CN109913200A - A kind of nano material and preparation method thereof with magnetism and fluorescent dual function - Google Patents
A kind of nano material and preparation method thereof with magnetism and fluorescent dual function Download PDFInfo
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Abstract
The invention discloses a kind of with magnetic and fluorescent dual function nano material and preparation method thereof, belongs to technical field of nano material.The present invention first uses sodium lignin sulfonate to mix with metal salt mixture, the sodium lignin sulfonate with magnetic particle is made by reacting, sodium lignin sulfonate with magnetic particle is mixed with through dopamine with the resulting carbon quantum dot of ammonium chloride after halogenated hydrocarbons mixes, freeze-drying, obtain blank, by blank after coagulating bath and formaldehyde treated, the nano material with magnetic and fluorescent dual function is made.It is prepared by the present invention that there is long-acting magnetism and fluorescence property with magnetic and fluorescent dual function nano material, and the dispersibility of product is preferably.
Description
Technical field
It is specifically a kind of that there is magnetic and fluorescent dual function nano material the present invention relates to technical field of nano material
And preparation method thereof.
Background technique
With further going deep into for nanotechnology research, the requirement to nano material is from monodispersity, the control of pattern
System is changed into the multi-component composite nanometer particle of building.It is combined a variety of different materials one by the methods of surface epitaxial growth
It rises, becomes the new hot spot of nanoscale science and technology research.Compared to the nano particle of one-component, multi-functional nanometer material is simultaneously
Have a variety of excellent performances, preferably solve physical presence have a single function make some nano materials using restricted
Problem, multi-functional nanometer material is fast-developing with its excellent performance, is more and more widely used different fields.Wherein,
Fluorescent material and magnetic material are received significant attention because it is in the extensive use of biochemical and medical domain.
Quantum dot is crystallite of the size in 1-100nm, is usually made of II-VI in the periodic table of elements or iii-v atom,
By adjusting particle size, the quantum dot of different fluorescence emission wavelengths can be obtained.Compared with traditional organic fluorescent dye, amount
Son, which is put, has adjustable fluorescence emission wavelengths, narrow and symmetrical fluorescence emission spectrum, wide and continuous ultra-violet absorption spectrum, and
Preferable photochemical stability.Currently, fluorescence quantum has been widely used in biological fluorescent labeling, biomedical imaging and is immunized
The fields such as detection and analysis.Ideal magnetic fluorescent microspheres require higher specific saturation magnetization, can generate it is stronger glimmering
Light and fluorescent stability is good, Microsphere Size is controllable, particle diameter distribution is narrow, chemical stability is good, surface function base rich in
Group, and the features such as preparation process is simple, repeatability is good, cheap, it acts not only as mri contrast agent and is used for
Medical diagnosis on disease is also used as separation of the pharmaceutical carrier for disease treatment and various albumen, cell etc..If by magnetic and
Fluorescent characteristic is dissolved in the composite nanoparticle for integrally preparing magnetic and fluorescent dual function, will be in biomarker, fluorescence immunoassay
Analysis, bio-separation, protein D NA enrichment with separate, the fields such as the preparation of medicine-carried system and target imaging are with very big application
Potentiality.
The preparation method of magnetic fluorescent nanometer particle mainly include coated with silica, polymer overmold, kind crystals growth with
And coupling method.However, in its preparation process generally existing quantum dot fluorescent quenching phenomenon.According to the literature, quantum is caused
The reason of point fluorescent quenching is main, and there are two aspects, are on the one hand the photochemical stabilities of quantum dot itself, due to application environment
Complexity, quantum dot stability is vulnerable to surrounding environment influence；It on the other hand is the influence of magnetic nano-particle, including the strong of magnetic
Absorption and magnetic-particle and quantum dot between fluorescence resonance energy transfer effect.
In the prior art, patent No. CN103525405A " the magnetic fluorescent dual-function nano material based on natural polymer
And preparation method thereof " one kind is disclosed using magnetic particle ferroso-ferric oxide as core, chitosan and polyanionic cellulose are shell
Layer material obtains magnetic fluorescence by LBL self-assembly method using the fluorescein isothiocynate of Chitosan-coated as fluorescent material
Particle, patent No. CN102020258A " a kind of preparation method of magnetic fluorescence hydroxyapatite nanocomposite structure " disclose one
Kind instills magnetism by control calcium/europium molar ratio, by the mixed solution of calcium nitrate and europium nitrate, ammonium dibasic phosphate solution simultaneously
Nano-particle solution is vigorously stirred down and obtains brown color precipitating, the magnetic of magnetic fluorescence hydroxyapatite nanocomposite structure is made
Property particle.But the generally existing magnetic particle of magnetic fluorescent nanometer particle prepared in the prior art is dispersed during the preparation process
It is bad, cause product saturation magnetic intensity not high, magnetic particle is easily contacted with fluorescent particles, so as to cause fluoride ions quenching, and
And the magnetic fluorescent nanometer particle intensity by being self-assembly of is lower, easily makes magnetic particle and fluorescent particles in use
The problem of being lost, product magnetism and fluorescence property caused to weaken.
Therefore, research and development has biocompatibility, and still has preferable magnetic strength after a period of use in product
The dual-function nano particle of degree and fluorescence property has important value.
Summary of the invention
For traditional technology there are the shortcomings that, the present invention provides a kind of with magnetic and fluorescent dual function nanometer material
Material and preparation method thereof.
To achieve the above object, the invention provides the following technical scheme:
A kind of nano material with magnetism and fluorescent dual function, which is characterized in that the dual-functional nanometer material mainly wraps
Include the raw material components of following parts by weight: 25 ~ 40 parts of sodium lignin sulfonates, 4 ~ 10 parts of halogenated hydrocarbons, 10 ~ 14 parts of metal salt mixing
Object, 8 ~ 10 parts of modified carbon quantum dots, sodium lignin sulfonate have good biocompatibility, and contain a large amount of activity in strand
Group, after being mixed with metal salt mixture, adsorbable iron ion and ferrous ion, and under the modification of halogenated hydrocarbons, by iron from
The ferroso-ferric oxide that son and ferrous ion are formed is fixed in three-dimensional network, to reduce the stream of magnetic particle in use process
It loses, and can avoid contacting with the direct of fluorescent particles after the sodium lignin sulfonate three-dimensional network that is modified is fixed, to keep long
The fluorescence property of effect.
A kind of nano material with magnetism and fluorescent dual function, which is characterized in that described that there is magnetic and fluorescence pair
The nano material of weight function further includes the raw material components of following parts by weight: 3 ~ 8 parts of formaldehyde, the addition of formaldehyde can make to pass through electrostatic
The modified sodium lignosulfonate that power is adsorbed on carbon modified quantum dot surface crosslinks, to improve the intensity of product, reduction makes
With the loss of fluoride ions in the process and magnetic particle.
As optimization, halogenated hydrocarbons 1,6- dibromo-hexane or 1, any one in 3- dibromopropane, the addition of halogenated hydrocarbons can
The network for making sodium lignin sulfonate form increasingly complex three-dimensional cross-linked network, and forming sodium lignin sulfonate has preferable
Intensity, while there is preferable dispersibility after forming nanoparticle.
As optimization, metal salt mixture is green vitriol and ferric chloride hexahydrate 1.00:1.75 in molar ratio
Mixed mixture, the modified carbon quantum dot are by carbon quantum dot through dopamine and ammonium chloride gained, carbon quantum dot
Positive charge is being had by the modification rear surface of dopamine and ammonium chloride, is easily passing through electrostatic force knot with modified sodium lignosulfonate
It closes.
As optimization, dual-functional nanometer material includes the raw material components of following parts by weight: 35 parts of sodium lignin sulfonates, and 8
Part halogenated hydrocarbons, 12 parts of metal salt mixtures, 8 parts of modified carbon quantum dots and 6 parts of formaldehyde.
As optimization, there is the preparation method of magnetic and fluorescent dual function nano material the following steps are included:
(1) sodium lignin sulfonate is mixed with the aqueous solution of metal salt mixture, after being stirred to react under atmosphere of inert gases, then
It is stirred to react under alkaline condition；
(2) step (1) obtained material is mixed with halohydrocarbon solution, and potassium iodide is added, after being stirred to react, extracted, filtering；
(3) carbon quantum dot solution is made through pyroreaction in citric acid, by carbon quantum dot solution and dopamine hybrid reaction, thoroughly
Analysis, and mixed with ammonium chloride, it is stirred to react, concentrated by rotary evaporation；
(4) step (2) obtained material is mixed with step (3) obtained material, is freeze-dried, blank is obtained, by blank and coagulating bath
After hybrid reaction, and formaldehyde is added, is stirred to react, filters, it is dry；
(5) index analysis is carried out to step (4) products obtained therefrom.
As optimization, there is the preparation method of magnetic and fluorescent dual function nano material to mainly comprise the steps that
(1) metal salt mixture is mixed with water 1:10 in mass ratio, and 2 ~ 4 times of metal salt mixture quality of lignin is added
Sodium sulfonate after being stirred to react, adjusts pH to 10 ~ 11, continues to be stirred to react in nitrogen atmosphere；
(2) step (1) obtained material is mixed to the mixing of 10:1 ~ 10:2 in mass ratio with halohydrocarbon solution, and step (1) institute is added
The potassium iodide for obtaining 0.01 ~ 0.02 times of material mass, after being stirred to react, obtains modified sodium lignosulfonate solution blank, by innovation wood
Quality sodium sulfonate solution blank petroleum ether extraction, removes extra halogenated hydrocarbons, and oil removing phase is gone in filtering；
(3) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, 5 are stirred to react under conditions of being 200 ~ 220 DEG C in temperature ~
After 8h, centrifuge separation takes upper liquid, and dialyse 10 ~ 30h in bag filter, carbon quantum dot solution is obtained, by carbon quantum dot solution and more
Bar amine 4:1 in mass ratio mixing, is stirred to react, and after the 8 ~ 10h that dialyses in bag filter, obtains carbon modified quantum dot solution blank, will
Carbon modified quantum dot solution blank is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, after being stirred to react, concentrated by rotary evaporation；
(4) step (2) obtained material is mixed with step (3) obtained material 40:1 ~ 45:1 in mass ratio, it is cold after being stirred to react
It is lyophilized dry, obtains blank, blank is mixed with coagulating bath 1:5 ~ 1:8 in mass ratio, after being stirred to react, adds blank quality 0.08
~ 0.12 times of formaldehyde after being stirred to react, filters, dry；
(5) index analysis is carried out to step (4) products obtained therefrom.
As optimization, step (2) halohydrocarbon solution is to mix halogenated hydrocarbons with dehydrated alcohol 1:3 in mass ratio, is obtained
Halohydrocarbon solution.
As optimization, step (3) described bag filter is the bag filter that molecular cut off is 1000 or molecular cut off is
Any one in 1200 bag filter.
As optimization, step (4) described coagulating bath is the ethanol water that mass fraction is 90%.
Compared with prior art, beneficial effects of the present invention make:
(1) present invention used first when preparation has magnetic and fluorescent dual function nano material sodium lignin sulfonate as
The fixation material of magnetic particle, sodium lignin sulfonate have good biocompatibility, and three-dimensional net structure rich in
It can be by iron ion and ferrous particle absorption in the three of sodium lignin sulfonate after being mixed with metal salt mixture with active group
It ties up in network structure, thus, magnetic particle can be uniformly fixed on to the network knot of sodium lignin sulfonate when forming magnetic particle
In structure, and then make the product of preparation that there is stronger saturation magnetic intensity, and show preferable superparamagnetism, secondly, of the invention
It the use of sodium lignin sulfonate is being also to be modified with halogenated hydrocarbons to sodium lignin sulfonate, sodium lignin sulfonate is after modification
Can make sodium lignin sulfonate three-dimensional crosslinked network structure is complicated change, to improve reservation of the magnetic particle after being used for a long time
Rate, and due to the presence of complex three-dimensional network, the product that the later period can be made to prepare has preferable intensity, while can be by magnetic particles
Son is preferably separated with carbon quantum dot, and prevents the loss of carbon quantum dot in use, makes product with long-acting glimmering
Photosensitiveness；
(2) present invention is modified carbon quantum dot when preparation has magnetic and fluorescent dual function nano material, and
Formaldehyde is added when preparing product in later period, on the one hand, after modification, surface can be adsorbed carbon quantum dot under the action of dopamine
A large amount of ammonium ions can be under the action of electrostatic force, by modified sodium lignosulfonate after mixing with modified sodium lignosulfonate
It is adsorbed in carbon modified quantum dot surface, to be formed to be modified carbon quantum dot as core, modified sodium lignosulfonate is the nanometer of shell
Particle, and due to the lesser reason of carbon quantum dot, it is wooden that part carbon quantum dot can be adsorbed in modification under the action of electrostatic force
In the cross-linked network structure of plain sodium sulfonate, and then it is effectively prevent the loss of carbon quantum dot, makes product that there is long-acting fluorescence property,
On the other hand, the later period is handled product using formaldehyde, and modified sodium lignosulfonate can be made to crosslink reaction, to improve
The intensity of product, and then effectively extend the magnetism and fluorescence property of product.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
In order to which clearer explanation method provided by the invention is described in detail by following embodiment, in following implementation
The test method with each index of magnetic and fluorescent dual function nano material made in example is as follows:
Dispersibility: with projection electron microscope measure each embodiment obtained by have magnetic and fluorescent dual function nano material and
The partial size of comparative example product；
Saturation magnetic intensity: measured respectively with magnetometer obtained by each embodiment have magnetic and fluorescent dual function nano material and
The saturation magnetic intensity of comparative example product；
Fluorescence: measuring each embodiment gained with fluophotometer has magnetic and fluorescent dual function nano material and comparison
The fluorescence intensity of example product；
Long-term effect；To be measured respectively with magnetometer obtained by each embodiment have magnetic and fluorescent dual function nano material with it is right
Ratio product in 0.9% sodium chloride solution, in temperature be 40 DEG C, revolving speed be 380r/min under conditions of be stirred 6h after,
Respectively with magnetometer and fluophotometer measure each embodiment obtained by have magnetic and fluorescent dual function nano material with it is right
The saturation magnetic intensity and fluorescence intensity of ratio product.
Embodiment 1:
A kind of functional nano material of tool specifically includes that 35 parts of sodium lignin sulfonates, 8 parts of 1,6- dibromos according to parts by weight
Hexane, 12 parts of metal salt mixtures, 8 parts of modified carbon quantum dots and 6 parts of formaldehyde.
A kind of preparation method of nano material with magnetism and fluorescent dual function, described kind has magnetic and fluorescent dual
The preparation method of nano material of function mainly comprises the steps that
(1) metal salt mixture and water 1:10 in mass ratio are mixed in flask, and metal salt mixture is added into flask
The sodium lignin sulfonate that 3 times of quality is passed through nitrogen into flask with the rate of 35mL/min, is 70 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 4h, the pH to 10 ~ 11 of material in flask is adjusted, continuing at temperature is 70 DEG C, revolving speed
Under conditions of 300r/min, it is stirred to react for 24 hours；
(2) step (1) obtained material and 1,6- dibromo-hexane solution are mixed 10:1 in mass ratio to mix, and step (1) is added
The potassium iodide that 0.02 times of obtained material quality, in temperature be 80 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react 8h,
Modified sodium lignosulfonate solution blank is obtained, by modified sodium lignosulfonate solution blank petroleum ether extraction 6h, it is extra to remove
1,6- dibromo-hexane, filtering, goes oil removing phase；
(3) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, after being stirred to react 8h under conditions of being 200 DEG C in temperature, in
After revolving speed is centrifugated 10min under conditions of being 3000r/min, upper liquid is taken, dialyses in bag filter for 24 hours, obtains carbon quantum dot
Solution mixes carbon quantum dot solution with dopamine 4:1 in mass ratio, is 40 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 3h after, in bag filter dialyse 8h after, carbon modified quantum dot solution blank is obtained, by carbon modified quantum dot solution base
Material is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, is 30 DEG C in temperature, revolving speed is stirred to react 4h under conditions of being 300r/min
It afterwards, is 50 DEG C then at temperature, revolving speed 180r/min, concentrated by rotary evaporation to moisture content is 0.1% under conditions of pressure is 500kPa；
(4) step (2) obtained material is mixed with step (3) obtained material 45:1 in mass ratio, 40 DEG C of Yu Wendu, revolving speed is
After being stirred to react 3h under conditions of 300r/min, freeze-drying obtains blank, blank and coagulating bath 1:8 in mass ratio is mixed in
In beaker, 30 DEG C of Yu Wendu, after revolving speed is stirred to react 2h under conditions of being 280r/min, then blank quality is added into beaker
0.12 times of formaldehyde, in temperature be 40 DEG C, revolving speed be 300r/min under conditions of be stirred to react 2h after, filtering, in temperature be 60
Dry 4h under conditions of DEG C；
(5) index analysis is carried out to step (4) products obtained therefrom.
As optimization, step (2) 1, the 6- dibromo-hexane solution is that 1,6- dibromo-hexane and dehydrated alcohol are pressed quality
It is mixed than 1:3, obtains 1,6- dibromo-hexane solution.
As optimization, step (3) described bag filter is the bag filter that molecular cut off is 1000.
As optimization, step (4) described coagulating bath is the ethanol water that mass fraction is 90%.
As optimization, step (1) metal salt mixture is to massage green vitriol and ferric chloride hexahydrate
You mix than 1.00:1.75, obtain metal salt mixture.
Embodiment 2:
A kind of functional nano material of tool specifically includes that 35 parts of sodium lignin sulfonates, 8 parts of 1,3- dibromos according to parts by weight
Propane, 12 parts of metal salt mixtures, 8 parts of modified carbon quantum dots and 6 parts of formaldehyde.
A kind of preparation method of nano material with magnetism and fluorescent dual function, described kind has magnetic and fluorescent dual
The preparation method of nano material of function mainly comprises the steps that
(1) metal salt mixture and water 1:10 in mass ratio are mixed in flask, and metal salt mixture is added into flask
The sodium lignin sulfonate that 3 times of quality is passed through nitrogen into flask with the rate of 35mL/min, is 70 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 4h, the pH to 10 ~ 11 of material in flask is adjusted, continuing at temperature is 70 DEG C, revolving speed
Under conditions of 300r/min, it is stirred to react for 24 hours；
(2) step (1) obtained material and 1,3- dibromopropane solution are mixed 10:1 in mass ratio to mix, and step (1) is added
The potassium iodide that 0.02 times of obtained material quality, in temperature be 80 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react 8h,
Modified sodium lignosulfonate solution blank is obtained, by modified sodium lignosulfonate solution blank petroleum ether extraction 6h, it is extra to remove
1,3- dibromopropane, filtering, goes oil removing phase；
(3) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, after being stirred to react 8h under conditions of being 200 DEG C in temperature, in
After revolving speed is centrifugated 10min under conditions of being 3000r/min, upper liquid is taken, dialyses in bag filter for 24 hours, obtains carbon quantum dot
Solution mixes carbon quantum dot solution with dopamine 4:1 in mass ratio, is 40 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 3h after, in bag filter dialyse 8h after, carbon modified quantum dot solution blank is obtained, by carbon modified quantum dot solution base
Material is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, is 30 DEG C in temperature, revolving speed is stirred to react 4h under conditions of being 300r/min
It afterwards, is 50 DEG C then at temperature, revolving speed 180r/min, concentrated by rotary evaporation to moisture content is 0.1% under conditions of pressure is 500kPa；
(4) step (2) obtained material is mixed with step (3) obtained material 45:1 in mass ratio, 40 DEG C of Yu Wendu, revolving speed is
After being stirred to react 3h under conditions of 300r/min, freeze-drying obtains blank, blank and coagulating bath 1:8 in mass ratio is mixed in
In beaker, 30 DEG C of Yu Wendu, after revolving speed is stirred to react 2h under conditions of being 280r/min, then blank quality is added into beaker
0.12 times of formaldehyde, in temperature be 40 DEG C, revolving speed be 300r/min under conditions of be stirred to react 2h after, filtering, in temperature be 60
Dry 4h under conditions of DEG C；
(5) index analysis is carried out to step (4) products obtained therefrom.
As optimization, step (2) 1, the 3- dibromopropane solution is that 1,3- dibromopropane and dehydrated alcohol are pressed quality
It is mixed than 1:3.Obtain 1,3- dibromopropane solution.
As optimization, step (3) described bag filter is the bag filter that molecular cut off is 1000.
As optimization, step (4) described coagulating bath is the ethanol water that mass fraction is 90%.
As optimization, step (1) metal salt mixture is to massage green vitriol and ferric chloride hexahydrate
You mix than 1.00:1.75, obtain metal salt mixture.
Embodiment 3:
A kind of functional nano material of tool specifically includes that 35 parts of sodium lignin sulfonates, 8 parts of 1,6- dibromos according to parts by weight
Hexane, 12 parts of metal salt mixtures, 8 parts of modified carbon quantum dots.
A kind of preparation method of nano material with magnetism and fluorescent dual function, described kind has magnetic and fluorescent dual
The preparation method of nano material of function mainly comprises the steps that
(1) metal salt mixture and water 1:10 in mass ratio are mixed in flask, and metal salt mixture is added into flask
The sodium lignin sulfonate that 3 times of quality is passed through nitrogen into flask with the rate of 35mL/min, is 70 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 4h, the pH to 10 ~ 11 of material in flask is adjusted, continuing at temperature is 70 DEG C, revolving speed
Under conditions of 300r/min, it is stirred to react for 24 hours；
(2) step (1) obtained material and 1,6- dibromo-hexane solution are mixed 10:1 in mass ratio to mix, and step (1) is added
The potassium iodide that 0.02 times of obtained material quality, in temperature be 80 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react 8h,
Modified sodium lignosulfonate solution blank is obtained, by modified sodium lignosulfonate solution blank petroleum ether extraction 6h, it is extra to remove
1,6- dibromo-hexane, filtering, goes oil removing phase；
(3) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, after being stirred to react 8h under conditions of being 200 DEG C in temperature, in
After revolving speed is centrifugated 10min under conditions of being 3000r/min, upper liquid is taken, dialyses in bag filter for 24 hours, obtains carbon quantum dot
Solution mixes carbon quantum dot solution with dopamine 4:1 in mass ratio, is 40 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 3h after, in bag filter dialyse 8h after, carbon modified quantum dot solution blank is obtained, by carbon modified quantum dot solution base
Material is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, is 30 DEG C in temperature, revolving speed is stirred to react 4h under conditions of being 300r/min
It afterwards, is 50 DEG C then at temperature, revolving speed 180r/min, concentrated by rotary evaporation to moisture content is 0.1% under conditions of pressure is 500kPa；
(4) step (2) obtained material is mixed with step (3) obtained material 45:1 in mass ratio, 40 DEG C of Yu Wendu, revolving speed is
After being stirred to react 3h under conditions of 300r/min, freeze-drying obtains blank, blank and coagulating bath 1:8 in mass ratio is mixed in
In beaker, 30 DEG C of Yu Wendu, after revolving speed is stirred to react 2h under conditions of being 280r/min, filtering, the condition for being 60 DEG C in temperature
Lower dry 4h；
(5) index analysis is carried out to step (4) products obtained therefrom.
As optimization, step (2) 1, the 6- dibromo-hexane solution is that 1,6- dibromo-hexane and dehydrated alcohol are pressed quality
It is mixed than 1:3, obtains 1,6- dibromo-hexane solution.
As optimization, step (3) described bag filter is the bag filter that molecular cut off is 1000.
As optimization, step (4) described coagulating bath is the ethanol water that mass fraction is 90%.
As optimization, step (1) metal salt mixture is to massage green vitriol and ferric chloride hexahydrate
You mix than 1.00:1.75, obtain metal salt mixture.
Embodiment 4:
A kind of functional nano material of tool specifically includes that 35 parts of sodium lignin sulfonates, 12 parts of metal salts according to parts by weight
Mixture, 8 parts of modified carbon quantum dots and 6 parts of formaldehyde.
A kind of preparation method of nano material with magnetism and fluorescent dual function, described kind has magnetic and fluorescent dual
The preparation method of nano material of function mainly comprises the steps that
(1) metal salt mixture and water 1:10 in mass ratio are mixed in flask, and metal salt mixture is added into flask
The sodium lignin sulfonate that 3 times of quality is passed through nitrogen into flask with the rate of 35mL/min, is 70 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 4h, the pH to 10 ~ 11 of material in flask is adjusted, continuing at temperature is 70 DEG C, revolving speed
Under conditions of 300r/min, it is stirred to react for 24 hours；
(2) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, after being stirred to react 8h under conditions of being 200 DEG C in temperature, in
After revolving speed is centrifugated 10min under conditions of being 3000r/min, upper liquid is taken, dialyses in bag filter for 24 hours, obtains carbon quantum dot
Solution mixes carbon quantum dot solution with dopamine 4:1 in mass ratio, is 40 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 3h after, in bag filter dialyse 8h after, carbon modified quantum dot solution blank is obtained, by carbon modified quantum dot solution base
Material is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, is 30 DEG C in temperature, revolving speed is stirred to react 4h under conditions of being 300r/min
It afterwards, is 50 DEG C then at temperature, revolving speed 180r/min, concentrated by rotary evaporation to moisture content is 0.1% under conditions of pressure is 500kPa；
(3) step (1) obtained material is mixed with step (2) obtained material 45:1 in mass ratio, 40 DEG C of Yu Wendu, revolving speed is
After being stirred to react 3h under conditions of 300r/min, freeze-drying obtains blank, blank and coagulating bath 1:8 in mass ratio is mixed in
In beaker, 30 DEG C of Yu Wendu, after revolving speed is stirred to react 2h under conditions of being 280r/min, then blank quality is added into beaker
0.12 times of formaldehyde, in temperature be 40 DEG C, revolving speed be 300r/min under conditions of be stirred to react 2h after, filtering, in temperature be 60
Dry 4h under conditions of DEG C；
(4) index analysis is carried out to step (3) products obtained therefrom.
As optimization, step (2) described bag filter is the bag filter that molecular cut off is 1000.
As optimization, step (3) described coagulating bath is the ethanol water that mass fraction is 90%.
As optimization, step (1) metal salt mixture is to massage green vitriol and ferric chloride hexahydrate
You mix than 1.00:1.75, obtain metal salt mixture.
Embodiment 5:
A kind of functional nano material of tool specifically includes that 35 parts of sodium lignin sulfonates, 8 parts of 1,6- dibromos according to parts by weight
Hexane, 12 parts of metal salt mixtures, 8 parts of modified carbon quantum dots and 6 parts of formaldehyde.
A kind of preparation method of nano material with magnetism and fluorescent dual function, described kind has magnetic and fluorescent dual
The preparation method of nano material of function mainly comprises the steps that
(1) metal salt mixture and water 1:10 in mass ratio are mixed in flask, and metal salt mixture is added into flask
The sodium lignin sulfonate that 3 times of quality is passed through nitrogen into flask with the rate of 35mL/min, is 70 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 4h, the pH to 10 ~ 11 of material in flask is adjusted, continuing at temperature is 70 DEG C, revolving speed
Under conditions of 300r/min, it is stirred to react for 24 hours；
(2) step (1) obtained material and 1,6- dibromo-hexane solution are mixed 10:1 in mass ratio to mix, and step (1) is added
The potassium iodide that 0.02 times of obtained material quality, in temperature be 80 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react 8h,
Modified sodium lignosulfonate solution blank is obtained, by modified sodium lignosulfonate solution blank petroleum ether extraction 6h, it is extra to remove
1,6- dibromo-hexane, filtering, goes oil removing phase；
(3) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, after being stirred to react 8h under conditions of being 200 DEG C in temperature, in
After revolving speed is centrifugated 10min under conditions of being 3000r/min, upper liquid is taken, dialyses in bag filter for 24 hours, obtains carbon quantum dot
Solution mixes carbon quantum dot solution with dopamine 4:1 in mass ratio, is 40 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 3h after, in bag filter dialyse 8h after, carbon modified quantum dot solution blank is obtained, by carbon modified quantum dot solution base
Material is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, is 30 DEG C in temperature, revolving speed is stirred to react 4h under conditions of being 300r/min
It afterwards, is 50 DEG C then at temperature, revolving speed 180r/min, concentrated by rotary evaporation to moisture content is 0.1% under conditions of pressure is 500kPa；
(4) step (2) obtained material is mixed with step (3) obtained material 45:1 in mass ratio, 40 DEG C of Yu Wendu, revolving speed is
After being stirred to react 3h under conditions of 300r/min, freeze-drying obtains blank, and blank is added in beaker, and is added into beaker
The formaldehyde that 0.12 times of blank quality, in temperature be 40 DEG C, revolving speed be 300r/min under conditions of be stirred to react 2h after, filtering, in
Temperature dry 4h under conditions of being 60 DEG C；
(5) index analysis is carried out to step (4) products obtained therefrom.
As optimization, step (2) 1, the 6- dibromo-hexane solution is that 1,6- dibromo-hexane and dehydrated alcohol are pressed quality
It is mixed than 1:3, obtains 1,6- dibromo-hexane solution.
As optimization, step (3) described bag filter is the bag filter that molecular cut off is 1000.
As optimization, step (1) metal salt mixture is to massage green vitriol and ferric chloride hexahydrate
You mix than 1.00:1.75, obtain metal salt mixture.
Comparative example:
A kind of functional nano material of tool specifically includes that 35 parts of sodium lignin sulfonates, 12 parts of metal salts according to parts by weight
Mixture, 8 parts of modified carbon quantum dots.
A kind of functional preparation method of nano material of tool, mainly comprises the steps that
(1) metal salt mixture and water 1:10 in mass ratio are mixed in flask, and metal salt mixture is added into flask
The sodium lignin sulfonate that 3 times of quality is passed through nitrogen into flask with the rate of 35mL/min, is 70 DEG C in temperature, revolving speed is
Under conditions of 320r/min, after being stirred to react 4h, the pH to 10 ~ 11 of material in flask is adjusted, continuing at temperature is 70 DEG C, revolving speed
Under conditions of 300r/min, it is stirred to react for 24 hours；
(2) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, after being stirred to react 8h under conditions of being 200 DEG C in temperature, in
After revolving speed is centrifugated 10min under conditions of being 3000r/min, upper liquid is taken, dialyses in bag filter for 24 hours, obtains carbon quantum dot
Solution mixes carbon quantum dot solution with dopamine 4:1 in mass ratio, is 40 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 3h after, in bag filter dialyse 8h after, carbon modified quantum dot solution blank is obtained, by carbon modified quantum dot solution base
Material is mixed with ammonium chloride 8:1 ~ 10:1 in mass ratio, is 30 DEG C in temperature, revolving speed is stirred to react 4h under conditions of being 300r/min
It afterwards, is 50 DEG C then at temperature, revolving speed 180r/min, concentrated by rotary evaporation to moisture content is 0.1% under conditions of pressure is 500kPa；
(3) step (1) obtained material is mixed with step (2) obtained material 45:1 in mass ratio, 40 DEG C of Yu Wendu, revolving speed is
After being stirred to react 3h under conditions of 300r/min, freeze-drying obtains blank, dry under conditions of being 60 DEG C in temperature by blank
4h；
(4) index analysis is carried out to step (3) products obtained therefrom.
As optimization, step (3) described bag filter is the bag filter that molecular cut off is 1000.
As optimization, step (1) metal salt mixture is to massage green vitriol and ferric chloride hexahydrate
You mix than 1.00:1.75, obtain metal salt mixture.
Effect example 1:
The following table 1 gives using the functional nano material of tool of the embodiment of the present invention 1 to 5 and comparative example and preparation method thereof
Index analysis result.
Table 1
| Partial size/mm | It is saturated magnetic intensity/(emu/g) | Fluorescence intensity | Magnetic intensity/(emu/g) is saturated after use | Use rear fluorescence intensity | |
| Embodiment 1 | 48 | 25.0 | By force | 21.9 | By force |
| Embodiment 2 | 47 | 24.5 | By force | 20.6 | By force |
| Embodiment 3 | 51 | 22.0 | By force | 18.9 | It is weak |
| Embodiment 4 | 55 | 19.7 | By force | 16.3 | It is weak |
| Embodiment 5 | 120 | 20.1 | By force | 17.8 | It is weak |
| Comparative example | 150 | 16.8 | By force | 10.3 | It is weak |
From 1 data of table it can be found that be added in the product halogenated hydrocarbons and formaldehyde can make product have long-acting fluorescence property and
It is magnetic；It can be obtained from the comparison of embodiment 1 and embodiment 2, different halogenated hydrocarbons, which is added, influences less the property that product is leavened dough,
Can be found from the comparison of embodiment 1 and embodiment 2, when being added without formaldehyde in product preparation process, sodium lignin sulfonate with
There was only simple electrostatic force between carbon quantum dot, after use, the loss of carbon quantum dot and magnetic particle is more serious, and comparison is real
Applying example 1 and embodiment 4 can obtain, and when being added without halogenated hydrocarbons in product, coach's network strength of sodium lignin sulfonate is inadequate, make
It will cause the loss of carbon quantum dot and magnetic particle after, simultaneously as the crosslink density of sodium lignin sulfonate is little, magnetic particles
Son and the contact probability of carbon quantum dot improve, to make the saturation magnetic intensity of product and fluorescence intensity reduce, from embodiment 1 and in fact
Applying 5 pairs of example of comparison can obtain, and when handling when product preparation without coagulating bath, the partial size of product is larger, and dispersibility is not high.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention, and should not be construed as limiting the claims involved any label in claim.
Claims (10)
1. a kind of with magnetic and fluorescent dual function nano material, which is characterized in that the dual-functional nanometer material is main
Raw material components including following parts by weight: 25 ~ 40 parts of sodium lignin sulfonates, 4 ~ 10 parts of halogenated hydrocarbons, 10 ~ 14 parts of metal salt mixing
Object, 8 ~ 10 parts of modified carbon quantum dots.
2. according to claim 1 a kind of with magnetic and fluorescent dual function nano material, which is characterized in that described
It further include the raw material components of following parts by weight: 3 ~ 8 parts of formaldehyde with magnetic and fluorescent dual function nano material.
3. according to claim 2 a kind of with magnetic and fluorescent dual function nano material, which is characterized in that described
Halogenated hydrocarbons is any one in 1,6- dibromo-hexane or 1,3- dibromopropane.
4. according to claim 3 a kind of with magnetic and fluorescent dual function nano material, which is characterized in that described
Metal salt mixture is green vitriol and the ferric chloride hexahydrate mixed mixture of 1.00:1.75 in molar ratio, institute
Stating modified carbon quantum dot is by carbon quantum dot through obtained by dopamine and ammonium chloride.
5. according to claim 4 a kind of with magnetic and fluorescent dual function nano material, which is characterized in that described
Dual-functional nanometer material includes the component of following parts by weight: 35 parts of sodium lignin sulfonates, 8 parts of halogenated hydrocarbons, and 12 parts of metal salts are mixed
Close object, 8 parts of modified carbon quantum dots and 6 parts of formaldehyde.
6. a kind of preparation method of dual-functional nanometer material, which is characterized in that specifically include following preparation step:
(1) sodium lignin sulfonate is mixed with the aqueous solution of metal salt mixture, after being stirred to react under atmosphere of inert gases, then
It is stirred to react under alkaline condition；
(2) step (1) obtained material is mixed with halohydrocarbon solution, and potassium iodide is added, after being stirred to react, extracted, filtering；
(3) carbon quantum dot solution is made through pyroreaction in citric acid, by carbon quantum dot solution and dopamine hybrid reaction, thoroughly
Analysis, and mixed with ammonium chloride, it is stirred to react, concentrated by rotary evaporation；
(4) step (2) obtained material is mixed with step (3) obtained material, is freeze-dried, blank is obtained, by blank and coagulating bath
After hybrid reaction, and formaldehyde is added, is stirred to react, filters, it is dry；
(5) index analysis is carried out to step (4) products obtained therefrom.
7. the preparation method of dual-functional nanometer material according to claim 6, which is characterized in that specifically include following preparation
Step:
(1) metal salt mixture is mixed with water 1:10 in mass ratio, and 2 ~ 4 times of metal salt mixture quality of lignin is added
Sodium sulfonate after being stirred to react, adjusts pH to 10 ~ 11, continues to be stirred to react in nitrogen atmosphere；
(2) step (1) obtained material is mixed to the mixing of 10:1 ~ 10:2 in mass ratio with halohydrocarbon solution, and step (1) institute is added
The potassium iodide for obtaining 0.01 ~ 0.02 times of material mass, after being stirred to react, obtains modified sodium lignosulfonate solution blank, by innovation wood
Quality sodium sulfonate solution blank petroleum ether extraction, removes extra halogenated hydrocarbons, and oil removing phase is gone in filtering；
(3) citric acid is mixed with water 1:30 ~ 1:40 in mass ratio, 5 are stirred to react under conditions of being 200 ~ 220 DEG C in temperature ~
After 8h, centrifuge separation takes upper liquid, dialyses in bag filter, obtain carbon quantum dot solution, carbon quantum dot solution is pressed with dopamine
Mass ratio 10:1 mixing, dialysis obtain carbon modified quantum dot solution blank, and carbon modified quantum dot solution blank and ammonium chloride are pressed matter
Amount is mixed than 8:1 ~ 10:1, after being stirred to react, concentrated by rotary evaporation；
(4) step (2) obtained material is mixed with step (3) obtained material 40:1 ~ 45:1 in mass ratio, it is cold after being stirred to react
It is lyophilized dry, obtains blank, blank is mixed with coagulating bath 1:5 ~ 1:8 in mass ratio, after being stirred to react, adds blank quality 0.08
~ 0.12 times of formaldehyde after being stirred to react, filters, dry；
(5) index analysis is carried out to step (4) products obtained therefrom.
8. the preparation method of dual-functional nanometer material according to claim 7, which is characterized in that step (2) is described halogenated
Hydrocarbon solution is to mix halogenated hydrocarbons with dehydrated alcohol 1:3 in mass ratio, obtains halohydrocarbon solution.
9. the preparation method of dual-functional nanometer material according to claim 8, which is characterized in that step (3) described dialysis
Bag is any one in the bag filter that molecular cut off is 1000 or the bag filter that molecular cut off is 1200.
10. the preparation method of dual-functional nanometer material according to claim 6, which is characterized in that step (4) described solidification
Bath is the ethanol water that mass fraction is 90%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321851A (en) * | 2020-11-05 | 2021-02-05 | 云南师范大学 | Lignin rare earth composite luminescent material and preparation and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174273A (en) * | 2011-03-08 | 2011-09-07 | 延边石岘白麓纸业股份有限公司 | Method for preparing lignin sulfonate dye dispersant |
| CN102020258B (en) * | 2010-10-26 | 2013-01-09 | 青岛科技大学 | Method for preparing magnetic fluorescence hydroxyapatite nanocomposite structure |
| CN102973948A (en) * | 2012-12-03 | 2013-03-20 | 上海交通大学 | Method for preparing drug carrier based on magnetic carbon quantum dot/chitosan composite microsphere |
| CN103525405A (en) * | 2013-10-21 | 2014-01-22 | 北京理工大学 | Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof |
| CN104004200A (en) * | 2014-05-26 | 2014-08-27 | 华南理工大学 | Alkane-bridged lignin-based polymer as well as preparation method and application of lignin-based polymer |
| CN104892952A (en) * | 2015-06-24 | 2015-09-09 | 济南圣泉集团股份有限公司 | Modified lignosulphonate and preparing method and application thereof |
| CN104971775A (en) * | 2014-04-01 | 2015-10-14 | 中国科学院大连化学物理研究所 | Solid acid catalyst and application thereof to synthesis of reproducible diesel oil or aviation kerosene |
| CN105251466A (en) * | 2015-10-09 | 2016-01-20 | 湖南大学 | Preparation method and application of magnetic chitosan lignosulfonate graphene oxide adsorbent |
| CN108020531A (en) * | 2016-11-03 | 2018-05-11 | 天津世起科技发展有限公司 | It is a kind of to carry out dopamine and Al using fluorescent carbon point3+Detection method |
| CN108048074A (en) * | 2018-01-15 | 2018-05-18 | 湖北大学 | A kind of hybrid inorganic-organic fluorescent nano particles for emitting glory and preparation method thereof |
| CN108414483A (en) * | 2018-02-28 | 2018-08-17 | 西华师范大学 | A kind of fluorescence probe and its preparation method and application for dopamine determination |
| CN108714423A (en) * | 2018-05-08 | 2018-10-30 | 中国科学院烟台海岸带研究所 | A kind of water process composite magnetic nano catalytic material and its preparation and application |
| CN109126746A (en) * | 2018-10-17 | 2019-01-04 | 北京林业大学 | A kind of preparation method of magnetism lignosulfonates adsorbent material |
| CN109406473A (en) * | 2018-11-08 | 2019-03-01 | 青岛大学 | A kind of preparation method of the phycoerythrin ratio fluorescent sensor based on magnetic molecularly imprinted core shell polymer |
-
2019
- 2019-03-28 CN CN201910240839.5A patent/CN109913200A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020258B (en) * | 2010-10-26 | 2013-01-09 | 青岛科技大学 | Method for preparing magnetic fluorescence hydroxyapatite nanocomposite structure |
| CN102174273A (en) * | 2011-03-08 | 2011-09-07 | 延边石岘白麓纸业股份有限公司 | Method for preparing lignin sulfonate dye dispersant |
| CN102973948A (en) * | 2012-12-03 | 2013-03-20 | 上海交通大学 | Method for preparing drug carrier based on magnetic carbon quantum dot/chitosan composite microsphere |
| CN103525405A (en) * | 2013-10-21 | 2014-01-22 | 北京理工大学 | Magnetic fluorescent difunctional nano material based on natural polymer and preparation method thereof |
| CN104971775A (en) * | 2014-04-01 | 2015-10-14 | 中国科学院大连化学物理研究所 | Solid acid catalyst and application thereof to synthesis of reproducible diesel oil or aviation kerosene |
| CN104004200A (en) * | 2014-05-26 | 2014-08-27 | 华南理工大学 | Alkane-bridged lignin-based polymer as well as preparation method and application of lignin-based polymer |
| CN104892952A (en) * | 2015-06-24 | 2015-09-09 | 济南圣泉集团股份有限公司 | Modified lignosulphonate and preparing method and application thereof |
| CN105251466A (en) * | 2015-10-09 | 2016-01-20 | 湖南大学 | Preparation method and application of magnetic chitosan lignosulfonate graphene oxide adsorbent |
| CN108020531A (en) * | 2016-11-03 | 2018-05-11 | 天津世起科技发展有限公司 | It is a kind of to carry out dopamine and Al using fluorescent carbon point3+Detection method |
| CN108048074A (en) * | 2018-01-15 | 2018-05-18 | 湖北大学 | A kind of hybrid inorganic-organic fluorescent nano particles for emitting glory and preparation method thereof |
| CN108414483A (en) * | 2018-02-28 | 2018-08-17 | 西华师范大学 | A kind of fluorescence probe and its preparation method and application for dopamine determination |
| CN108714423A (en) * | 2018-05-08 | 2018-10-30 | 中国科学院烟台海岸带研究所 | A kind of water process composite magnetic nano catalytic material and its preparation and application |
| CN109126746A (en) * | 2018-10-17 | 2019-01-04 | 北京林业大学 | A kind of preparation method of magnetism lignosulfonates adsorbent material |
| CN109406473A (en) * | 2018-11-08 | 2019-03-01 | 青岛大学 | A kind of preparation method of the phycoerythrin ratio fluorescent sensor based on magnetic molecularly imprinted core shell polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321851A (en) * | 2020-11-05 | 2021-02-05 | 云南师范大学 | Lignin rare earth composite luminescent material and preparation and application thereof |
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