CN109913977B - Nucleic acid gel fiber and preparation method thereof - Google Patents
Nucleic acid gel fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of biological materials, in particular to a nucleic acid gel fiber and a preparation method thereof. The preparation method of the invention comprises the steps of carrying out electrostatic reaction on nucleic acid and a cationic surfactant in a water phase to obtain a compound, carrying out centrifugal precipitation, washing, freeze-drying, adding an organic solvent, swelling and wire drawing to obtain the nucleic acid gel fiber. The nucleic acid gel fiber prepared by the invention has high tensile strength, high modulus and excellent ductility, and keeps a liquid crystal structure in an organic phase, and the toughness of the fiber is comparable to that of natural spider silk fiber. Meanwhile, the preparation method has simple process, no need of special equipment and low cost.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to a nucleic acid gel fiber and a preparation method thereof.
Background
Nucleic acid is a large-scale biomolecule usually located in cell nucleus, is responsible for carrying and transmitting genetic information of organism, can be used as a structural motif for assembling nano structure, and is always one of the most studied biological macromolecules in the technical field of biological materials. In recent years, the development of automated solid phase synthesis, molecular cloning techniques and polymerase chain reaction has made possible the study of both short and long nucleic acids. Due to the unique properties of nucleic acids, such as self-recognition capability, sequence programmability and excellent stability. Making it a hotspot in the field of functional biomaterial research. Among them, due to its sequence length and base programmability, nucleic acids are widely used in the fields of drug delivery, gene transduction and detection technology.
Macromolecular soft materials, such as liquid crystals, hydrogels and organogels, have attracted increasing attention due to their excellent properties and functional versatility. Among them, liquid crystal and hydrogel materials prepared using nucleic acid as a matrix are particularly prominent. The molecular recognition ability of nucleic acids makes them programmable and can be used to stimulate corresponding materials and biomedical applications. The nucleic acid with the property has great application prospect as a soft substance, but the poor mechanical property prevents the practical application of the nucleic acid in the field needing mechanical integrity and adjustability. In addition, nucleic acid-based gel systems are mostly amorphous materials, lacking ordered internal structures within the gel network, which has recently prevented their research in anisotropic electrical, optical, magnetic or mechanical properties. Therefore, how to prepare the high-strength nucleic acid gel with the liquid crystal structure has important practical significance for basic scientific research and technical application.
Disclosure of Invention
In view of the above, the present invention provides a nucleic acid gel fiber and a method for preparing the same. The prepared nucleic acid gel fiber has a liquid crystal structure and has excellent tensile strength and ductility.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of nucleic acid gel fiber, which comprises the following steps:
mixing and reacting nucleic acid with a cationic surfactant to obtain a compound;
adding an organic solvent into the compound for swelling to obtain nucleic acid gel;
and drawing the nucleic acid gel to obtain the nucleic acid gel fiber.
In the preparation method provided by the invention, the nucleic acid and the cationic surfactant react in a water phase through electrostatic interaction to obtain a compound.
Before the reaction, the nucleic acid is prepared into a nucleic acid solution, and then the cationic surfactant is added for reaction. The nucleic acid may be dissolved in ultrapure water to prepare a nucleic acid solution, or the nucleic acid may be dissolved in a PBS buffer solution to prepare a nucleic acid solution.
In some embodiments, the nucleic acid solution contains 2-10 mg/ml of nucleic acid. In some embodiments, the nucleic acid solution comprises 10mg/ml, 5mg/ml, or 2mg/ml of nucleic acid.
In some embodiments, the nucleic acid is present in a molar ratio of 1:1 to 1:10 based on the number of bases. In some embodiments, the molar ratio of nucleic acid to cationic surfactant is 1: 5.
In some embodiments, the nucleic acid is a long-chain deoxyribonucleic acid comprising 200 to 2686 base pairs. In some embodiments, the long-chain deoxyribonucleic acid comprises 200, 500, 1000, 2000, or 2686 base pairs.
In some embodiments, the nucleic acid is a short strand deoxyribonucleic acid comprising 14 to 22 base pairs. In some embodiments, the short-chain deoxyribonucleic acid comprises 14 or 22 base pairs.
In some embodiments, the cationic surfactant is selected from one or more of didodecyldimethylammonium bromide, cetyltrimethylammonium bromide, or didecyldimethylammonium bromide.
In some embodiments, the cationic surfactant is didodecyldimethylammonium bromide, cetyltrimethylammonium bromide, or didecyldimethylammonium bromide.
After the compound is obtained, the compound is firstly centrifugally precipitated, washed and freeze-dried. In some embodiments, the centrifugation is 10000rpm for 30 minutes; the washing is deionized water washing, and the washing times are 3 times; the freeze-drying is to put the compound in a freeze-dryer overnight, or to put the compound in liquid nitrogen for freezing and then put the compound in the freeze-dryer for freeze-drying for two hours.
After the freeze-dried compound is obtained, an organic solvent is added for swelling. In some embodiments, the organic solvent is selected from one or more of dimethylsulfoxide, tetrahydrofuran, chloroform, toluene, ethanol, ethylene glycol, or glycerol. In some embodiments, the organic solvent is toluene, dimethyl sulfoxide, tetrahydrofuran, or ethanol.
In some embodiments, the swelling time is between 10min and 2h, preferably 30min or 60 min.
The invention also provides the nucleic acid gel fiber prepared by the preparation method.
The nucleic acid and the cationic surfactant are subjected to electrostatic reaction in a water phase to obtain a compound, and the compound is subjected to centrifugal precipitation, washing, freeze-drying, organic solvent addition, swelling and wire drawing to obtain the nucleic acid gel fiber. The invention has the following beneficial effects:
1. the product obtained by the invention has a liquid crystal structure and excellent tensile strength and ductility. The resulting nucleic acid gel may extend more than 300 times its length.
2. The nucleic acid gel obtained by the invention has a regular structure and excellent mechanical properties, and can become a starting point for constructing a novel functional nucleic acid material, widen the research range of a nucleic acid nano structure, and even realize an operable molecular material in an organic environment.
3. The invention has simple preparation process, low cost and no need of special equipment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a swelling diagram of the nucleic acid gel of example 1;
FIG. 2 is a graph showing a ductility test of the nucleic acid gel fiber according to example 2, wherein FIG. 2-A shows the nucleic acid gel prepared according to example 2, FIG. 2-B shows the nucleic acid gel stretched to about 80 times its length, FIG. 2-C shows the nucleic acid gel stretched to about 170 times its length, and FIG. 2-D shows the nucleic acid gel stretched to about 330 times its length;
FIG. 3 is a graph showing mechanical properties of the nucleic acid gel fiber in example 3, wherein FIG. 3-A is a graph showing the results of Young's modulus measurement of the nucleic acid gel fiber, and FIG. 3-B is a graph showing the measurement of tenacity of the nucleic acid gel fiber.
Detailed Description
The invention discloses a nucleic acid gel fiber and a preparation method thereof, and a person skilled in the art can realize the nucleic acid gel fiber by appropriately improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The test materials adopted by the invention are all common commercial products and can be purchased in the market.
The invention is further illustrated by the following examples:
example 1
210 mu L of 5.4mM 22bp (22 base pairs) DNA solution and 5mL of 50mM didodecyldimethylammonium bromide are put into a centrifuge tube and stirred for 1 minute with shaking to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 100. mu.L of toluene was added to the freeze-dried sample, and the mixture was left at room temperature for 30 minutes to obtain a nucleic acid gel, and the nucleic acid gel was subjected to drawing to obtain a nucleic acid gel fiber. FIG. 1 shows the nucleic acid gel prepared in this example, which shows that the nucleic acid gel of the present invention has a liquid crystal structure.
Example 2
210. mu.L of 5.4mM DNA solution (200 base pairs) and 5mL of 50mM didodecyldimethylammonium bromide were placed in a centrifuge tube and stirred with shaking for 1 minute to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 100. mu.L of toluene was added to the freeze-dried sample, and the mixture was left at room temperature for 30 minutes to obtain a nucleic acid gel, and the nucleic acid gel was subjected to drawing to obtain a nucleic acid gel fiber. FIG. 1 shows the nucleic acid gel prepared in this example, which shows that the nucleic acid gel of the present invention has a liquid crystal structure.
Example 3
210. mu.L of 5.4mM DNA solution (1000 base pairs) and 5mL of 50mM didodecyldimethylammonium bromide were placed in a centrifuge tube and stirred with shaking for 1 minute to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 100. mu.L of toluene was added to the freeze-dried sample, and the mixture was left at room temperature for 30 minutes to obtain a nucleic acid gel, and the nucleic acid gel was subjected to drawing to obtain a nucleic acid gel fiber. FIG. 2 is a nucleic acid gel ductility test prepared in this example, which shows that the nucleic acid liquid crystal gel has a large elongation at break.
Example 4
600 μ L of 10mg/mL salmon DNA (2000 base pairs) solution and 3mL of 50mM didodecyldimethylammonium bromide were put into a centrifuge tube, and stirred for 1 minute with shaking to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 50. mu.L of dimethyl sulfoxide was added to the freeze-dried sample, and the mixture was left at room temperature for 30 minutes to obtain a nucleic acid gel, and then the nucleic acid gel fiber was obtained by drawing. FIG. 2 is a graph showing the ductility test of the nucleic acid gel prepared in this example, and the fibers of the nucleic acid gel obtained therefrom are ductile up to 330 times their length, which shows that the nucleic acid gel of the present invention has excellent ductility.
Example 5
800. mu.L of 10mg/mL salmon DNA (2000 base pairs) solution and 4mL of 50mM didodecyldimethylammonium bromide were put into a centrifuge tube, and stirred with shaking for 1 minute to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then 80. mu.L of tetrahydrofuran was added to the lyophilized sample and left at room temperature for 30 minutesAnd drawing to obtain the nucleic acid gel fiber. FIG. 3 shows the mechanical properties of the nucleic acid gel fiber prepared in this example, and the calculated Young's modulus and toughness were 32MPa and 18MJ/m, respectively3. The nucleic acid gel fiber of the invention is much higher than other reported nucleic acid soft material systems, and the toughness is comparable to natural spider silk.
Example 6
1mL of 10mg/mL salmon DNA (2000 base pairs) solution and 5mL of 50mM cetyltrimethylammonium bromide were put into a centrifuge tube, and stirred with shaking for 1 minute to obtain a white suspension. And then placing the precipitate into a centrifuge, centrifuging the precipitate for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water to wash the precipitate, centrifuging the precipitate again, repeatedly washing the precipitate for three times, removing supernatant, freeze-drying the precipitate obtained by centrifugation, and placing the precipitate into a freeze-dryer for overnight. Then 60 mu L of ethanol is added into the freeze-dried sample, the sample is placed at room temperature for 30 minutes to obtain nucleic acid gel, and the nucleic acid gel fiber is obtained by manual drawing. The nucleic acid gel has a liquid crystal structure, and the results of the mechanical property test and the ductility test of the prepared nucleic acid gel fiber are similar to those of the examples 2-3 and have no significant difference (p is more than 0.05)
Example 7
8mL of a 5mg/mL DNA solution of 2686bp (2686 base pairs) and 4mL of 50mM didecyldimethylammonium bromide were placed in a centrifuge tube and stirred with shaking for 1 minute to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 50. mu.L of dimethyl sulfoxide was added to the freeze-dried sample, and the mixture was left at room temperature for 30 minutes to obtain a nucleic acid gel, and the nucleic acid gel fiber of the present invention was obtained by hand drawing. The nucleic acid gel has a liquid crystal structure, and the results of the mechanical property test and the ductility test of the prepared nucleic acid gel fiber are similar to those of the examples 2-3 and have no significant difference (p is more than 0.05)
Comparative example 1
100 μ L of a 2000 base pair DNA solution of 5mM and 5mL of 50mM monododecyltrimethylammonium bromide were placed in a centrifuge tube and stirred with shaking for 1 minute to form a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 100. mu.L of water was added to the lyophilized sample and left at room temperature for 60 minutes to obtain a nucleic acid hydrogel which had no birefringence, i.e., no liquid crystal structure, and which was not stretchable and not malleable.
Comparative example 2
100 μ L of 5mM DNA solution of 2000 base pairs and 5mL of 50mM ammonium bromide polyethylene glycol were put into a centrifuge tube and stirred with shaking for 1 minute to obtain a white suspension. And then placing the mixture into a centrifuge, centrifuging the mixture for 30 minutes at a centrifugal speed of 10000rpm, removing supernatant, adding deionized water, washing the mixture, centrifuging the mixture, repeatedly washing the mixture for three times, removing the supernatant, placing the compound precipitate obtained by centrifugation into liquid nitrogen for freezing, and then placing the compound precipitate into a freeze dryer for freeze-drying for two hours. Then, 100. mu.L of water was added to the lyophilized sample and left at room temperature for 60 minutes to obtain a nucleic acid hydrogel which had no birefringence, i.e., no liquid crystal structure, and which was not stretchable and not malleable.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. A preparation method of nucleic acid gel fiber is characterized by comprising the following steps:
reacting nucleic acid with a cationic surfactant to obtain a compound;
centrifuging and precipitating the compound, washing, freeze-drying, and adding an organic solvent for swelling to obtain nucleic acid gel;
drawing the nucleic acid gel to obtain nucleic acid gel fibers;
the molar ratio of the nucleic acid to the cationic surfactant is 1: 1-1: 10 based on the number of bases;
the nucleic acid is long-chain deoxyribonucleic acid, and the long-chain deoxyribonucleic acid contains 200-2686 base pairs;
the nucleic acid is short-chain deoxyribonucleic acid, and the short-chain deoxyribonucleic acid contains 14-22 base pairs;
the compound is obtained by reacting nucleic acid with a cationic surfactant through electrostatic interaction;
the cationic surfactant is selected from one or more of didodecyldimethylammonium bromide, hexadecyltrimethylammonium bromide or didecyldimethylammonium bromide;
the organic solvent is selected from one or more of dimethyl sulfoxide, tetrahydrofuran, chloroform, toluene, ethanol, glycol or glycerol;
the swelling time is 10min-2 h;
2. the nucleic acid gel fiber produced by the production method according to claim 1.
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