CN106047340B - The preparation and application of the graphene quantum dot of terpyridine moieties modification - Google Patents

The preparation and application of the graphene quantum dot of terpyridine moieties modification Download PDF

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CN106047340B
CN106047340B CN201610375550.0A CN201610375550A CN106047340B CN 106047340 B CN106047340 B CN 106047340B CN 201610375550 A CN201610375550 A CN 201610375550A CN 106047340 B CN106047340 B CN 106047340B
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王克志
亢思元
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Abstract

The invention discloses a kind of method of preparation method and applications ferrous ion concentration in water by Spectrophotometry sample of the graphene quantum dot of terpyridine moieties modification.This method has high sensitivity and selectivity.

Description

The preparation and application of the graphene quantum dot of terpyridine moieties modification
Technical field
The invention belongs to optochemical sensor field, it is related to the preparation method of the graphene quantum dot of terpyridine moieties modification And its application in the association area such as ferrous ion spectral detection and colorimetric sensing.
Background technology
Iron is the transition metal that content is most abundant in organism, is played an important role in many vital movements.Its Central Asia Iron ion is even more to play very important effect in oxygen transportation, DNA synthesis, electronics transfer and enzyme reaction etc..Ferro element Content and biochemistry, pharmacology and toxicological processes are closely bound up, and the shortage of ferro element or excess can all be destroyed in organism The homeostasis and metabolic processes of cell.Therefore ferrous ion is optionally detected for health with highly important Meaning.
Spectroscopic methodology, chromatography, voltammetry and inductivity coupled plasma mass spectrometry are all once used for the detection of ferro element, compared to it Under, with spectrum detection method that particular ligand is complexed it is simplest based on ferrous ion, has that detection speed is fast, environmental pollution Small, high sensitivity, the advantage such as easy to operate, cost is low, if forming colored complex, can carry out colorimetric biography to ferrous ion Sense, realizes fast and convenient qualitative and quantitative detection.Therefore research prepares the photochemistry for being used for ferrous ion detection and colorimetric passes Sensor has great importance [J.P.Desvergne, A.W.Czarnik, Chemosensors of Ion and Molecule Recognition.Dordrecht,Netherlands:Kluwer Academic Publishers,1997].But, with Fe3+ Compare, high sensitivity, high selectivity optical sensing Fe2+Report seldom [P.Wu, Y.Li, X.P.Yan, CdTe Quantum Dots(QDs)based kinetic discrimination of Fe2+and Fe3+,and CdTe QDs-Fenton hybrid system for sensitive photoluminescent detection of Fe2+,Anal.Chem., 2009,81(15),6252-6257；Z.Q.Liang,C.X.Wang,J.X.Yang,H.W.Gao,Y.P.Tian,X.T.Tao, M.H.Jiang,A highly selective colorimetric chemosensor for detecting the respective amounts of iron(II)and iron(III)ions in water,New J.Chem.,2007,31, 906-910.], especially colorimetric sensing Fe2+Extremely challenging [K.Chaiendoo, T.Tuntulani, W.Ngeontae, A highly selective colorimetric sensor for ferrous ion based on polymethylacrylic acid-templated silver nanoclusters,Sensors and Actuators B 207 (2015) 658-667.] completed because sensing may be identified by bore hole, it is not necessary to by optical instrument.
Composite organic-inorganic material is the new direction of sensor exploitation in recent years, wherein organic molecule covalent modification graphite It is even more a new breakthrough in ion sensor field that alkene quantum dot, which forms composite material, the compound of the formation stability in aqueous systems Height, has a good application prospect in biosystem.We, which organize, once reported that one kind was based on nano silicon dioxide ferrous ion Colorimetric sensor [J.Jia；H.Y.Zhou；S.Y.Kang；K.Z.Wang,Terpyridyl covalently functionalized silica microsphere for“naked-eye”colorimetric detection of ferrous ion in fully aqueous system,Colloids and Surfaces A:Physicochemical 499 (2016) 54-59. of and Engineering Aspects], in contrast, graphene quantum dot sensor has size It is small, the advantages that high sensitivity, detection range is big, and biocompatibility is more preferable.It can be seen from the above that research prepares graphene quantum dot ferrous iron Ion colorimetric sensor has huge application value.
The content of the invention
The purpose of the present invention is prepare a kind of 2,6- bis- (2- pyridine radicals) isonicotinic acid covalent modification graphene quantum dot to answer Condensation material sensor, and for the ferrous ion in high sensitivity and high selectivity detection aqueous systems.The concrete structure of sensor It is shown below：
Technical scheme is as follows：First, a kind of graphene of small size is largely synthesized using nitropyrene hydro-thermal method Quantum dot；Then surface is carried out to graphene quantum dot with silane coupling agent 3-aminopropyltriethoxysilane (APTES) to change Property, make the amino on quantum dot surface band with reactivity；Again using 2- acetylpyridines and glyoxylic acid ethyl ester as Material synthesis Organic molecule 2,6- bis- (2- pyridine radicals) isonicotinic acid with coordination site；Finally using the method for traditional organic synthesis by 2,6- Two (2- pyridine radicals) isonicotinic acid covalent modifications are on graphene quantum dot surface, you can the graphene of terpyridine moieties modification is made Quantum dot.
Graphene quantum dot sensor the present invention also provides the modification of above-mentioned 2,6- bis- (2- pyridine radicals) isonicotinic acid is in ferrous iron The application of the detection field of ion.
Compared with prior art, advantage of the invention is that：
The graphene quantum dot sensor of terpyridyl modification prepared by the present invention can be passed under aqueous systems using colorimetric Feel qualitative detection ferrous ion to exist and detect ferrous ion content in 0.1-10 μM of scope quantification, and with resist well from Sub- interference performance.Therefore the graphene quantum dot that the terpyridyl in the present invention is modified is in aqueous systems to the spectrum of ferrous ion Learning measure and colorimetric sensing has very wide application value.
Brief description of the drawings
Fig. 1 (a) is x- X-ray photoelectron spectroscopy Xs (XPS) gamut scanning figure of graphene quantum dot (GQDs)；Fig. 1 (b) For amido modified graphene quantum dot (GQDs-NH2) XPS gamut scanning figures；Fig. 1 (c) modifies graphite for terpyridyl The XPS gamut scanning figures of alkene quantum dot (GQDs-tpy)；Fig. 1 (d) is the high-resolution C1s XPS collection of illustrative plates of GQDs；Fig. 1 (e) is GQDs-NH2High-resolution C1s XPS collection of illustrative plates；Fig. 1 (f) is the high-resolution C1s XPS collection of illustrative plates of GQDs-tpy.Fig. 1 (g) is GQDs High-resolution N1s XPS collection of illustrative plates；Fig. 1 (h) is GQDs-NH2The high-resolution N1s XPS collection of illustrative plates of s；Fig. 1 (i) is the height of GQDs-tpy Differentiate N1s XPS collection of illustrative plates.
Fig. 2 is that the grapheme modified quantum dot of 40mg/L terpyridyls is acted on 20 μM of excessive 13 kinds of different metal ions Photo afterwards.
Fig. 3 (a) is with Fe2+The addition of (0-14 μM), causes the grapheme modified quantum dot of terpyridyl (40mg/L) The change of N- (2- ethoxys) piperazine-N'-2- ethane sulfonic acids (Hepes) solution (20mM, pH=7.2) uv-vis spectra, is inserted Figure represents absorbance of the grapheme modified quantum dot of terpyridyl at 565nm with Fe2+The situation of change of concentration.Fig. 3 (b) be with Fe2+The addition of (0-14 μM), cause the grapheme modified quantum dot of terpyridyl (40mg/L) Hepes solution (20mM,
PH=7.2) emission spectrum (λex=280nm) change, illustration represent the grapheme modified quantum dot of terpyridyl exist Fluorescence intensity at 372nm is with Fe2+The situation of change of concentration.
Fig. 4 is in the grapheme modified quantum dot of 40mg/L terpyridyls while adds Fe2+With other metal ions, cause The change of uv-vis spectra, wherein [Fe2+]=[other metals]=20 μM.
Embodiment
Embodiment 1：The preparation of 2,6- bis- (2- pyridine radicals) isonicotinic acid covalent modification graphene quantum dot is complete according to following 4 step Into：
(1) document [L.Wang is pressed；Y.Wang；T.Xu；H.Liao；C.Yao；Y.Liu；Z.Li；Z.Chen；D.Pan； L.Sun；M.Wu,Gram-scale synthesis of single-crystalline graphene quantum dots With superior optical properties, Nat.commun., 2014, (5), 5357.] method synthesizing graphite alkene amount Sub- point.The pyrene of 1.0g is taken in the round-bottomed flask of 250mL, adds 100mL concentrated nitric acids, reaction 12h, filtering are stirred at reflux at 80 DEG C Obtain 1,3,6- trinitro- pyrenes 1.52g.To obtain 1,3,6- trinitro- pyrenes are put into the NaOH solution of 300mL 0.2M, ultrasound Scattered 45min, rear to add in 100mL reaction kettles, 200 DEG C of reaction 10h, with aperture are 0.22 μm of filtering with microporous membrane after reaction, Remove unreacted carbon.Solution is dialysed two days in the bag filter of 3500Da, drying obtains graphene quantum dot (GQDs) 1.134g。
(2) graphene quantum dot surface is modified with coupling agent 3-aminopropyltriethoxysilane.By 0.30g stones Black alkene quantum dot, 0.5g 3- aminopropyl front three oxosilanes ((CH3CH2O)3Si(CH2)3NH2) be put into 180mL ethanol, ultrasound point Dissipate 0.5h, at 80 DEG C heating stirring flow back 6h, filtration washing it is dry 0.2267g GQDs-NH2Product.
(3) document [Z.B.Zheng, Z.M.Duan, Y.Y.Ma, K.Z.Wang, Highly Sensitive and are pressed Selective Difunctional Ruthenium(II)Complex-Based Chemosensor for Dihydrogen Phosphate Anion and Ferrous Cation, Inorg.Chem., 2013,52,2306.] synthesis (the 2- pyrroles of 2,6- bis- Piperidinyl) isonicotinic acid.By the toluene solution of 2- acetylpyridines (0.29g, 2.4mmol) and glyoxylic acid ethyl ester (50%, 0.24mL, 1.2mmol) it is dissolved in 8mL methanol, stirring after five minutes, adds 15% KOH solution (7.2mL) and concentrated ammonia liquor (0.8mL), Mixed liquor is stirred at room temperature 3 days, separates out a large amount of precipitations.Collected by suction precipitates, and precipitation is cold with 4mL chloroforms and 4mL successively CH3OH/H2O(V:V=1:1) wash.Obtained crude product is distributed in the mixed liquor of 80mL methanol and 20mL water, is heated to 35 DEG C, Stirring makes it all dissolve.Then 1M hydrochloric acid tune pH=2 are added, separate out a large amount of white precipitates.Filter, washed with cold water, vacuum is done GQDs-tpy products 0.34g is obtained after dry.
(4) by 2,6- bis- (2- pyridine radicals) isonicotinic acid covalent modification on graphene quantum dot surface.Take (the 2- pyridines of 2,6- bis- Base) isonicotinic acid (94mg, 0.3mM), it is dissolved in 10mL SOCl2In, mixture is in N21h is stirred at reflux under protection, vacuum distillation removes Remove solvent.The anhydrous THF of 10mL, 2mLEt are sequentially added into remaining solid3N, 50mg GQDs-NH2, mixture is in N2Under protection It is stirred at reflux 12h.After reaction stops, filtering, precipitation is washed repeatedly with dichloromethane, dries to obtain product 40.6mg.
Embodiment 2：The characterization of graphene quantum dot sensor
Whether graphene quantum dot is accessed for verification terpyridyl, using XPS respectively to GQDs, GQDs-NH2, GQDs- Tpy, is characterized.Except fairly obvious C 1s it can be seen from the XPS gamut scanning figures shown in Fig. 1 (a), (b), (c) Outside the characteristic peak of O1s, with amination and the introducing of terpyridyl ,~400eV N 1s feature peak intensities gradually strengthen.Fig. 1 (d), (e), (f) and Fig. 1 (g), (h), (i) are GQDs, GQDs-NH respectively2, GQDs-tpy high-resolution C 1s and N 1s XPS figure Spectrum.It was found that after amination, there occurs red shift by a small margin for C 1s and N 1s spectrum.Shown in Fig. 1 (f) and Fig. 1 (i), three pyrroles are accessed After pyridine, for C 1s spectrum in 286.0eV, there is C-N, C=O, O=C-N-H new characteristic peak, N 1s light in 286.4eV, 288.7eV There is N-C, N-C=O, N-H new characteristic peak in 398.9eV, 399.8eV and 400.6eV in spectrum.This explanation terpyridine moieties It is connected by amido link with graphene quantum dot.
Embodiment 3：Colorimetric sensing of the graphene quantum dot sensor to ferrous ion
In 14 cuvettes, 3mL Hepes buffer solutions (20mM, pH=7.2), three pyrroles of 40mg/L are separately added into The grapheme modified quantum dot of pyridine.First cuvette is separately added into 20 μM 13 as blank control in remaining 13 cuvette Kind different metal ions (Na+,Mg2+,Ba2+,Mn2+,Fe2+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Cd2+,Hg2+,Ag+), such as Fig. 2 Shown, the addition of remaining 12 metal ion species, solution adds Fe without significant change2+Solution is changed into purple from colourless afterwards.This Illustrate, the grapheme modified quantum dot of terpyridyl is a very good Fe2+Colorimetric sensor.
Embodiment 4：Graphene quantum dot sensor is to working curve in the spectral response of ferrous ion and quantitative detection Draw
Uv-visible absorption spectra measures on UV-2600 spectrophotometry instrument, and fluorescence emission spectrum exists Measured on Cary Eclipse sepectrophotofluorometers (Varian).With Hepes buffer solutions (20mM, pH=7.2) during measure As reference liquid, Asia is continuously added into Hepes (20mM, pH=7.2) solution of 40mg/L covalent modification graphene quantum dots Ferric ion solutions (0-14 μM), and measure ultraviolet and fluorescence spectrum.It was found that solution is changed into purple from colourless after adding ferrous ion, And deepen with the increase purple of ferrous ion concentration.According to absorption spectrum, after adding ferrous ion, the suction of nano-particle Receive spectrum and occur new absworption peak at 565nm, show that the terpyridyl part of organic molecule is coordinated with ferrous ion Effect, so as to cause spectrum change, new absworption peak appears in visible region, and the complex of formation is colored complex, is Realize and provide the foundation to the colorimetric sensing of ferrous ion.In the range of ferrous ion concentration is 0-10 μM, terpyridyl modification Absorbance of the graphene quantum dot at 565nm have good linear response to ferrous ion concentration, can obtain such as Fig. 3 accordingly (a) the measure Fe in shown in illustration2+Working curve.With Fe as shown in Fig. 3 (b)2+Addition, 375nm (λex=280nm) The intensity of place's emission peak, which is gradually reduced until, to be quenched.Illustration is the working curve drawn according to fluorescence spectrum.
Embodiment 5：Measure of the graphene quantum dot sensor to the test limit of ferrous ion
3mL Hepes buffer solutions (20mM, pH=7.2) are sequentially added in cuvette, the terpyridyl of 40mg/L is repaiied Graphene quantum dot is adornd, and measures uv-vis spectra, records the absorbance at 565nm.5 groups of experiments are done in repetition, draw 6 groups Data simultaneously calculate standard deviation=6.05 × 10-10, i.e. the signal-to-noise ratio of instrument.Working curve in Fig. 3 (a), obtains 0- 10 μM of working curve slope K=0.0127.And then it can draw test limit of the graphene quantum dot sensor to ferrous ion For 1.43 × 10-7M(3σ/K).
Embodiment 6：Selectivity of the graphene quantum dot sensor to ferrous ion
Reference liquid is used as with Hepes solution (20mM, pH=7.2), to 40mg/L covalent modification graphene quantum dots 20 μM of Fe is added in Hepes (20mM, pH=7.2) solution2+, then it is separately added into 12 kinds of different metal ions of same concentrations (Na+,Mg2+,Ba2+,Mn2+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Cd2+,Hg2+,Ag+), and ultraviolet-visible spectrum is measured, observe The change of absworption peak at 565nm.As shown in figure 4, excessive interfering ion is to identifying Fe2+Interference is little, wherein Fe3+And Ni2+Meeting The absworption peak at 585nm is set slightly to strengthen, and Co2+,Cu2+And Hg2+The absworption peak at 585nm can be made to lose lustre, but be easy to It was observed that the presence of the absworption peak.Na+,Mg2+,Ba2+,Mn2+,Zn2+,Cd2+, and Ag+Influence very little to the absworption peak.As a result Illustrate, the graphene quantum dot of terpyridyl modification is to Fe2+Selectivity have good colorimetric detection selectivity.
Embodiment 7：Concentration mensuration of the graphene quantum dot sensor to water sample ferrous ions
3mL water samples to be measured and concentration is taken to be mixed in for the graphene quantum dot of 40mg/L terpyridyls modification in cuvette, Stand after five minutes, measure uv-vis spectra.Absorbance at 565nm and the working curve in Fig. 3 (a) are contrasted, into And draw Fe2+Concentration.
Embodiment 8：Graphene quantum dot sensor measures the anti-interference of ferrous ion
Reference liquid is used as with Hepes solution (20mM, pH=7.2), to 40mg/L covalent modification graphene quantum dots 13 kinds of different metal ions (Na of same concentrations are added in Hepes (20mM, pH=7.2) solution at the same time+,Mg2+,Ba2+,Mn2+, Fe2+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Cd2+,Hg2+,Ag+), and ultraviolet-visible spectrum is measured, observe absworption peak at 565nm Intensity.It was found that add different kinds of ions after solution color and 565nm place absorption peak strength do not have significant change, this illustrate this The graphene quantum dot of terpyridyl modification is to Fe2+Colorimetric identification there is good anti-interference.

Claims (2)

  1. A kind of 1. graphene quantum dot of terpyridine moieties covalent modification, it is characterised in that：The graphene quantum dot of the modification With such as lower structure
  2. A kind of 2. purposes of the graphene quantum dot of the modification described in claim 1, it is characterised in that：Graphene after the modification Quantum dot is used for the spectrophotometry of ferrous ion in aqueous solution.
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Terpyridyl covalently functionalized silica microsphere for"naked-eye" colorimetric detection of ferrous ion in fully aqueous system;Jia Jia et al.;《Colloids and Surfaces A: Physicochemical and Engineering Aspects》;20160401;54-59 *

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