CN108565048A - Conformal biodegradable implanted flexibility energy supply device and preparation method thereof - Google Patents

Conformal biodegradable implanted flexibility energy supply device and preparation method thereof Download PDF

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Publication number
CN108565048A
CN108565048A CN201810350519.0A CN201810350519A CN108565048A CN 108565048 A CN108565048 A CN 108565048A CN 201810350519 A CN201810350519 A CN 201810350519A CN 108565048 A CN108565048 A CN 108565048A
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energy supply
supply device
biodegradable
conformal
layer
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CN108565048B (en
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栗大超
蒲治华
于海霞
张兴国
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Tianjin University
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Tianjin University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables

Abstract

A kind of conformal biodegradable implanted flexibility energy supply device and preparation method thereof, for providing electric energy to embedded micro-/ nano implantable medical devices in vivo, it include flexible base layer, the flexible energy supply device cathode and flexible energy supply device anode being separately positioned in the flexible base layer, the flexible energy supply device cathode and flexible energy supply device anode with the redox reaction of glucose and oxygen in biological tissue of human body liquid by obtaining electric energy, the negative wire and positive wire being powered for connecting embedded micro-/ nano implantable medical devices in vivo are drawn respectively on the flexible energy supply device cathode and flexible energy supply device anode.The present invention has the function of certain counter-bending and stretch-proof, can be conformal with other built-in type devices, is used to the micro-/ nano implantable medical devices energy supply of arbitrary shape, energy long-time stable energy supply, energy transmission efficiency height.

Description

Conformal biodegradable implanted flexibility energy supply device and preparation method thereof
Technical field
The present invention relates to a kind of implanteds to energize device.It is flexible more particularly to a kind of conformal biodegradable implanted Energize device and preparation method thereof.
Background technology
In recent years, with the fast development of new technology, new process, new material etc., implantable medical devices are constantly prominent Broken technical bottleneck, more and more micro-/ nano implantable medical devices are applied to human body.These micro-/ nano implantable medicals Instrument can be used to continuously monitor Human Physiology health status, to provide illness variation tendency to contribute to the treatment of disease; It can also be used to accurately treat the disease etc. of privileged site.In these micro-/ nano implantable medical devices, there is a kind of claimed For biodegradable device in recent years by the extensive concern of various circles of society.Such device can work one section in human body It voluntarily decomposes after time, as the physiology of human body recycles and excretes, be advantageous in that harmless and be not necessarily to secondary hand Art extracts.
It is limited by current technology is horizontal, these biodegradable micro-/ nano implantable medical devices are mostly It is worked using electric energy, however, being up to the present still a challenge for carrying out power supply in vivo to built-in type device. There is researcher to be energized using degradable radio frequency energy transmission module, but this method is firstly the need of an outside Energy supply source, the problem of secondly there are the limitation in energy transmission direction and low energy transmission efficiencies.Also there is researcher In such a way that energy collector collects the mechanical energy of human motion and then is then converted to electric energy, however this method is needed device It is implanted into specific long-term motion position, such as heart, which has limited the use scopes of device.More important is by material supply section The limitation of development is learned, the implanted energy supply device that these current methods are utilized is not Wholly-degradable, it is still desirable to Second operation is taken out.In contrast, it is proposed that conformal biodegradable implanted flexibility energize device, energy passes It is defeated efficient, it can not be limited by implantation position with the variously-shaped conformal combination of built-in type device, energy complete biodegradable, It can be used for solving the problems, such as the energy supply of biodegradable micro-/ nano implantable medical devices.
Invention content
The technical problem to be solved by the invention is to provide a kind of micro-/ nano implanteds being used to arbitrary shape Conformal biodegradable implanted flexibility energy supply device of medical instrument energy supply and preparation method thereof.
The technical solution adopted in the present invention is:A kind of conformal biodegradable implanted flexibility energy supply device, is used for Electric energy is provided to embedded micro-/ nano implantable medical devices in vivo, includes flexible base layer, is separately positioned on described soft Property basal layer on flexible energy supply device cathode and flexible energy supply device anode, the flexible energy supply device cathode and flexible supply For energy device anode by obtaining electric energy with the redox reaction of glucose and oxygen in biological tissue of human body liquid, described is soft Property energy supply device cathode and flexible energy supply device anode on drawn respectively for connecting embedded micro-/ nano implanted doctor in vivo Treat negative wire and positive wire that instrument is powered.
The described flexible energy supply device cathode include be successively set on from the bottom to top in the flexible base layer can Biodegradable negative electrode layer, can biodegradable ferroso-ferric oxide and glucose oxidase molecules layer and can biology drop The cathode chitosan film layer of solution, the negative wire are integrally formed in a side of negative electrode layer.
The described flexible energy supply device anode include be successively set on from the bottom to top in the flexible base layer can Biodegradable anode electrode layer, being capable of biodegradable ferroso-ferric oxide and laccase molecular layer and being capable of biodegradable anode Chitosan film layer, the positive wire are integrally formed in a side of anode electrode layer.
The flexible base layer is using the polylactic acid or polyvinyl alcohol or polycaprolactone for capableing of complete biodegradable or gathers Succinic acid-butanediol ester material.
The negative electrode layer, anode electrode layer, negative wire and positive wire are adulterated using aluminium-doped zinc oxide or magnesium Zinc oxide or zinc or magnesium are capable of the conductive material of complete biodegradable.
A kind of preparation method of conformal biodegradable implanted flexibility energy supply device, including following technical process:
1) processing flexibility basal layer:Flexible base material particle is incorporated in dichloromethane and forms uniform solution, is extracted The solution of set amount is placed on tablet, is uniformly coated on tablet solution with coated rod, is waited for that the dichloromethane in solution is complete Pervaporation is to get to flexible base layer;
2) conductive ink is printed respectively according to the pattern of negative electrode layer and anode electrode layer using ink-jet print system In ready-made PLA flexible base layers, including correspondence prints negative wire and positive wire respectively, and then heating makes electrode move back Fire is completed, that is, completes the processing of negative electrode layer and anode electrode layer and negative wire and positive wire;
3) ferroferric oxide nano granules ink and glucose oxidase ink printed are constituted four on negative electrode layer Then Fe 3 O and glucose oxidase molecules layer drip upper chitosan solution and constitute cathode chitosan film layer, after air-drying i.e. Complete the preparation of flexible energy supply device cathode;
4) ferroferric oxide nano granules ink and laccase ink printed are constituted into ferroso-ferric oxide on anode electrode layer It with laccase molecular layer, then drips upper chitosan solution and constitutes positive chitosan film layer, flexible energy supply device is completed after air-drying The preparation of anode, to complete the preparation that conformal biodegradable implanted flexibility energizes device.
Tablet described in step 1) is the polypropylene board not reacted with dichloromethane or glass plate or stainless steel plate or aluminium sheet.
The flexible base material is using the polylactic acid or polyvinyl alcohol or polycaprolactone for capableing of complete biodegradable Or polybutylene succinate material.
The negative electrode layer and anode electrode layer and negative wire and positive wire using aluminium-doped zinc oxide or Magnesium doping zinc-oxide or zinc or magnesium are capable of the conductive material of complete biodegradable.
Conformal biodegradable implanted flexibility energy supply device of the present invention and preparation method thereof, has the following advantages that:
1, energy supply element manufacturing is in polylactic acid (polylactic acid:PLA) in film substrate, energy device is formed Chitosan film, PLA are flexible materials, have the function of certain counter-bending and stretch-proof, can be with other implanted devices Part is conformal, is used to the micro-/ nano implantable medical devices energy supply of arbitrary shape.
2, the redox reaction of glucose and oxygen of the energy sources of energy supply device in in-vivo tissue liquid, due to body Concentration of glucose in inner tissue's liquid stablize relatively and glucose continually, therefore can long-time stable energy supply, and do not planted Enter the limitation of position.
3, the redox reaction of glucose and oxygen of the energy sources of energy supply device in in-vivo tissue liquid, this base Other energy devices are compared in the energy of glucose, energy transmission efficiency is high, and does not need outside resources excitation.
4, all composition materials of energy supply device include PLA, aluminium-doped zinc oxide, four three body nano particles of oxidation, grape Carbohydrate oxidase, laccase and chitosan are all Biodegradable materials, so constitute energy supply device can complete biodegradable, keep away The problem of second operation takes out is exempted from.
Description of the drawings
Fig. 1 is the use state diagram of the conformal biodegradable implanted flexibility energy supply device of the present invention;
Fig. 2 is the structural schematic diagram of the conformal biodegradable implanted flexibility energy supply device of the present invention;
Fig. 3 is the structural schematic diagram of flexible energy supply device cathode in the present invention;
Fig. 4 is the structural schematic diagram of flexible energy supply device anode in the present invention.
In figure
1:Biological tissue of human body 2:Micro-/ nano implantable medical devices
3:Conformal biodegradable implanted flexibility energizes device
4:Flexibility energy supply device cathode 5:Flexibility energy supply device anode
6a:Cathode chitosan film layer 6b:Positive chitosan film layer
7:Ferroso-ferric oxide and glucose oxidase molecules layer 8:Ferroso-ferric oxide and laccase molecular layer
9a:Negative electrode layer 9b:Anode electrode layer
10:Flexible base layer 11:Negative wire
12:Positive wire
Specific implementation mode
With reference to embodiment and attached drawing to the conformal biodegradable implanted flexibility energy supply device of the present invention and its Preparation method is described in detail.
The conformal biodegradable implanted flexibility of the present invention energizes device, mainly by flexible substrates from bottom to top Layer, basal electrode layer, nano particle and enzyme molecule layer and chitosan film layer are constituted;The basal electrode layer is poly- with the shell Sugared film interlayer solidification has ferroferric oxide nano granules and laccase molecular layer, and primary battery anode is constituted after solidification;The substrate Electrode layer has ferroferric oxide nano granules and glucose oxidase molecules layer with chitosan film interlayer solidification, after solidification Constitute primary battery cathode.The flexible base layer is polylactic acid film layer.The basal electrode layer is aluminium-doped zinc oxide electrode.
The conformal biodegradable implanted flexibility of the present invention energizes device, as shown in Figure 1, being for being embedded in body Interior micro-/ nano implantable medical devices 2 provide electric energy.The conformal biodegradable implanted flexibility of the present invention energizes device 3 Micro-/ nano implantable medical devices 2 to be implanted into biological tissue of human body 1 energize, and conformal biodegradable implanted flexibility supplies Energy device 3 can be conformal with the micro-/ nano implantable medical devices 2 of arbitrary shape, to provide stable electric energy for it.This hair Bright conformal biodegradable implanted flexibility energy supply device is conformal with flexibility, energy transmission efficiency is high, can be completely biological The advantages of degrading and not limited by implantation position can be used for energizing to micro-/ nano implantable medical devices.
Concrete structure is separately positioned on soft in the flexible base layer 10 as shown in Fig. 2, include flexible base layer 10 Property energy supply device cathode 4 and flexible energy supply device anode 5, the flexible energy supply device cathode 4 and flexible energy supply device anode 5 By obtaining electric energy, the flexible energy supply device with the redox reaction of glucose and oxygen in 1 liquid of biological tissue of human body It is drawn respectively on part cathode 4 and flexible energy supply device anode 5 for connecting embedded micro-/ nano implantable medical devices in vivo 2 negative wires 11 being powered and positive wire 12.
The flexible base layer 10 is using using the polylactic acid (PLA) or polyvinyl alcohol for capableing of complete biodegradable (PHA) or the materials such as polycaprolactone (PCL) or poly butylene succinate (PBS).
As shown in figure 3, the flexible energy supply device cathode 4 includes to be successively set on the flexible substrates from the bottom to top Layer 10 on can biodegradable negative electrode layer 9a, being capable of biodegradable ferroso-ferric oxide and glucose oxidase molecules Layer 7 and can biodegradable cathode chitosan film layer 6a, the negative wire 11 is integrally formed in negative electrode layer 9a's A side.
As shown in figure 4, the flexible energy supply device anode 5 includes to be successively set on the flexible substrates from the bottom to top Layer 10 on can biodegradable anode electrode layer 9b, being capable of biodegradable ferroso-ferric oxide and laccase molecular layer 8 and energy Enough biodegradable positive chitosan film layer 6b, the positive wire 12 are integrally formed in a side of anode electrode layer 9b.
The negative electrode layer 9a, anode electrode layer 9b, negative wire 11 and positive wire 12 use aluminium-doped zinc oxide Or magnesium doping zinc-oxide or zinc or magnesium are capable of the conductive material of complete biodegradable.
The course of work of conformal biodegradable implanted flexibility energy supply device in the present invention is to be total to energy supply device The surface for being attached at implanted micro-/ nano implantable medical devices of shape, with a small amount of aluminium-doped zinc oxide ink by electrode and device Part energization input bonds together, and is implanted into tissue and works together.It is by two interelectrode oxidations to generate energy Reduction reaction, the glucose molecule in the cathode of primary battery, biological tissue's liquid generate titanium dioxide by glucose oxidase Carbon and water;In this process, glucose molecule is decomposed into hydrogen peroxide, and ferroferric oxide nano granules are used for being catalytically decomposed Hydrogen peroxide avoids hydrogen peroxide from influencing the activity of glucose oxidase, while the nano particle is also used for enhancing electron transmission Efficiency.Oxygen in the anode of primary battery, biological tissue's liquid is reduced to water by laccase, and ferroferric oxide nano granules are for increasing Strong electron transmission efficiency.Electronics is transferred to anode by the cathode of primary battery.Then, in external micro-/ nano implantable medical devices The both ends of power input just generate electromotive force.
It works after a period of time, which can be with degradable implanted Micro-/ nano medical instrument is degraded by body together, avoids the problem of second operation takes out.
The preparation method of the conformal biodegradable implanted flexibility energy supply device of the present invention, including following technique mistake Journey:
1) PLA flexible base layers are processed:Flexible base material particle is incorporated in dichloromethane and forms uniform solution, is carried It takes the solution of set amount to be placed on tablet, solution is uniformly coated on tablet with coated rod, waits for the dichloromethane in solution Evaporating completely is to get to PLA flexible base layers;The tablet be the polypropylene board not reacted with dichloromethane or glass plate or Stainless steel plate or aluminium sheet etc..The flexible base material be using be capable of complete biodegradable polylactic acid or polyvinyl alcohol or Polycaprolactone or polybutylene succinate material.
2) utilize ink-jet print system (can also be other printing technology) by aluminium-doped zinc oxide ink according to negative electricity The pattern of pole layer and anode electrode layer is printed upon respectively in ready-made PLA flexible base layers, including correspondence prints cathode respectively Lead and positive wire, then being heated one hour at 100 DEG C makes annealing complete, that is, completes negative electrode layer and anode electrode layer And the processing of negative wire and positive wire;
3) ferroferric oxide nano granules ink and glucose oxidase ink printed are constituted four on negative electrode layer Then Fe 3 O and glucose oxidase molecules layer drip upper chitosan solution and constitute cathode chitosan film layer, after air-drying i.e. Complete the preparation of flexible energy supply device cathode;
4) ferroferric oxide nano granules ink and laccase ink printed are constituted into ferroso-ferric oxide on anode electrode layer It with laccase molecular layer, then drips upper chitosan solution and constitutes positive chitosan film layer, flexible energy supply device is completed after air-drying The preparation of anode, to complete the preparation that conformal biodegradable implanted flexibility energizes device.
The negative electrode layer and anode electrode layer and negative wire and positive wire using aluminium-doped zinc oxide or Magnesium doping zinc-oxide or zinc or magnesium are capable of the conductive material of complete biodegradable.
All combinations that the present invention is disclosed and disclosed can be generated by using for reference disclosure, although the group of the present invention Conjunction is described by detailed implementation process, but those skilled in the art can obviously not depart from the content of present invention, essence Device of the present invention is spliced or changed in god and range, or the certain components of increase and decrease, it is more specifically, all similar As replace and change it is apparent to those skilled in the art, they be considered as being included in spirit of that invention, Among range and content.

Claims (9)

1. a kind of conformal biodegradable implanted flexibility energizes device, for embedded micro-/ nano implanted in vivo Medical instrument (2) provides electric energy, which is characterized in that includes flexible base layer (10), is separately positioned on the flexible base layer (10) the flexible energy supply device cathode (4) and flexible energy supply device on are positive (5), it is described it is flexible energize device cathode (4) and Flexibility energy supply device positive (5) with the redox reaction of glucose and oxygen in biological tissue of human body (1) liquid by obtaining Electric energy, the flexible energy supply device cathode (4) and flexibility energize to draw respectively on device positive (5) is embedded in body for connection The negative wire (11) and positive wire (12) that interior micro-/ nano implantable medical devices (2) are powered.
2. conformal biodegradable implanted flexibility according to claim 1 energizes device, which is characterized in that described Flexibility energy supply device cathode (4) include be successively set on from the bottom to top in the flexible base layer (10) can be biodegradable Negative electrode layer (9a), can biodegradable ferroso-ferric oxide and glucose oxidase molecules layer (7) and can biology drop The cathode chitosan film layer (6a) of solution, the negative wire (11) are integrally formed in a side of negative electrode layer (9a).
3. conformal biodegradable implanted flexibility according to claim 1 energizes device, which is characterized in that described Flexibility energy supply device positive (5) include be successively set on from the bottom to top in the flexible base layer (10) can be biodegradable Anode electrode layer (9b), being capable of biodegradable ferroso-ferric oxide and laccase molecular layer (8) and being capable of biodegradable anode Chitosan film layer (6b), the positive wire (12) are integrally formed in a side of anode electrode layer (9b).
4. conformal biodegradable implanted flexibility according to claim 1 energizes device, which is characterized in that described Flexible base layer (10) is using the polylactic acid or polyvinyl alcohol or polycaprolactone or poly-succinic fourth two for capableing of complete biodegradable Alcohol ester material.
5. conformal biodegradable implanted flexibility according to claim 1 energizes device, which is characterized in that described negative Pole electrode layer (9a), anode electrode layer (9b), negative wire (11) and positive wire (12) are mixed using aluminium-doped zinc oxide or magnesium Miscellaneous zinc oxide or zinc or magnesium are capable of the conductive material of complete biodegradable.
6. a kind of preparation method of conformal biodegradable implanted flexibility energy supply device described in claim 1, feature It is, including following technical process:
1) processing flexibility basal layer:Flexible base material particle is incorporated in dichloromethane and forms uniform solution, extraction setting The solution of amount is placed on tablet, is uniformly coated on tablet solution with coated rod, is waited for that the dichloromethane in solution steams completely Hair is to get to flexible base layer;
2) conductive ink is printed upon respectively using ink-jet print system according to the pattern of negative electrode layer and anode electrode layer and is done In good PLA flexible base layers, including correspondence prints negative wire and positive wire respectively, and then heating keeps electrode anneal complete At the i.e. processing of completion negative electrode layer and anode electrode layer and negative wire and positive wire;
3) ferroferric oxide nano granules ink and glucose oxidase ink printed are constituted to four oxidations on negative electrode layer Then three-iron and glucose oxidase molecules layer drip upper chitosan solution and constitute cathode chitosan film layer, completed after air-drying The preparation of flexibility energy supply device cathode;
4) ferroferric oxide nano granules ink and laccase ink printed are constituted into ferroso-ferric oxide and paint on anode electrode layer Enzyme molecule layer, then drips upper chitosan solution and constitutes positive chitosan film layer, and flexible energy supply device anode is completed after air-drying Preparation, to complete the preparation that conformal biodegradable implanted flexibility energizes device.
7. the preparation method of conformal biodegradable implanted flexibility energy supply device according to claim 6, feature It is, the tablet described in step 1) is the polypropylene board not reacted with dichloromethane or glass plate or stainless steel plate or aluminium sheet.
8. the preparation method of conformal biodegradable implanted flexibility energy supply device according to claim 6, feature It is, the flexible base material is using the polylactic acid or polyvinyl alcohol or polycaprolactone for capableing of complete biodegradable or to gather Succinic acid-butanediol ester material.
9. the preparation method of conformal biodegradable implanted flexibility energy supply device according to claim 6, feature It is, the negative electrode layer and anode electrode layer and negative wire and positive wire are mixed using aluminium-doped zinc oxide or magnesium Miscellaneous zinc oxide or zinc or magnesium are capable of the conductive material of complete biodegradable.
CN201810350519.0A 2018-04-18 2018-04-18 Conformal biodegradable implantable flexible energy supply device and preparation method thereof Expired - Fee Related CN108565048B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110025818A (en) * 2019-03-11 2019-07-19 温州大学 A kind of chitosan piezoelectric membrane and the preparation method and application thereof
CN110613449A (en) * 2019-09-23 2019-12-27 清华大学 Degradable flexible blood vessel detection device and system

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CN101834301A (en) * 2010-04-30 2010-09-15 清华大学 Biochemical nano generator and preparation method thereof
CN102023181A (en) * 2009-09-21 2011-04-20 清华大学 Enzyme electrode and preparation method thereof
US8785058B2 (en) * 2006-04-07 2014-07-22 New Jersey Institute Of Technology Integrated biofuel cell with aligned nanotube electrodes and method of use thereof
CN107800323A (en) * 2016-09-07 2018-03-13 北京纳米能源与系统研究所 A kind of full degradable nano generator of natural material

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN1737560A (en) * 2005-09-02 2006-02-22 天津大学 Static electricity spinning prepared fixed enzymic electrode and method thereof
US8785058B2 (en) * 2006-04-07 2014-07-22 New Jersey Institute Of Technology Integrated biofuel cell with aligned nanotube electrodes and method of use thereof
CN102023181A (en) * 2009-09-21 2011-04-20 清华大学 Enzyme electrode and preparation method thereof
CN101834301A (en) * 2010-04-30 2010-09-15 清华大学 Biochemical nano generator and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110025818A (en) * 2019-03-11 2019-07-19 温州大学 A kind of chitosan piezoelectric membrane and the preparation method and application thereof
CN110613449A (en) * 2019-09-23 2019-12-27 清华大学 Degradable flexible blood vessel detection device and system

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