KR101271535B1 - Ultra thin film comprising carbon nanotube polymer composites for increasing biocompatibility and controlling mechanical strength and a method of preparing the same - Google Patents
Ultra thin film comprising carbon nanotube polymer composites for increasing biocompatibility and controlling mechanical strength and a method of preparing the same Download PDFInfo
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- KR101271535B1 KR101271535B1 KR20100107561A KR20100107561A KR101271535B1 KR 101271535 B1 KR101271535 B1 KR 101271535B1 KR 20100107561 A KR20100107561 A KR 20100107561A KR 20100107561 A KR20100107561 A KR 20100107561A KR 101271535 B1 KR101271535 B1 KR 101271535B1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/422—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of carbon
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/121—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L31/122—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of carbon
Abstract
The present invention relates to a coating film having a thickness of 200 nm or less by mixing carbon nanotubes with a biocompatible polymer and a method for manufacturing the same, wherein the biocompatibility of the coating film having the ultra-thin film thickness is controlled by controlling the synthesis ratio of the polymer and carbon nanotubes. It has been shown that it can increase and control the mechanical strength, by using this feature can be applied to medical devices that are inserted into the microvascular in vivo, such as nanomedical devices and wire coating.
Description
The present invention relates to a bio-insertable polymer coating film comprising a biocompatible polymer and carbon nanotubes and having a thickness of nanometer and submicron meter and a method of manufacturing the same. More specifically, the present invention relates to a coating film for a bio-insertable medical device and a method of manufacturing the same, having an ultra-thin film thickness of less than micron manufactured by synthesizing carbon nanotubes to a biocompatible polymer, and improving biocompatibility and controlling surface strength. .
In general, carbon nanotubes have a graphite sheet rounded to a nano-sized diameter to form a tubular shape, and the diameter of the tube is a very small region of several to several tens of nanometers. While such carbon nanotubes are known as new materials having excellent mechanical strength, electrical conductivity and thermal conductivity, excellent field emission characteristics, and high efficiency hydrogen storage medium characteristics, efforts to manufacture high performance advanced materials using these characteristics are active. Do.
In addition, thanks to the development of biotechnology and nanotechnology, attempts are being made to apply carbon nanotubes to the medical field, for example, molecular diagnostic technology, and nano-drug complex development, and new nanomaterials for regenerative tissue engineering and implants. The research on is also active. In particular, in the case of artificial blood vessels that are inserted into the microvascular in vivo, it is required to be coated with a coating agent having a high thickness and durability and excellent biocompatibility. In addition, in order to improve the utilization and the physical properties required for in vivo applications, there is also a need for a method of controlling the physical properties of the coating film having such an ultra-thin film thickness.
However, in the past, a method of manufacturing a polymer composite using carbon nanotubes has been known, but the structure of such a composite has a thickness of several tens of microns or more, and thus it is difficult to be used in a living body such as microvascular vessels. There is a disadvantage in that it is not possible to control the nano surface properties that can adjust the surface strength associated with improved biocompatibility, mitigate immune toxicity, and durability. In other words, until now, no technique for simultaneously controlling nano surface energy and surface strength in a coating film having an ultra-thin film thickness has been reported.
Accordingly, the present inventors have made efforts to manufacture a coating film having an ultra-thin thickness that can be applied to a medical device inserted into a microvascular in vivo. As a result, the inventors have developed a coating film having a thickness of 200 nm or less by mixing carbon nanotubes with a biocompatible polymer. By adjusting the synthesis ratio of the polymer and the carbon nanotube, the present invention was found to be the first to increase the biocompatibility of the coating film having the ultra-thin film thickness and to control the mechanical strength.
It is an object of the present invention to provide a polymer composite coating film comprising a biocompatible polymer and carbon nanotubes and having a thickness of nanometers and submicrons.
Another object of the present invention is to provide a method of manufacturing the coating film and a method of controlling the nano-surface roughness and surface tension of the coating film.
As one aspect for achieving the above object, the present invention provides a polymer composite coating film comprising a biocompatible polymer and carbon nanotubes and has a thickness of nano (nanometer) and submicron (submicron-meter).
In the present invention, the term "biocompatible polymer" has affinity with blood or cellular tissues, and when applied to a living body, is not recognized as an external foreign substance and has undesirable long-term effects such as clot formation, inflammation, and physical property change. It means a polymer that does not induce. In general, when the polymer material is in contact with blood, the adsorption of blood protein components occurs on the surface of the material within a few seconds after contact with the blood, and platelet thrombosis reaction and red thrombus appear. The biocompatible polymer of the present invention has a surface modification to improve blood compatibility. Included polymers. Biocompatible polymers that can be used in the present invention include polymers surface-modified with high hydrophilic polymer materials such as polyethylene glycol and polyacrylamide. In addition, the biocompatible polymer includes a polymer having cell compatibility, and includes a polymer having little or no effect on the number or growth of cells, cell membrane maintenance, biosynthesis process or enzyme activity.
According to the object of the present invention, the biocompatible polymer of the present invention may mean a non-degradable polymer, polyolefin, polystyrene, polyethylene oxide, polyvinyl chloride, polyamide, polymethyl methacrylate, polyurethane, polyester or these Combinations of but are not limited to. Preferably, it has excellent blood compatibility and is widely used in artificial blood vessels, artificial heart, etc., which are in direct contact with blood, and has excellent mechanical and thermal resistance, and polycarbonates, which are applied to heart, lung assistive devices, artificial heart valve switch, etc. to be. More preferably, the biocompatible polymer of the present invention may be polycarbonate urethane (hereinafter referred to as PCU). The PCU is an FDA approved polymer medical polymer for clinical applications such as heart valves, meniscus or artificial blood, and because it is not degraded by oxygen, it can maintain a constant mechanical strength even in body fluids. The PCU may be synthesized with carbon nanotubes as a matrix to exhibit good dispersibility.
In the present invention, the term "carbon nanotube" is a honeycomb-shaped planar carbon structure in which one carbon atom is bonded to three other carbon atoms is rolled to have a tube shape, and generally has a diameter of 1 to 100 nanometers (nm) and a length. Refers to a carbon material having a high aspect ratio ranging from several nanometers (nm) to several tens of micrometers (μm). There are various types of carbon nanotubes, and among them, multi-walled nanotubes (MWCNTs) consisting of two or more walls, and a single wall made of only one wall, depending on the number of walls enclosing the longitudinal direction. It can be divided into single-walled nanotube (SWCNT). In the present invention, carbon nanotubes include all of them without limitation, but are preferably multi-walled carbon nanotubes. The diameter of the carbon nanotubes usable in the present invention may be 1 to 100nm.
The polymer composite coating film of the present invention can be used to coat a living body implantable medical device.
In the present invention, the term "bioinsertion medical device" is a medical device for artificial blood vessels, artificial vessel support, fusion power electrode source or power supply wire in the blood vessel, biochip, nano robot, implant, artificial heart valve, artificial bladder and artificial urinary tract, artificial It may be selected from the group consisting of meniscus, artificial blood vessel, artificial heart, pacemaker insulator, catheter, and stent, but is not limited thereto.
The biocompatible polymer and the carbon nanotube content included in the coating film of the present invention may be included in a ratio of 1: 1 to 1:10 wt%. The coating film is composed of a polymer-nanocomposite obtained by synthesizing the biocompatible polymer and carbon nanotubes. In the present invention, the polymer-nanocomplex has all the features of the coating film disclosed in the present invention.
As used herein, the term "composite" means that two or more individual materials are synthesized.
The polymer composite coating film of the present invention may have a thickness of nano (nanometer) and submicron (submicron-meter), preferably has a thickness of 30 to 200 nm and is characterized in that the transparent. The nanometer thickness refers to one millionth of one meter, and means a thickness range of 100 nm or less for the purposes of the present invention. In addition, the submicron means a thickness range of 100nm to 1μm.
In the present invention, by adjusting the biocompatible polymer and carbon nanotubes to the thickness of the nano and submicron meters, preferably 100nm or less, it is possible to form a coating of the biomedical device to be inserted into the microvascular and coronary artery, transparent It can be used to analyze the activity of living cells.
In addition, the coating film is characterized in that the carbon nanotubes have a structure that is not directly exposed to the surface of the biocompatible polymer. Since the carbon nanotubes are not directly exposed to the surface, the chemical composition of the biocompatible polymer is maintained, but the biocompatibility and toxicity are improved compared to the existing biopolymer materials by generating the carbon nanotube-like nanoforms in the biocompatible polymer. The mechanical strength can be controlled by the synthesis ratio of carbon nanotubes. As shown in FIG. 5, when the polymer sphere generated when the heat is applied is also generated on the carbon nanotubes (30 nm thick), the carbon nanotubes are not exposed on the surface and covered with an ultra-thin film of about 30 nm. I could confirm it.
In addition, the coating film has insulation unlike a polymer-carbon nanotube composite used in an information and communication device for medical use.
As another aspect, the present invention comprises the steps of sonicating each of the biocompatible polymer and carbon nanotubes in each solvent in a synthesis ratio of 1: 1 to 1:10 wt%; Mixing the two sonicated solutions; Coating the mixed solution on glass using a spin coater; Drying the glass coated with the mixed solution at room temperature; And to provide a method for producing a polymer composite coating film having a thickness of nano (nanometer) and submicron (submicron-meter), comprising the step of sterilizing and disinfecting the dried glass by ultraviolet rays.
For the biocompatible polymer in the production method of the present invention is the same as described above, preferably polycarbonate-based, more preferably may be a polycarbonate urethane.
In the manufacturing method of the present invention, the solvent of the carbon nanotube may be any one or more selected from the group consisting of water, 1,2-dichloroethane, tetrahydrofuran, dimethylformamide, toluene, ethanol, and mixtures thereof. And preferably 1,2-dichloroethane.
The solvent of the polycarbonate urethane is preferably chloroform.
In the sonication step, tip and bath ultrasonic equipment may be used, and the sonication time may be 1 to 24 hours, but is not limited thereto and may be easily selected by those skilled in the art according to the purpose.
In a specific embodiment of the present invention, polycarbonate urethane is mixed with chloroform, carbon nanotubes are mixed with 1,2-dichloroethane, and each solution is sonicated and dispersed, and then coated on glass using a spin coater. It dried at room temperature, sterilized and disinfected with ultraviolet rays to prepare a coating film having a thickness of less than 100nm.
The coating film may be used as a coating material of a bio-invasive medical device, and the above-described bio-invasive medical device may be applied in the same manner, and preferably, a microvascular medical device, an artificial vessel support, a source of fusion power electrode in a blood vessel, or Power supply wire, nanorobot, implant, artificial heart valve, artificial bladder and urinary tract, artificial meniscus, artificial blood vessel, artificial heart, heart pacemaker insulator.
The manufacturing method of the present invention may further include adjusting the surface strength of the coating film by adjusting the synthesis ratio of the biocompatible polymer and the carbon nanotubes.
Conventionally, a process technology for a single-layer biopolymer-nano composite having a thickness of nano and submicron meters having high biocompatibility has not been developed, and until now, it is possible to simultaneously control nano surface energy and surface strength in an ultra thin film coating layer. No technology has been reported at all. In the present invention, it was found that the surface strength of the ultra-thin nanocoated film can be controlled by revealing that the mechanical surface strength increases with increasing the weight% content ratio of the carbon nanotubes during the synthesis between the biocompatible polymer and the carbon nanotubes.
In addition, the manufacturing method of the present invention may further comprise the step of checking the biocompatibility by controlling the roughness at the nanoscale of the coating film by adjusting the synthesis ratio of the biocompatible polymer and the carbon nanotubes.
In the present invention, as the weight percent content ratio of the carbon nanotubes is increased during the synthesis between the biocompatible polymer and the carbon nanotubes, the roughness at the nanoscale of the nanocoating film is increased and the surface energy is increased. It was confirmed that biocompatibility can be increased by controlling the adsorption of proteins in vivo by increasing the surface energy in the polymer-nano composite coating film having a thickness of.
In a specific embodiment of the present invention synthesized biocompatible polymers and carbon nanotubes in a ratio of 1: 1 to 1:10, and experiments while varying the synthesis ratio in order to determine the tendency of the physical properties of the composite, the polycarbonate urethane The addition of 1,2-dichloroethane to the surface energy was reduced and the surface strength was softened, and as the synthesis ratio of carbon nanotubes to the polycarbonate urethane increases, the surface energy increases and roughness at nanoscale. It was found that the degree increased and the surface strength increased (see FIG. 7). From this fact, it can be seen that biocompatible polymers and nanocomposites having a thickness of nano and submicron meters can control surface energy and surface strength by controlling the synthesis ratio of polymer and carbon nanotubes.
In addition, the roughness of the nano-surface can be controlled to adjust the adsorption of the protein in the living body can be prepared to suit the biocompatibility of the polymer-nanocomplex. In a specific embodiment of the present invention, in order to investigate the effect of carbon nanotube-polycarbonate urethane complex on the adsorption regulation of proteins in vivo, vitronectin, which is a cell-adhesive glycoprotein present in plasma and serum connective tissue, and animals As a result of examining the adsorption degree of FBS used as an essential protein of cultured cell beige, it was found that the adsorption was good as the content of carbon nanotubes was increased in the case of Vitronectin and FBS. As shown in FIG. 8, as the carbon nanotubes increase, more proteins are adsorbed, and it was confirmed that the roughness of the nano-surface affects protein adsorption more than surface energy. In addition, as the carbon nanotubes increase, the nano-surface roughness increases and accordingly, the surface tension increases (see FIG. 6), and when the surface tension increases, the adsorption of immune cells increases and the proliferation also increases by the increased adsorption. It can be seen (see Fig. 9).
Through the control method of the present invention as described above, when the biopolymer is coated on the human implantable device by synthesizing the nanotubes on the biopolymer to form a nano topo by adjusting the surface tension, biocompatibility and toxicity of the existing biopolymer material It can be seen that the present invention can be improved in comparison with the present invention, and can be applied to more implant polymer applications by controlling the mechanical properties by controlling the mechanical strength by the synthesis ratio of the nanotubes.
A coating film having a thickness of nano and submicron meters manufactured by the manufacturing method, ie, nanotube polymer ultra-thin film structure, may be used for artificial blood vessel support, artificial bladder and urinary tract, coating of fusion power electrode source in blood vessel and power supply wire of power source. It can be used as a bio coating material. The ultra-thin structure has the effect of inhibiting human immune toxicity, the method of the present invention improves the biocompatibility of tissue cells (or stem cells) and immune by inhibiting the activity of macrophage (macrophage) which is a representative immune active cell It may be a coating method to reduce the toxicity. The polymer-nanocomposite or coating film may be used in all bio-invasive medical devices, and may be suitable for an environment such as capillary and micro-vessel insertion that requires ultra-thin thickness while maintaining nanotopos.
The present invention relates to a coating film having a thickness of nano (nanometer) and submicron (submicron-meter) by mixing carbon nanotubes with a biocompatible polymer, and a method of manufacturing the same, by controlling the synthesis ratio of the polymer and carbon nanotubes It revealed that it is possible to increase the biocompatibility of the coating film having the ultra-thin film thickness and to control the mechanical strength, and by using such a feature, there is an effect that can be applied to a medical device inserted into the microvascular in vivo such as a nano medical device and a wire coating. .
Figure 1 shows a coating of the surface of the power supply wire and the electrode source module as an application example of the coating film according to the present invention.
Figure 2 schematically shows the manufacturing process of the coating film according to the present invention.
Figure 3 shows a sample of the coating film prepared while varying the synthesis ratio of CNT and PCU.
Figure 4 shows the result of measuring the thickness of the polymer coating film according to the present invention. The figure below shows the thickness of the carbon nanotube and polymer composites (AFM analysis) and is about 31 nm thick.
FIG. 5 shows that the polymer spheres generated when the heat is applied are also generated on the carbon nanotubes (thickness of 30 nm), and the carbon nanotubes are not exposed on the surface and covered with an ultra-thin film of about 30 nm. .
Figure 6 shows the nano-scale surface roughness of the coating film prepared by varying the synthesis ratio of CNT and PCU with an atomic force microscope (AFM). The bottom plot shows the change in surface tension due to the synthesis of carbon nanotubes (the y-axis represents the angle). As the nanotubes increase, the surface roughness increases and thus the surface tension increases.
Figure 7 shows the results of measuring the dynamic hardness of the coating film prepared while varying the synthesis ratio of the weight of the CNT and PCU. It can be seen that as the carbon nanotubes increase, the surface hardness increases (the surface hardness increases more than twice when the CNT weight is increased by 10 times).
Figure 8 shows the degree of protein adsorption according to the synthesis ratio of CNT and PCU weight in the coating film of the present invention. It can be seen that the roughness of the nanosurface rather than the surface energy affects the protein adsorption. As carbon nanotubes increase, more proteins are adsorbed. The lower figure shows the degree of adsorption of Vitronectin according to the synthesis ratio of the coating film. As the carbon nanotube ratio increases, more protein is adsorbed.
Figure 9 shows the adsorption and proliferation of immune cells according to the synthesis ratio of CNTs and PCU in the coating film of the present invention (upper figure). As the surface tension increases, the adsorption of immune cells increases (3 hours). . It can also be seen that the growth (24 hours) is also increased by the increased adsorption. The lower figure shows the adsorption and proliferation of messenchymal stem cells, and it can be seen that the self-renewal is regulated according to the increased degree of nanoroughness and the degree of protein adsorption.
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.
Example One: CNT - PCU Of composite coating film Produce
A solution was prepared by injecting 1 g of polycarbonate urethane (Lubrizol, PC-3575A) into 16 ml of chloroform. 0.3g of carbon nanotubes were injected into 60 ml of 1,2-dichloroethane to prepare a solution. Then, polycarbonate urethane was subjected to ultrasonic waves at room temperature for 1 hour and carbon nanotubes for 24 hours, respectively. Then the two solutions were mixed. Thus, the content of carbon nanotubes compared to the polycarbonate urethane is 100 and 1000% by weight. Then, two spin coaters were used to coat the glass, followed by drying in vacuo at room temperature. And CNT-PCU was prepared by sterilization and disinfection by exposing to UV. The mixing degree of chemcal solution to make a specific combination is as follows.
(1) PCU: 1, 2-Dichloroethane (1: 1) → 2ml: 25ml
(2) PCU: 1, 2-Dichloroethane (1: 10) → 0.2ml: 25ml
(3) PCU: CNT (1: 1) → 2ml: 25ml
(4) PCU: CNT (1:10) → 0.2ml: 25ml
After sonication (PCU + 1, 2-Dichloroethane = 30min, PCU + CNT = 1hr), coat each composite solution on glass using a spin coater. It is then dried (vacuum at room temperature) and then stored under sterilization and disinfection by exposure to UV light.
As a result, a coating film having a nano thin film structure having a thickness of 100 or 200 nm or less was obtained (see FIG. 4).
Example 2: CNT - PCU Investigation of surface properties of composite coating film
transparency
As a result of examining the degree of transparency of the CNT-PCU composite coating film of the present invention, it can be seen that the carbon nanotubes are coated at 100 nm or less, thereby maintaining a transparent state.
Measurement of Surface Hardness: Dynamic Hardness
Surface hardness measured the dynamic hardness which is a new definition hardness currently being JIS (Japanese Industrial Standard). The dynamic hardness is a hardness that can be obtained from the test force and the indent depth in the process of pushing the indenter as a method of measuring how the indenter penetrates into the sample. When the amount (Indent depth) D [µm], the hardness was determined using the Dynamic hardness DH defined by the following equation:
DH = αX P / D 2
(α is an integer by indenter shape. 115 ° triangle pyramid indenter: given by α = 3.8584)
As a result, as shown in Figure 7 it was confirmed that the hardness increases with increasing the CNT synthesis ratio for PCU. It was found that the addition of CNTs increased the surface energy (roughness at the nanoscale) and the surface hardness (hardness). In addition, it can be seen that as the 1, 2-dichloroethane is added to the PCU chemically, the surface energy decreases and the surface strength becomes smooth. Through this, it was found that the surface energy and the surface strength can be controlled by controlling the CNT ratio of the polymer in the thin film structure of the biopolymer nanocomposite having a thickness of 100 nm or less.
Example 3: CNT - PCU Of composite coating film In vivo protein adsorption regulation effect
In order to perform protein adsorption test (ELISA or absorbance KIT) on the CNT-PCU composite coating membrane, cell culture protein stocks (FBS, Gibco) were diluted to 1/5, and the adsorption experiment was performed on the surface of each sample. . After 3 hours, the protein was removed using detergent (
Adsorption experiments were also carried out using Vitronectin (V 8379, Sigma). After 3 hours, the protein was separated using detergent (
As a result, the degree of protein adsorption of the coating film was found to increase with the CNT / PCU ratio. In addition, it was found that nanoscale surface roughness is very important in protein adsorption, and vitronectin adsorption also increased with the CNT / PCU ratio. Therefore, by adjusting the surface energy by adjusting the CNT / PCU ratio of the coating film, it was confirmed that the adsorption of protein in vivo can be adjusted to make it more suitable for living (see Figure 8).
Example 4: CNT - PCU Effect of complex on intracellular adhesion and proliferation
Macrophages (J774, ATCC) were incubated at 100000 / cm 2 in each coated sample, and the number of cells was measured by MTT after 3 and 24 hours. In addition, after 3 hours and 24 hours after incubating the stem cells (MSC, Lonza) in each coated sample at 2500 / cm 2 The number of cells was measured using a Dapi (fluorescence microscope) measuring method.
As a result, it was found that adhesion and proliferation of the coating membrane to immune cells and mesenchymal stem cells increased with the CNT / PCU ratio. Therefore, in the interaction with the stem cells and immune cells of the coating film of the present invention improves the degree of adhesion, and the proliferation also shows that the coating film of the present invention can improve the biocompatibility by controlling the CNT / PCU ratio I could confirm it.
Claims (10)
Mixing the two sonicated solutions;
Coating the mixed solution on glass using a spin coater;
Drying the glass coated with the mixed solution at room temperature; And
Sterilizing and disinfecting the dried glass by irradiation with ultraviolet rays, characterized in that the surface strength of the coating film can be adjusted by adjusting the synthesis ratio of the biocompatible polymer and the carbon nanotubes, the polymer of claim 1 Method for producing a composite coating film.
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| Application Number | Priority Date | Filing Date | Title |
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| KR20100107561A KR101271535B1 (en) | 2010-11-01 | 2010-11-01 | Ultra thin film comprising carbon nanotube polymer composites for increasing biocompatibility and controlling mechanical strength and a method of preparing the same |
| PCT/KR2011/008193 WO2012060592A2 (en) | 2010-11-01 | 2011-10-31 | Carbon nanotube polymer composite coating film which suppresses toxicity and inflammation and has improved biocompatibility and adjusted surface strength |
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| KR20100107561A KR101271535B1 (en) | 2010-11-01 | 2010-11-01 | Ultra thin film comprising carbon nanotube polymer composites for increasing biocompatibility and controlling mechanical strength and a method of preparing the same |
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| US8652386B2 (en) | 2010-09-16 | 2014-02-18 | Georgia Tech Research Corporation | Alignment of carbon nanotubes comprising magnetically sensitive metal oxides in nanofluids |
| ES2706124T3 (en) | 2013-01-30 | 2019-03-27 | Estrada Alfredo Vega | Carbon nanostructures for the reinforcement of an ocular tissue |
| WO2015034930A1 (en) * | 2013-09-03 | 2015-03-12 | William Marsh Rice University | Treatment of inflammatory diseases by carbon materials |
| US9312046B2 (en) | 2014-02-12 | 2016-04-12 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles having enhanced electrical properties and methods of preparation |
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