CN104155277A - Preparation method of sulfur ion fluorescent chemical sensor based on silicon nanowire or silicon nanowire array - Google Patents
Preparation method of sulfur ion fluorescent chemical sensor based on silicon nanowire or silicon nanowire array Download PDFInfo
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- CN104155277A CN104155277A CN201410429525.7A CN201410429525A CN104155277A CN 104155277 A CN104155277 A CN 104155277A CN 201410429525 A CN201410429525 A CN 201410429525A CN 104155277 A CN104155277 A CN 104155277A
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Abstract
The invention belongs to a fluorescent chemical sensor in a one-dimension nano structure and especially relates to a preparation method of sulfur ion fluorescent chemical sensor based on silicon nanowire or silicon nanowire array. Surfaces of the silicon nanowire or the silicon nanowire array are covalently modified successively by 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxy silane and 4-amino-1,8-naphthalic anhydride. An obtained silicon nanowire, or silicon nanowire array, of which the surfaces are modified by 4-amino-1,8-naphthalic dimethylamide fluorescent groups is further reacted with copper ion to form a complex for obtaining the sulfur ion fluorescent chemical sensor based on the silicon nanowire or the silicon nanowire array. The sulfur ion fluorescent chemical sensor based on the silicon nanowire or the silicon nanowire array can be used in detection of sulfur ion in a solution system containing the sulfur ion and has a wide application prospect in detection of the sulfur ion in a water body in real time and in situ.
Description
Technical field
The invention belongs to the fluorescence chemical sensor of one-dimensional nano structure, particularly the preparation method of the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array.
Background technology
Sulphion is a kind of poisonous environmental contaminants.The sulphion producing in commercial production and the ecosystem, has caused serious pollution to environment.In the method for the detection sulphion that document has been reported, fluorometry has highly sensitive, the unique advantage of grade simple to operate.In recent years, based on the machine-processed sulphion fluorescence probe of displacement due to highly sensitive, fast response time and having been a great concern, as K.Sasakura, JACS.2011,133,18003; H.Xianfeng, yet Nanotechnololy.2013.24.335502., these fluorescence probes overwhelming majority is micromolecular compound, minority is based semiconductor fluorescence quantum.Their shortcoming is that synthesis step is more loaded down with trivial details, and is all that probe is distributed to the detection of realization to sulphion in solution.If the molecule that sulphion is had to fluorescence response is integrated into a substrate, be prepared into portable sulfide ion sensor part, in real time, in in-situ monitoring environment, sulphion will have great importance.
Research shows, silicon nanowires is easy to modify owing to having, nontoxic, good stability, be easy to the advantages such as integrated, has been widely used in and constructed fluorescent optical sensor, and shown good detection performance.
Summary of the invention
To the object of the invention is the problem existing in existing sulphion detection in order overcoming, a kind of preparation method of the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array to be provided.
The present invention is by 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane and 4-amino-1,8-naphthalic anhydride successively covalent modification to the surface of silicon nanowires or silicon nanowire array, the finishing obtaining has 4-amino-1, the silicon nanowires of 8-aphthalimide fluorophore or silicon nanowire array further form complex compound with copper ion, obtain the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array.
The preparation method of the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array of the present invention comprises the following steps:
1) under room temperature, silicon nanowires or silicon nanowire array that 30～50mg is processed through hydroxylation, the dry toluene of 10～30mL and the 3-[2-of 0.1～0.4mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under inert gas shielding, be heated to after 50～90 ℃, isothermal reaction 12～48 hours, then be cooled to room temperature, with organic solvent ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires or the silicon nanowire array of propyl group-trimethoxy silane,
2) under room temperature, by step 1) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane or the 4-that silicon nanowire array is immersed in 0.5～1.5mol/L amino-1, in the ethanol solution of 8-naphthalic anhydride, under inert gas shielding, be heated to 40～90 ℃, isothermal reaction 5～15 hours, be cooled to room temperature, then with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1, 8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowires of 8-aphthalimide fluorophore or silicon nano-array,
3) by step 2) finishing that obtains has 4-amino-1, the silicon nanowires of 8-aphthalimide fluorophore is dispersed in 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution (HEPES, 20mM, pH=7.0), be made into the solution that concentration is 30～80 μ g/mL, add 6 * 10
-6～16 * 10
-6mol/L copper chloride solution, forming finishing has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore and the complex compound of copper ion, obtain the sulphion fluorescence chemical sensor based on silicon nanowires;
Or by step 2) finishing that obtains has 4-amino-1, and the silicon nanowire array of 8-aphthalimide fluorophore is immersed in 10 * 10
-6～50 * 10
-6in mol/L copper chloride solution, (the general time of immersing is 2～5 minutes), with deionized water washing, after naturally drying, obtains the sulphion fluorescence chemical sensor based on silicon nanowire array after taking-up.
Described silicon nanowires is the silicon nanowires that chemical vapour deposition technique prepares, and diameter is 10～15nm.
Described silicon nanowire array is the silicon nanowire array that chemical etching method prepares, and the diameter of the silicon nanowires in silicon nanowire array is 200～400nm, and length is 15～20 μ m.
Described hydroxylation is processed adoptable method: silicon nanowires or silicon nanowire array are immersed in to the concentrated sulphuric acid that volume ratio is 1:1～8:1 (massfraction is 50%～98%) and H
2o
2in the mixed liquor of (massfraction is 5%～30%), in temperature, be at 70～95 ℃, to process after 30～90 minutes, with deionized water, wash to neutrality the H that soaking at room temperature is 3:1:1～9:1:1 in volume ratio
2o:H
2o
2(massfraction is 5%～30%): NH
4in the mixed liquor of OH 1～2.5 hour, be washed to neutrality, vacuum drying.
Described organic solvent is methyl alcohol, ethanol, methylene chloride or acetone.
The detection of sulphion in the solution system that the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array that preparation method of the present invention obtains can be used for containing sulphion.
The 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution (HEPES of the sulphion fluorescence chemical sensor based on silicon nanowires will be contained, 20mM, pH=7.0) join in fluorescence cuvette, on Fluorescence spectrophotometer, detect, along with adding of sulfur-containing anion material (as sodium sulphide), the fluorescence intensity of solution system to be detected strengthens gradually; By drawing the concentration of known sulphion and the calibration curve of fluorescent characteristics peak intensity, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowires by described in solution system to be detected detects, determine the concentration of sulphion in solution system to be detected;
By the sulphion fluorescence chemical sensor based on silicon nanowire array, after being immersed in the aqueous solution (as the aqueous solution of sodium sulphide) that contains sulphion, on fluorescent microscope, detect, the fluorescence intensity of the described sulphion fluorescence chemical sensor based on silicon nanowire array in solution system to be detected obviously strengthens, by drawing the calibration curve of the concentration of known sulphion and the fluorescence intensity of silicon nanowire array fluorescent optical sensor, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowire array by described in solution system to be detected detects, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
The light that the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array that preparation method of the present invention obtains is launched in detection system is green glow.
Described Fluorescence spectrophotometer or fluorescent microscope, excitation source used is all xenon lamp (excitation wavelength is 400～450nm) or mercury lamp (excitation wavelength is 450～480nm).
The invention has the advantages that:
1. preparation method is simple.
2. prepare sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array and provide a kind of method for the sulphion in real-time, in situ detection water or in in-situ monitoring environment, and fast response time, highly sensitive.
Below in conjunction with specific embodiment and accompanying drawing, the present invention is further illustrated.
Accompanying drawing explanation
Fig. 1. the chemical modification process of the silicon nanowires in the embodiment of the present invention 1～4 or silicon nanowire array.
Fig. 2. the sulphion fluorescence chemical sensor based on silicon nanowires of the embodiment of the present invention 1 and the fluorescent emission figure after the effect of variable concentrations sulphion.
Fig. 3. the fluorescence intensity of the sulphion fluorescence chemical sensor based on silicon nanowires of the embodiment of the present invention 1 and the linear relationship of sulphion concentration.
Fig. 4. the fluoroscopic image in the sulphion aqueous solution of the sulphion fluorescence chemical sensor immersion variable concentrations based on silicon nanowire array of the embodiment of the present invention 2.
A is the fluoroscopic image of the sulphion fluorescence chemical sensor based on silicon nanowire array;
B, for the sulphion fluorescence chemical sensor based on silicon nanowire array was placed in 50 μ M sodium sulfide solutions after 2 minutes, carries out observable fluoroscopic image under fluorescent microscope;
C, for the sulphion fluorescence chemical sensor based on silicon nanowire array was placed in 100 μ M sodium sulfide solutions after 2 minutes, carries out observable fluoroscopic image under fluorescent microscope.
Embodiment
Embodiment 1.
1) silicon nanowires that is 10～15nm by the diameter of being prepared by chemical vapour deposition technique is immersed in the concentrated sulphuric acid that volume ratio is 1:1 (massfraction is 98%) and H
2o
2in the mixed liquor of (massfraction is 5%), in temperature, be at 95 ℃, to process after 30 minutes, with deionized water, wash to neutrality the H that soak at room temperature is 3:1:1 in volume ratio
2o:H
2o
2(massfraction is 30%): NH
4in the mixed liquor of OH 2.5 hours, be washed to neutrality, vacuum drying, obtains the silicon nanowires that hydroxylation is processed;
2) under room temperature, by dry 30mg step 1) silicon nanowires processed of the process hydroxylation that obtains, the dry toluene of 10mL and the 3-[2-of 0.1mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under nitrogen protection, be heated to after 50 ℃, isothermal reaction 48 hours, then be cooled to room temperature, with ethanol ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane,
3) under room temperature, by step 2) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane is immersed in the 4-amino-1 of 0.5mol/L, in the ethanol solution of 8-naphthalic anhydride, under nitrogen protection, be heated to 40 ℃, isothermal reaction 15 hours, after cool to room temperature, with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1,8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowires (seeing Fig. 1) of 8-aphthalimide fluorophore;
4) by step 3) finishing that obtains has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore is dispersed in HEPES (20mM, pH=7.0), is made into the solution that concentration is 30 μ g/mL, adds 6 * 10
-6mol/L copper chloride solution, forming finishing has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore and the complex compound of copper ion, obtain the sulphion fluorescent optical sensor based on silicon nanowires.
Substrate using the sulphion fluorescence chemical sensor based on silicon nanowires obtained above as fluoroscopic examination, with Fluorescence spectrophotometer, to this, the sensing capabilities of the fluorescence chemical sensor based on silicon nanowires characterizes, and excitation source is xenon lamp (excitation wavelength is 400～450nm).
The HEPES buffer solution system of the 2mL 20mM that contains the described fluorescence chemical sensor based on silicon nanowires is joined in fluorescence cuvette, on Fluorescence spectrophotometer, detect, the sodium sulfide solution that adds known variable concentrations, optical excitation with 405nm, the described fluorescence chemical sensor based on silicon nanowires of solution system to be detected can produce fluorescence to be strengthened, and find that the fluorescence intensity of solution system to be detected strengthens gradually along with the increase of the concentration of known sulphion.The fluorescence chemical sensor based on silicon nanowires as shown in Figure 2 and variable concentrations sulphion to be detected is made the change curve (concentration of sulphion is respectively 0,2.5,5,7.5,10,12.5,15,17.5,20,25,30 μ M) of the fluorescence spectrum that the used time surveys.As shown in Figure 3, by drawing known sulphion concentration and the calibration curve of fluorescent characteristics peak intensity, and the fluorescence intensity at the fluorescent characteristics peak detecting with the fluorescence chemical sensor based on silicon nanowires by described in solution system to be detected compares, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.The intensity at fluorescent characteristics peak (maximum emission wavelength is 545nm) and sulphion concentration linear (seeing Fig. 3).
Embodiment 2.
1) silicon chip size is immersed in to the concentrated sulphuric acid that volume ratio is 1:1 (massfraction is 98%) and H for the silicon nanowire array of being prepared by chemical etching method of 1cm * 1cm (diameter of the silicon nanowires in silicon nanowire array is 200～400nm, and length is 15～20 μ m)
2o
2in the mixed liquor of (massfraction is 5%), in temperature, be at 95 ℃, to process after 30 minutes, with deionized water, wash to neutrality the H that soak at room temperature is 3:1:1 in volume ratio
2o:H
2o
2(massfraction is 30%): NH
4in the mixed liquor of OH 2.5 hours, be washed to neutrality, vacuum drying, obtains the silicon nanowire array that hydroxylation is processed;
2) under room temperature, by dry step 1) silicon nanowire array processed of the process hydroxylation that obtains, the dry toluene of 10mL and the 3-[2-of 0.1mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under nitrogen protection, be heated to after 50 ℃, isothermal reaction 48 hours, then be cooled to room temperature, with ethanol ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowire array of propyl group-trimethoxy silane,
3) under room temperature, by step 2) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowire array of propyl group-trimethoxy silane is immersed in the 4-amino-1 of 0.5mol/L, in the ethanol solution of 8-naphthalic anhydride, under nitrogen protection, be heated to 40 ℃, isothermal reaction 15 hours, after cool to room temperature, with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1,8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowire array of 8-aphthalimide fluorophore;
4) by step 3) finishing that obtains has 4-amino-1, and the silicon nanowire array of 8-aphthalimide fluorophore is immersed in 10 * 10
-6in the copper chloride solution of mol/L 5 minutes, then take out and with deionized water washing, after naturally drying, obtain the sulphion fluorescence chemical sensor based on silicon nanowire array.
Detection by the sulphion fluorescence chemical sensor based on silicon nanowire array obtained above for the sulphion of the solution system that contains sulphion, coupling fluorescent microscope, excitation source is mercury lamp (excitation wavelength is 450～480nm).
By the sulphion fluorescence chemical sensor based on silicon nanowire array, after being immersed in the aqueous solution that contains sodium sulphide, on fluorescent microscope, detect, the described sulphion fluorescence chemical sensor based on silicon nanowire array in solution system to be detected can produce fluorescence to be strengthened, the fluoroscopic image that the sulphion fluorescence chemical sensor based on silicon nanowire array as shown in Figure 4 detects the sulphion of variable concentrations in solution, wherein: a is the fluorescence photo of the sulphion fluorescence chemical sensor (when there is no sulphion) based on silicon nanowire array; B is for the sulphion fluorescence chemical sensor based on silicon nanowire array and be placed in 1mL water, and adds the sodium sulphide of 50 μ M as solution system to be detected, carries out observable fluorescence photo after 2 minutes under fluorescent microscope; C is for the sulphion fluorescence chemical sensor based on silicon nanowire array and be placed in 1mL water, and adds the sodium sulphide of 100 μ M as solution system to be detected, carries out observable fluorescence photo after 2 minutes under fluorescent microscope.By drawing the calibration curve of the concentration of known sulphion and the fluorescence intensity of silicon nanowire array fluorescent optical sensor, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowire array by described in solution system to be detected detects, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
Embodiment 3.
1) silicon nanowires that is 10～15nm by the diameter of being prepared by chemical vapour deposition technique is immersed in the concentrated sulphuric acid that volume ratio is 8:1 (massfraction is 50%) and H
2o
2in the mixed liquor of (massfraction is 30%), in temperature, be at 70 ℃, to process after 90 minutes, with deionized water, wash to neutrality the H that soak at room temperature is 9:1:1 in volume ratio
2o:H
2o
2(massfraction is 5%): NH
4in the mixed liquor of OH 1 hour, be washed to neutrality, vacuum drying, obtains the silicon nanowires that hydroxylation is processed;
2) under room temperature, by 50mg step 1) silicon nanowires processed of the process hydroxylation that obtains, the dry toluene of 30mL and the 3-[2-of 0.4mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under nitrogen protection, be heated to after 90 ℃, isothermal reaction 12 hours, then be cooled to room temperature, with acetone ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, filter to collect and to obtain finishing and have 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane,
3) under room temperature, by step 2) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane is immersed in the 4-amino-1 of 1.5mol/L, in the ethanol solution of 8-naphthalic anhydride, under nitrogen protection, be heated to 90 ℃, isothermal reaction 5 hours, after cool to room temperature, with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1,8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowires of 8-aphthalimide fluorophore;
4) by step 3) finishing that obtains has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore is dispersed in HEPES (20mM, pH=7.0), is made into the solution that concentration is 80 μ g/mL, adds 16 * 10
-6mol/L copper chloride solution, forming finishing has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore and the complex compound of copper ion, obtain the sulphion fluorescent optical sensor based on silicon nanowires.
Substrate using the sulphion fluorescence chemical sensor based on silicon nanowires obtained above as fluoroscopic examination, with Fluorescence spectrophotometer, to this, the sensing capabilities of the fluorescence chemical sensor based on silicon nanowires characterizes, and excitation source is xenon lamp (excitation wavelength is 400～450nm).
The HEPES buffer solution system of the 2mL 20mM that contains the described fluorescence chemical sensor based on silicon nanowires is joined in fluorescence cuvette, on Fluorescence spectrophotometer, detect, the sodium sulfide solution that adds known variable concentrations, optical excitation with 405nm, the described sulphion fluorescence chemical sensor based on silicon nanowires of solution system to be detected can produce fluorescence to be strengthened, and find that the fluorescence intensity of solution system to be detected strengthens gradually along with the increase of the concentration of known sulphion.By drawing known sulphion concentration and the calibration curve of fluorescent characteristics peak intensity, and the fluorescence intensity at the fluorescent characteristics peak detecting with the fluorescence chemical sensor based on silicon nanowires by described in solution system to be detected compares, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
Embodiment 4
1) silicon chip size is immersed in to the concentrated sulphuric acid that volume ratio is 8:1 (massfraction is 50%) and H for the silicon nanowire array of being prepared by chemical etching method of 1cm * 1cm (diameter of the silicon nanowires in silicon nanowire array is 200～400nm, and length is 15～20 μ m)
2o
2in the mixed liquor of (massfraction is 30%), in temperature, be at 70 ℃, to process after 90 minutes, with deionized water, wash to neutrality the H that soak at room temperature is 9:1:1 in volume ratio
2o:H
2o
2(massfraction is 5%): NH
4in the mixed liquor of OH 1 hour, be washed to neutrality, vacuum drying, obtains the silicon nanowire array that hydroxylation is processed;
2) under room temperature, by dry step 1) silicon nanowire array processed of the process hydroxylation that obtains, the dry toluene of 30mL and the 3-[2-of 0.4mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under nitrogen protection, be heated to after 90 ℃, isothermal reaction 12 hours, then be cooled to room temperature, with methyl alcohol ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowire array of propyl group-trimethoxy silane,
3) under room temperature, by step 2) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowire array of propyl group-trimethoxy silane is immersed in the 4-amino-1 of 1.5mol/L, in the ethanol solution of 8-naphthalic anhydride, under nitrogen protection, be heated to 90 ℃, isothermal reaction 5 hours, after cool to room temperature, with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1,8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowire array of 8-aphthalimide fluorophore;
4) by step 3) finishing that obtains has 4-amino-1, and the silicon nanowire array of 8-aphthalimide fluorophore is immersed in 50 * 10
-6in the copper chloride solution of mol/L 2 minutes, then take out and with deionized water washing, after naturally drying, obtain the sulphion fluorescence chemical sensor based on silicon nanowire array.
By the sulphion fluorescence chemical sensor based on silicon nanowire array obtained above, after being immersed in the aqueous solution that contains sulphion, on fluorescent microscope, detect, excitation source is mercury lamp (excitation wavelength is 450～480nm).The fluorescence intensity of the described sulphion fluorescence chemical sensor based on silicon nanowire array in solution system to be detected obviously strengthens, by drawing the calibration curve of the concentration of known sulphion and the fluorescence intensity of the fluorescent optical sensor based on silicon nanowire array, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowire array by described in solution system to be detected detects, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
Embodiment 5
1) silicon nanowires that is 10～15nm by the diameter of being prepared by chemical vapour deposition technique is immersed in the concentrated sulphuric acid that volume ratio is 5:1 (massfraction is 75%) and H
2o
2in the mixed liquor of (massfraction is 15%), in temperature, be at 80 ℃, to process after 60 minutes, with deionized water, wash to neutrality the H that soak at room temperature is 6:1:1 in volume ratio
2o:H
2o
2(massfraction is 15%): NH
4in the mixed liquor of OH 1.5 hours, be washed to neutrality, vacuum drying, obtains the silicon nanowires that hydroxylation is processed;
2) under room temperature, by dry 40mg step 1) silicon nanowires processed of the process hydroxylation that obtains, the dry toluene of 20mL and the 3-[2-of 0.25mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under nitrogen protection, be heated to after 70 ℃, isothermal reaction 30 hours, then be cooled to room temperature, with methylene chloride ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane,
3) under room temperature, by step 2) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane is immersed in the 4-amino-1 of 1.0mol/L, in the ethanol solution of 8-naphthalic anhydride, under nitrogen protection, be heated to 65 ℃, isothermal reaction 10 hours, after cool to room temperature, with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1,8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowires of 8-aphthalimide fluorophore;
4) by step 3) finishing that obtains has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore is dispersed in HEPES (20mM, pH=7.0), is made into the solution that concentration is 55 μ g/mL, adds 11 * 10
-6mol/L copper chloride solution, forming finishing has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore and the complex compound of copper ion, obtain the sulphion fluorescent optical sensor based on silicon nanowires.
Substrate using the sulphion fluorescence chemical sensor based on silicon nanowires obtained above as fluoroscopic examination, with Fluorescence spectrophotometer, to this, the sensing capabilities of the fluorescence chemical sensor based on silicon nanowires characterizes, and excitation source is xenon lamp (excitation wavelength is 400～450nm).
The HEPES buffer solution system of the 2mL 20mM that contains the described fluorescence chemical sensor based on silicon nanowires is joined in fluorescence cuvette, on Fluorescence spectrophotometer, detect, the sodium sulfide solution that adds known variable concentrations, optical excitation with 400nm, the described fluorescence chemical sensor based on silicon nanowires of solution system to be detected can produce fluorescence to be strengthened, and find that the fluorescence intensity of solution system to be detected strengthens gradually along with the increase of the concentration of known sulphion.By drawing known sulphion concentration and the calibration curve of fluorescent characteristics peak intensity, and the fluorescence intensity at the fluorescent characteristics peak detecting with the fluorescence chemical sensor based on silicon nanowires by described in solution system to be detected compares, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
Embodiment 6
1) silicon chip size is immersed in to the concentrated sulphuric acid that volume ratio is 5:1 (massfraction is 75%) and H for the silicon nanowire array of being prepared by chemical etching method of 1cm * 1cm (diameter of the silicon nanowires in silicon nanowire array is 200～400nm, and length is 15～20 μ m)
2o
2in the mixed liquor of (massfraction is 15%), in temperature, be at 80 ℃, to process after 60 minutes, with deionized water, wash to neutrality the H that soak at room temperature is 6:1:1 in volume ratio
2o:H
2o
2(massfraction is 15%): NH
4in the mixed liquor of OH 1.5 hours, be washed to neutrality, vacuum drying, obtains the silicon nanowire array that hydroxylation is processed;
2) under room temperature, by dry step 1) silicon nanowire array processed of the process hydroxylation that obtains, the dry toluene of 20mL and the 3-[2-of 0.25mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under nitrogen protection, be heated to after 70 ℃, isothermal reaction 30 hours, then be cooled to room temperature, with ethanol ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowire array of propyl group-trimethoxy silane,
3) under room temperature, by step 2) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowire array of propyl group-trimethoxy silane is immersed in the 4-amino-1 of 1.0mol/L, in the ethanol solution of 8-naphthalic anhydride, under nitrogen protection, be heated to 65 ℃, isothermal reaction 10 hours, after cool to room temperature, with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1,8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowire array of 8-aphthalimide fluorophore;
4) by step 3) finishing that obtains has 4-amino-1, and the silicon nanowire array of 8-aphthalimide fluorophore is immersed in 30 * 10
-6in the copper chloride solution of mol/L 3.5 minutes, then take out and with deionized water washing, after naturally drying, obtain the sulphion fluorescence chemical sensor based on silicon nanowire array.
By the sulphion fluorescence chemical sensor based on silicon nanowire array obtained above, after being immersed in the aqueous solution that contains sulphion, on fluorescent microscope, detect, excitation source is mercury lamp (excitation wavelength is 450～480nm).The fluorescence intensity of the described sulphion fluorescence chemical sensor based on silicon nanowire array in solution system to be detected obviously strengthens, by drawing the calibration curve of the concentration of known sulphion and the fluorescence intensity of the fluorescent optical sensor based on silicon nanowire array, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowire array by described in solution system to be detected detects, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
Claims (9)
1. a preparation method for the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array, is characterized in that, described preparation method comprises the following steps:
1) under room temperature, silicon nanowires or silicon nanowire array that 30～50mg is processed through hydroxylation, the dry toluene of 10～30mL and the 3-[2-of 0.1～0.4mL (2-aminoethylamino) ethylamino] propyl group-trimethoxy silane joins in reactor, under inert gas shielding, be heated to after 50～90 ℃, isothermal reaction 12～48 hours, then be cooled to room temperature, with organic solvent ultrasonic cleaning, remove unreacted 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane, collection obtains finishing 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires or the silicon nanowire array of propyl group-trimethoxy silane,
2) under room temperature, by step 1) finishing that obtains has 3-[2-(2-aminoethylamino) ethylamino] silicon nanowires of propyl group-trimethoxy silane or the 4-that silicon nanowire array is immersed in 0.5～1.5mol/L amino-1, in the ethanol solution of 8-naphthalic anhydride, under inert gas shielding, be heated to 40～90 ℃, isothermal reaction 5～15 hours, be cooled to room temperature, then with absolute ethyl alcohol repeatedly ultrasonic cleaning remove unreacted 4-amino-1, 8-naphthalic anhydride molecule, obtain finishing and have 4-amino-1, the silicon nanowires of 8-aphthalimide fluorophore or silicon nano-array,
3) by step 2) finishing that obtains has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore is dispersed in 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution, is made into the solution that concentration is 30～80 μ g/mL, adds 6 * 10
-6～16 * 10
-6mol/L copper chloride solution, forming finishing has 4-amino-1, and the silicon nanowires of 8-aphthalimide fluorophore and the complex compound of copper ion, obtain the sulphion fluorescence chemical sensor based on silicon nanowires;
Or by step 2) finishing that obtains has 4-amino-1, and the silicon nanowire array of 8-aphthalimide fluorophore is immersed in 10 * 10
-6～50 * 10
-6in mol/L copper chloride solution, after taking-up, with deionized water washing, after naturally drying, obtain the sulphion fluorescence chemical sensor based on silicon nanowire array.
2. preparation method according to claim 1, is characterized in that: step 3) time of described immersion is 2～5 minutes.
3. preparation method according to claim 1, is characterized in that, described hydroxylation is processed the method adopting and is: silicon nanowires or silicon nanowire array are immersed in to the concentrated sulphuric acid and the H that volume ratio is 1:1～8:1
2o
2mixed liquor in, in temperature, be at 70～95 ℃, to process after 30～90 minutes, with deionized water, wash to neutrality the H that soaking at room temperature is 3:1:1～9:1:1 in volume ratio
2o:H
2o
2: NH
4in the mixed liquor of OH 1～2.5 hour, be washed to neutrality, vacuum drying.
4. preparation method according to claim 3, is characterized in that, the massfraction of the described concentrated sulphuric acid is 50%～98%, H
2o
2massfraction be 5%～30%.
5. according to the preparation method described in claim 1 or 3, it is characterized in that: described silicon nanowires is the silicon nanowires that chemical vapour deposition technique prepares, diameter is 10～15nm;
Described silicon nanowire array is the silicon nanowire array that chemical etching method prepares, and the diameter of the silicon nanowires in silicon nanowire array is 200～400nm, and length is 15～20 μ m.
6. preparation method according to claim 1, is characterized in that: described organic solvent is methyl alcohol, ethanol, methylene chloride or acetone.
7. the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array, it is to be prepared by the preparation method described in claim 1～6 any one.
8. an application for the sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array claimed in claim 7, is characterized in that: the described sulphion fluorescence chemical sensor based on silicon nanowires or silicon nanowire array is for the detection of the solution system sulphion that contains sulphion.
9. application according to claim 8, it is characterized in that: the described detection for the solution system sulphion that contains sulphion, that the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution that contains the sulphion fluorescence chemical sensor based on silicon nanowires is joined in fluorescence cuvette, on Fluorescence spectrophotometer, detect, along with adding of sulfur-containing anion material, the fluorescence intensity of solution system to be detected strengthens gradually; By drawing the concentration of known sulphion and the calibration curve of fluorescent characteristics peak intensity, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowires by described in solution system to be detected detects, determine the concentration of sulphion in solution system to be detected;
Or by the sulphion fluorescence chemical sensor based on silicon nanowire array, after being immersed in the aqueous solution that contains sulphion, on fluorescent microscope, detect, the fluorescence intensity of the described sulphion fluorescence chemical sensor based on silicon nanowire array in solution system to be detected obviously strengthens, by drawing the calibration curve of the concentration of known sulphion and the fluorescence intensity of silicon nanowire array fluorescent optical sensor, and compare with the fluorescence intensity that the fluorescence chemical sensor based on silicon nanowire array by described in solution system to be detected detects, determine the concentration of the sulphion in solution system to be detected, thereby realized the detection to the sulphion in solution system to be detected.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104792758A (en) * | 2015-04-22 | 2015-07-22 | 中国科学院理化技术研究所 | Preparation method for hydrogen sulfide fluorescent chemosensor based on silicon nanowire or silicon nanowire array |
| CN108913120A (en) * | 2018-06-21 | 2018-11-30 | 中国科学院理化技术研究所 | A kind of single silicon nanowire fluorescence chemical sensor and its preparation method and application for detecting hypochlorite |
| CN109897630A (en) * | 2019-04-17 | 2019-06-18 | 中国科学院理化技术研究所 | A kind of nano wire, preparation method, the Ratio-type fluorescence chemical sensor comprising the nano wire and application |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191794A (en) * | 2007-08-27 | 2008-06-04 | 中国科学院理化技术研究所 | One-dimensional nanostructured fluorescent chemical biosensor and method for making same and uses |
| CN101671020A (en) * | 2008-12-22 | 2010-03-17 | 中国科学院理化技术研究所 | Silicon nanowire-based fluorescence chemical logic switch and preparation method thereof |
| CN101968445A (en) * | 2010-03-11 | 2011-02-09 | 大连理工大学 | Mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and application thereof |
| CN102020231A (en) * | 2010-10-25 | 2011-04-20 | 中国科学院理化技术研究所 | Enhanced Raman scattering substrates of silicon semiconductor and a manufacturing method and application for the same |
| CN102127088A (en) * | 2010-12-24 | 2011-07-20 | 中国科学院烟台海岸带研究所 | Naphthalimide-modified rhodamine derivative (naphthalimide modified rhodamine B chemosensor, NRC) and preparation and use thereof |
| CN102351140A (en) * | 2011-07-06 | 2012-02-15 | 东南大学 | Preparation method of growth-controllable silicon nanowire sensor |
| CN102419319A (en) * | 2011-09-08 | 2012-04-18 | 中国科学院理化技术研究所 | Silicon nano wire based sensor having selective fluorescence response on nitric oxide |
| CN102503875A (en) * | 2011-11-18 | 2012-06-20 | 厦门大学 | Fluorescent probe for detecting copper ions and preparation method thereof |
| CN102504105A (en) * | 2011-11-21 | 2012-06-20 | 湖北大学 | Water-soluble naphthalene imide fluorescent polymer as well as synthesis method and purpose thereof |
| CN103712968A (en) * | 2014-01-06 | 2014-04-09 | 中国科学院理化技术研究所 | Silicon-nanowire-based fluorescence chemical sensor with selective fluorescence response to free copper ions and complexing copper ions |
| CN103937488A (en) * | 2014-03-25 | 2014-07-23 | 中国科学院理化技术研究所 | Silicon-nanowire-based alkaline phosphatase fluorescent chemosensor, preparation method and application |
-
2014
- 2014-08-27 CN CN201410429525.7A patent/CN104155277A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191794A (en) * | 2007-08-27 | 2008-06-04 | 中国科学院理化技术研究所 | One-dimensional nanostructured fluorescent chemical biosensor and method for making same and uses |
| CN101671020A (en) * | 2008-12-22 | 2010-03-17 | 中国科学院理化技术研究所 | Silicon nanowire-based fluorescence chemical logic switch and preparation method thereof |
| CN101968445A (en) * | 2010-03-11 | 2011-02-09 | 大连理工大学 | Mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and application thereof |
| CN102020231A (en) * | 2010-10-25 | 2011-04-20 | 中国科学院理化技术研究所 | Enhanced Raman scattering substrates of silicon semiconductor and a manufacturing method and application for the same |
| CN102127088A (en) * | 2010-12-24 | 2011-07-20 | 中国科学院烟台海岸带研究所 | Naphthalimide-modified rhodamine derivative (naphthalimide modified rhodamine B chemosensor, NRC) and preparation and use thereof |
| CN102351140A (en) * | 2011-07-06 | 2012-02-15 | 东南大学 | Preparation method of growth-controllable silicon nanowire sensor |
| CN102419319A (en) * | 2011-09-08 | 2012-04-18 | 中国科学院理化技术研究所 | Silicon nano wire based sensor having selective fluorescence response on nitric oxide |
| CN102503875A (en) * | 2011-11-18 | 2012-06-20 | 厦门大学 | Fluorescent probe for detecting copper ions and preparation method thereof |
| CN102504105A (en) * | 2011-11-21 | 2012-06-20 | 湖北大学 | Water-soluble naphthalene imide fluorescent polymer as well as synthesis method and purpose thereof |
| CN103712968A (en) * | 2014-01-06 | 2014-04-09 | 中国科学院理化技术研究所 | Silicon-nanowire-based fluorescence chemical sensor with selective fluorescence response to free copper ions and complexing copper ions |
| CN103937488A (en) * | 2014-03-25 | 2014-07-23 | 中国科学院理化技术研究所 | Silicon-nanowire-based alkaline phosphatase fluorescent chemosensor, preparation method and application |
Non-Patent Citations (9)
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104792758A (en) * | 2015-04-22 | 2015-07-22 | 中国科学院理化技术研究所 | Preparation method for hydrogen sulfide fluorescent chemosensor based on silicon nanowire or silicon nanowire array |
| CN108913120A (en) * | 2018-06-21 | 2018-11-30 | 中国科学院理化技术研究所 | A kind of single silicon nanowire fluorescence chemical sensor and its preparation method and application for detecting hypochlorite |
| CN108913120B (en) * | 2018-06-21 | 2021-04-02 | 中国科学院理化技术研究所 | Single silicon nanowire fluorescence chemical sensor for detecting hypochlorite, and preparation method and application thereof |
| CN109897630A (en) * | 2019-04-17 | 2019-06-18 | 中国科学院理化技术研究所 | A kind of nano wire, preparation method, the Ratio-type fluorescence chemical sensor comprising the nano wire and application |
| CN109897630B (en) * | 2019-04-17 | 2021-12-14 | 中国科学院理化技术研究所 | Nanowire, preparation method thereof, ratio type fluorescence chemical sensor containing nanowire and application |
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