CN107552807A - It is a kind of to prepare the preparation method with the size gold nanorods controllable with dispersiveness on a large scale - Google Patents
It is a kind of to prepare the preparation method with the size gold nanorods controllable with dispersiveness on a large scale Download PDFInfo
- Publication number
- CN107552807A CN107552807A CN201610501110.5A CN201610501110A CN107552807A CN 107552807 A CN107552807 A CN 107552807A CN 201610501110 A CN201610501110 A CN 201610501110A CN 107552807 A CN107552807 A CN 107552807A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- paa
- atrp
- template
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The preparation method with the size gold nanorods controllable with dispersiveness can be prepared on a large scale the invention discloses a kind of, belong to the multi-crossed disciplines fields such as high molecular reactive polymerization, functional polymer MOLECULE DESIGN and inorganic crystal growth.This method comprises the following steps：（1）Ionic liquid AMIMCl is used as solvent, anhydrous dimethyl formamide and N methyl pyrrolidones are diluent and acid absorbent, with the hydroxyl on 2 bromine isobutyl acylbromide modified cellulose chains, make it switch to can be used for ATRP（ATRP）Macromole evocating agent；（2）Using cellulose Br as macromole evocating agent, using technologies such as the ATRP of continuous polymerization, " link " chemistry, a series of brush bi-block copolymers are prepared：cellulose‑g‑[PAA‑bPS] and celluloseg‑[PAA‑b‑PEG]；（3）Based on solution phase synthesis, using a certain amount of brush bi-block copolymer as unimolecule template, with gold chloride（HAuCl4·3H2O）For precursor compound and tert-butylamine boron（TBAB）The golden rice rod of oil-dispersing property and water dispersible is prepared for reducing agent.
Description
Technical field
The preparation method with the size gold nanorods controllable with dispersiveness, category can be prepared on a large scale the present invention relates to a kind of
In multi-crossed disciplines fields such as high molecular reactive polymerization, functional polymer MOLECULE DESIGN and inorganic crystal growths.Particularly
It is unimolecule template to be related to one kind using bottle brush shape functional polymer, and a series of sizes are prepared by the method for crystal growth in situ
Controllable, draw ratio is controllable and dispersed controllable gold nanorods.
Background technology
After in 1984 Germany scientist Gleiter prepares nanocrystalline copper, iron, palladium for the first time, research
Nano material is increasingly becoming a study hotspot field.It in 1 ~ 100nm material is generally referred to as nanometer material to have one-dimensional dimensions above
Material.Under normal circumstances, the substantial amounts of free electron on the inside of the noble metal such as gold, silver and surface, can form free electron air mass.When
When incident light and its surface free electron resonance, surface plasma body resonant vibration can be formed.Shape, size, the surrounding of nano particle
The change of the factors such as environment dielectric constant, surface free electron frequency of oscillation can be caused to change.Its specificity in structure, gold
Nanometer rods have special optical property, make gold nanorods in biomedicine, sewage disposal, the information transmission technology and catalyst etc.
Aspect has broad application prospects.
The development of contemporary science and technology is changed, and largely relies on the generation of new material：Energy requirements new material has
Excellent energy conversion characteristic, the silicon plate material that can be converted solar energy into electrical energy such as in terms of photoelectricity；Information and date transmits
Memory requirement new material meets higher transmission speed, bigger storage density, while must also have certain stability；Aviation
Space flight requires that new material has bigger intensity, and smaller density generally also needs to good air-tightness, and high temperature resistant is resistance to
A series of materials that can remain to keep its characteristic under severe conditions such as high pressure.
Molecule rank InterWorking Equipment is the key for realizing high intensity logical operation and storage circuit.Nanometer rods can exactly be realized
The basic module of such interconnection.These nanometer rods are widely used in building nanoelectronic in sensor, waveguide and photonic propulsion
Equipment application.The chemical inertness and relatively low resistivity of gold, these attributes make ideal of the gold nanorods as connection molecule equipment
Material.It can be formed by CTAB and with a small amount of gold chloride in aqueous, or in oleic acid/oleyl amine organic solvent, it is a small amount of
Gold chloride simultaneously passes through Nano-porous Anodic Aluminum Oxide Template or other template generations.After generation, these gold nanorods can be with
It is assembled into by aquation or in the electric field on substrate.However, the gold nanorods obtained by this method are more crystalline phases
, surface is very coarse.Transmission research shows the resistivity of polycrystalline gold nanorods higher than gold.Therefore, the conjunction of monocrystalline gold nanorods
Into being significant.
In different subsciences, such as chemical catalysis, Nano medication, nanoelectronics etc., gold nanorods and other your gold
Category nanocrystal plays an important role.For most of applications, to the granule size and size distribution of nano material
Control it is most important.Many aspects in building-up process can have influence on the size distribution and granule size of nano material, such as
The concentration [[i]] of the selection of surfactant, acid-base value, temperature, reductant concentration, and other metal salts.
The gold nanorods of synthesis, self assembly can be brought it about by other method.The self assembly of gold nanorods can be
On one-dimensional, self assembly can be also carried out in two dimension.Likewise, also can three-dimensional self assembly.Research shows that the electric field of nano material increases
The structure of strong intensity and nano material, size, polarization and excitation wavelength have relation.Therefore, we can be by setting
Count the structure of nano-particle, size, shape etc. adjusts the resonance characteristics of surface plasma, and SERS unimolecules are improved with this
Detection sensitivity.
In recent years, gold nanorods are got over as SERS optical probe in the application of large biological molecule, treatment of cancer etc.
Come more extensive.Gold nanorods can be used to mark large biological molecule containing specific receptor, be realized with this to living body biological
Interior various active material dynamic analysis and quantitative analysis.Some organic dye molecules either polymer can also be wrapped in gold
Nanorod surfaces make SERS probes, and detection imaging is carried out to some positions of cell.Living imaging is one of gold nanorods
Application in important directions.Photo-thermal therapy is the application on the another direction of rising in recent years.It is it is possible, firstly, to SERS probes is defeated
It is sent at lesion cancer cell, then in the irradiation of resonant wavelength laser, the gold nanorods in probe can absorb a large amount of luminous energy, then
Heat energy generation high temperature is converted into kill sick cell.
The synthetic method of gold nanorods has many kinds, mainly there is four kinds, including：Photochemistry, crystal seed method, template and electrochemistry
Method etc..Although existing preparation method has successfully prepared gold nanorods, existing traditional synthetic method has a system
Limitation prepared by row, mainly including the following aspects：
（1）It is difficult to the accurate control to nanoparticle size；
（2）Isolate and purify process complexity, it is difficult to extensive to prepare；
（3）Preparation condition is harsh；
（4）The nanostructured heterogeneity of preparation；
（5）In order to next step application, it is necessary to do further surface ligand modification etc. to prepared monodimension nanometer material.
Science and technology problem for more than encountered in gold nanorods design synthesis, the present invention propose a kind of convenient
, the method with size with the controllable gold nanorods of dispersiveness can be prepared on a large scale.
The content of the invention
It is a kind of convenient present invention aims at providing, it can on a large scale prepare, there is the size Jenner controllable with dispersiveness
The preparation method of rice rod.
To realize the object of the invention, we use native cellulose as initial reaction raw material, continuous ATRP technologies, and
ATRP and " link " chemistry（Click Chemistry）The technology being combined, prepare a series of molecular weight and structure and composition
Controllable brush graft block copolymer, using the brush polymer as unimolecule functional template, it is controllable to prepare a series of length, long
Footpath is than controllable and dispersed controllable gold nanorods.
The synthetic method specifically comprises the following steps：（1）ATRP macromole evocating agents based on cellulosic molecule
（cellulose-Br）Preparation with classification use ionic liquid 1-allyl-3-methylimidazolium chloride
(AMIMCl) it is solvent, dry DMF and NMP are diluent and acid absorbent, with 2- bromine isobutyl acylbromide modified cellulose chains
Hydroxyl, it is switched to the macromole evocating agent available for ATRP.Because native cellulose has the molecular weight point of non-constant width
Cloth, in order to obtain the macromole evocating agent of narrow ditribution, the crude product of the macromole evocating agent of synthesis is carried out by fractional precipitation
Fractional precipitation, using acetone as solvent, deionized water prepares a series of macromolecular of different molecular weights and narrow ditribution as precipitating reagent
Initiator.And prepared macromole evocating agent is characterized using nuclear-magnetism, infrared and GPC.
（2）The preparation of scopiform block polymer：Using cellulose-Br as macromole evocating agent, continuous polymerization is utilized
ATRP technologies, trigger tert-butyl acrylate monomer respectively（tBA）, styrene monomer (St), it is PS to prepare a series of outermost sections
Brush bi-block copolymer：cellulose-g-[PAA-b- PS], and using cellulose-Br as macromole evocating agent,
The experimental method that comprehensive utilization ATRP technologies are combined with " link " chemistry, reunites by the simple function with alkynyl of end group modification
Ethylene glycol mPEG is the presoma of outermost section block, prepares a series of brush bi-block copolymer that outermost sections are PEG：
cellulose-g-[PAA-b-PEG]。
（3）The preparation of gold nanorods：Based on solution phase synthesis, with a number of cellulose-g-[PAA-b- PS] unimolecule template, prepare oil-soluble golden rice rod：First a certain amount of template molecule cellulose-g-[PAA-b-PS]
It is dissolved in good solvent（Such as DMF）, unimolecular micelle template solution is made, target material is next added in reaction system
Precursor compound gold chloride（HAuCl4·3H2O）（The mol ratio of acrylic acid repeat unit and gold chloride is 1 in template：
10）, the precursor compound is because core template phase PAA ligand complex acts on, so as to selective diffusion aggregation to PAA moulds
Plate phase, then add tert-butylamine boron（TBAB）For reducing agent（The mol ratio of reducing agent and gold chloride is 10：1）, 60oUnder the conditions of C
Reaction 2 hours, precursor compound are former as part in gold nanorods corresponding to template phase in-situ preparation, outermost PS phases
Position is covered in the surface of nanometer rods, and the nanometer rods of generation can be enable to be scattered in corresponding solvent（Such as toluene, tetrahydrochysene furan
Mutter, acetone etc.）, while prevent the nanometer rods from reuniting in organic solvent.With identical reaction condition, with cellulose-g-
[PAA-b- PEG] it is unimolecule template, water miscible gold is prepared using identical synthetic method, experiment condition and characterization method
Nanometer rods.
The present invention compared with prior art, has the following advantages that：（1）The mentality of designing of innovation：Different from by self assembly
The polymolecular micella soft template of the dynamic stability of formation, also different from the hard template with extremely limited surface area, this project according to
By activity polymerizating technology, careful design has the function brush graft copolymer of rigid linear chain structure, with the scopiform copolymer
Unimolecular micelle is the template of growth inorganic nanocrystal.The clear and definite function linear copolymer of structure is grafted on just by covalent bond
Property main polymer chain on, can be formed in good solvent steady stability and the unimolecular micelle knot with high grafting density
Structure.During template of the micellar structure of the steady stability as crystal growth, due to selected template gathering compound（PAA）To gold
Category ion has ligand complex ability, so after the structure of template determines with shape, the precursor compound of gold is added, in crystalline substance
Under conditions of required for body generation, you can form the gold nanorods structure consistent with shape of template.
（2）The research contents and research method of innovation：Applicant is the natural macromolecular fiber with rigid linear chain structure
Element introduces polymer template preparation system, and the rigid chain of cellulosic molecule, which is characterized as preparing, has linear chain structure monodimension nanometer material
Provide possibility.The Component units of cellulose are glucose so that each repeat unit has 3 on the large biological molecule main chain
Individual hydroxy functional group and in space multistory be distributed so that prepared brush polymer has very high grafting density and grafted chain
It is distributed in space multistory, a greater amount of precursor compounds is thus mutually adsorbed for template so as to form continuous, regular one
Dimension crystal structure provides possibility.In addition, prepare brush polymer template using ATRP active free radical polymerization means so that
The polymer architecture of preparation is clear and definite, and the controllable of molecular weight can be achieved in each component, so as to realize more chis to template polymer
Degree control.
Brief description of the drawings
Fig. 1：The synthesis schematic diagram of gold nanorods of the surface covered with PS.
Fig. 2：Gold nanorods TEM picture of the surface covered with PS（Diameter is about 10nm, and length is about 50nm）.
Fig. 3：Gold nanorods TEM picture of the surface covered with PS（Diameter is about 10nm, and length is about 100nm）.
Fig. 4：Gold nanorods EDS collection of illustrative plates of the surface covered with PS（Diameter is about 10nm, and length is about 100nm）.
Fig. 5：Gold nanorods XRD analysis of the surface covered with PS（Diameter is about 10nm, and length is about 100nm）.
Fig. 6：The synthesis schematic diagram of gold nanorods of the surface covered with water-soluble PEG.
Fig. 7：Gold nanorods TEM picture of the surface covered with PEG（Diameter is about 10nm, and length is about 100nm）.
Embodiment
Embodiment 1（Fig. 1）With reference to embodiment, the invention will be further described, but present invention is not limited in
This.
（1）ATRP macromole evocating agents based on cellulosic molecule（cellulose-Br）Preparation and classification：
In 250mL single-necked flasks, 10g native celluloses are added, are dissolved in 100mL ionic liquids 1-allyl-3-
In methylimidazolium chloride (AMIMCl), after being completely dissolved, 10mL dry DMFs and 10mL are separately added into
NMP is diluent and acid absorbent, is cooled under the conditions of zero degree and 50mL 2- bromine isobutyl acylbromides are slowly added dropwise within 1 hour,
Hydroxyl on modified cellulose chain is modified, it is switched to the macromole evocating agent available for ATRP.Then heat up naturally
To room temperature（25oC）, react 24 hours at ambient temperature.It is finally precipitating reagent with 500mL deionized waters, tated end product.
Then using 50mL acetone as solvent, using 500mL deionized waters as precipitating reagent repurity once, be finally putting into vacuum drying oven, 50oC
Under the conditions of 24 hours, yield 87%.Because native cellulose has the molecular weight distribution of non-constant width, in order to obtain narrow ditribution
Macromole evocating agent, fractional precipitation is carried out to the crude product of the macromole evocating agent of synthesis by fractional precipitation, using acetone to be molten
Agent, deionized water prepare a series of macromole evocating agent of different molecular weights and narrow ditribution as precipitating reagent.
（2）The preparation of scopiform block polymer：Using cellulose-Br as macromole evocating agent, continuous polymerization is utilized
ATRP technologies, trigger tert-butyl acrylate monomer respectively（tBA）, styrene monomer (St), it is PS to prepare a series of outermost sections
Brush bi-block copolymer：cellulose-g-[PAA-b-PS].It is specific as follows.
（a）cellulose-g-PtBA preparation：Pass through ATRP polymerization machine by macromole evocating agent of cellulose-Br
Reason triggers tert-butyl acrylate monomer（tBA）Process it is as follows：Be separately added into 50mL ampoule bottles CuBr (58.3 mg,
0.4 mmol), PMDETA (70.3 mg, 0.4 mmol), cellulose-Br (Mn = 11.2K g/mol, 0.25
G, 0.021 mmol), tert-butyl acrylatetBA (3 mL, 21 mmol), acetone (3.0mL), reaction system passes through cold
Freeze-vacuumizing-and lead to nitrogen-thaw cycles three times, be placed in 60 DEG C of oil baths and react after closed.Then, by between the regular hour
Every taking out ampoule bottle respectively, and put into liquid nitrogen, with terminating reaction.After crude product is diluted in tetrahydrofuran, in neutral oxygen
Change in aluminium column packing and be filtered to remove the impurity such as colored bivalent cupric ion, lurid filtrate is obtained, in normal heptane after concentration
Middle precipitation, repeat dissolution/precipitation operation and obtain thick pale yellow product afterwards twice, be dried in vacuo 12 hours at 40 DEG C.
（b）cellulose-g-[PtBA-b- PS] preparation：By polyfunctional group cyclic macromolecular initiator cellulose-g-PtBA triggers the process of styrene polymerization as follows by ATRP polymerization mechanism：CuBr is separately added into a collection of 50mL ampoule bottles
(54.6 mg, 0.38 mmol), PMDETA (70.3 mg, 0.4 mmol), cellulose-g-PtBA (each PtBA
Arm molecular weight Mn=8.6K g/mol;0.2 g, 0.017 mmol), St (8 mL, 69.8 mmol), reaction system is put
By freezing-vacuumizing degassing-thaw cycles three times in liquid nitrogen, it is placed in 90 DEG C of oil baths and reacts after closed.Then one is pressed
Fixed time interval takes out ampoule bottle respectively, and is put into liquid nitrogen, terminating reaction.Crude product dichloromethane dissolved dilution
Afterwards, by neutral alumina pillar, to remove the impurity such as colored bivalent cupric ion, then precipitated in cold methanol.Weight
After redissolving solution/precipitation operation twice, gained white powder product is placed at 35 DEG C and is dried in vacuo 12 hours.
（c）cellulose-g-[PAA-b- PS] preparation：Polymer cellulose-g-[PtBA-b-PS] (0.3g)
It is dissolved in 30mL dichloromethane, 0oC is stirred vigorously lower addition trifluoroacetic acid (in 5 times of brush polymerstThe thing of BA units
The amount of matter), 0oAfter C is kept for 3 hours, continue stirring reaction at room temperature 21 hours.With the progress of hydrolysis, occur
White depositions, after having reacted, filtering, and rinsed with dichloromethane, sediment is dissolved in two containing a small amount of absolute methanol
(absolute methanol in the ring of oxygen six：Dioxane=1：10) in, the polymer of white is obtained by vacuum freeze drying
cellulose-g-[PAA-b-PS]。
（3）The preparation of the gold nanorods of oil-dispersing property（Fig. 2, Fig. 3, Fig. 4 and Fig. 5）：Weigh 10 mg bottle brush-like structures
cellulose-g-[PAA-b- PS] template, it is dissolved at ambient temperature in 10mL DMF, next adds the presoma of gold
Compound (HAuCl43H2O; 0.2548 g).Purpose is mutually completely filled in order to PAA templates, next in reactant
The precursor compound gold chloride of excessive target material is added in system（HAuCl4·3H2O）（Acrylic acid repeat unit in template
Mol ratio with gold chloride is 1：10）, the precursor compound is because core template phase PAA ligand complex acts on, so as to select
Property diffusion aggregation to PAA template phases, then add tert-butylamine boron（TBAB）For reducing agent（Mole of reducing agent and gold chloride
Than for 10：1）, 60oReacted 2 hours under the conditions of C, precursor compound is in gold nanorods, outermost corresponding to template phase in-situ preparation
The PS phases of layer are covered in the surface of nanometer rods, the nanometer rods of generation can be enable to be scattered in corresponding solvent as part, original position
In（Such as toluene, tetrahydrofuran, acetone etc.）, while prevent the nanometer rods from reuniting in organic solvent.Removed with low speed centrifuge
Remove accessory substance（Rotating speed is that 1000 rpm are centrifuged 5 minutes）, the gold nanorods after purification that finally obtain are 0.0670 g, yield
52.6%。
Embodiment 2（Fig. 6）The preparation of the gold nanorods of water dispersible.
（1）The preparation of scopiform block polymer：Using cellulose-Br as macromole evocating agent, ATRP skills are comprehensively utilized
Art is the simple function group polyethylene glycol mPEG with alkynyl as most using end group modification with the experimental method that is combined of " link " chemistry
The presoma of outer section of block, prepare a series of brush bi-block copolymer that outermost sections are PEG：cellulose-g-[PAA-b-PEG]。
（a）End group is the mPEG of alkynyl preparation：By nucleophilic substitution, mPEG that end group is alkynyl is prepared (i.e.
MPEG-propargyl), the mPEG of two kinds of molecular weight used（Not to beMn=5,000 and Mn=10,000）.Specific steps
It is as follows：In 250mL three-necked flask, add 10g end groups for the drying of hydroxyl mPEG (10.0 g, 2.0
Mmol), 150 milliliters of dry tetrahydrofuran THF is then added, whole process is all carried out under argon gas protection.Then in solution
In be slowly added to benzhydryl sodium, until the color of reaction system is changed into brownish red.Then under conditions of ice bath, in reactant
The propargyl bromide reagent for being slowly added to 10mmol is added in system, then reaction system is warming up to room temperature（25oC）, it is small to continue reaction 24
When.Crude product adds 100mL dchloromethanes, then crosses neutral alumina pillar to remove accessory substance sodium salt.Then it is whole
After reaction product solution concentration, precipitated in cold ether.50oC vacuum drying ovens are dried, and obtain white powder.Another molecule
Measure as 10, the modification of 000 g/mol mPEG samples, and with identical method.
End group is the cellulose- of azido groupg-(PtBA-N3 synthesis)：Scopiform polymer cellulose-g-
(PtBA-Br) BBCP (1.0 g) is dissolved in the DMF of 20mL dryings, adds quantitative sodium azide solid powder
(cellulose-g-(PtBA-Br terminal bromine atoms and the mol ratio of sodium azide) are 1:10).Room temperature reaction 24 hours.So
50mL dchloromethane reaction systems are added afterwards, are crossed neutral alumina pillar and are removed accessory substance.Then products therefrom spend from
Son washing three times, is then dried with anhydrous magnesium sulfate, is precipitated after solution concentration in the mixed solution of first alcohol and water（Volume ratio is
1 to 1）.Vacuum drying oven is placed 6 hours under the conditions of final product 40oC.
With click chemistry synthesis brush polymer cellulose-g-[PtBA-b-PEG]：Synthesized using click chemistry means
A series of brush polymer cellulose-g-[PtBA-b-PEG].Specific reaction scheme is as follows：In the ampoule bottle that 50mL is dried
Reactant needed for middle addition（cellulose-g-(Pt), BA-N3 mPEG-alkyne, CuBr, PMDETA and solvent
DMF）.Cellulose-g-(PtBA-N3) azido group in polymer, mPEG-alkyne, CuBr and PMDETA mole
Than for 1:2 : 10 : 10.Reaction system is put in liquid nitrogen by freezing-vacuumizing degassing-thaw cycles three times, closed
After be placed in 90 DEG C of oil baths anti-24 hours.After crude product is diluted in tetrahydrofuran, it is filtered to remove in neutral alumina column packing
The impurity such as colored bivalent cupric ion, lurid filtrate is obtained, precipitated after concentration in cold methanol, repeat to dissolve/sink
Operation of forming sediment obtains thick pale yellow product afterwards twice, is dried in vacuo 12 hours at 60 DEG C.
（d）cellulose-g-[PAA-b- PEG] preparation：Polymer cellulose-g-[PtBA-b-PEG]
(0.3g) is dissolved in 30mL dichloromethane, 0oC is stirred vigorously lower addition trifluoroacetic acid (in 5 times of brush polymerstBA is mono-
The amount of the material of member), 0oAfter C is kept for 3 hours, continue stirring reaction at room temperature 21 hours.With the progress of hydrolysis,
There are white depositions, after having reacted, filtering, and rinsed with dichloromethane, sediment is dissolved in containing on a small quantity without water beetle
(absolute methanol in the dioxane of alcohol：Dioxane=1：10) in, the polymer of white is obtained by vacuum freeze drying
cellulose-g-[PAA-b-PEG]。
（3）The preparation of the gold nanorods of water dispersible（Fig. 7）：Weigh the cellulose- of 10 mg bottle brush-like structuresg-
[PAA-b- PEG] template, it is dissolved at ambient temperature in 10mL DMF, next adds the precursor compound of gold
(HAuCl4·3H2O; 0.2548 g).Purpose is mutually completely filled in order to PAA templates, is next added in reaction system
The precursor compound gold chloride of excessive target material（HAuCl4·3H2O）（Acrylic acid repeat unit and gold chloride in template
Mol ratio be 1：10）, the precursor compound is because core template phase PAA ligand complex acts on, so as to the diffusion of selectivity
PAA template phases are gathered, then add tert-butylamine boron（TBAB）For reducing agent（Mole of 0.1416g, reducing agent and gold chloride
Than for 10：1）, 60oReacted 2 hours under the conditions of C, precursor compound is in gold nanorods, outermost corresponding to template phase in-situ preparation
The PEG phases of layer are covered in the surface of nanometer rods, the nanometer rods of generation can be enable to be scattered in the aqueous solution as part, original position,
Prevent the nanometer rods from reuniting in organic solvent simultaneously.Accessory substance is removed with low speed centrifuge（Rotating speed is 1000 rpm centrifugations 5
Minute）, the gold nanorods after purification that finally obtain are 0.0725 g, yield 56.9%.
Claims (3)
1. a kind of can prepare the method with the size gold nanorods controllable with dispersiveness on a large scale, it is characterised in that including such as
Lower step：
（1）Ionic liquid 1-allyl-3-methylimidazolium chloride (AMIMCl) are used as solvent, anhydrous dimethyl
Base formamide（DMF）And 1-METHYLPYRROLIDONE（NMP）For diluent and acid absorbent, modified with 2- bromine isobutyl acylbromides natural
Hydroxyl on cellulose chain, it is set to switch to can be used for ATRP（ATRP）Macromole evocating agent；
（2）Using cellulose-Br as macromole evocating agent, using the ATRP technologies of continuous polymerization, trigger acrylic acid uncle respectively
Butyl ester monomer（tBA）, styrene monomer (St), prepare a series of outermost sections be PS brush bi-block copolymer：
cellulose-g-[PAA-b-PS]；Using cellulose-Br as macromole evocating agent, comprehensive utilization ATRP technologies and " chain
Connect " experimental method that is combined of chemistry is outermost section block using end group modification as the simple function group polyethylene glycol mPEG with alkynyl
Presoma, prepare a series of outermost sections be PEG brush bi-block copolymer：cellulose-g-[PAA-b-PEG]；
（3）Based on solution phase synthesis, with a number of cellulose-g-[PAA-b- PS] unimolecule template, prepare
Oil-soluble golden rice rod.
2. according to the method for claim 1, it is characterised in that based on solution phase synthesis, with a number of
cellulose-g-[PAA-b- PS] unimolecule template, oil-soluble golden rice rod is prepared, target material is added in reaction system
Precursor compound gold chloride（HAuCl4·3H2O）, then add tert-butylamine boron（TBAB）For reducing agent, 60oIt is anti-under the conditions of C
Answer 2 hours.
3. according to the method for claim 2, it is characterised in that the mol ratio of acrylic acid repeat unit and gold chloride in template
For 1：10；The mol ratio of reducing agent and gold chloride is 10：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610501110.5A CN107552807B (en) | 2016-06-30 | 2016-06-30 | Preparation method capable of preparing gold nanorods with controllable size and dispersibility on large scale |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610501110.5A CN107552807B (en) | 2016-06-30 | 2016-06-30 | Preparation method capable of preparing gold nanorods with controllable size and dispersibility on large scale |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107552807A true CN107552807A (en) | 2018-01-09 |
| CN107552807B CN107552807B (en) | 2020-01-17 |
Family
ID=60969460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610501110.5A Active CN107552807B (en) | 2016-06-30 | 2016-06-30 | Preparation method capable of preparing gold nanorods with controllable size and dispersibility on large scale |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107552807B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109431831A (en) * | 2018-12-26 | 2019-03-08 | 郑州科斗科技有限公司 | A kind of gold nano-negative ion facial mask liquid of Whitening, spot, facial mask and preparation method thereof |
| CN109793515A (en) * | 2019-01-31 | 2019-05-24 | 中国科学院电工研究所 | A kind of conductive particles imaging method and signal supervisory instrument |
| CN110182768A (en) * | 2019-05-21 | 2019-08-30 | 南京工业大学 | A method of CdSe nanometer rods are formed by templating self-assembly of grafting block polymer |
| CN111876757A (en) * | 2020-06-28 | 2020-11-03 | 华南理工大学 | Preparation method of inorganic two-dimensional nano material based on plane patterning polymer brush |
| CN112592431A (en) * | 2020-12-16 | 2021-04-02 | 陈凤春 | Degradable cellulose grafted acrylic acid-based high-water-absorptivity hydrogel and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103945966A (en) * | 2011-09-23 | 2014-07-23 | 南洋理工大学 | Methods for forming gold nanowires on a substrate and gold nanowires formed thereof |
| CN105441069A (en) * | 2015-11-17 | 2016-03-30 | 大连理工大学 | Method for synthesizing high-fluorescent alloy nano cluster by taking small molecules as template |
| CN105618730A (en) * | 2014-10-28 | 2016-06-01 | 深圳先进技术研究院 | Small-size gold nanorod and preparation method and applications thereof |
-
2016
- 2016-06-30 CN CN201610501110.5A patent/CN107552807B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103945966A (en) * | 2011-09-23 | 2014-07-23 | 南洋理工大学 | Methods for forming gold nanowires on a substrate and gold nanowires formed thereof |
| CN105618730A (en) * | 2014-10-28 | 2016-06-01 | 深圳先进技术研究院 | Small-size gold nanorod and preparation method and applications thereof |
| CN105441069A (en) * | 2015-11-17 | 2016-03-30 | 大连理工大学 | Method for synthesizing high-fluorescent alloy nano cluster by taking small molecules as template |
Non-Patent Citations (2)
| Title |
|---|
| HU, HAO ET AL.: "Gold nanoparticle-conjugated heterogeneous polymer brush-wrapped cellulose nanocrystals prepared by combining different controllable polymerization techniques for theranostic applications", 《POLYMER CHEMISTRY》 * |
| 陈熙: "金纳米粒子和嵌段共聚物新型复合胶束的制备及性能研究", 《读秀》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109431831A (en) * | 2018-12-26 | 2019-03-08 | 郑州科斗科技有限公司 | A kind of gold nano-negative ion facial mask liquid of Whitening, spot, facial mask and preparation method thereof |
| CN109793515A (en) * | 2019-01-31 | 2019-05-24 | 中国科学院电工研究所 | A kind of conductive particles imaging method and signal supervisory instrument |
| CN109793515B (en) * | 2019-01-31 | 2022-08-02 | 中国科学院电工研究所 | Electric particle imaging method and signal detection device |
| CN110182768A (en) * | 2019-05-21 | 2019-08-30 | 南京工业大学 | A method of CdSe nanometer rods are formed by templating self-assembly of grafting block polymer |
| CN110182768B (en) * | 2019-05-21 | 2022-12-16 | 南京工业大学 | Method for forming CdSe nanorod by self-assembly by taking grafted block polymer as template |
| CN111876757A (en) * | 2020-06-28 | 2020-11-03 | 华南理工大学 | Preparation method of inorganic two-dimensional nano material based on plane patterning polymer brush |
| CN112592431A (en) * | 2020-12-16 | 2021-04-02 | 陈凤春 | Degradable cellulose grafted acrylic acid-based high-water-absorptivity hydrogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107552807B (en) | 2020-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107552807A (en) | It is a kind of to prepare the preparation method with the size gold nanorods controllable with dispersiveness on a large scale | |
| Qiu et al. | The marriage of aggregation‐induced emission with polymer science | |
| Hailes et al. | Polyferrocenylsilanes: synthesis, properties, and applications | |
| CN107552806A (en) | A kind of preparation method with the size Fe3O4@Au core@shell structure nanorod controllable with dispersiveness that can be prepared on a large scale | |
| Müllner et al. | Template-directed mild synthesis of anatase hybrid nanotubes within cylindrical core–shell–corona polymer brushes | |
| CN102328095B (en) | Preparation method of metal silver nanowires with adjustable length and diameter | |
| Kynaston et al. | Uniform polyselenophene block copolymer fiberlike micelles and block co-micelles via living crystallization-driven self-assembly | |
| CN104211127B (en) | A kind of α-Fe 2o 3the preparation method of hollow microsphere | |
| Song et al. | Uniform 1D micelles and patchy & block comicelles via scalable, one-step crystallization-driven block copolymer self-assembly | |
| Song et al. | Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes | |
| CN107189072B (en) | Janus rod-like nano material and preparation method thereof | |
| CN102963898A (en) | Preparation method of dual-functional group organically modified montmorillonite | |
| Mugemana et al. | Functionalized nanoporous thin films from metallo-supramolecular diblock copolymers | |
| Jiang et al. | Charge-transfer resonance and surface defect-dominated WO3 hollow microspheres as SERS substrates for the miRNA 155 assay | |
| CN104014815A (en) | Cobalt-based amorphous nanometer wave-absorbing material and synthetic method of cobalt-based amorphous nanometer wave-absorbing material | |
| CN101875708A (en) | Preparation method of cagelike silsesquioxane-contained polymethyl methacrylate hybrid material | |
| Huang et al. | Self-assembly of 2D nanosheets into 3D dendrites based on the organic small molecule ANPZ and their size-dependent thermal properties | |
| Baute et al. | Properties of the silica layer during the formation of MCM-41 studied by EPR of a silica-bound spin probe | |
| CN100534907C (en) | Zinc oxide synthesizing process | |
| CN103755849B (en) | A kind of preparation method of CNT-polysilane-organic polymer composite | |
| CN105111233A (en) | Preparation method of octaphenyl silsesquioxane | |
| CN106279677B (en) | Rich in heteroatomic phosphine amidine quasi polymer and prepares the multicomponent polymerization of the polymer and apply | |
| Dai et al. | Tuning Dimensionality of Benzimidazole Aggregates by Using Tetraoctylammonium Bromide: Enhanced Electrochemiluminescence Studies | |
| Lu et al. | Controllable synthesis of hierarchical polysilsesquioxane surfaces: From spheres-on-sphere to bowls-on-sphere structure | |
| Xue et al. | Controlled fabrication of polypyrrole capsules and nanotubes in the presence of Rhodamine B |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 450001, Henan, Zhengzhou province hi tech Park Road 11, Henan Provincial University of science and technology incubator, building 2, block B, building 17 Applicant after: Zhengzhou science and Technology Co., Ltd. bracket Address before: 450001, Henan, Zhengzhou province hi tech Park Road 11, Henan Provincial University of science and technology incubator, building 2, block B, building 17 Applicant before: Zhengzhou Kedou Chuangke Technology Co., Ltd. |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |