生物基N,S双掺杂荧光碳点的制备及其应用
|
摘要
为了扩展造纸废液中的木质素磺酸钠的应用,以木质素磺酸钠和半胱氨酸为原料通过绿色的一步水热反应制备N, S双掺杂碳点,利用紫外可见光谱、荧光光谱和透射电镜等表征了碳点的光学性能、结构和对金属离子的选择性检测性能,结果表明制备的N,S双掺杂碳点可以识别Fe~(3+),在0.5～100μmol×L~(-1),Fe~(3+)的浓度与制备的碳点的荧光猝灭强度有良好的线性关系(R2=0.995)。将制备的碳点用于实际水样,结果表明可实现水样中3价铁离子的检测。此荧光探针原料成本低廉,制备绿色简便,在检测领域和生物质资源的高附加值应用领域有着很好的应用前景。
In order to expand the application of sodium lignosulfonate from pulping wastes, a green hydrothermal synthesis strategy was applied to synthesize nitrogen and sulfur co-doped carbon quantum dots using sodium lignosulfonate and L-cysteine. UV-vis spectroscopy, fluorescence spectroscopy and transmission electron microscopy were used to investigate optical properties, structure and metal ion selective detection of the carbon dots. The carbon dots can sensitively determine Fe~(3+) with a good linear relationship in the range of 0.5～100 μmol×L~(-1). The carbon dots were successfully used to measure Fe~(3+) concentration in environmental water samples. Furthermore, this fluorescent probe has properties of low cost, simple and green preparation,which has good potential in metal ion detection and can increase biomass added values.
In order to expand the application of sodium lignosulfonate from pulping wastes, a green hydrothermal synthesis strategy was applied to synthesize nitrogen and sulfur co-doped carbon quantum dots using sodium lignosulfonate and L-cysteine. UV-vis spectroscopy, fluorescence spectroscopy and transmission electron microscopy were used to investigate optical properties, structure and metal ion selective detection of the carbon dots. The carbon dots can sensitively determine Fe~(3+) with a good linear relationship in the range of 0.5～100 μmol×L~(-1). The carbon dots were successfully used to measure Fe~(3+) concentration in environmental water samples. Furthermore, this fluorescent probe has properties of low cost, simple and green preparation,which has good potential in metal ion detection and can increase biomass added values.
引文
[1] GILLET S, AGUEDO M, PETITJEAN L, et al. Lignin transformations for high value applications:Towards targeted modifications using green chemistry[J]. Green Chemistry, 2017, 19(18):4200-4233.
[2]李伟,佟国宾,王梦茹,等.碱木质素基碳量子点/TiO2复合光催化剂的制备[J].林业工程学报, 2016, 1(5):84-88.LI W, TONG G B, WANG M R, et al. Preparation of the alkaline lignin pyrolytic based carbon quantum dots/TiO2 composite photocatalyst[J]. Journal of Forestry Engineering, 2016, 1(5):84-88.
[3] RAGAUSKAS A J, BECKHAM G T, BIDDY M J, et al. Lignin valorization:Improving lignin processing in the biorefinery[J].Science, 2014, 344(6185):1246843.
[4]许利娜,黄坤,李守海,等.木质素磺酸钙-石墨烯复合量子点的制备及性能[J].化工进展, 2016, 35(11):3595-3599.XU L N, HUANG K, LI S H, et al. Synthesis and properties of lignin/graphene quantum dots composites as fluorescent sensor[J].Chemical Industry and Engineering Progress, 2016, 35(11):3595-3599.
[5] RENDERS T, VAN DEN BOSCH S, KOELEWIJN S F, et al. Lignin-first biomass fractionation:The advent of active stabilisation strategies[J]. Energy&Environmental Science, 2017, 10(7):1551-1557.
[6] SLUITER A, HAMES B, RUIZ R, et al. Determination of structural carbohydrates and lignin in biomass[J]. Laboratory Analytical Procedure, 2008, 1617:1-16.
[7] ALBADARIN A B, COLLINS M N, NAUSHAD M, et al. Activated lignin-chitosan extruded blends for efficient adsorption of methylene blue[J]. Chemical Engineering Journal, 2017, 307:264-272.
[8]冯雪敏,邱学青,楼宏铭,等.氧化改性对木质素磺酸盐络合性能的影响[J].高校化学工程学报, 2015, 29(6):1415-1421.FENG X M, QIU X Q, LOU H M, et al. Effects of oxidative modification on the chelating capacity of sodium lignosulfonate[J].Journal of Chemical Engineering of Chinese Universities, 2015, 29(6):1415-1421.
[9] NAIR V, PANIGRAHY A, VINU R. Development of novel chitosan-lignin composites for adsorption of dyes and metal ions from wastewater[J]. Chemical Engineering Journal, 2014, 254:491-502.
[10] JIA K, HE X H, ZHOU X F, et al. Solid state effective luminescent probe based on CdSe@CdS/amphiphilic co-polyarylene ether nitrile core-shell superparticles for Ag+detection and optical strain sensing[J]. Sensors and Actuators B:Chemical, 2018, 257:442-450.
[11] XU L N, FAN H, HUANG L X, et al. Eosinophilic nitrogen-doped carbon dots derived from tribute chrysanthemum for label-free detection of Fe3+ions and hydrazine[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78:247-253.
[12] JIANG Y L, WEI G, ZHANG W J, et al. Solid phase reaction method for preparation of carbon dots and multi-purpose applications[J]. Sensors and Actuators B:Chemical, 2016, 234:15-20.
[13] LI J J, ZUO G C, PAN X H, et al. Nitrogen-doped carbon dots as a fluorescent probe for the highly sensitive detection of Ag+and cell imaging[J]. Luminescence, 2018, 33(1):243-248.
[14] XU L N, MAO W, HUANG J R, et al. Economical, green route to highly fluorescence intensity carbon materials based on ligninsulfonate/graphene quantum dots composites:Application as excellent fluorescent sensing platform for detection of Fe3+ions[J]. Sensors and Actuators B:Chemical, 2016, 230:54-60.
[15] ZAN M H, RAO L, HUANG H M, et al. A strong green fluorescent nanoprobe for highly sensitive and selective detection of nitrite ions based on phosphorus and nitrogen co-doped carbon quantum dots[J]. Sensors and Actuators B:Chemical, 2018, 262:555-561.
[16] LI H T, KANG Z H, LIU Y, et al. Carbon nanodots:Synthesis, properties and applications[J]. Journal of Materials Chemistry,2012, 22(46):24230-24253.
[17] WANG F Y, LU Y X, CHEN Y, et al. Colorimetric nanosensor based on the aggregation of AuNP triggered by carbon quantum dots for detection of Ag+ions[J]. ACS Sustainable Chemistry&Engineering, 2018, 6(3):3706-3713.
[18] LIM S Y, SHEN W, GAO Z. Carbon quantum dots and their applications[J]. Chemical Society Reviews, 2015, 44(1):362-381.
[19] ZHU S J, SONG Y B, ZHAO X H, et al. The photoluminescence mechanism in carbon dots(graphene quantum dots, carbon nanodots, and polymer dots):Current state and future perspective[J]. Nano Research, 2015, 8(2):355-381.
[20] ZHENG X T, ANANTHANARAYANAN A, LUO K Q, et al. Glowing graphene quantum dots and carbon dots:Properties, syntheses,and biological applications[J]. Small, 2015, 11(14):1620-1636.
[21] LI L L, JI J, FEI R, et al. A facile microwave avenue to electrochemiluminescent two-color graphene quantum dots[J]. Advanced Functional Materials, 2012, 22(14):2971-2979.
[22] WEI W L, XU C, WU L, et al. Non-enzymatic-browning-reaction:A versatile route for production of nitrogen-doped carbon dots with tunable multicolor luminescent display[J]. Scientific Reports, 2014, 4:3564.
[23] ZHU A, QU Q, SHAO X, et al. Carbon-dot-based dual-emission nanohybrid produces a ratiometric fluorescent sensor for in vivo imaging of cellular copper ions[J]. Angewandte Chemie, 2012, 124(29):7297-7301.
[24] FREIRE R M, LE N D B, JIANG Z, et al. NH2-rich carbon quantum dots:A protein-responsive probe for detection and identification[J]. Sensors and Actuators B:Chemical, 2018, 255:2725-2732.
[25] ZHENG X T, ANANTHANARAYANAN A, LUO K Q, et al. Glowing graphene quantum dots and carbon dots:Properties, syntheses,and biological applications[J]. Small, 2015, 11(14):1620-1636.
[26] NIU W J, LI Y, ZHU R H, et al. Ethylenediamine-assisted hydrothermal synthesis of nitrogen-doped carbon quantum dots as fluorescent probes for sensitive biosensing and bioimaging[J]. Sensors and Actuators B:Chemical, 2015, 218:229-236.
[27] ZHANG R, CHEN W. Nitrogen-doped carbon quantum dots:Facile synthesis and application as a “turn-off” fluorescent probe for detection of Hg2+ions[J]. Biosensors and Bioelectronics, 2014, 55:83-90.
[28] XU Q, PU P, ZHAO J, et al. Preparation of highly photoluminescent sulfur-doped carbon dots for Fe(III)detection[J]. Journal of Materials Chemistry A, 2015, 3(2):542-546.
[29] YANG Z, XU M, LIU Y, et al. Nitrogen-doped, carbon-rich, highly photoluminescent carbon dots from ammonium citrate[J].Nanoscale, 2014, 6(3):1890-1895.
[30] ZENG Y W, MA D K, WANG W, et al. N, S co-doped carbon dots with orange luminescence synthesized through polymerization and carbonization reaction of amino acids[J]. Applied Surface Science, 2015, 342:136-143.
[31]徐源,陈艳华,丁兰.微波辅助法一步合成荧光碳点用于水中三价铁离子的检测[J].高等学校化学学报, 2018, 39(7):1420-1426.XU Y, CHEN Y H, DING L. One-pot microwave-assisted synthesis of passivated fluorescent carbon dots for Fe(III)detection[J].Chemical Research in Chinese Universities, 2018, 39(7):1420-1426.
[2]李伟,佟国宾,王梦茹,等.碱木质素基碳量子点/TiO2复合光催化剂的制备[J].林业工程学报, 2016, 1(5):84-88.LI W, TONG G B, WANG M R, et al. Preparation of the alkaline lignin pyrolytic based carbon quantum dots/TiO2 composite photocatalyst[J]. Journal of Forestry Engineering, 2016, 1(5):84-88.
[3] RAGAUSKAS A J, BECKHAM G T, BIDDY M J, et al. Lignin valorization:Improving lignin processing in the biorefinery[J].Science, 2014, 344(6185):1246843.
[4]许利娜,黄坤,李守海,等.木质素磺酸钙-石墨烯复合量子点的制备及性能[J].化工进展, 2016, 35(11):3595-3599.XU L N, HUANG K, LI S H, et al. Synthesis and properties of lignin/graphene quantum dots composites as fluorescent sensor[J].Chemical Industry and Engineering Progress, 2016, 35(11):3595-3599.
[5] RENDERS T, VAN DEN BOSCH S, KOELEWIJN S F, et al. Lignin-first biomass fractionation:The advent of active stabilisation strategies[J]. Energy&Environmental Science, 2017, 10(7):1551-1557.
[6] SLUITER A, HAMES B, RUIZ R, et al. Determination of structural carbohydrates and lignin in biomass[J]. Laboratory Analytical Procedure, 2008, 1617:1-16.
[7] ALBADARIN A B, COLLINS M N, NAUSHAD M, et al. Activated lignin-chitosan extruded blends for efficient adsorption of methylene blue[J]. Chemical Engineering Journal, 2017, 307:264-272.
[8]冯雪敏,邱学青,楼宏铭,等.氧化改性对木质素磺酸盐络合性能的影响[J].高校化学工程学报, 2015, 29(6):1415-1421.FENG X M, QIU X Q, LOU H M, et al. Effects of oxidative modification on the chelating capacity of sodium lignosulfonate[J].Journal of Chemical Engineering of Chinese Universities, 2015, 29(6):1415-1421.
[9] NAIR V, PANIGRAHY A, VINU R. Development of novel chitosan-lignin composites for adsorption of dyes and metal ions from wastewater[J]. Chemical Engineering Journal, 2014, 254:491-502.
[10] JIA K, HE X H, ZHOU X F, et al. Solid state effective luminescent probe based on CdSe@CdS/amphiphilic co-polyarylene ether nitrile core-shell superparticles for Ag+detection and optical strain sensing[J]. Sensors and Actuators B:Chemical, 2018, 257:442-450.
[11] XU L N, FAN H, HUANG L X, et al. Eosinophilic nitrogen-doped carbon dots derived from tribute chrysanthemum for label-free detection of Fe3+ions and hydrazine[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78:247-253.
[12] JIANG Y L, WEI G, ZHANG W J, et al. Solid phase reaction method for preparation of carbon dots and multi-purpose applications[J]. Sensors and Actuators B:Chemical, 2016, 234:15-20.
[13] LI J J, ZUO G C, PAN X H, et al. Nitrogen-doped carbon dots as a fluorescent probe for the highly sensitive detection of Ag+and cell imaging[J]. Luminescence, 2018, 33(1):243-248.
[14] XU L N, MAO W, HUANG J R, et al. Economical, green route to highly fluorescence intensity carbon materials based on ligninsulfonate/graphene quantum dots composites:Application as excellent fluorescent sensing platform for detection of Fe3+ions[J]. Sensors and Actuators B:Chemical, 2016, 230:54-60.
[15] ZAN M H, RAO L, HUANG H M, et al. A strong green fluorescent nanoprobe for highly sensitive and selective detection of nitrite ions based on phosphorus and nitrogen co-doped carbon quantum dots[J]. Sensors and Actuators B:Chemical, 2018, 262:555-561.
[16] LI H T, KANG Z H, LIU Y, et al. Carbon nanodots:Synthesis, properties and applications[J]. Journal of Materials Chemistry,2012, 22(46):24230-24253.
[17] WANG F Y, LU Y X, CHEN Y, et al. Colorimetric nanosensor based on the aggregation of AuNP triggered by carbon quantum dots for detection of Ag+ions[J]. ACS Sustainable Chemistry&Engineering, 2018, 6(3):3706-3713.
[18] LIM S Y, SHEN W, GAO Z. Carbon quantum dots and their applications[J]. Chemical Society Reviews, 2015, 44(1):362-381.
[19] ZHU S J, SONG Y B, ZHAO X H, et al. The photoluminescence mechanism in carbon dots(graphene quantum dots, carbon nanodots, and polymer dots):Current state and future perspective[J]. Nano Research, 2015, 8(2):355-381.
[20] ZHENG X T, ANANTHANARAYANAN A, LUO K Q, et al. Glowing graphene quantum dots and carbon dots:Properties, syntheses,and biological applications[J]. Small, 2015, 11(14):1620-1636.
[21] LI L L, JI J, FEI R, et al. A facile microwave avenue to electrochemiluminescent two-color graphene quantum dots[J]. Advanced Functional Materials, 2012, 22(14):2971-2979.
[22] WEI W L, XU C, WU L, et al. Non-enzymatic-browning-reaction:A versatile route for production of nitrogen-doped carbon dots with tunable multicolor luminescent display[J]. Scientific Reports, 2014, 4:3564.
[23] ZHU A, QU Q, SHAO X, et al. Carbon-dot-based dual-emission nanohybrid produces a ratiometric fluorescent sensor for in vivo imaging of cellular copper ions[J]. Angewandte Chemie, 2012, 124(29):7297-7301.
[24] FREIRE R M, LE N D B, JIANG Z, et al. NH2-rich carbon quantum dots:A protein-responsive probe for detection and identification[J]. Sensors and Actuators B:Chemical, 2018, 255:2725-2732.
[25] ZHENG X T, ANANTHANARAYANAN A, LUO K Q, et al. Glowing graphene quantum dots and carbon dots:Properties, syntheses,and biological applications[J]. Small, 2015, 11(14):1620-1636.
[26] NIU W J, LI Y, ZHU R H, et al. Ethylenediamine-assisted hydrothermal synthesis of nitrogen-doped carbon quantum dots as fluorescent probes for sensitive biosensing and bioimaging[J]. Sensors and Actuators B:Chemical, 2015, 218:229-236.
[27] ZHANG R, CHEN W. Nitrogen-doped carbon quantum dots:Facile synthesis and application as a “turn-off” fluorescent probe for detection of Hg2+ions[J]. Biosensors and Bioelectronics, 2014, 55:83-90.
[28] XU Q, PU P, ZHAO J, et al. Preparation of highly photoluminescent sulfur-doped carbon dots for Fe(III)detection[J]. Journal of Materials Chemistry A, 2015, 3(2):542-546.
[29] YANG Z, XU M, LIU Y, et al. Nitrogen-doped, carbon-rich, highly photoluminescent carbon dots from ammonium citrate[J].Nanoscale, 2014, 6(3):1890-1895.
[30] ZENG Y W, MA D K, WANG W, et al. N, S co-doped carbon dots with orange luminescence synthesized through polymerization and carbonization reaction of amino acids[J]. Applied Surface Science, 2015, 342:136-143.
[31]徐源,陈艳华,丁兰.微波辅助法一步合成荧光碳点用于水中三价铁离子的检测[J].高等学校化学学报, 2018, 39(7):1420-1426.XU Y, CHEN Y H, DING L. One-pot microwave-assisted synthesis of passivated fluorescent carbon dots for Fe(III)detection[J].Chemical Research in Chinese Universities, 2018, 39(7):1420-1426.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |