CN105384769A - Preparation and application of terpyridine group modified nano silica particles - Google Patents
Preparation and application of terpyridine group modified nano silica particles Download PDFInfo
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- CN105384769A CN105384769A CN201510423330.6A CN201510423330A CN105384769A CN 105384769 A CN105384769 A CN 105384769A CN 201510423330 A CN201510423330 A CN 201510423330A CN 105384769 A CN105384769 A CN 105384769A
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Abstract
The present invention discloses a preparation method of terpyridine group modified nano silica particles, and an application of applying the nano silica particles in spectrophotometry and a naked eye semi-quantitative method to measure a ferrous ion concentration in a water sample. The method has high sensitivity and selectivity.
Description
Technical field
The invention belongs to optochemical sensor field, relate to the preparation method of nanometer titanium dioxide silicon nano and the application in the association areas such as ferrous ion spectral detection and colorimetric sensing thereof of terpyridine moieties modification.
Background technology
Iron is the transition metal that in organism, content is the abundantest, and because ferrous ion and many enzymes and protein bound are extensively present in vital movement, therefore it plays important physiological regulatory action in organism.As ferrous ion can be combined by the oxyphorase in blood, by oxygen from each cell being transported to organism.The shortage of ferro element or excessive homeostasis and the metabolic processes all destroying cell in organism.The accumulation of ferro element in central nervous system may cause the diseases such as Huntington Chorea, Parkinson's disease and senile dementia.Baby, pregnant woman and children in adolescence are easy to the situation occurring iron deficiency, thus cause the symptom such as anaemia, hypoimmunity, affect growing up healthy and sound of human body.Therefore optionally detect ferrous ion HUMAN HEALTH tool is of great significance.
Spectrography, chromatography, voltammetry and inductivity coupled plasma mass spectrometry are all once for the detection of ferro element, by contrast, spectrum detection method based on ferrous ion and particular ligand complexing is the simplest, there is the advantages such as detection speed is fast, environmental pollution is little, highly sensitive, easy and simple to handle, cost is low, if formation colored complex, then can carry out colorimetric sensing to ferrous ion, realize fast and convenient quantitative and semi-quantitative and detect.Therefore the photochemistry that detects for the preparation of ferrous ion is studied and colorimetric sensor has great importance [J.P.Desvergne, A.W.Czarnik, ChemosensorsofIonandMoleculeRecognition.Dordrecht, Netherlands:KluwerAcademicPublishers, 1997].But, with Fe
3+compare, highly sensitive, highly selective optical sensing Fe
2+report seldom [P.Wu, Y.Li, X.P.Yan, CdTeQuantumDots (QDs) basedkineticdiscriminationofFe
2+andFe
3+, andCdTeQDs-Fentonhybridsystemforsensitivephotoluminescen tdetectionofFe
2+, 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, Ahighlyselectivecolorimetricchemosensorfordetectingthere spectiveamountsofiron (II) andiron (III) ionsinwater, NewJ.Chem., 2007,31,906-910.], especially colorimetric sensing Fe
2+has challenge [K.Chaiendoo, T.Tuntulani, W.Ngeontae, Ahighlyselectivecolorimetricsensorforferrousionbasedonpo lymethylacrylicacid-templatedsilvernanoclusters, SensorsandActuatorsB207 (2015) 658-667.], because sensing can complete by bore hole identification, need not by opticinstrument.
Composite organic-inorganic material is the new direction of sensor exploitation in recent years, and wherein this kind of matrix material of organic molecule covalent modification nano silicon is widely used in ion sensor.Nano silicon has larger specific surface area, its synthesis and covalent modification simple, the composite gauge of formation is little, and in aqueous systems, stability is high, nontoxic, has good bio-compatibility, has good application prospect in living things system.The mode of covalent modification can effectively avoid organic molecule to leach from matrix material, improves the wearing quality of sensor, makes its recycle become possibility.As can be seen here, research and develop nano silicon compound sensor, in detection ferrous ion, there is huge potential using value.
Summary of the invention
The object of the invention is to prepare a kind of 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] the matrix material sensor of phenylformic acid covalent modification nano silicon, and the ferrous ion in aqueous systems is detected for high sensitivity and highly selective.The concrete structure of sensor is shown below:
Technical scheme of the present invention is as follows: first, adopts classical tetraethoxy (TEOS) hydrolysis method synthesis to have the nano-silicon dioxide particle of certain size; Then use silane coupling agent APTES (APTES) to surface modification of silica, silicon dioxide meter is worn have the amino of reactive behavior; Again with 2-acetylpyridine and terephthalaldehydic acid for Material synthesis has organic molecule 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid of coordination site; Finally adopt method that 1-(3-dimethylamino-propyl)-3-ethyl carbon inferior amine salt hydrochlorate (EDC) and N-hydroxy-succinamide (NHS) activate by 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid covalent modification is at nano-silica surface; the nanometer titanium dioxide silicon sensor that 4-[(2; 2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid is modified can be obtained.
The nanometer titanium dioxide silicon sensor that the present invention also provides above-mentioned 4-[(2,2 ': 6 ', 2 "-terpyridyl) 4 '-Ji] phenylformic acid to modify is in the application of the detection field of ferrous ion.
Compared with prior art, advantage of the present invention is:
4-[(2 prepared by the present invention, 2 ': 6 ', 2 "-terpyridyl) 4 '-Ji] the phenylformic acid nanometer titanium dioxide silicon sensor institute of modifying can the concentration range of ferrous ion of detection by quantitative be 0.1-4 μM, and by colorimetric sensing realization to the qualitative detection of ferrous ion and the half-quantitative detection in 1-10 μM of concentration range.Can carry out in the aqueous systems being in physiological pH the detection of ferrous ion, the concentration of the ferrous ion that can detect is very low, and has good anti-ion interference ability.Therefore the nanometer titanium dioxide silicon sensor that 4-in the present invention [(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid is modified has using value to the spectroscopy determining of ferrous ion and colorimetric sensing in aqueous systems.Nano-sensor prepared by the present invention can also be coated in test paper filter paper being made half-quantitative detection ferrous ion, detects ferrous ion quickly and easily.
Accompanying drawing explanation
Fig. 1 (a) is that HEPES (20mM, the pH=7.2) saturated solution of 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 ' yl] phenylformic acid decorated nanometer silicon-dioxide is at Fe
2+concentration is the uv-visible absorption spectra within the scope of 0-5 μM, and illustration is the working curve of the mensuration aqueous solution ferrous ions drawn according to the experimental data of Fig. 2 (a); Fig. 2 (b) is that HEPES (20mM, the pH=7.2) saturated solution of 4-[(2,2 ': 6 ', 2 "-terpyridyl) 4 '-Ji] phenylformic acid decorated nanometer silicon-dioxide is at Fe
2+concentration is within the scope of 0-5 μM, and excitation wavelength is the fluorescence emission spectrum of 275nm.
Fig. 2 is excessive 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid decorated nanometer silicon-dioxide is scattered in the supernatant liquor that HEPES (20mM; pH=7.2) solution obtains change comparison diagram (a) after adding 5 μMs of different metal ions respectively, adds in colorimetric sensing figure (b) after the ferrous ion (1-10 μM) of different concns and supernatant liquor the comparison diagram (d) adding separately 5 μMs of ferrous ions (c) and add disturbance ion under 5 μMs of ferrous ions exist in supernatant liquor.
Fig. 3 be 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid decorated nanometer silica-coating on filter paper after drip the change comparison diagram after the ferrous ions soln of isopyknic different concns.
Embodiment
The preparation of the silica nanometer sensor of embodiment 1:4-[(2,2 ': 6 ', 2 "-terpyridyl) 4 '-Ji] phenylformic acid covalent modification completes according to following 4 steps:
(1) synthetic silica nanoparticle.The 62.5mL ethanolic soln being added with 3.75mL ammoniacal liquor be pre-mixed is joined in the 12.5mL ethanolic soln containing 5mLTEOS, after mixing, adds 5mL water.Mixture is stirring reaction 24h then supersound process 10 minutes under constant temperature 40 DEG C, constant speed stir 40 revolutions per seconds of conditions.Centrifugation again (12000 revs/min, 3 minutes), then washes 3 times with ethanol, in 100 DEG C of dry 4h.
(2) with coupling agent APTES, modification is carried out to nano-silica surface.Get nano silicon that 1g obtains to be mixed into and to have dissolved in the 75mL ethanolic soln of 0.25mLAPTES, ultrasonic 30min obtains homogeneous suspension.Then mixture is at 60 DEG C of stirring reaction 8h, by particulate centrifugation (12000 revs/min after having reacted, 3min) and respectively wash 3 times to remove remaining coupling agent with ethanol and deionized water, the solid obtained in vacuum drying oven in 70 DEG C of complete dryinies.
(3) 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 ' yl] phenylformic acid is synthesized.By 2-acetylpyridine (1.45g; 12mmol) be dissolved in 40mL methyl alcohol with terephthalaldehydic acid (6mmol); after stirring 5min; add KOH solution (36mL) and the strong aqua (4mL) of 15%; mixed solution at room temperature stirs 3 days, separates out and precipitates in a large number.Collected by suction precipitates, and uses 20mL chloroform and cold CH successively
3oH/H
2o (1: 1,10mL) washes.The thick product obtained is distributed in the mixed solution of 100mL methyl alcohol and 25mL water, is heated to 35 DEG C, stirs and makes it all dissolve.Then add 1M salt acid for adjusting pH to 2, separate out a large amount of white precipitate.Suction filtration with cold water washing, the product obtained in vacuum drying oven in 70 DEG C of complete dryinies.
(4) by 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid covalent modification on Nano particles of silicon dioxide surface.Get 4-[(2,2 ': 6 ', 2 "-terpyridyl)-4 '-Ji] phenylformic acid joins in the ethanolic soln of 10mL200mMEDC, adds the ethanolic soln of 10mL50mMNHS more wherein; mix rear continuation ultrasonic disperse, stirring at room temperature 1h after being uniformly dispersed after ultrasonic 15min.The Nano particles of silicon dioxide getting the APTES modification of the above-mentioned preparation of 0.1g is again mixed in reaction solution, stirring at room temperature 24h.Particulate centrifugation (12000rpm, 3min), respectively washes 3 times with a water and ethanol.The solid obtained in vacuum drying oven in 70 DEG C of complete dryinies.
Embodiment 2: nano-sensor is drawn the spectral response of ferrous ion and working curve
Uv-visible absorption spectra measures on UV-2600 spectrophotometry instrument, with HEPES solution (20mM during mensuration, pH=7-2) as reference liquid, to the HEPES (20mM of covalent modification nanoparticle, pH=7.2) constantly add ferrous ions soln in saturated solution, being determined at ferrous ion concentration is absorption spectrum within the scope of 0-5 μM.According to absorption spectrum, after adding ferrous ion, new absorption peak is there is in the absorption spectrum of nanoparticle at 569nm place, and there is isobestic point at 283nm place, show that terpyridyl part and the ferrous ion of organic molecule there occurs coordination, thus cause spectrum change, new absorption peak appears at visible region, the title complex formed is colored complex, for realizing providing the foundation to the colorimetric sensing of ferrous ion.Be within the scope of 0-4 μM at ferrous ion concentration, the absorbancy of nanoparticle at 596nm place has good linear response to ferrous ion concentration, can obtain the mensuration Fe as shown in illustration in Fig. 1 (a) accordingly
2+working curve.
Fluorescence emission spectrum measures on CaryEclipse spectrophotofluorometer, excitation wavelength is 275nm, excite and launch slit and be 2.5nm, to the HEPES (20mM of covalent modification nanoparticle, pH=7.2) constantly ferrous ions soln is added in saturated solution, being determined at ferrous ion concentration is emmission spectrum within the scope of 0-5 μM, and nanoparticle increases at the emission peak intensity ferrous ion concentration of 363nm and constantly reduces, until cancellation completely.
Embodiment 3: nano-sensor is to the selectivity of ferrous ion
5mg covalent modification nanoparticle and 2mLHEPES solution (20mM is added respectively in 13 3mL vials, pH=7.2), ultrasonic disperse makes nanoparticle be dispersed in HEPES solution, adds 5 μMs of different metal ion (Ba in each dispersion liquid respectively
2+, Co
2+, Hg
2+, Cd
2+, Na
+, Mg
2+, Fe
2+, Ni
2+, Ag
+, Cu
2+, Mn
2+, Zn
2+, Fe
3+), stirring makes metal ion and nanoparticle fully react, leave standstill 5 minutes, undissolved nanoparticle is settled down, the change of different metal ion is added in contrast nano-sensor, only add supernatant liquor in the bottle of ferrous ion and obviously become purple, undissolved nanoparticle is still almost white, adds in the bottle of other metal ions and has no significant change.Above-mentioned phenomenon shows that this nano-sensor is to Fe
2+there is highly selective, can qualitative detection Fe
2+.
Embodiment 4: nano-sensor is to the concentration determination of water sample ferrous ions
Measure Fe
2+the drafting of working curve: in 8 3mL vials, add 5mg covalent modification nanoparticle and 2mLHEPES solution (20mM respectively, pH=7.2), ultrasonic disperse makes nanoparticle be dispersed in HEPES solution, adds 2 μ l in each dispersion liquid respectively, 3 μ l, 4 μ l, 5 μ l, 6 μ l, 10 μ, 15 μ l, the 1mMFe of 20 μ l and 50 μ l
2+the aqueous solution concentration made it in solution is respectively 1 μM, 1.5 μMs, 2 μMs, 2.5 μMs, 3 μMs, 5 μMs, 7.5 μMs, 10 μMs, 25 μMs of Fe
2+, stir and ferrous ion and nanoparticle are fully reacted, leave standstill 5 minutes, make the complete sedimentation of undissolved nanoparticle, contrast the colour-change under different ferrous ion concentration, under the concentration measured, Fe
2+concentration is larger, and the purple that supernatant liquor shows is darker, works as Fe
2+concentration more than 10 μMs after, supernatant liquor purple no longer includes obvious intensification.Above-mentioned phenomenon shows that this nano-sensor can realize Fe
2+colorimetric sensing.From the illustration in Fig. 1 (a), in 0-10 μM of concentration range, Fe in absorbancy and solution
2+concentration is directly proportional, and obtains quantitative assay Fe
2+working curve.
The concentration determination of water sample ferrous ions: get 1mLHEPES buffered soln (40mM, pH=7.2), after 1mL water sample to be measured and 5mg covalent modification nanoparticle, ultrasonic disperse, left standstill after 5 minutes, measured the absorbance of supernatant liquor, by above-mentioned working curve, Fe in water sample can be recorded
2+concentration.
Embodiment 5: nano-sensor measures the freedom from jamming of ferrous ion
In 2 3mL vials, add 5mg covalent modification nanoparticle and 2mLHEPES solution (20mM, pH=7.2) respectively, ultrasonic disperse makes nanoparticle be dispersed in HEPES solution, adds 5 μMs of Fe wherein in a bottle
2+, in another bottle, add different metal ion (Ba
2+, Co
2+, Hg
2+, Cd
2+, Na
+, Mg
2+, Fe
2+, Ni
2+, Ag
+, Cu
2+, Mn
2+, Zn
2+, Fe
3+) each 5 μMs, stirring makes metal ion and nanoparticle fully react, leave standstill 5 minutes, make the complete sedimentation of undissolved nanoparticle, contrast the change of the system not adding interfering ion and add multiple interfering ion, in two kinds of situations, supernatant liquor all shows purple, and the system supernatant liquor purple adding interfering ion is slightly shallow, but change not obvious (as shown in Figure 2), prove that this nano-sensor is to Fe
2+detection there is good freedom from jamming.
Embodiment 6: the preparation of nanosensor test paper and test
5mg covalent modification nanoparticle is added in 1.5mL ethanol, ultrasonicly makes it be uniformly dispersed.Get a neutral filter paper, on filter paper, upper left corner area drips the alcohol dispersion liquid of the above-mentioned nanoparticle of 300 μ L, then drips 200 μ L dispersion liquids respectively to other 4 regions, dropwises naturally to dry afterwards, and nanoparticle is applied on filter paper.It is the Fe of 1mM that the region applying more nanoparticle to the upper left corner drips 30 μ L concentration
2+the aqueous solution, the region to the nanoparticle of other 4 coating equivalent drips 30 μ L concentration respectively and is respectively 0.01mM, the Fe of 0.05mM, 0.1mM, 1mM
2+the aqueous solution, dropwises and naturally to dry afterwards, contrast different nanoparticle coated weight and different Fe
2+concentration is on the impact of colour developing.When nanoparticle coated weight is equal, Fe
2+concentration is larger, the purple on test paper more obvious (as shown in Fig. 3 second row); The Fe dripped
2+when concentration is identical, the colour developing more obvious (as shown in Fig. 3 the first row) that nanoparticle coated weight is many.Above-mentioned phenomenon shows to utilize the nanoparticle of this covalent modification to make Fe
2+test paper, can more quickly and easily to Fe in aqueous systems
2+carry out quantitative and semi-quantitative detection, there is good using value.
Claims (2)
1. a nano silicon nanometer for terpyridine moieties covalent modification, is characterized in that: this matrix material is the reaction product of the Nano particles of silicon dioxide after having phenylformic acid to modify with APTES after acylations activates by grafting.
2. a purposes for the nano composite material of claim 1, is characterized in that: this material is used for spectrophotometry and the bore hole colorimetric method for determining of ferrous ion in the aqueous solution.
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Cited By (6)
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| CN106047340A (en) * | 2016-06-01 | 2016-10-26 | 北京师范大学 | Preparation and application of graphene quantum dots modified by terpyridine groups |
| 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 |
| CN110455732A (en) * | 2019-08-28 | 2019-11-15 | 吉林大学 | Biological sample processing method, the ferrous ion of biological sample or total iron ion measuring method and detection kit |
| CN110560173A (en) * | 2019-09-17 | 2019-12-13 | 哈尔滨工业大学 | preparation method and application method of bipyridine amide iron-loaded nano silica heterogeneous catalyst |
| CN113184861A (en) * | 2021-04-29 | 2021-07-30 | 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106047340A (en) * | 2016-06-01 | 2016-10-26 | 北京师范大学 | Preparation and application of graphene quantum dots modified by terpyridine groups |
| 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 |
| CN110455732A (en) * | 2019-08-28 | 2019-11-15 | 吉林大学 | Biological sample processing method, the ferrous ion of biological sample or total iron ion measuring method and detection kit |
| CN110560173A (en) * | 2019-09-17 | 2019-12-13 | 哈尔滨工业大学 | preparation method and application method of bipyridine amide iron-loaded nano silica heterogeneous catalyst |
| 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 |
| CN113184861A (en) * | 2021-04-29 | 2021-07-30 | 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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