CN108773831B - L-arginine nanoparticle and nitric oxide are the degradable nano-motor and preparation method thereof of power source - Google Patents
L-arginine nanoparticle and nitric oxide are the degradable nano-motor and preparation method thereof of power source Download PDFInfo
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Abstract
The invention discloses the degradable nano-motor and preparation method thereof that a kind of L-arginine nanoparticle and nitric oxide are power source, which is self-assembly of by L-arginine and the substance rich in electropositive functional group ultrabranching polyamide by electrostatical binding；Using L-arginine nanoparticle as fuel, degradable nano-motor can be formed by power source of nitric oxide.The present invention releases nitric oxide bubble using the redox reaction of L-arginine and hydrogen peroxide, thus nanoparticle movement is pushed, becomes nano-motor, and with the consumption of L-arginine, L-arginine nanoparticle is gradually degraded, and being finally degraded to water-soluble substances can be excreted by human body.
Description
Technical field
The invention belongs to novel biomaterials, and in particular to L-arginine nanoparticle and nitric oxide be power source can
Degradation-type nano-motor and preparation method thereof.
Background technique
With the development of science and technology, nanotechnology and material science have also been made significant headway.Nano science gradually starts
By materialogy, physics, biology, electronics educational circles numerous researchers extensive concern, become an important friendship
Pitch subject.Inspiration of the people by molecular motor copies the working principle of molecular motor to prepare using nanoscale science and technology means
Nano-motor is gone out.Existing nano-motor can be divided into the three categories such as rodlike motor, tubular motor, spherical motor from shape；
It simultaneously also include some motors in irregular shape, such as dish type, spiral shape, cryptomere, tubaeform.From power source can be divided into
Lower two major classes: one kind is extraneous physical stimulation driving, usually there is magnetic field, electric field, ultrasonic wave, illumination etc.；Another kind of is chemical energy
Source driving, usually water, hydrogen peroxide, acid solution, hydrazine, urea, bromine and iodide etc. are used as fuel, by catalyst and fuel
Reaction generates the movement that the gases such as hydrogen, oxygen, ammonia push nano-motor as power source.
The power source and the product in reaction process of the nano-motor of current research are mostly the unwanted exhaust gas of human body
(such as ammonia, hydrogen) or waste material (such as bromide ion), and most of catalyst can not degrade in vivo, residual causes human body in vivo
Burden.Mariana Medina-Sanchez in 2017 et al. is published in an article on Nature and proposes current nano-motor
Research needs emphasis to consider the nano-motor that can control, stop and remove, and does not have the consumption that can utilize material itself also at present
And realize the report of the degradation of nano-motor.Therefore, need exploitation prepare it is degradable, using useful constituent as power source, generate
Beneficial to human body, the degradable novel nano motor of by-product.
Summary of the invention
Goal of the invention: in view of the problems of the existing technology, the present invention provides a kind of L-arginine nanoparticle, the nanometer
Particle can realize the degradation of the nano-motor of formation by the consumption of material itself.
The present invention also provides the degradable nano-motors and preparation method thereof that a kind of nitric oxide is power source.
Technical solution: to achieve the goals above, a kind of L-arginine nanoparticle as described herein, by L- essence ammonia
The nanoparticle that acid is formed with the substance rich in electropositive functional group.
Preferably, the substance rich in electropositive functional group is the ultrabranching polyamide or poly- bad in two generations or more
Propylhomoserin or chitosan.
The preparation method of L-arginine nanoparticle of the present invention by L-arginine and is rich in electropositive functional group
Substance is configured to solution respectively, and after the two ultrasonic mixing, centrifuging and taking lower sediment distillation washing, drying are made.
Preferably, the concentration of the L-arginine solution is 2.5-15mg/mL.
Preferably, the concentration of the substance solution rich in electropositive functional group is 0.1-1mg/mL.
Wherein, the L-arginine presses 1-10mLL- arginine solution and 1-10mL with the substance rich in electropositive functional group
Substance solution ultrasonic mixing 1-60min rich in electropositive functional group.
It is of the present invention using nitric oxide as the degradable nano-motor of power source, with L-arginine nanoparticle and mistake
The nitric oxide that hydrogen oxide reaction generates is power source, is formed by fuel of hydrogen peroxide.
Nitric oxide of the present invention is the preparation method of the degradable nano-motor of power source, is received by L-arginine
The redox reaction of rice corpuscles and hydrogen peroxide releases nitric oxide bubble, pushes nanoparticle movement, becomes a nanometer horse
It reaches, with the consumption of L-arginine, L-arginine nanoparticle is gradually degraded, and is finally degraded to water-soluble substances.
Specially L-arginine/ultrabranching polyamide nanoparticle is added dropwise and is dried on glass slide, hydrogen peroxide is added dropwise
Solution is placed in observation motor movement situation on microscope.The redox reaction of L-arginine and hydrogen peroxide releases an oxygen
Change nitrogen bubble, thus pushes nanoparticle movement, formed using nitric oxide as the degradable nano-motor of power source.
Wherein, the mass concentration of the hydrogenperoxide steam generator is 5-20%.
The present invention is with the degradable nano-motor (partial size 50-200nm) of L-arginine nanoparticle, by electropositive base
Group's substance abundant and L-arginine are obtained by way of electrostatical binding self assembly.
Mechanism: the present invention is using hydrogen peroxide as fuel, with L-arginine nanoparticle and the one of hydroperoxidation generation
Nitrogen oxide is the degradable nano-motor of power source in application, being released using the redox reaction of L-arginine and hydrogen peroxide
Nitric oxide bubble is released, nanoparticle movement is thus pushed, becomes nano-motor, and with the consumption of L-arginine, L- essence
Propylhomoserin nanoparticle is gradually degraded, and being finally degraded to water-soluble substances can be excreted by human body.Nitric oxide has in promotion
Skin growth, migration, adjusts the effects of collage synthesis, other cell factors at the proliferation for inhibiting smooth muscle cell；L-arginine then has
There is immunoloregulation function, the degeneration (degeneration especially after injury) of thymus gland can be prevented, supplement arginine can increase thymus gland
Weight, promote the growth of thymic lymphocytes；Citrulling then can be improved function of immune system, maintenance joint motions function,
Balance normal blood glucose level, harmful free radical absorbed containing antioxidant abundant, the normal level for assisting in keeping cholesterol,
It safeguards the lung function in Jiankang, can also be acted in human body with ammonia, generate arginine and nitric oxide.Either nano-motor
The by-product citrulling that raw material L-arginine, power source nitric oxide still react is required important substance in human body, because
This synthetic method provided by the invention has broad application prospects in field of biomedicine.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
The present invention synthesizes L-arginine nanoparticle using the method for electrostatical binding self assembly, utilizes L-arginine and peroxide
The redox reaction for changing hydrogen releases nitric oxide bubble, thus pushes nanoparticle movement, becomes nano-motor, while with
The consumption of L-arginine, L-arginine nanoparticle gradually degrade, be finally degraded to water-soluble substances.Nanometer of the present invention
Particle can realize the degradation of the nano-motor of formation by the consumption of material itself, and preparation manipulation method is simple, close
At mild condition, nano-motor is generated without exhaust gas, waste material during the motion, and raw material L-arginine, the power of nano-motor
Source nitric oxide and the by-product citrulling of reaction are required important substance in human body, are had in field of biomedicine wide
Application prospect.
Detailed description of the invention
Fig. 1 is L-arginine/ultrabranching polyamide nanoparticle TEM figure that embodiment 1 obtains；
Fig. 2 is L-arginine/ultrabranching polyamide nanoparticle TEM figure that embodiment 2 obtains；
Fig. 3 is L-arginine/ultrabranching polyamide nanoparticle TEM figure that embodiment 3 obtains；
Fig. 4 is L-arginine/polylysine nanoparticle TEM figure that embodiment 4 obtains；
Fig. 5 is L-arginine/chitin nanometer TEM figure that embodiment 5 obtains；
Fig. 6 is sport video screenshot of the L-arginine/ultrabranching polyamide nanoparticle in 20% hydrogenperoxide steam generator:
(A) the moving line figure in the motion state of different time and (B) 10s；
Fig. 7 is sport video screenshot of the L-arginine/ultrabranching polyamide nanoparticle in 10% hydrogenperoxide steam generator:
(A) the moving line figure in the motion state of different time and (B) 10s；
Fig. 8 is sport video screenshot of the L-arginine/ultrabranching polyamide nanoparticle in 5% hydrogenperoxide steam generator:
(A) the moving line figure in the motion state of different time and (B) 10s；
Fig. 9 is the obtained L-arginine/ultrabranching polyamide nanoparticle of embodiment 1 in 10%H2O2In NO discharge feelings
Condition；
Figure 10 is that embodiment 1 obtains L-arginine/ultrabranching polyamide nanoparticle in 10%H2O2In degradation situation,
(a)0h,(b)1h,(c)3h,(d)6h,(e)18h。
Specific embodiment
Embodiment 1
The synthesis of L-arginine/ultrabranching polyamide nanoparticle:
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 5mg/mL is weighed；
(2) it weighs a certain amount of ultrabranching polyamide (HPAM) and is made into the solution that concentration is 0.5mg/mL.
(3) the L-arginine solution of the above-mentioned configuration of 1mL is taken, ultrasound, and the hyperbranched of 0.5mg/mL is added dropwise thereto
Polyamide solution 1mL.After continual ultrasonic 5min, 12000rpm/min centrifugation, lower sediment distilled water washes twice drying, obtains
L-arginine/ultrabranching polyamide nanoparticle is stand-by.L-arginine/ultrabranching polyamide nanoparticle prepared by the present embodiment 1
The TEM of son schemes to have synthesized L-arginine/hyperbranched poly that partial size is about 130nm by this method as shown in Figure 1, can be seen that in figure
Amide nanoparticle, with relatively regular geometric shape.
Embodiment 2
The synthesis of L-arginine/ultrabranching polyamide nanoparticle:
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 2.5mg/mL is weighed；
(2) it weighs a certain amount of ultrabranching polyamide (HPAM) and is made into the solution that concentration is 0.5mg/mL.
(3) the L-arginine solution of the above-mentioned configuration of 1mL is taken, ultrasound, and the hyperbranched of 0.5mg/mL is added dropwise thereto
Polyamide solution 1mL.After continual ultrasonic 5min, 12000rpm/min centrifugation, lower sediment distilled water washes twice dried for standby.
L-arginine/ultrabranching polyamide nanoparticle TEM prepared by the present embodiment 2 schemes as shown in Fig. 2, can be seen that in figure through this
Method has synthesized L-arginine/ultrabranching polyamide nanoparticle that partial size is about 100nm.
Embodiment 3
The synthesis of L-arginine/ultrabranching polyamide nanoparticle:
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 15mg/mL is weighed；
(2) solution that a certain amount of ultrabranching polyamide (HPAM) is 0.5mg/mL at concentration is weighed.
(3) the L-arginine solution of the above-mentioned configuration of 1mL is taken, ultrasound, and the hyperbranched of 0.5mg/mL is added dropwise thereto
Polyamide (HPAM) 1mL.After continual ultrasonic 5min, 12000rpm/min centrifugation, lower sediment distilled water wash twice it is dry to
With.L-arginine/ultrabranching polyamide nanoparticle TEM prepared by the present embodiment 3 schemes as shown in figure 3, with L-arginine
The increase of concentration, L-arginine/ultrabranching polyamide nanoparticle partial size gradually increase, when L-arginine concentration reaches
When 15mg/mL, partial size has been greater than 500 μm, and apparent crystalline polamer occurs.
Embodiment 4
The synthesis of L-arginine/polylysine nanoparticle:
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 5mg/mL is weighed；
(2) it weighs a certain amount of polylysine and is made into the solution that concentration is 0.5mg/mL.
(3) the L-arginine solution of the above-mentioned configuration of 1mL is taken, ultrasound, and the poly- bad ammonia of 0.5mg/mL is added dropwise thereto
Acid solution 1mL.After continual ultrasonic 5min, 12000rpm/min centrifugation, lower sediment distilled water washes twice dried for standby.This reality
L-arginine/polylysine nanoparticle TEM the figure for applying the preparation of example 4 is synthesized as shown in figure 4, can be seen that in figure by this method
L-arginine/polylysine nanoparticle that partial size is about 800nm.
Embodiment 5
The synthesis of L-arginine/chitin nanometer:
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 5mg/mL is weighed；
(2) it weighs a certain amount of chitosan and is made into the solution that concentration is 0.5mg/mL.
(3) the L-arginine solution of the above-mentioned configuration of 1mL is taken, ultrasound, and the poly- bad ammonia of 0.5mg/mL is added dropwise thereto
Acid solution 1mL.After continual ultrasonic 5min, 12000rpm/min centrifugation, lower sediment distilled water washes twice dried for standby.This reality
L-arginine/chitin nanometer TEM the figure for applying the preparation of example 5 is synthesized as shown in figure 5, can be seen that in figure by this method
L-arginine/chitin nanometer that partial size is about 200-500nm.
Embodiment 6
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 2.5mg/mL is weighed；
(2) it weighs a certain amount of ultrabranching polyamide (HPAM) and is made into the solution that concentration is 0.1mg/mL.
(3) the L-arginine solution of the above-mentioned configuration of 5mL is taken, ultrasound, and the hyperbranched of 0.1mg/mL is added dropwise thereto
Polyamide solution 5mL.After continual ultrasonic 1min, 12000rpm/min centrifugation, lower sediment distilled water washes twice dried for standby.
Embodiment 7
(1) L-arginine (L-Arg) solution soluble in water for being made into concentration as 2.5mg/mL is weighed；
(2) it weighs a certain amount of ultrabranching polyamide (HPAM) and is made into the solution that concentration is 1mg/mL.
(3) the L-arginine solution of the above-mentioned configuration of 10mL is taken, ultrasound, and the hyperbranched poly of 1mg/mL is added dropwise thereto
Amide solution 10mL.After continual ultrasonic 60min, 12000rpm/min centrifugation, lower sediment distilled water washes twice dried for standby.
Embodiment 8
Using nitric oxide as the degradable nano-motor of power source:
L-arginine prepared by embodiment 1/ultrabranching polyamide nanoparticle is added dropwise on glass slide, in 37 DEG C of baking ovens
Middle drying.The hydrogenperoxide steam generator that mass concentration is 20% is added dropwise, is placed in observation motor movement situation on microscope.L-arginine
The redox reaction of nanoparticle and hydrogen peroxide releases nitric oxide bubble, thus pushes nanoparticle movement, is formed
Using nitric oxide as power source, using hydrogen peroxide as the degradable nano-motor of fuel.
As shown in fig. 6, L-arginine/ultrabranching polyamide nanoparticle is in 20% hydrogenperoxide steam generator of mass concentration
Motion state, You Tuzhong can be seen that the motor energy continuous uniform generates NO gas and moving line is linear, and move speed
Rate is very fast.
Embodiment 9
Using nitric oxide as the degradable nano-motor of power source:
L-arginine prepared by embodiment 1/ultrabranching polyamide nanoparticle is added dropwise on glass slide, in 37 DEG C of baking ovens
Middle drying.The hydrogenperoxide steam generator that mass concentration is 10% is added dropwise, is placed in observation L-arginine/ultrabranching polyamide on microscope
The motion conditions of nanoparticle.The redox reaction of L-arginine nanoparticle and hydrogen peroxide releases nitric oxide gas
Thus bubble pushes nanoparticle movement, is formed using nitric oxide as power source, using hydrogen peroxide as the degradable nanometer of fuel
Motor.
As shown in fig. 7, L-arginine/ultrabranching polyamide nanoparticle is in 10% hydrogenperoxide steam generator of mass concentration
Motion state, You Tuzhong can be seen that the motor energy continuous uniform generates NO gas and moving line in circle type, this and over-expense
It is related that asymmetric L-arginine unbalance stress when it is with hydroperoxidation is loaded in change polyamide cavity.
Embodiment 10
Using nitric oxide as the degradable nano-motor of power source:
L-arginine prepared by embodiment 1/ultrabranching polyamide nanoparticle is added dropwise on glass slide, in 37 DEG C of baking ovens
Middle drying.The hydrogenperoxide steam generator that mass concentration is 5% is added dropwise, is placed in observation L-arginine/ultrabranching polyamide on microscope
Nanoparticle motion conditions.The redox reaction of L-arginine nanoparticle and hydrogen peroxide releases nitric oxide bubble,
Thus nanoparticle movement is pushed, is formed using nitric oxide as power source, using hydrogen peroxide as the degradable nanometer horse of fuel
It reaches.
As shown in figure 8, L-arginine/ultrabranching polyamide nanoparticle is in 5% hydrogenperoxide steam generator of mass concentration
Motion state, You Tuzhong can be seen that the motor energy continuous uniform generates NO gas and moving line is curved.
Embodiment 11
It is discharged by the NO of the degradable nano-motor of power source of nitric oxide.
L-arginine/ultrabranching polyamide nanoparticle prepared by embodiment 1 is divided into 7 groups, every group of addition 1mL10%
H2O210min, 30min, 1h, 2h, 3h, 6h, 9h are reacted in solution respectively, with manganese dioxide stopped reaction, 12000rpm/min from
The heart takes supernatant, for use.By containing for the NO of above-mentioned supernatant nitric oxide kit (nitrate reductase method) detection each sample
Amount.NO release conditions in embodiment 9 are as shown in figure 9, NO is released in the time range of experimental group setting as can be seen from Figure
High-volume continuing to increase, the NO total volume of 9h is up to 15.9 μm of olL-1And in preceding 1h, the rate of release of NO is very fast, and burst size reaches
The 52% of total volume.
Embodiment 12
Using nitric oxide as the degradation process of the degradable nano-motor of power source.
L-arginine/ultrabranching polyamide nanoparticle prepared by embodiment 1 is placed in the peroxide that mass concentration is 10%
Change in hydrogen solution, 1h, 3h, 6h, 18h are incubated at 37 DEG C.12000rpm/min centrifuging and taking lower layer tem observation L-arginine/over-expense
Change the degradation situation of polyamide nano particle, TEM is shown in Figure 10.By can be seen that L-arginine/ultrabranching polyamide is received in Figure 10
Degradation process of the rice corpuscles in 10% hydrogenperoxide steam generator at any time, with the extension of reaction time, L-arginine/over-expense
Changing polyamide nano particle surface gradually becomes coarse, and partial size is gradually reduced.
Claims (7)
1. a kind of using nitric oxide as the degradable nano-motor of power source, which is characterized in that the degradable nanometer horse
Up to the nitric oxide generated using L-arginine nanoparticle and hydroperoxidation as power source, using hydrogen peroxide as fuel shape
At；The L-arginine nanoparticle passes through electrostatical binding self assembly by L-arginine and the substance rich in electropositive functional group
The nanoparticle of formation；The substance rich in electropositive functional group is ultrabranching polyamide, chitosan or polylysine.
2. according to claim 1 using nitric oxide as the degradable nano-motor of power source, which is characterized in that described
The preparation method of L-arginine nanoparticle: being configured to solution for L-arginine and the substance rich in electropositive functional group respectively,
After the two ultrasonic mixing, centrifuging and taking lower sediment distillation washing, drying are made.
3. according to claim 2 using nitric oxide as the degradable nano-motor of power source, which is characterized in that described
The concentration of L-arginine solution is 2.5-15 mg/mL.
4. according to claim 2 using nitric oxide as the degradable nano-motor of power source, which is characterized in that described
The concentration of substance solution rich in electropositive functional group is 0.1-1 mg/mL.
5. according to claim 2 using nitric oxide as the degradable nano-motor of power source, which is characterized in that described
L-arginine and positive electricity group organic matter abundant press 1-10 mL L-arginine solution and 1-10 mL is rich in electropositive function
The substance solution ultrasonic mixing 1-60 min of group.
6. a kind of nitric oxide described in claim 1 is the preparation method of the degradable nano-motor of power source, feature
It is, nitric oxide bubble is released by the redox reaction of L-arginine nanoparticle and hydrogen peroxide, pushes nanoparticle
Son movement, becomes nano-motor, with the consumption of L-arginine, L-arginine nanoparticle is gradually degraded, and is finally degraded to water
Soluble substance.
7. preparation method according to claim 6, which is characterized in that the mass concentration of the hydrogenperoxide steam generator is 5-
20%。
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| EP3663257A1 (en) * | 2018-12-05 | 2020-06-10 | Fundació Institut de Bioenginyeria de Catalunya (IBEC) | Functionalized enzyme-powered nanomotors |
| ES2834732B2 (en) * | 2019-12-17 | 2022-03-24 | Univ Valladolid | AQUEOUS SOLUTION THAT INCLUDES AN INCLUSION COMPLEX, METHOD OF OBTAINING AND ITS USE FOR APPLICATION IN CROPS AND THE IMPROVEMENT OF ITS YIELD |
| CN113402661B (en) * | 2021-05-08 | 2022-07-26 | 南京师范大学 | Zwitterionic polymer-based nitric oxide-driven nano motor and preparation method and application thereof |
| CN113403270B (en) * | 2021-05-08 | 2023-09-22 | 南京师范大学 | Engineering exosome nano motor and preparation method thereof |
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