CN202604833U - Minimally invasive blood glucose monitoring microneedle - Google Patents
Minimally invasive blood glucose monitoring microneedle Download PDFInfo
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- CN202604833U CN202604833U CN 201120456571 CN201120456571U CN202604833U CN 202604833 U CN202604833 U CN 202604833U CN 201120456571 CN201120456571 CN 201120456571 CN 201120456571 U CN201120456571 U CN 201120456571U CN 202604833 U CN202604833 U CN 202604833U
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Abstract
The utility model discloses a minimally invasive blood glucose monitoring microneedle which comprises a needle handle, a needle body and a needle point which are sequentially connected, wherein after one of an amino group, an aldehyde group, a hydroxide radical and a carboxyl group is modified on the surfaces of the needle body and needle point of the microneedle, the microneedle can be covered by a metal nano material layer modified by a pH response molecule, the microneedle is inserted in a solution consisting of a water-soluble polymer and a water-insoluble polymer, a porous polymer material layer is coated on the metal nano material layer, then the microneedle is inserted in a glucose oxidase solution, and therefore the water-soluble polymer is dissolved and a plurality of pores are formed in a polymer layer; and glucose oxidase is adsorbed on the surface of the porous polymer layer or in the holes, and the metal nano material has a grain size of 20-1000nm. On the basis of the fact that the minimally invasive blood glucose monitoring microneedle is characterized by different intensities of Raman signals for different concentrations of glucose, the purpose of minimally invasively detecting the glucose in vivo and in vitro can be achieved.
Description
Technical field
This utility model relates to a kind of Wicresoft blood sugar test technical field, more specifically, has the detection micropin of the Wicresoft's blood glucose that strengthens Raman signal.
Background technology
Diabetes (I type and II type) have become a kind of important disease that jeopardizes health, and trend towards rejuvenation.The expense that is used to diagnose, guard and treat diabetes rises year by year.Diabetics is because of the fluctuation of blood sugar level in the body causes multiple complications, comprises kidney disease, heart disease, blind, nerve injury and gangrene.To dissimilar diabetes, present Therapeutic Method mainly is through frequent monitoring blood sugar level, in conjunction with suitable diet, drug administration and injection of insulin.Most of patient obtains a little blood examination blood sugar level with the device of finger tip blood sampling, then monitors by glucose with indirect electrochemical monitoring method.Though utilize this frequent blood sample collection painful and inconvenient; But can suffer from the danger of various complication like the blood sugar level that most of patients can not be monitored them in time, continually, therefore more fast, technical method more convenient, that can alleviate sore spot and the frequent detection blood sugar level of using will benefit individual, medical industry and even the whole society.
Just because of the importance of this problem, a lot of seminar are devoted to study Wicresoft, good biocompatibility, quantitatively accurate blood sugar test technology.As a quite promising technology, middle INFRARED ABSORPTION absorbs very responsive to the competitiveness of temperature, pH value and water.Present middle INFRARED ABSORPTION research and utilization the probe of an indwelling reduce the influence of complicated factor.Development place method in another promptly utilizes chiral molecule (like glucose) that polarized light is rotated when passing the aqueous humor of eyes in laser polarization is measured.This technology can be surveyed low 20mg/mL (～1.0mM) the glucose that reaches of concentration in health check-up.Yet other constituents of aqueous humor, the optical activity of (like Ascorbate, albumin) and the birefringence effect of cornea make the extremely difficult realization of this method.The indirect detection of glucose also can realize through fluorescence or other optical technology.But but the similar this method that needs multistep to handle of biomolecule interfere of analyte, thereby produce false positive results.
In the traditional Chinese medical science, used several thousand through acupuncture needle being inserted the method that human body treats; Its main feature is the invasive in the therapeutic process; So acupuncture needle is the instrument that a kind of people of discrepancy experiences the ideal Wicresoft of life. acupuncture needle will have the detection micropin that the nano material that strengthens Raman and fluorescence signal forms the human body of coming in and going out as the carrier load. when in the micropin entering body or when organizing; The tissue fluid meeting is diffused in the gap between the gold nanoshell; When micropin is pulled out; Can the testing molecule in the tissue fluid being carried out. external SERS detects can avoid the decay of Raman signal in tissue, and the degree of depth of thrusting according to the detection micropin simultaneously can obtain the hypodermic enhancing Raman signal of certain depth.
The utility model content
Technical problem: the purpose of this utility model provides a kind of Wicresoft blood sugar test probe, has the characteristics that body is interior or extracorporeal glucose detects that are used for.
This utility model is with the preparation main body of medical needle acupuncture needle as the detection micropin; The metal nano material surface that utilizes the detector probe needle body to cover has the variation of enhancing Raman signal of the molecule of pH response and measures glucose level, a kind of glucose detection method that can be used for external and intravital Wicresoft of utility model.
This utility model adopts following technical scheme:
The described a kind of Wicresoft of this utility model blood sugar test micropin; Comprise: the needle handle, the needle body and the needle point that connect successively; On the surface of the needle body and needle point, be coated with metal nano material layer by pH response molecular modification; On the metal nano material layer, be coated with porous polymer material layer, in porous macromolecular material laminar surface or hole, be adsorbed with glucoseoxidase, described metal nano material particle diameter is 20-1000nm.
Beneficial effect: compared with prior art, the utlity model has following advantage:
(1) this utility model is compared with existing business-like detection technique, need not get blood, and be Wicresoft; This utility model not only can detect the blood sugar concentration of peripheral blood, but also the concentration of glucose in can the tissue fluid of Wicresoft's detection of biological body soft tissue.There are some researches show that enzyme is fixed on the activity that nano-material surface helps keeping enzyme, that is to say that the product of this utility model helps long-time preservation.
(2) this utility model and similar optical analysis compared with techniques can be realized surveying in health check-up of blood glucose, and little to the injury of organism.
(3) the blood sugar test micropin of this utility model is based on the acupuncture needle preparation, that is to say, when acupuncture and moxibustion health-care or treatment, just can carry out the detection of blood glucose.
Description of drawings
Fig. 1 is a kind of detection microneedle configuration sketch map that strengthens Raman and fluorescence signal that has.
Fig. 2 is a kind of detection micropin optical enhancement layer structural representation that strengthens Raman and fluorescence signal that has.
Fig. 3 has been the Electronic Speculum figure of metal nano material that detected the micropin surface adsorption.
Fig. 4 is the Electronic Speculum figure that detects the porous polymer materials layer of the surperficial metal nano material layer expoeridium of micropin.
Fig. 5 is the microcosmic sketch map (21: acupuncture needle of the detection micropin of glucose responding; 22: the metal shell; 23: the dielectric nucleome; The molecule of 24:pH response; 25: macromolecule layer; 26: hole; 27: glucoseoxidase).
Fig. 6 is detection micropin SERS in different pH solution of pH response
1143/ SERS
1180Ratio figure.
Fig. 7 is detection micropin SERS in different glucose solutions of glucose responding
1143/ SERS
1180Ratio figure.
Fig. 8 is the Raman spectrogram that detects concentration of glucose gained in the White Rabbit tissue with Wicresoft's blood glucose micropin.
The specific embodiment
The described a kind of Wicresoft of this utility model blood sugar test micropin; Comprise: the needle handle, the needle body and the needle point that connect successively; On the surface of the needle body and needle point, be coated with metal nano material layer by pH response molecular modification; On the metal nano material layer, be coated with porous polymer material layer, in porous macromolecular material laminar surface or hole, be adsorbed with glucoseoxidase, described metal nano material particle diameter is 20-1000nm.In the present embodiment,
Porous polymer material layer is the not mixing of one or more in dissolved polystyrene layer, polylactic acid layers, layer of polyurethane or the polyethylene polypropylene layer of water.
The metal nano material layer can be one of following four kinds:
1) the metal nano material layer is golden nanometer particle layer, nano grain of silver sublayer, copper nano-particle layer or nano platinum particle layer.
2) the metal nano material layer is the spherical composite nano particle layer, the metal composite nano particle layer of two or more that described spherical composite nano particle layer is gold, silver, copper and platinum.
3) the metal nano material layer is the composite nano-granule sublayer of spheric nucleocapsid structure, and the composite nano-granule sublayer of described spheric nucleocapsid structure comprises galactic nucleus gold shell composite nanometer particle layer, the compound core/shell nanoparticles layer of copper nuclear gold silver, copper nuclear gold silver double shells nanoparticle layers.
4) the metal nano material layer is nonmetallic SiO
2Examine golden shell, silver-colored shell, copper shell, platinum shell or compound core/shell nanoparticles layer, described compound core/shell nanoparticles is the core/shell nanoparticles of two or more metal composite in gold, silver, copper and the platinum.
The described blood sugar test microneedle preparation method of this utility model is following:
Step 1) is modified the micropin that a kind of group in amino, aldehyde radical, carboxyl and the hydroxyl obtains functionalization at least at the needle body of micropin and needle surface, and method therefor is known in this area.
Described micropin is clinical used various types of acupuncture needles.
Step 2) needle body and the needle point insertion concentration with step 1 is 10
8-10
18Individual particle/liter the metal nanoparticle suspension in leave standstill 12-48 hour after, take out micropin and get final product;
Described metal nanoparticle layer is spheric nanoparticle layers, can be that single metal nanoparticle layer comprises golden nanometer particle layer, nano grain of silver sublayer, copper nano-particle layer, nano platinum particle layer; Can be spheric composite nano-granule sublayer, that is: described spherical composite nano particle layer two or more the metal composite nano particle layer that is gold, silver, copper and platinum comprises gold silver composite nano-granule sublayer and gold, copper and platinum composite nano-granule sublayer; Can be the composite nano-granule sublayer of spheric nucleocapsid structure, comprise galactic nucleus gold shell composite nanometer particle layer, the compound core/shell nanoparticles layer of copper nuclear gold silver, copper nuclear gold silver double shells nanoparticle layers; Can be nonmetal SiO
2Examine golden shell, silver-colored shell, copper shell, platinum shell or compound core/shell nanoparticles layer, described compound core/shell nanoparticles is the core/shell nanoparticles of two or more metal composite in gold, silver, copper and the platinum.
The macromolecule mixture quality that the needle body after step 3) is handled step 2 and needle point insert in the macromolecular solution is taken out after second for leaving standstill 1-60 in the macromolecule mixture solution of 0.1-10% with the liquor capacity ratio; Wherein macromolecule mixture is divided into water and does not dissolve macromolecule and water dissolution macromolecule; The mol ratio of the former with the latter is 1: 0.1-1: 2, and last water flush away water dissolution macromolecule;
It can be polystyrene solution that described water does not dissolve macromolecular solution; Can be polylactic acid solution; It can be polyurethane solutions; Can be polyethylene polypropylene solution.
Described water dissolution macromolecular solution can be a polyvinylpyrrolidone; It can be Polyethylene Glycol.
The needle body and needle point after step 4) is handled step 3 insert in the molecular solution of pH response, soak more than 30 minutes the molecule of the pH response that taking-up back flush away does not adsorb;
The molecule of described pH response can be the 4-mercaptobenzoic acid; It can be the 2-mercaptopyridine; It can be 2-sulfydryl phenylboric acid; It can be cysteine.
The needle body after step 5) is handled step 4 inserts in the glucose oxidase solution with needle point, and 37 ℃ were spent the night in two hours or 4 ℃, takes out the glucoseoxidase molecule that back flush away does not adsorb, and promptly gets Wicresoft's blood sugar test micropin; Wicresoft's blood sugar test micropin of above-mentioned preparation can carry out external or intravital glucose detection.With the position that Wicresoft's blood sugar test micropin of above-mentioned preparation directly inserts solution or executes pin, be detained and take out behind the certain hour and make raman detection, can detect solution or execute the glucose level of pin position tissue fluid composition.
Embodiment 1: a kind of preparation of golden nanometer particle
The preparation of gold nano grain utilizes the method for sodium borohydride reduction gold chloride, the gold nano grain of preparation diameter 50nm.The chlorauric acid solution of getting 3ml 1% adds in the 200ml pure water that stirs, and adds the solution of potassium carbonate of 1ml 0.2M again.The freshly prepared 0.5m g/ml sodium borohydride solution 3ml of last adding fast.Solution becomes atropurpureus by glassy yellow and becomes claret again.Continue to stir 5min, it is subsequent use to place 4 ℃ of refrigerators to preserve.
Embodiment 2: a kind of preparation of Nano silver grain
The preparation of silver nano-grain utilizes the method for sodium citrate reduction silver nitrate, the silver nano-grain of preparation diameter 40nm.The silver nitrate solution of getting 3ml 1% adds in the 200ml pure water that stirs, and the sodium citrate solution that adds 5ml 0.1M again is heated to boiling, and reheat is natural cooling after 5 minutes, and solution has the colourless glassy yellow that becomes gradually.Being placed on 4 ℃ of refrigerators to room temperature preserves subsequent use.
Embodiment 3: a kind of preparation of golden shell silica nuclear particle
Preparing spherical SiO 2 particles with diameter 110 nanometers is a nuclear preparation gold nanoshell particles.With 5 microlitre 3-amino ethoxy silane be added to 100 milliliters contain 1 the gram silicon dioxide alcosol in, 37 ℃ are spent the night.Being transferred to baking oven interior (80 ℃) then solidified 3 hours.Centrifugally remove unnecessary 3-amino ethoxy silane and promptly get amidized silicon dioxide.With stirring 3 hours in the amidized silicon dioxide adding golden nanometer particle colloid solution, centrifugalize goes out silicon dioxide/gold nano composite particles.Silicon dioxide/gold nano composite particles is added in 0.01% chlorauric acid solution, add Reducing agents such as formaldehyde or hydrogen peroxide again and make gold chloride be deposited on silica surface formation gold nanoshell.
Embodiment 4: a kind of preparation of galactic nucleus gold core/shell nanoparticles
Regulate the delustring intensity to 1.0 of the Nano silver grain colloidal sol of diameter 40 nanometers; Get 1 milliliter and join in 100 milliliter 0.01% the chlorauric acid solution, add Reducing agents such as formaldehyde or hydrogen peroxide again and make gold chloride be deposited on the nano grain of silver sub-surface to form galactic nucleus gold shell nanoshell particle.
Embodiment 5: the preparation of a kind of Wicresoft blood sugar test micropin
Get the micropin method of sulfydryl (modify be known in this area) of functionalization at the needle body finishing sulfydryl of acupuncture needle, regulating the golden nanometer particle suspension, to make its concentration be 1 * 10
8-18Individual/liter.Again the micropin of functionalization is left standstill in the metal nanoparticle suspension and take out after 12-48 hour.Because the sulfydryl on micropin surface and the chemical b ` of golden nanometer particle, golden nanometer particle can be adsorbed on the acupuncture needle surface, forms nanostructured 1-2 layer structure homogeneous, that enhancing Raman and fluorescence signal are arranged.Again the part that is coated with metal nanoparticle of micropin is inserted in the polystyrene solution; (high molecule mass is 0.1-10% with the liquor capacity ratio; Wherein the mol ratio of polystyrene and Polyethylene Glycol is 1: (0.1-2)) in leave standstill 1-60 and take out after second, Polyethylene Glycol is removed in washing; Taking out the room temperature placement gets final product.The polystyrene layer that forms can not rubbed off by the protective money nanoparticle in the process of inserting and taking out pin.Forming hole can adsorb glucoseoxidase and in the process of inserting and taking out pin, protect glucoseoxidase not rubbed off.Again the needle body and needle point are inserted in the molecule 4-mercaptobenzoic acid solution of pH response, soak more than 30 minutes, take out the 4-mercaptobenzoic acid that the back flush away does not adsorb.The needle body and needle point are inserted in the glucose oxidase solution, 37 ℃ were spent the night in two hours or 4 ℃, took out the glucoseoxidase molecule that the back flush away does not adsorb, and promptly got and detected micropin again.Shown in Figure 3 is the golden shell silica nuclear nanoparticle layers on needle body surface, the polystyrene layer that hole is arranged for the inside of metal nanoparticle layer surface coverage shown in Figure 4.With reference to figure 5; The 21 expression needle body and tip portion, 22 are expressed as the golden shell of nanoparticle, and 23 are expressed as the silica core of nanoparticle; 24 are expressed as the signaling molecule of the pH response that is adsorbed on the metal nanoparticle layer surface; 25 be expressed as the metal nanoparticle layer surface coverage inside the polystyrene layer of hole is arranged, 26 are expressed as the hole in the polystyrene layer, 27 are expressed as glucoseoxidase.
Embodiment 6: the glucose detection standard curve of Wicresoft's blood sugar test micropin
With the soft tissue of agarose aquogel simulation organism, preparing w/v with the glucose solution of series concentration (0.5,0.7,0.9,1.1,1.3 and 1.5g/L) is 1.5% agarose aquogel.The Wicresoft glucose detection micropin of above-mentioned preparation inserted in 1.5% the agarose aquogel 37 ℃ and hatched 5-30 minute, take out and survey Raman spectrum, calculate SERS
1143/ SERS
1180The ratio at two characteristic Raman peaks.Draw the concentration of glucose and the SERS of different incubation times
1143/ SERS
1180The curve of ratio at two characteristic Raman peaks be the glucose detection standard curve.With reference to figure 6, Fig. 7, in solution concentration of glucose not simultaneously, just different by the amount of the gluconic acid of glucoseoxidase reduction back gained, the pH of solution also can be to some extent with, Fig. 6, Fig. 7 have represented in solution not SERS simultaneously of pH, concentration of glucose respectively
1143/ SERS
1180The variation of two characteristic peak ratios.
Embodiment 7: the application during Wicresoft's blood sugar test micropin detects in vivo
The Wicresoft blood sugar test micropin of above-mentioned preparation is inserted fasting but in the soft tissue (muscle) of the circadian White Rabbit of drinking water, was detained 10 minutes, take out and survey Raman spectrum, calculate and dissociate in the spectrum and the ratio at not dissociated two characteristic Raman peaks, as shown in Figure 8, SERS
1143/ SERS
1180Two characteristic peak ratios are about 0.5.Concentration calculating glucose in the liquid to be measured according to corresponding glucose detection standard curve is 0.75 ± 0.12 grams per liter.Detect auricular vein blood with the steady bold and unconstrained type blood sugar test paper of business-like Johnson & Johnson, the concentration of glucose is 0.74 ± 0.14 grams per liter.Statistical analysis shows that the testing result of two kinds of methods has comparability.
Claims (3)
1. Wicresoft's blood sugar test micropin; Comprise: the needle handle (13), the needle body (12) and the needle point (11) that connect successively; It is characterized in that, on the surface of the needle body (12) and needle point (11), be coated with metal nano material layer (2), on metal nano material layer (2), be coated with porous polymer material layer (3) by pH response molecular modification; In porous macromolecular material laminar surface or hole, be adsorbed with glucoseoxidase, described metal nano material particle diameter is 20-1000nm.
2. Wicresoft according to claim 1 blood sugar test micropin is characterized in that, the metal nano material layer is golden nanometer particle layer, nano grain of silver sublayer, copper nano-particle layer or nano platinum particle layer.
3. Wicresoft according to claim 1 blood sugar test micropin; It is characterized in that; The metal nano material layer is the composite nano-granule sublayer of spheric nucleocapsid structure, and the composite nano-granule sublayer of described spheric nucleocapsid structure comprises galactic nucleus gold shell composite nanometer particle layer, the compound core/shell nanoparticles layer of copper nuclear gold silver, copper nuclear gold silver double shells nanoparticle layers.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512181A (en) * | 2011-11-17 | 2012-06-27 | 东南大学 | Minimally invasive blood glucose monitoring microneedle and preparation method thereof |
| CN107412201A (en) * | 2017-05-22 | 2017-12-01 | 莎穆(上海)生物科技有限公司 | A kind of glucose responding Exenatide microneedle patch and preparation method thereof |
| CN108845012A (en) * | 2018-04-18 | 2018-11-20 | 北京化工大学 | A kind of conducting polymer microneedle electrodes and preparation method thereof for biomolecule detection |
| CN108926709A (en) * | 2018-07-02 | 2018-12-04 | 深圳大学 | A kind of nanometer cooperative therapeutic agent and the preparation method and application thereof |
| CN109199400A (en) * | 2018-09-10 | 2019-01-15 | 中山大学 | Blood glucose electrochemical sensor based on microneedle array |
-
2011
- 2011-11-17 CN CN 201120456571 patent/CN202604833U/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512181A (en) * | 2011-11-17 | 2012-06-27 | 东南大学 | Minimally invasive blood glucose monitoring microneedle and preparation method thereof |
| CN107412201A (en) * | 2017-05-22 | 2017-12-01 | 莎穆(上海)生物科技有限公司 | A kind of glucose responding Exenatide microneedle patch and preparation method thereof |
| CN107412201B (en) * | 2017-05-22 | 2020-06-19 | 莎穆(上海)生物科技有限公司 | Glucose-responsive exenatide microneedle patch and preparation method thereof |
| CN108845012A (en) * | 2018-04-18 | 2018-11-20 | 北京化工大学 | A kind of conducting polymer microneedle electrodes and preparation method thereof for biomolecule detection |
| CN108926709A (en) * | 2018-07-02 | 2018-12-04 | 深圳大学 | A kind of nanometer cooperative therapeutic agent and the preparation method and application thereof |
| CN108926709B (en) * | 2018-07-02 | 2021-07-13 | 深圳大学 | Nano-synergistic therapeutic agent and preparation method and application thereof |
| CN109199400A (en) * | 2018-09-10 | 2019-01-15 | 中山大学 | Blood glucose electrochemical sensor based on microneedle array |
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