CN105384769B - The preparation and application of the nano-silicon dioxide particle of terpyridine moieties modification - Google Patents
The preparation and application of the nano-silicon dioxide particle of terpyridine moieties modification Download PDFInfo
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- CN105384769B CN105384769B CN201510423330.6A CN201510423330A CN105384769B CN 105384769 B CN105384769 B CN 105384769B CN 201510423330 A CN201510423330 A CN 201510423330A CN 105384769 B CN105384769 B CN 105384769B
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Abstract
The invention discloses a kind of method of preparation method and applications ferrous ion concentration in AAS and bore hole semiquantitative determination water sample of the nanometer titanium dioxide silicon nano of terpyridine moieties modification.This method has high sensitivity and selectivity.
Description
Technical field
The invention belongs to optochemical sensor field, is related to the nanometer titanium dioxide silicon nano of terpyridine moieties modification
Preparation method 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, because ferrous ion is combined extensively with many enzymes and protein
It is present in vital movement, therefore it plays important physiological regulatory action in organism.As ferrous ion can be with blood
In hemoglobin combine, by oxygen from each cell for being transported to organism.In organism the shortage of ferro element or it is excessive all
The homeostasis and metabolic processes of cell can be destroyed.Accumulation of the ferro element in central nervous system may cause Huntingdon
The diseases such as disease, Parkinson's and senile dementia.Baby, pregnant woman and children in adolescence are easy to the situation for iron deficiency occur, so as to draw
The symptoms such as anaemia, hypoimmunity are sent out, influence the healthy growth of human body.Therefore optionally detection ferrous ion is good for for human body
Health tool is of great significance.
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, realize fast and convenient quantitative and semi-quantitative detection.Therefore research prepares the photochemistry and colorimetric for being used for ferrous ion detection
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 nanometer
This kind of composite of silica is widely used in terms of ion sensor.Nano silicon has larger specific surface area,
It is synthesized and covalent modification is simple and easy, and the composite gauge of formation is small, and stability is high in aqueous systems, nontoxic, is had good
Good bio-compatibility, there is good application prospect in biosystem.The mode of covalent modification can effectively avoid organic molecule
Leached from composite, improve the durability of sensor, make it possible that it is recycled.As can be seen here, research and develop
Nano silicon compound sensor has huge potential using value in terms of ferrous ion is detected.
The content of the invention
The purpose of the present invention is to prepare a kind of 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid covalent modification receives
The composite sensor of rice silica, and for the ferrous ion in high sensitivity and high selectivity detection aqueous systems.Pass
The concrete structure of sensor is shown below：
Technical scheme is as follows：First, have one using tetraethyl orthosilicate (TEOS) Hydrolyze method synthesis of classics
The nano-silicon dioxide particle being sized；Then with silane coupler APTES (APTES) to nanometer
It is silica surface modified, make the amino on silica surface band with reactivity；Again with 2- acetylpyridines and to aldehyde
Yl benzoic acid is organic molecule the 4- [(2,2' that Material synthesis has coordination site:6', 2 "-terpyridyl) -4'- bases] benzene first
Acid；Finally use 1- (3- dimethylamino-propyls) -3- ethyl carbon inferior amine salt hydrochlorates (EDC) and n-hydroxysuccinimide (NHS)
The method of activation is by 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid covalent modification in nano-silica surface,
It can be prepared by 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid modification nanometer titanium dioxide silicon sensor.
The present invention also provides above-mentioned 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid modification nanometer titanium dioxide
Application of the silicon sensor in the detection field of ferrous ion.
Compared with prior art, advantage of the invention is that：
4- [(2,2' prepared by the present invention:6', 2 "-terpyridyl) -4'- bases] benzoic acid modification nano silicon
Sensor can quantify detection ferrous ion concentration range be 0.1-4 μM, and can by colorimetric sensing realize to ferrous iron from
The qualitative detection and the half-quantitative detection in 1-10 μM of concentration range of son.Detection to ferrous ion can be in physiological pH
Being carried out in aqueous systems, the concentration for the ferrous ion that can be detected is very low, and with good anti-ion interference ability.Therefore originally
4- [(2,2' in invention:6', 2 "-terpyridyl) -4'- bases] benzoic acid modification nanometer titanium dioxide silicon sensor in aqueous systems
In have application value to the spectroscopy determining and colorimetric sensing of ferrous ion.Nano-sensor prepared by the present invention can also be coated in
The test paper of half-quantitative detection ferrous ion is made on filter paper, quickly and easily detects ferrous ion.
Brief description of the drawings
Fig. 1 (a) is 4- [(2,2':6', 2 "-terpyridyl) -4' bases] benzoic acid modification nano silicon HEPES
(20mM, pH=7.2) saturated solution is in Fe2+Concentration is the uv-visible absorption spectra in the range of 0-5 μM, and illustration is according to Fig. 1
(a) working curve for the measure aqueous solution ferrous ions that experimental data is drawn；Fig. 1 (b) is 4- [(2,2':6', 2 "-three connection
Pyridine) -4'- bases] benzoic acid modification nano silicon HEPES (20mM, pH=7.2) saturated solution in Fe2+Concentration is 0-5
In the range of μM, excitation wavelength is 275nm fluorescence emission spectrum.
Fig. 2 is excessive 4- [(2,2':6', 2 "-terpyridyl) -4 '-yl] benzoic acid modification nano silicon disperses
Change comparison diagram after being separately added into 5 μM of different metal ions in the supernatant that HEPES (20mM, pH=7.2) solution obtains
(a) it is individually added into the colorimetric sensing figure (b) and supernatant that, are added in supernatant after the ferrous ion (1-10 μM) of various concentrations
5 μM of ferrous ions (c) and the comparison diagram (d) that disturbance ion is added in the presence of 5 μM of ferrous ions.
Fig. 3 is 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid modification nano silicon is coated in filter paper
The change comparison diagram after the ferrous ions soln of isometric various concentrations is added dropwise after upper.
Embodiment
Embodiment 1：4-[(2,2':6', 2 "-terpyridyl) -4'- bases] silica nanometer of benzoic acid covalent modification passes
The preparation of sensor is completed according to following 4 step：
(1) synthetic silica nano-particle.The 62.5mL ethanol solutions added with 3.75mL ammoniacal liquor being pre-mixed
It is added in the 12.5mL ethanol solutions containing 5mL TEOS, 5mL water is added after being well mixed.Mixture is in 40 DEG C of constant temperature, perseverance
Under the conditions of 40 revolutions per seconds of speed stirring then stirring reaction 24h is ultrasonically treated 10 minutes.(12000 revs/min, 3 points are centrifuged again
Clock), then washed 3 times with ethanol, in 100 DEG C of dry 4h.
(2) nano-silica surface is modified with coupling agent APTES.1g is taken to be made
Nano silicon be mixed into the 75mL ethanol solutions for having dissolved 0.25mL APTES, ultrasonic 30min obtains homogeneous outstanding
Supernatant liquid.Then particulate is centrifuged (12000 revs/min, 3min) simultaneously in 60 DEG C of stirring reaction 8h by mixture after the completion of reaction
3 times are respectively washed to remove remaining coupling agent with ethanol and deionized water, and obtained solid is completely dry in 70 DEG C in vacuum drying oven
It is dry.
(3) 4- [(2,2' are synthesized:6', 2 "-terpyridyl) -4' bases] benzoic acid.By 2- acetylpyridines (1.45g,
12mmol) it is dissolved in terephthalaldehydic acid (6mmol) in 40mL methanol, after stirring 5min, adds 15% KOH solution
(36mL) and concentrated ammonia liquor (4mL), mixed liquor are stirred at room temperature 3 days, separate out a large amount of precipitations.Collected by suction precipitates, and uses successively
20mL chloroforms and cold CH3OH/H2O(1:1,10mL) wash.Obtained crude product is distributed to the mixing of 100mL methanol and 25mL water
In liquid, 35 DEG C are heated to, stirring makes it all dissolve.Then 1M salt acid for adjusting pH is added to 2, separates out a large amount of white precipitates.Take out
Filter and washed with cold water, obtained product is being completely dried in vacuum drying oven in 70 DEG C.
(4) by 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid covalent modification is in Nano particles of silicon dioxide
Surface.Take 4- [(2,2':6', 2 "-terpyridyl) -4'- bases] benzoic acid is added in 10mL200mM EDC ethanol solution,
Add 10mL50mM NHS ethanol solution after ultrasonic 15min thereto again, continue ultrasonic disperse after well mixed, be uniformly dispersed
After 1h is stirred at room temperature.The Nano particles of silicon dioxide for taking the APTES of the above-mentioned preparations of 0.1g to be modified again mixes
Close in reaction solution, 24h is stirred at room temperature.Particulate centrifuges (12000rpm, 3min), is respectively washed 3 times with a water and ethanol.
To solid be completely dried in vacuum drying oven in 70 DEG C.
Embodiment 2：Nano-sensor is drawn to the spectral response and working curve of ferrous ion
Uv-visible absorption spectra determines on UV-2600 spectrophotometry instrument, with HEPES solution during measure
(20mM, pH=7.2) is used as reference liquid, into HEPES (20mM, pH=7.2) saturated solution of covalent modification nano-particle not
Disconnected to add ferrous ions soln, it is the absorption spectrum in the range of 0-5 μM to determine in ferrous ion concentration.Can according to absorption spectrum
Know, after adding ferrous ion, new absworption peak, and appearance etc. at 283nm occurs at 569nm in the absorption spectrum of nano-particle
Point is absorbed, shows the terpyridyl part of organic molecule and ferrous ion there occurs coordination, so as to cause spectrum change,
New absworption peak appears in visible region, and the complex of formation is colored complex, to realize the colorimetric sensing to ferrous ion
Provide the foundation.It is that absorbance of the nano-particle at 596nm is dense to ferrous ion in the range of 0-4 μM in ferrous ion concentration
Degree has good linear response, can obtain the measure Fe as shown in illustration in Fig. 1 (a) accordingly2+Working curve.
Fluorescence emission spectrum determines on Cary Eclipse sepectrophotofluorometers, excitation wavelength 275nm, excite and
Transmite slit is 2.5nm, and Asia is continuously added into HEPES (20mM, pH=7.2) saturated solution of covalent modification nano-particle
Ferric ion solutions, it is the emission spectrum in the range of 0-5 μM, emission peak of the nano-particle in 363nm to determine in ferrous ion concentration
Intensity increases with ferrous ion concentration and constantly reduced, until being quenched completely.
Embodiment 3：Selectivity of the nano-sensor to ferrous ion
5mg covalent modifications nano-particle and 2mLHEPES solution (20mM, pH are separately added into 13 3mL vials
=7.2), ultrasonic disperse makes nano-particle be dispersed in HEPES solution, be separately added into each dispersion liquid 5 μM it is different
Metal ion (Ba2+,Co2+,Hg2+,Cd2+,Na+,Mg2+,Fe2+,Ni2+,Ag+,Cu2+,Mn2+,Zn2+,Fe3+), stirring make metal from
Son fully reacts with nano-particle, stands 5 minutes, undissolved nano-particle is settled down, and contrasts in nano-sensor and adds
Enter the change of different metal ions, only add supernatant in the bottle of ferrous ion and be substantially changed into purple, undissolved nanometer
Particle is almost still white, adds in the bottle of other metal ions and has no significant change.Above-mentioned phenomenon shows the nanosensor
Device is to Fe2+, can qualitative detection Fe with high selectivity2+。
Embodiment 4：Concentration mensuration of the nano-sensor to water sample ferrous ions
Determine Fe2+Working curve drafting：5mg covalent modification nano-particles are separately added into 8 3mL vials
With 2mLHEPES solution (20mM, pH=7.2), ultrasonic disperse makes nano-particle be dispersed in HEPES solution, disperses to each
2 μ l, 3 μ l, 4 μ l, 5 μ l, the 6 μ μ of l, 10 μ, 15 l, 20 μ l and 50 μ l 1mMFe are separately added into liquid2+The aqueous solution is allowed in solution
Concentration is respectively 1 μM, 1.5 μM, 2 μM, 2.5 μM, 3 μM, 5 μM, 7.5 μM, 10 μM, 25 μM of Fe2+, stirring makes ferrous ion with receiving
Rice corpuscles fully reacts, and stands 5 minutes, undissolved nano-particle is settled completely, contrast under different ferrous ion concentrations
Color change, under the concentration of measure, Fe2+Concentration is bigger, and the purple that supernatant is shown is deeper, works as Fe2+Concentration is more than 10 μM
Afterwards, supernatant purple is deepened there is no obvious.Above-mentioned phenomenon shows that the nano-sensor can be realized to Fe2+Colorimetric sensing.By
Illustration in Fig. 1 (a) is understood, in 0-10 μM of concentration range, absorbance and Fe in solution2+Concentration is directly proportional, obtains quantitative survey
Determine Fe2+Working curve.
The concentration mensuration of water sample ferrous ions：Take 1mL HEPES cushioning liquid (40mM, pH=7.2), 1mL water to be measured
After sample and 5mg covalent modification nano-particles, ultrasonic disperse, after standing 5 minutes, the absorbance of supernatant is determined, by above-mentioned work
Make curve, Fe in water sample can be measured2+Concentration.
Embodiment 5：Nano-sensor determines the anti-interference of ferrous ion
5mg covalent modifications nano-particle and 2mLHEPES solution (20mM, pH=are separately added into 2 3mL vials
7.2), ultrasonic disperse makes nano-particle be dispersed in HEPES solution, adds 5 μM of Fe in a bottle thereto2+, to another
Different metal ion (Ba is added in one bottle2+,Co2+,Hg2+,Cd2+,Na+,Mg2+,Fe2+,Ni2+,Ag+,Cu2+,Mn2+,
Zn2+,Fe3+) each 5 μM, stirring makes metal ion fully be reacted with nano-particle, stands 5 minutes, makes undissolved nano-particle
Sedimentation completely, contrast do not add interfering ion and add the change of the system of a variety of interfering ions, and supernatant is aobvious in the case of two kinds
Reveal purple, it is slightly shallow to add the system supernatant purple of interfering ion, but changes unobvious (as shown in Figure 2), it was demonstrated that the nanometer
Sensor is to Fe2+Detection there is good anti-interference.
Embodiment 6：The preparation and test of nanosensor test paper
5mg covalent modifications nano-particle is added in 1.5mL ethanol, ultrasound makes it be uniformly dispersed.A neutral filter paper is taken,
The alcohol dispersion liquid of the 300 above-mentioned nano-particles of μ L is added dropwise in upper left corner area on to filter paper, then is added dropwise respectively to other 4 regions
200 μ L dispersion liquids, are added dropwise rear naturally dry, nano-particle is applied on filter paper.More nanoparticle is coated to the upper left corner
The Fe that 30 μ L concentration are 1mM is added dropwise in the region of son2+The aqueous solution, dripped respectively to the region of the nano-particle of other 4 coating equivalent
30 μ L concentration are added to be respectively 0.01mM, 0.05mM, 0.1mM, 1mM Fe2+The aqueous solution, rear naturally dry is added dropwise, contrast is not
With nano-particle coated weight and different Fe2+Influence of the concentration to colour developing.When nano-particle coated weight is equal, Fe2+Concentration is got over
Greatly, the purple on test paper is more obvious (as shown in the rows of Fig. 3 second)；In the Fe of dropwise addition2+When concentration is identical, nano-particle coated weight is more
Colour developing become apparent from (as shown in Fig. 3 the first rows).Above-mentioned phenomenon shows that using the nano-particle of this covalent modification Fe can be made2+
Test paper, can be more quickly and easily to Fe in aqueous systems2+Quantitative and semi-quantitative detection is carried out, there is good application
Value.
Claims (2)
1. a kind of nanometer silicon dioxide composite material of terpyridine moieties covalent modification, its concrete structure are shown below：
A kind of 2. purposes of the nanometer silicon dioxide composite material described in claim 1, it is characterised in that：The material is used for water-soluble
The AAS of ferrous ion and bore hole colorimetric method for determining in liquid.
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| CN106047340B (en) * | 2016-06-01 | 2018-04-20 | 北京师范大学 | The preparation and application of the graphene quantum dot of terpyridine moieties modification |
| CN106699597A (en) * | 2017-02-21 | 2017-05-24 | 中国人民解放军军事医学科学院卫生学环境医学研究所 | Synthetic method for covalently coupled matrix of alpha-cyan-4-hydroxyl cinnamic acid (CHCA) and silicon-based mesoporous material |
| CN110455732B (en) * | 2019-08-28 | 2021-09-28 | 吉林大学 | Biological sample treatment method, ferrous ion or total ferric ion determination method of biological sample and detection kit |
| CN110560173B (en) * | 2019-09-17 | 2022-03-04 | 哈尔滨工业大学 | Preparation method and application method of bipyridine amide iron-loaded nano silica heterogeneous catalyst |
| CN113184861B (en) * | 2021-04-29 | 2022-11-01 | 胡晓青 | Mesoporous silica, carboxylated mesoporous silica, drug-loading system, and preparation method and application thereof |
| CN116328746A (en) * | 2023-04-10 | 2023-06-27 | 新特能源股份有限公司 | Terpyridine-silica gel composite material and preparation method thereof |
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