TA08660H doi: 10.1039/C6TA08660H
2. [2]
  Li, S. H.; Weng, B.; Lu, K. Q.; Xu, Y. J. Acta Phys. -Chim. Sin. 2018, 34 (6), 708. doi: 10.3866/PKU.WHXB201710162
3. [3]
  Lu, K. Q.; Quan, Q.; Zhang, N.; Xu, Y. J. J. Energy Chem. 2016, 25 (6), 927. doi: 10.1016/j.jechem.2016.09.015 doi: 10.1016/j.jechem.2016.09.015
4. [4]
  Wang, X.; Cao, L.; Lu, F. S.; Meziani, M. J.; Li, H. T.; Qi, G.; Zhou, B.; Harruff, B. A.; Kermarrec, F.; Sun, Y. P. Chem. Commun. 2009, 46 (25), 3774. doi: 10.1039/B906252A doi: 10.1039/B906252A
5. [5]
  Kumar, A.; Chowdhuri, A. R.; Laha, D.; Mahto, T. K.; Karmakar, P.; Sahu, S. K. Sensor Actuat. B-Chem. 2017, 242, 679. doi: 10.1016/j.snb. 2016.11.109 doi: 10.1016/j.snb.2016.11.109
6. [6]
  Ge, J. C.; Jia, Q. Y.; Liu, W. M.; Guo, L.; Liu, Q. Y.; Lan, M. H.; Zhang, H. Y.; Meng, X. M.; Wang, P. F. Adv. Mater. 2015, 27 (28), 4169. doi: 10.1002/adma. 201500323 doi: 10.1002/adma.201500323
7. [7]
  Lin, F.; He, W. N.; Guo, X. Q. Adv. Mater. Res. 2011, 415-417, 1319. doi: 10.4028/www.scientific.net/AMR.415-417.1319 doi: 10.4028/www.scientific.net/AMR.415-417.1319
8. [8]
  Lin, F.; Pei, D. J.; He, W. N.; Huang, Z. X.; Huang, Y. J.; Guo, X. Q. J. Mater. Chem. 2012, 22 (23), 11801. doi: 10.1039/c2jm31191g doi: 10.1039/c2jm31191g
9. [9]
  Anjana, R. R.; Anjali Devi, J. S.; Jayasree, M.; Aparna, R. S.; Aswathy, B.; Praveen, G. L.; Lekha, G. M.; Sony, G. Microchim. Acta 2018, 185 (1), 11. doi: 10.1007/s00604-017-2574-8 doi: 10.1007/s00604-017-2574-8
10. [10]
  Jiang, K.; Sun, S.; Zhang, L.; Lu, Y.; Wu, A. G; Cai, C. Z.; Lin, H. W. Angew. Chem. Int. Edit. 2015, 54 (18), 5360. doi: 10.1002/ange.201501193 doi: 10.1002/ange.201501193
11. [11]
  Wang, X. D.; Wolfbeis, O. S.; Meier, R. J. Chem. Soc. Rev. 2013, 42 (19), 7834. doi: 10.1039/c3cs60102a doi: 10.1039/c3cs60102a
12. [12]
  Zu, F. L.; Yan, F. Y.; Bai, Z. J.; Xu, J. X.; Wang, Y. Y.; Huang, Y. C.; Zhou, X. G. Microchim. Acta 2017, 184 (7), 1899. doi: 10.1007/s00604-017-2318-9 doi: 10.1007/s00604-017-2318-9
13. [13]
  Sun, Y. P.; Zhou, B.; Lin, Y.; Wang, W.; Fernando, K. A.; Pathak, P.; Meziani, M. J.; Harruff, B. A.; Wang, X.; Wang, H. J. Am. Chem. Soc. 2006, 128 (24), 7756. doi: 10.1021/ja062677d doi: 10.1021/ja062677d
14. [14]
  Yang, S. T.; Wang, X.; Wang, H. F.; Lu, F. S.; Luo, P. G.; Cao, L.; Meziani, M. J.; Liu, J. H.; Liu, Y. F.; Chen, M.; et al. J. Phys. Chem. C 2009, 113 (42), 18110. doi: 10.1021/jp9085969 doi: 10.1021/jp9085969
15. [15]
  Dong, Y. Q.; Zhou, N. N.; Lin, X. M.; Lin J. P.; Chi, Y. W.; Chen, G. N. Chem. Mater. 2010, 22 (21), 5895. doi: 10.1021/cm1018844 doi: 10.1021/cm1018844
16. [16]
  Bourlinos, A. B.; Stassinopoulos, A.; Anglos, D.; Zboril, R.; Georgakilas, V.; Giannelis, E. P. Chem. Mater. 2008, 20 (14), 4539. doi: 10.1021/cm800506r doi: 10.1021/cm800506r
17. [17]
  Lim, S. Y.; Shen, W.; Gao, Z. Q. Chem. Soc. Rev. 2015, 44 (1), 362. doi: 10.1039/C4CS00269E doi: 10.1039/C4CS00269E
18. [18]
  Balandin, A. A. Nat. Mater. 2011, 10 (8), 569. doi: 10.1038/nmat3064 doi: 10.1038/nmat3064
19. [19]
  Zhou, J. J.; Sheng, Z. H.; Han, H. Y; Zou, M. Q.; Li, C. X. Mater. Lett. 2012, 66 (1), 222. doi: 10.1016/j.matlet.2011.08.081 doi: 10.1016/j.matlet.2011.08.081
20. [20]
  Wang, L.; Zhou, H. S. Anal. Chem. 2014, 86 (18), 8902. doi: 10.1021/ac502646x doi: 10.1021/ac502646x
21. [21]
  Xu, J. Y.; Zhou, Y.; Liu, S. X.; Dong, M. T.; Huang, C. B. Anal. Methods 2014, 6 (7), 2086. doi: 10.1039/C3AY41715H doi: 10.1039/C3AY41715H
22. [22]
  Zhu, S. J.; Meng, Q. N.; Wang, L.; Zhang, J. H.; Song, Y. B.; Jin, H.; Zhang, K.; Sun, H. C.; Wang, H.; Yang, B. Angew. Chem. Int. Edit. 2013, 52 (14), 3953. doi: 10.1002/anie.201300519 doi: 10.1002/anie.201300519
23. [23]
  Sun, D.; Ban, R.; Zhang P. H.; Wu G. H.; Zhang J. R.; Zhu J. J. Carbon 2013, 64 (11), 424. doi: 10.1016/j.carbon.2013.07.095. doi: 10.1016/j.carbon.2013.07.095
24. [24]
  Wang, J.; Wang, C. F.; Chen, S. Angew. Chem. Int. Edit. 2012, 51 (37), 9297. doi: 10.1002/anie.201204381 doi: 10.1002/anie.201204381
25. [25]
  Liu, K. P.; Zhang, J. J.; Cheng, F. F.; Zheng, T. T.; Wang, C. M.; Zhu, J. J. J. Mater. Chem. 2011, 21 (32), 12034. doi: 10.1039/C1JM10749F doi: 10.1039/C1JM10749F
26. [26]
  Zong, J.; Yang, X. L.; Trinchi, A.; Hardin, S.; Cole, I.; Zhu, Y. H.; Li, C. Z.; Muster, T.; Wei, G. Biosens. Bioelectron. 2014, 51, 330. doi: 10.1016/j.bios.2013.07.042 doi: 10.1016/j.bios.2013.07.042
27. [27]
  Wei, W. L.; Xu, C.; Ren, J. S.; Xu, B. L.; Qu, X. G. Chem. Commun. 2012, 48 (9), 1284. doi: 10.1039/C2CC16481G doi: 10.1039/C2CC16481G
28. [28]
  Tang, M. X.; Huang, Y. J.; Wang, Y.; Fu, L. M. Dalton T. 2015, 44 (16), 7449. doi: 10.1039/C5DT00611B doi: 10.1039/C5DT00611B
29. [29]
  Faustino, W. M.; Nunes, L. A.; Terra, I. A. A.; Felinto, M. C. F. C.; Brito, H. F.; Malta, O. L. J. Lumin. 2013, 137, 269. doi: 10.1016/j.jlumin. 2013.01.008 doi: 10.1016/j.jlumin.2013.01.008
30. [30]
  Pan, D. Y.; Zhang, J. C.; Li, Z.; Wu, C.; Yan, X. M.; Wu, M. H. Chem. Commun. 2010, 46 (21), 3681. doi: 10.1039/C000114G doi: 10.1039/C000114G
31. [31]
  Paraknowitsch, J. P.; Zhang, Y. J.; Wienert, B.; Thomas, A. Chem. Commun. 2013, 49 (12), 1208. doi: 10.1039/c2cc37398j doi: 10.1039/c2cc37398j
32. [32]
  Liu, H.; Zhang, Y.; Liu, J. H.; Hou, P.; Zhou, J.; Huang, C. Z. RSC Adv. 2017, 7 (80), 50584. doi: 10.1039/C7RA10130A doi: 10.1039/C7RA10130A
33. [33]
  Wu, Z. L.; Zhang, P.; Gao, M. X.; Liu, C. F.; Wang, W.; Leng, F.; Huang, C. Z. J. Mater. Chem. B 2013, 1 (22), 2868. doi: 10.1039/C3TB20418A doi: 10.1039/C3TB20418A
34. [34]
  Zhu, L. L.; Yin, Y. J.; Wang, C. F.; Chen, S. J. Mater. Chem. C 2013, 1 (32), 4925. doi: 10.1039/C3TC30701H doi: 10.1039/C3TC30701H
1. [1]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-Scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-. doi: 10.3866/PKU.WHXB202403005
2. [2]
  Zunyuan Xie , Lijin Yang , Zixiao Wan , Xiaoyu Liu , Yushan He . Exploration of the Preparation and Characterization of Nano Barium Titanate and Its Application in Inorganic Chemistry Laboratory Teaching. University Chemistry, 2024, 39(4): 62-69. doi: 10.3866/PKU.DXHX202310137
3. [3]
  Juan Yuan , Bin Zhang , Jinping Wu , Mengfan Wang . Design of a Comprehensive Experiment on Preparation and Characterization of Cu₂(Salen)₂ Nanomaterials with Two Distinct Morphologies. University Chemistry, 2024, 39(10): 420-425. doi: 10.3866/PKU.DXHX202402014
4. [4]
  Simin Fang , Wei Huang , Guanghua Yu , Cong Wei , Mingli Gao , Guangshui Li , Hongjun Tian , Wan Li . Integrating Science and Education in a Comprehensive Chemistry Design Experiment: The Preparation of Copper(I) Oxide Nanoparticles and Its Application in Dye Water Remediation. University Chemistry, 2024, 39(8): 282-289. doi: 10.3866/PKU.DXHX202401023
5. [5]
  Zian Fang , Qianqian Wen , Yidi Wang , Hongxia Ouyang , Qi Wang , Qiuping Li . The Test Paper for Metal Ion: A Popular Science Experiment Based on Color Aesthetics. University Chemistry, 2024, 39(5): 108-115. doi: 10.3866/PKU.DXHX202310032
6. [6]
  Chengcheng Si , Linshan Chai , Huiyuan Liu , Liye Sun , Shijian Cheng , Hailing Li , Wenyun Wang , Fang Liu , Qing Feng , Min Liu . Harry Potter China Tour Themed Innovative Science Popularization Experiment: Chemistry Magic Meets the Real World at Wuhan Station. University Chemistry, 2024, 39(9): 283-287. doi: 10.12461/PKU.DXHX202401069
7. [7]
  YanYuan Jia , Rong Rong , Jie Liu , Jing Guo , GuoYu Jiang , Shuo Guo . Unity is Strength, and Independence Shines: A Science Popularization Experiment on AIE and ACQ Effects. University Chemistry, 2024, 39(9): 349-358. doi: 10.12461/PKU.DXHX202402035
8. [8]
  Qin Li , Kexin Yang , Qinglin Yang , Xiangjin Zhu , Xiaole Han , Tao Huang . Illuminating Chlorophyll: Innovative Chemistry Popularization Experiment. University Chemistry, 2024, 39(9): 359-368. doi: 10.3866/PKU.DXHX202309059
9. [9]
  Wenjun Zheng . Application in Inorganic Synthesis of Ionic Liquids. University Chemistry, 2024, 39(8): 163-168. doi: 10.3866/PKU.DXHX202401020
10. [10]
  Jianjun Liu , Xue Yang , Chi Zhang , Xueyu Zhao , Zhiwei Zhang , Yongmei Chen , Qinghong Xu , Shao Jin . Preparation and Fluorescence Characterization of CdTe Semiconductor Quantum Dots. University Chemistry, 2024, 39(7): 307-315. doi: 10.3866/PKU.DXHX202311031
11. [11]
  Siyi ZHONG , Xiaowen LIN , Jiaxin LIU , Ruyi WANG , Tao LIANG , Zhengfeng DENG , Ao ZHONG , Cuiping HAN . Targeting imaging and detection of ovarian cancer cells based on fluorescent magnetic carbon dots. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1483-1490. doi: 10.11862/CJIC.20240093
12. [12]
  Shuwen SUN , Gaofeng WANG . Two cadmium coordination polymers constructed by varying Ⅴ-shaped co-ligands: Syntheses, structures, and fluorescence properties. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 613-620. doi: 10.11862/CJIC.20230368
13. [13]
  Miaomiao He , Zhiqing Ge , Qiang Zhou , Jiaqing He , Hong Gong , Lingling Li , Pingping Zhu , Wei Shao . Exploring the Fascinating Realm of Quantum Dots. University Chemistry, 2024, 39(6): 231-237. doi: 10.3866/PKU.DXHX202310040
14. [14]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
15. [15]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
16. [16]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
17. [17]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
18. [18]
  Yan ZHAO , Xiaokang JIANG , Zhonghui LI , Jiaxu WANG , Hengwei ZHOU , Hai GUO . Preparation and fluorescence properties of Eu³⁺-doped CaLaGaO₄ red-emitting phosphors. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1861-1868. doi: 10.11862/CJIC.20240242
19. [19]
  Tengjiao Wang , Tian Cheng , Rongjun Liu , Zeyi Wang , Yuxuan Qiao , An Wang , Peng Li . Conductive Hydrogel-based Flexible Electronic System: Innovative Experimental Design in Flexible Electronics. University Chemistry, 2024, 39(4): 286-295. doi: 10.3866/PKU.DXHX202309094
20. [20]
  Fang Niu , Rong Li , Qiaolan Zhang . Analysis of Gas-Solid Adsorption Behavior in Resistive Gas Sensing Process. University Chemistry, 2024, 39(8): 142-148. doi: 10.3866/PKU.DXHX202311102

Get Citation

PDF

XML

Metrics

PDF Downloads(14)
Abstract views(654)
HTML views(199)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142