CN102776536A - Mercapto-beta-cyclodextrin modified silver nano-rode array, its preparation method and its use - Google Patents
Mercapto-beta-cyclodextrin modified silver nano-rode array, its preparation method and its use Download PDFInfo
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- CN102776536A CN102776536A CN2011101219008A CN201110121900A CN102776536A CN 102776536 A CN102776536 A CN 102776536A CN 2011101219008 A CN2011101219008 A CN 2011101219008A CN 201110121900 A CN201110121900 A CN 201110121900A CN 102776536 A CN102776536 A CN 102776536A
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Abstract
The invention discloses a mercapto-beta-cyclodextrin modified silver nano-rod array, its preparation method and its use. The array is a silver nano-rod array with the surface modified by mercapto-beta-cyclodextrin, wherein the lengths of silver nano-rods are 150-600nm, the diameters of the silver nano-rods are 60-90nm, the space between each two silver nano-rods is 10-40nm, and the substrate of the array is formed by superposing one or more than two of a silver film, a gold film, a copper film and a nickel film which have the thicknesses of 20-50mum. The preparation method comprises the following steps: obtaining a through hole alumina template through using a secondary anode oxidation method, sputtering a metal conductive film on one surface of the through hole alumina template through using an ion sputtering method to obtain an alumina template with the metal conductive film, carrying out electric deposition through placing the alumina template with the metal conductive film in a silver electrolyte to obtain an alumina template with holes provided with the silver nano-rods and one surface coated with the metal conductive film, etching off the alumina template through putting the resultant alumina template in an acidic or strongly alkaline solution, and immersing the resultant material in an aqueous solution of the mercapto-beta-cyclodextrin for at least 1h to prepare the mercapto-beta-cyclodextrin modified silver nano-rod array. The mercapto-beta-cyclodextrin modified silver nano-rod array can be used for rapidly detecting trace PCB77 or PCB101.
Description
Technical field
The present invention relates to a kind of nanometer stick array and preparation method and purposes, the silver-colored nanometer stick array that especially a kind of sulfydryl-beta-cyclodextrin is modified.
Background technology
Under the effect that adds alternating electromagnetic field, the unbound electron on nano unit top layers such as precious metal silver can polarize, and produces collective oscillation.When the frequency that adds EM field equates with the oscillation frequency of unbound electron, will produce surface plasmon resonance (SPR) phenomenon, the SPR effect can make the electromagnetic intensity of local significantly improve.People have done some trials and effort in order to make full use of the SPR effect, like " a kind of highly sensitive nano biosensor production method " that discloses among the disclosed Chinese invention patent Shen Qing Publication specification sheets CN 101144809A on March 19th, 2008.This making method is earlier on as the glass of base material or quartz, to make the silver metal nano-array; Through immersion the silver metal surface is with and the corresponding reactive group of biomolecules again; Make antigen and silver particles array combine be more prone to, then, earlier antigenic solution and zero-distance coupling reagent solution are mixed the back and drip at substrate surface; The processing of again substrate being washed, drying up obtains nano biological sensor.But, no matter be nano biological sensor, or its making method, all exist weak point; At first, nano biological sensor only can carry out highly sensitive detection to the antigen vitamin H target molecule that contains long-chain in the testing process of biomolecules, and can not be to environment toxic pollutant 3,3 '; 4,4 '-tetrachloro biphenyl or 2,2 '; 4,5,5 '-pentachlorodiphenyl carries out trace detection; Secondly, making method can not make environment toxic pollutant 3,3 ', 4,4 '-tetrachloro biphenyl or 2,2 ', 4,5,5 '-pentachlorodiphenyl carries out the transmitter of trace detection.
Summary of the invention
The technical problem that the present invention will solve provides a kind of rational in infrastructure for overcoming weak point of the prior art, can be to environment toxic pollutant 3,3 '; 4,4 '-tetrachloro biphenyl or 2,2 '; 4,5,5 '-pentachlorodiphenyl carries out the silver-colored nanometer stick array that the sulfydryl of trace detection-beta-cyclodextrin is modified.
Another technical problem that the present invention will solve is the preparation method that the silver-colored nanometer stick array of a kind of above-mentioned sulfydryl-beta-cyclodextrin modification is provided.
The technical problem that also has that the present invention will solve is the purposes that the silver-colored nanometer stick array of a kind of above-mentioned sulfydryl-beta-cyclodextrin modification is provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: the silver-colored nanometer stick array that sulfydryl-beta-cyclodextrin is modified comprises suprabasil silver-colored nano-array, particularly,
Said silver-colored nano-array is silver-colored nanometer stick array, and the finishing of the silver-colored nanometer rod of said formation silver nanometer stick array has sulfydryl-beta-cyclodextrin;
The rod length of said silver-colored nanometer rod is that 150～600nm, excellent diameter are that 60～90nm, interrod spacing are 10～40nm;
Said substrate is a metal conductive film, and the thickness of said metal conductive film is 20～50 μ m, and it is made up of one or more stacks in silverskin, golden film, copper film, the nickel film.
The further improvement of the silver-colored nanometer stick array of modifying as sulfydryl-beta-cyclodextrin, the thickness of described sulfydryl-beta-cyclodextrin is 1～2nm.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of the silver-colored nanometer stick array that above-mentioned sulfydryl-beta-cyclodextrin is modified comprises the two-step anodization method, and particularly completing steps is following:
Step 2; It is 10～15 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode, is that 0.2～0.8V, frequency are that 0.8～1.2KHz, waveform are that square wave, dutycycle are galvanic deposit 1～5min under 48～52% the pulsed voltage in deposition voltage, obtains being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film; Wherein, silver electrolyte is by the Silver Nitrate (AgNO of 10g/L
3), the YD 30 (EDTA) of 5g/L, the S-WAT (Na of 50g/L
2SO
3), the potassium hydrogenphosphate (K of 20g/L
2HPO
4) mix with aqueous solvent; Place acid solution or strong base solution to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Obtain the silver-colored nanometer stick array that the bottom is covered with metal conductive film; Afterwards, it is 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-2～10
-4Soak 1h at least in the sulfydryl of mol/L-beta-cyclodextrin aqueous solution, make the silver-colored nanometer stick array that sulfydryl-beta-cyclodextrin is modified.
The preparing method's of the silver-colored nanometer stick array of modifying as sulfydryl-beta-cyclodextrin further improvement; The procurement process of described through hole alumina formwork does; Earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4mol/L, is anodic oxidation 4～8h under the 40V in volts DS, is placed in 60 ℃ the chromic acid mixing solutions of phosphoric acid and 1.8wt% of 6wt% to soak 10h again; Then; It once more after carrying out the anodizing second time 13～20h under the same processing condition, is removed the unoxidized aluminium in the back side with Cupric Chloride Solution or tin chloride solution earlier, erode the aluminum oxide barrier layer that is positioned at bottom the hole with the phosphate aqueous solution of 5～10wt% again; Described acid solution is that concentration is the phosphoric acid solution of 5～10wt%; Described strong base solution is a sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution; The process for preparation of described sulfydryl-beta-cyclodextrin does, is that the aqueous sodium hydroxide solution of 0.823～0.827mol/L is added drop-wise in the beta-cyclodextrin aqeous suspension that concentration is 0.12～0.16mol/L with concentration earlier, obtains clarifying yellow solution; Wherein, sodium hydroxide in the clarifying yellow solution and the weight ratio between the beta-cyclodextrin are 1: 10～11, are that the Methyl benzenesulfonyl chloromethyl cyanide drips of solution of 1.75～1.79mol/L is added in the clarifying yellow solution with concentration again; Obtain the beta-cyclodextrin solution of sulfonylation, wherein, beta-cyclodextrin and the weight ratio between the Methyl benzenesulfonyl chlorine in the beta-cyclodextrin solution of sulfonylation are 6.8～7.1: 1; Then, earlier with the beta-cyclodextrin solution of sulfonylation after stirring at least 2h under 18～22 ℃, place under 2～5 ℃ and leave standstill 24～48h; With the beta-cyclodextrin xln that obtains sulfonylation after twice in solid recrystallization of separating out and the drying, afterwards, beta-cyclodextrin xln and the thiocarbamide with sulfonylation is dissolved in the mixed solvent of methyl alcohol and water earlier again; Wherein, Weight ratio between beta-cyclodextrin xln, thiocarbamide and the methyl alcohol of sulfonylation and the mixed solvent of water is 2: 2.0～2.4: 82～86, and methyl alcohol and the weight ratio between the water in the mixed solvent are 62～66: 20, obtain mixed solution; In mixed solution, add 1 again; The 2-ethylene dichloride, wherein, the beta-cyclodextrin xln and 1 of the sulfonylation in the mixed solution; Weight ratio between the 2-ethylene dichloride is 2: 28～32, obtains sulfydryl-beta-cyclodextrin; It is 1～3h that the described silver-colored nanometer stick array that the bottom is covered with metal conductive film places the time that sulfydryl-the beta-cyclodextrin aqueous solution soaks.
For solving the technical problem that also has of the present invention, the technical scheme that also has that is adopted is: the purposes of the silver-colored nanometer stick array that above-mentioned sulfydryl-beta-cyclodextrin is modified does,
The surface enhanced Raman scattering effect performance of utilizing finishing to have the silver-colored nanometer stick array of sulfydryl-beta-cyclodextrin to have detects trace 3, and 3 ', 4,4 '-tetrachloro biphenyl (PCB77) or 2,2 ', 4,5,5 '-pentachlorodiphenyl (PCB101).
The further improvement of the purposes of the silver-colored nanometer stick array of modifying as sulfydryl-beta-cyclodextrin, the light wavelength that excites that described surface enhanced Raman scattering effect is required is 514.5nm or 532nm, power is 0.1～1mW.
Beneficial effect with respect to prior art is, one of which uses ESEM and IR to characterize respectively to the title product that makes, and can be known by its result, and title product is for being overlying on suprabasil silver-colored nanometer stick array; Wherein, The finishing that constitutes the silver-colored nanometer rod of silver-colored nanometer stick array has sulfydryl-beta-cyclodextrin; The rod length of silver nanometer rod is that 150～600nm, excellent diameter are that 60～90nm, interrod spacing are 10～40nm; Substrate is that thickness is the metal conductive film of 20～50 μ m, and it is made up of one or more stacks in silverskin, golden film, copper film, the nickel film.Its two, use the burnt micro-Raman spectroscopy of copolymerization to characterize to the title product that contains trace PCB77 or PCB101, can know by its result, when the concentration of PCB77 is low to moderate 2 * 10
-7The concentration of mol/L or PCB101 is low to moderate 2 * 10
-5During mol/L, title product still can detect it effectively.The mechanism that title product detects trace PCB77 or PCB101 does; Title product is on the basis of material with strong surface enhanced Raman scattering (SERS) effect of generation and pattern; Also to PCB77 or PCB101 bulk of molecule; In its finishing sulfydryl-beta-cyclodextrin; Thereby make its surface with having gone up the molecule that contains the nano-sized hydrophobic cavity, and then be able to utilize the nano-sized hydrophobic cavity of this molecule to catch that be difficult to adsorb and PCB77 or PCB101 molecule its cavity size coupling, realized effective detection PCB77 or PCB101.This SERS substrate through sulfydryl-beta-cyclodextrin functionalization is expected to as the selective sensitivity unit material in the detection means, is used for the PCB77 or the PCB101 of environment are carried out quick trace detection.They are three years old; Preparing method's science, effective; Both prepared silver-colored nanometer stick array, and made again and modify the thickness that is merely molecular layer in the sulfydryl-beta-cyclodextrin of silver-colored nanorod surfaces, thereby do not had influence on the SERS performance of silver-colored nanometer stick array with stronger SERS effect pattern; The title product of preparing has been satisfied environment toxic pollutant PCB77 or PCB101 are carried out the requirement of quick trace detection, advantage with low cost, as to be easy to suitability for industrialized production is also arranged.
Further embodiment as beneficial effect; The one, the thickness of sulfydryl-beta-cyclodextrin is preferably 1～2nm; After silver-colored nanometer rod combines with the Ag-S key; Make the PCB molecule of absorption be positioned at silver-colored nanorod surfaces, guaranteed that not only sulfydryl-beta-cyclodextrin can effectively modify in silver-colored nanorod surfaces, also satisfied when detecting trace PCB77 or PCB101 requirement its sensitivity; The 2nd, the procurement process of through hole alumina formwork is preferably; Earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4mol/L; In volts DS is anodic oxidation 4～8h under the 40V, is placed in 60 ℃ the chromic acid mixing solutions of phosphoric acid and 1.8wt% of 6wt% to soak 10h, then again; With it once more after carrying out the anodizing second time 13～20h under the same processing condition; Remove the unoxidized aluminium in the back side with Cupric Chloride Solution or tin chloride solution earlier, the phosphate aqueous solution with 5～10wt% erodes the aluminum oxide barrier layer that is positioned at the bottom, hole again, has guaranteed the suitability of the through hole alumina formwork of acquisition; The 3rd, acid solution is preferably the phosphoric acid solution that concentration is 5～10wt%, and strong base solution is preferably sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution, erodes the alumina formwork except that being beneficial to, and also makes preparation technology more be prone to enforcement and flexible; The 4th, the process for preparation of sulfydryl-beta-cyclodextrin is preferably, and is that the aqueous sodium hydroxide solution of 0.823～0.827mol/L is added drop-wise in the beta-cyclodextrin aqeous suspension that concentration is 0.12～0.16mol/L with concentration earlier, obtains clarifying yellow solution; Wherein, sodium hydroxide in the clarifying yellow solution and the weight ratio between the beta-cyclodextrin are 1: 10～11, are that the Methyl benzenesulfonyl chloromethyl cyanide drips of solution of 1.75～1.79mol/L is added in the clarifying yellow solution with concentration again; Obtain the beta-cyclodextrin solution of sulfonylation, wherein, beta-cyclodextrin and the weight ratio between the Methyl benzenesulfonyl chlorine in the beta-cyclodextrin solution of sulfonylation are 6.8～7.1: 1; Then, earlier with the beta-cyclodextrin solution of sulfonylation after stirring at least 2h under 18～22 ℃, place under 2～5 ℃ and leave standstill 24～48h; Again with the beta-cyclodextrin xln that obtains sulfonylation after twice in solid recrystallization of separating out and the drying; Afterwards, elder generation is dissolved in the beta-cyclodextrin xln and the thiocarbamide of sulfonylation in the mixed solvent of methyl alcohol and water, wherein; Weight ratio between beta-cyclodextrin xln, thiocarbamide and the methyl alcohol of sulfonylation and the mixed solvent of water is 2: 2.0～2.4: 82～86; Methyl alcohol and the weight ratio between the water in the mixed solvent are 62～66: 20, obtain mixed solution, in mixed solution, add 1 again; The 2-ethylene dichloride; Wherein, the beta-cyclodextrin xln and 1 of the sulfonylation in the mixed solution, the weight ratio between the 2-ethylene dichloride is 2: 28～32; Obtain sulfydryl-beta-cyclodextrin, be beneficial to and obtain its hydroxyl by the substituted sulfydryl-beta-cyclodextrin of sulfydryl part; The 5th, the silver-colored nanometer stick array that the bottom is covered with metal conductive film places the time that sulfydryl-the beta-cyclodextrin aqueous solution soaks to be preferably 1～3h, promptly can short soak time obtain to satisfy the title product that quick trace detection requires; The 6th, the light wavelength that excites that surface enhanced Raman scattering effect is required is preferably 514.5nm or 532nm, and power is preferably 0.1～1mW, has guaranteed that title product has best Effect on Detecting.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that ESEM (SEM) characterizes to the title product that makes.Visible by the SEM photo, the excellent diameter of title product is about 90nm, and interrod spacing is about 10nm.
Fig. 2 is one of result who respectively beta-cyclodextrin and title product use ir spectra (FTIR) appearance that makes is characterized.Curve a in the FTIR spectrogram is the FTIR spectral line of beta-cyclodextrin, and curve b is the FTIR spectral line of title product; By being positioned at 2570cm on the curve b
-1The weak tympanum of the S-H key at place can know that the hydroxyl of beta-cyclodextrin has partly been replaced by sulfydryl.
Fig. 3 uses one of result that the burnt micro-Raman spectroscopy of copolymerization characterizes to the title product that contains trace PCB77.It is 2 * 10 to concentration that curve a among the figure, curve b, curve c and curve d are respectively title product
-4Mol/L, 2 * 10
-5Mol/L, 2 * 10
-6Mol/L and 2 * 10
-7The SERS spectral line of the PCB77 of mol/L, curve e are the SERS spectral line of title product, and curve f is the standard Raman line of solid PCB77.
Fig. 4 uses one of result that the burnt micro-Raman spectroscopy of copolymerization characterizes to the title product that contains trace PCB101.Curve a among the figure is an intermediate product---the bottom is covered with the SERS spectral line of the silver-colored nanometer stick array of metal conductive film to PCB101, and curve b is the SERS spectral line of title product, and it is 2 * 10 to concentration that curve c and curve d are respectively title product
-4Mol/L and 2 * 10
-5The SERS spectral line of the PCB101 of ol/L, curve e are the standard Raman scattering light spectral line of solid PCB101.
Embodiment
At first buy or make with ordinary method from market:
Purity is >=99.9% aluminium flake;
Silver Nitrate (AgNO as the silver electrolyte raw material
3), YD 30 (EDTA), S-WAT (Na
2SO
3) and potassium hydrogenphosphate (K
2HPO
4);
Phosphoric acid solution as acid solution;
Sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as strong base solution;
Using the two-step anodization method to obtain bore dia is the through hole alumina formwork of 60～90nm; Its process does; Earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4mol/L, is anodic oxidation 4～8h under the 40V in volts DS, is placed in 60 ℃ the chromic acid mixing solutions of phosphoric acid and 1.8wt% of 6wt% to soak 10h again; Then; It once more after carrying out the anodizing second time 13～20h under the same processing condition, is removed the unoxidized aluminium in the back side with Cupric Chloride Solution or tin chloride solution earlier, erode the aluminum oxide barrier layer that is positioned at bottom the hole with the phosphate aqueous solution of 5～10wt% again;
Use following method preparation sulfydryl-beta-cyclodextrin, its process does, is that the aqueous sodium hydroxide solution of 0.823～0.827mol/L is added drop-wise in the beta-cyclodextrin aqeous suspension that concentration is 0.12～0.16mol/L with concentration earlier; Obtain clarifying yellow solution, wherein, sodium hydroxide in the clarifying yellow solution and the weight ratio between the beta-cyclodextrin are 1: 10～11; Be that the Methyl benzenesulfonyl chloromethyl cyanide drips of solution of 1.75～1.79mol/L is added in the clarifying yellow solution with concentration again, obtain the beta-cyclodextrin solution of sulfonylation, wherein; Beta-cyclodextrin and the weight ratio between the Methyl benzenesulfonyl chlorine in the beta-cyclodextrin solution of sulfonylation are 6.8～7.1: 1, then, earlier with the beta-cyclodextrin solution of sulfonylation after stirring at least 2h under 18～22 ℃; Place under 2～5 ℃ and leave standstill 24～48h, again with the beta-cyclodextrin xln that obtains sulfonylation after twice in solid recrystallization of separating out and the drying, afterwards; Beta-cyclodextrin xln and thiocarbamide with sulfonylation is dissolved in the mixed solvent of methyl alcohol and water earlier, and wherein, the weight ratio between beta-cyclodextrin xln, thiocarbamide and the methyl alcohol of sulfonylation and the mixed solvent of water is 2: 2.0～2.4: 82～86; Methyl alcohol in the mixed solvent and the weight ratio between the water are 62～66: 20; Obtain mixed solution, in mixed solution, add 1 again, the 2-ethylene dichloride; Wherein, The beta-cyclodextrin xln and 1 of the sulfonylation in the mixed solution, the weight ratio between the 2-ethylene dichloride is 2: 28～32, obtains sulfydryl-beta-cyclodextrin.
Then,
The concrete steps of preparation are:
Step 2; It is 10 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode; In deposition voltage is that 0.2V, frequency are that 0.8KHz, waveform are that square wave, dutycycle are galvanic deposit 5min under 48% the pulsed voltage, obtains being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film; Wherein, silver electrolyte is mixed by the Silver Nitrate of 10g/L, the YD 30 of 5g/L, the S-WAT of 50g/L, potassium hydrogenphosphate and the aqueous solvent of 20g/L.Place acid solution (or strong base solution) to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Wherein, acid solution is that concentration is the phosphoric acid solution of 5wt%, obtains the bottom and is covered with the silver-colored nanometer stick array of metal conductive film, and afterwards, it is 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-2Soak 3h in the sulfydryl of mol/L-beta-cyclodextrin aqueous solution, make be similar to shown in Figure 1, the silver-colored nanometer stick array that and the sulfydryl shown in the curve b among Fig. 2-beta-cyclodextrin is modified.
Embodiment 2
The concrete steps of preparation are:
Step 2; It is 12 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode; In deposition voltage is that 0.35V, frequency are that 0.9KHz, waveform are that square wave, dutycycle are galvanic deposit 4min under 49% the pulsed voltage, obtains being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film; Wherein, silver electrolyte is mixed by the Silver Nitrate of 10g/L, the YD 30 of 5g/L, the S-WAT of 50g/L, potassium hydrogenphosphate and the aqueous solvent of 20g/L.Place acid solution (or strong base solution) to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Wherein, acid solution is that concentration is the phosphoric acid solution of 6wt%, obtains the bottom and is covered with the silver-colored nanometer stick array of metal conductive film, and afterwards, it is 5 * 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-2Soak 2.5h in the sulfydryl of mol/L-beta-cyclodextrin aqueous solution, make be similar to shown in Figure 1, the silver-colored nanometer stick array that and the sulfydryl shown in the curve b among Fig. 2-beta-cyclodextrin is modified.
Embodiment 3
The concrete steps of preparation are:
Step 2; It is 13 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode; In deposition voltage is that 0.5V, frequency are that 1KHz, waveform are that square wave, dutycycle are galvanic deposit 3min under 50% the pulsed voltage, obtains being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film; Wherein, silver electrolyte is mixed by the Silver Nitrate of 10g/L, the YD 30 of 5g/L, the S-WAT of 50g/L, potassium hydrogenphosphate and the aqueous solvent of 20g/L.Place acid solution (or strong base solution) to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Wherein, acid solution is that concentration is the phosphoric acid solution of 8wt%, obtains the bottom and is covered with the silver-colored nanometer stick array of metal conductive film, and afterwards, it is 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-3Soak 2h in the sulfydryl of mol/L-beta-cyclodextrin aqueous solution, make be similar to shown in Figure 1, the silver-colored nanometer stick array that and the sulfydryl shown in the curve b among Fig. 2-beta-cyclodextrin is modified.
Embodiment 4
The concrete steps of preparation are:
Step 2; It is 14 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode; In deposition voltage is that 0.65V, frequency are that 1.1KHz, waveform are that square wave, dutycycle are galvanic deposit 2min under 51% the pulsed voltage, obtains being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film; Wherein, silver electrolyte is mixed by the Silver Nitrate of 10g/L, the YD 30 of 5g/L, the S-WAT of 50g/L, potassium hydrogenphosphate and the aqueous solvent of 20g/L.Place acid solution (or strong base solution) to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Wherein, acid solution is that concentration is the phosphoric acid solution of 9wt%, obtains the bottom and is covered with the silver-colored nanometer stick array of metal conductive film, and afterwards, it is 5 * 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-3Soak 1.5h in the sulfydryl of mol/L-beta-cyclodextrin aqueous solution, make be similar to shown in Figure 1, the silver-colored nanometer stick array that and the sulfydryl shown in the curve b among Fig. 2-beta-cyclodextrin is modified.
Embodiment 5
The concrete steps of preparation are:
Step 2; It is 15 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode; In deposition voltage is that 0.8V, frequency are that 1.2KHz, waveform are that square wave, dutycycle are galvanic deposit 1min under 52% the pulsed voltage, obtains being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film; Wherein, silver electrolyte is mixed by the Silver Nitrate of 10g/L, the YD 30 of 5g/L, the S-WAT of 50g/L, potassium hydrogenphosphate and the aqueous solvent of 20g/L.Place acid solution (or strong base solution) to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Wherein, acid solution is that concentration is the phosphoric acid solution of 10wt%, obtains the bottom and is covered with the silver-colored nanometer stick array of metal conductive film, and afterwards, it is 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-4Soak 1h in the sulfydryl of ol/L-beta-cyclodextrin aqueous solution, make as shown in Figure 1, the silver-colored nanometer stick array that and the sulfydryl shown in the curve b among Fig. 2-beta-cyclodextrin is modified.
Select phosphoric acid solution more respectively for use as acid solution; Sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution as strong base solution; Using the two-step anodization method to obtain bore dia is the through hole alumina formwork of arbitrary bore dia among 60～90nm; Sulfydryl-the beta-cyclodextrin that uses the arbitrary parameter preparation in the scope in preparation sulfydryl-beta-cyclodextrin process to obtain; Repeat the foregoing description 1～5, made equally as or be similar to shown in Figure 1, and the silver-colored nanometer stick array modified of the sulfydryl shown in the curve b among Fig. 2-beta-cyclodextrin.
The purposes of the silver-colored nanometer stick array that sulfydryl-beta-cyclodextrin is modified does,
The surface enhanced Raman scattering effect performance of utilizing finishing to have the silver-colored nanometer stick array of sulfydryl-beta-cyclodextrin to have detects trace 3, and 3 ', 4,4 '-tetrachloro biphenyl or 2,2 ', 4,5,5 '-pentachlorodiphenyl; Wherein, the light wavelength that excites that surface enhanced Raman scattering effect is required is 514.5nm or 532nm, and power is 0.1～1mW, obtain as or be similar to the detected result shown in the curve among Fig. 3 or Fig. 4.
Obviously, the silver-colored nanometer stick array that can modify sulfydryl of the present invention-beta-cyclodextrin of those skilled in the art and its production and use carry out various changes and modification and do not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. the silver-colored nanometer stick array that sulfydryl-beta-cyclodextrin is modified comprises suprabasil silver-colored nano-array, it is characterized in that:
Said silver-colored nano-array is silver-colored nanometer stick array, and the finishing of the silver-colored nanometer rod of said formation silver nanometer stick array has sulfydryl-beta-cyclodextrin;
The rod length of said silver-colored nanometer rod is that 150～600nm, excellent diameter are that 60～90nm, interrod spacing are 10～40nm;
Said substrate is a metal conductive film, and the thickness of said metal conductive film is 20～50 μ m, and it is made up of one or more stacks in silverskin, golden film, copper film, the nickel film.
2. the silver-colored nanometer stick array that sulfydryl according to claim 1-beta-cyclodextrin is modified, the thickness that it is characterized in that sulfydryl-beta-cyclodextrin is 1～2nm.
3. the preparation method of the silver-colored nanometer stick array of the said sulfydryl of claim 1-beta-cyclodextrin modification comprises the two-step anodization method, it is characterized in that completing steps is following:
Step 1 is used the two-step anodization method to obtain bore dia to aluminium flake earlier and is the through hole alumina formwork of 60～90nm, re-uses the splash-proofing sputtering metal conducting film of ion sputtering method in the through hole alumina formwork, obtains the alumina formwork that one side has metal conductive film;
Step 2; It is 10～15 ℃ silver electrolyte that the alumina formwork that earlier one side is had a metal conductive film places temperature; With it is working electrode; In deposition voltage is that 0.2～0.8V, frequency are that 0.8～1.2KHz, waveform are that square wave, dutycycle are galvanic deposit 1～5min under 48～52% the pulsed voltage; Obtain being equipped with in the hole alumina formwork that silver-colored nanometer rod, one side are covered with metal conductive film, wherein, silver electrolyte is mixed by the Silver Nitrate of 10g/L, the YD 30 of 5g/L, the S-WAT of 50g/L, potassium hydrogenphosphate and the aqueous solvent of 20g/L; Place acid solution or strong base solution to erode alumina formwork with being equipped with the alumina formwork that silver-colored nanometer rod, one side be covered with metal conductive film in the hole again; Obtain the bottom and be covered with the silver-colored nanometer stick array of metal conductive film, afterwards, it is 10 that the silver-colored nanometer stick array that the bottom is covered with metal conductive film places concentration
-2～10
-4Soak 1h at least in the sulfydryl of mol/L-beta-cyclodextrin aqueous solution, make the silver-colored nanometer stick array that sulfydryl-beta-cyclodextrin is modified.
4. the preparation method of the silver-colored nanometer stick array that sulfydryl according to claim 3-beta-cyclodextrin is modified; The procurement process that it is characterized in that the through hole alumina formwork does; Earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4mol/L, is anodic oxidation 4～8h under the 40V in volts DS, is placed in 60 ℃ the chromic acid mixing solutions of phosphoric acid and 1.8wt% of 6wt% to soak 10h again; Then; It once more after carrying out the anodizing second time 13～20h under the same processing condition, is removed the unoxidized aluminium in the back side with Cupric Chloride Solution or tin chloride solution earlier, erode the aluminum oxide barrier layer that is positioned at bottom the hole with the phosphate aqueous solution of 5～10wt% again.
5. the preparation method of the silver-colored nanometer stick array that sulfydryl according to claim 3-beta-cyclodextrin is modified is characterized in that acid solution is that concentration is the phosphoric acid solution of 5～10wt%.
6. the preparation method of the silver-colored nanometer stick array that sulfydryl according to claim 3-beta-cyclodextrin is modified is characterized in that strong base solution is a sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution.
7. the preparation method of the silver-colored nanometer stick array that sulfydryl according to claim 3-beta-cyclodextrin is modified is characterized in that the process for preparation of sulfydryl-beta-cyclodextrin does, is that the aqueous sodium hydroxide solution of 0.823～0.827mol/L is added drop-wise in the beta-cyclodextrin aqeous suspension that concentration is 0.12～0.16mol/L with concentration earlier; Obtain clarifying yellow solution, wherein, sodium hydroxide in the clarifying yellow solution and the weight ratio between the beta-cyclodextrin are 1: 10～11; Be that the Methyl benzenesulfonyl chloromethyl cyanide drips of solution of 1.75～1.79mol/L is added in the clarifying yellow solution with concentration again, obtain the beta-cyclodextrin solution of sulfonylation, wherein; Beta-cyclodextrin and the weight ratio between the Methyl benzenesulfonyl chlorine in the beta-cyclodextrin solution of sulfonylation are 6.8～7.1: 1, then, earlier with the beta-cyclodextrin solution of sulfonylation after stirring at least 2h under 18～22 ℃; Place under 2～5 ℃ and leave standstill 24～48h; With the beta-cyclodextrin xln that obtains sulfonylation after twice in solid recrystallization of separating out and the drying, afterwards, beta-cyclodextrin xln and the thiocarbamide with sulfonylation is dissolved in the mixed solvent of methyl alcohol and water earlier again; Wherein, Weight ratio between beta-cyclodextrin xln, thiocarbamide and the methyl alcohol of sulfonylation and the mixed solvent of water is 2: 2.0～2.4: 82～86, and methyl alcohol and the weight ratio between the water in the mixed solvent are 62～66: 20, obtain mixed solution; In mixed solution, add 1 again; The 2-ethylene dichloride, wherein, the beta-cyclodextrin xln and 1 of the sulfonylation in the mixed solution; Weight ratio between the 2-ethylene dichloride is 2: 28～32, obtains sulfydryl-beta-cyclodextrin.
8. the preparation method of the silver-colored nanometer stick array that sulfydryl according to claim 3-beta-cyclodextrin is modified is characterized in that it is 1～3h that the silver-colored nanometer stick array that the bottom is covered with metal conductive film is placed the time that sulfydryl-the beta-cyclodextrin aqueous solution soaks.
9. the purposes of the silver-colored nanometer stick array modified of the said sulfydryl of claim 1-beta-cyclodextrin is characterized in that:
The surface enhanced Raman scattering effect performance of utilizing finishing to have the silver-colored nanometer stick array of sulfydryl-beta-cyclodextrin to have detects trace 3, and 3 ', 4,4 '-tetrachloro biphenyl or 2,2 ', 4,5,5 '-pentachlorodiphenyl.
10. the purposes of the silver-colored nanometer stick array that sulfydryl according to claim 9-beta-cyclodextrin is modified is characterized in that the required light wavelength that excites of surface enhanced Raman scattering effect is 514.5nm or 532nm, and power is 0.1～1mW.
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