CN109187449A - Environmental response type Intelligent sensing device and the preparation method and application thereof - Google Patents
Environmental response type Intelligent sensing device and the preparation method and application thereof Download PDFInfo
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- CN109187449A CN109187449A CN201810834073.9A CN201810834073A CN109187449A CN 109187449 A CN109187449 A CN 109187449A CN 201810834073 A CN201810834073 A CN 201810834073A CN 109187449 A CN109187449 A CN 109187449A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
Abstract
The invention discloses a kind of environmental response type Intelligent sensing devices and the preparation method and application thereof.The environmental response type Intelligent sensing device includes: patterned substrate, the substrate surface is formed at least two spaced recess, fills the first polymer containing initiator at least two recess and forms the planar pattern as sensitive zones in substrate surface；And a plurality of second polymer grafted chains, the second polymer grafted chain head end is covalently bonded in the planar pattern and reacting with the active function groups on first polymer surface, the terminal covalent of second polymer grafted chain is bonded with dying high-molecular simultaneously, the dying high-molecular is selected from short block polymer, the functional group that the short block polymer has fluorophor and can specifically bind with selected small molecule.Polymer grafted chain can generate response to different solvents in the present invention, or generate response to specific molecular, realize the automatic control function under the conditions of environmental response.
Description
Technical field
The present invention relates to a kind of sensing devices, and in particular to a kind of environmental response type Intelligent sensing device and preparation method thereof
With application.
Background technique
" research and development of environmental response type intellectual material optimize with performance " attempts to utilize the environmental response material of independent research, normal
It is modified and is assembled in rule device substrate, to realize the control to substrate surface performance by the means for changing environmental condition
And adjusting.It, can be by the physical quantity or chemical quantity of these variations by the detection of detection or fluorescence signal to substrate topography
Identifiable signal is converted to, to realize performance required for intellectual material.Such intellectual material can be used in environmental monitoring and lead
Domain and automation control area.Normal procedure intelligent sensing material can cause material conformation change by the change of environmental condition, such as
It can be completed by the isomerization of material function base, such as cis-trans isomerization reaction, the ionization of chromophore, and these will lead
Cause the change of material property.Atom transfer radical polymerization (Atom transfer radical polymerization,
It ATRP) is controllable polymerization method (WANG J S, MATYJASZEWSKI K.Controlled/ very widely used at present
“living”radical polymerization.Atom transfer radical polymerization in the
presence oftransition-mental complexs[J].Journal ofthe American Chemical
Society, 1995,117 (20): 5614-5615.), it can be widely applied to composite material block design and functional high-polymer
In the preparation of material, but industry not yet reports that it is used to prepare environmental response type Intelligent sensing device at present.
Summary of the invention
The main purpose of the present invention is to provide a kind of environmental response type Intelligent sensing device and the preparation method and application thereof,
To overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of environmental response type Intelligent sensing devices comprising:
Patterned substrate, the substrate surface are formed at least two spaced recess, at least two recess
It is interior to fill the first polymer containing initiator and form the planar pattern as sensitive zones in the substrate surface；And
A plurality of second polymer grafted chains, the second polymer grafted chain head end by with first polymer surface
Active function groups are reacted and are covalently bonded in the planar pattern, while the terminal covalent key of the second polymer grafted chain
Conjunction has a dying high-molecular, and the dying high-molecular is selected from short block polymer, the short block polymer have fluorophor with
And the functional group that can be specifically bound with selected small molecule.
Further, when being placed in good solvent, the second polymer grafted chain is rendered as tensional state, and works as quilt
When being placed in poor solvent, the second polymer grafted chain is rendered as collapse state, and the second polymer grafted chain
Length in a stretched state is at least 6~10 times of its length under collapse state.
The embodiment of the invention also provides the preparation methods of aforesaid environmental response type intelligent sensing device comprising following step
It is rapid:
(1) patterned substrate is provided, the substrate surface is formed at least two spaced recess；
(2) precursor of the first polymer containing active function groups is backfilled in the recess of the substrate surface, then
Under polymerization temperature, the substrate surface and a planar alignment are pressed, the surface of the plane can be higher than the substrate surface, from
And it is formed in planar pattern of the substrate surface formation as sensitive zones；
(3) active function groups of the head end and first polymer surface that make a plurality of second polymer grafted chains pass through atom
Transition free radical polymerization reaction and covalent bonding；
(4) make the end of the second polymer grafted chain and there is dying high-molecular to pass through nucleophilic substitution covalent bond
It closes.
The embodiment of the invention also provides a kind of detection methods, it is real based on aforesaid environmental response type intelligent sensing device
It applies, the detection method includes: to ring the liquid sample to be measured comprising poor solvent and selected small molecule and the environment
The sensitive zones of type Intelligent sensing device are answered, and detect the fluorescence intensity change of sensitive zones, to realize to liquid-like to be measured
The detection of small molecule is selected in product.
Compared with the prior art, advantages of the present invention at least that:
Environmental response type Intelligent sensing device provided by the invention accurately controls sensing dress by changing solvent property
It sets, or a possibility that design particular substrate measurement solution molecule characteristic, by adjusting the material kind of polymer grafting chain end
Class, can make sensing device to diversified environmental condition generate response, such as different reagent concentrations, different temperature and humidity,
Different electric and magnetic fields realize the automatic control function under the conditions of environmental response.This provides one for design intellectual material
A new way is fixed in micelle stable state, adsorptivity control, liquid crystal display, moisture contamination monitor automatically etc., and fields have
Wide application prospect and the important foundation information search unit of Future Data exploitation.
Detailed description of the invention
Fig. 1 is to prepare patterned substrate using earth-filling method in a typical embodiments of the invention, and generate the second polymerization
The schematic diagram of object grafted chain.
Fig. 2 a and Fig. 2 b are the Si substrate surface that polystyrene graft chain is grown in a typical embodiments of the invention respectively
Microscope figure, wherein Fig. 2 a is the Si substrate of linear pattern, and Fig. 2 b is flat patterned substrate.
Fig. 3 is the infrared spectrum spectrogram of filled substrate in a typical embodiments of the invention.
Fig. 4 a and Fig. 4 c are the flat patterned substrates that polystyrene graft chain is grown in a typical embodiments of the invention
Liquid phase atom mechanics microscope figure and structural scan curve graph in ethanol.
Fig. 4 b and Fig. 4 d are the flat patterned substrates that polystyrene graft chain is grown in a typical embodiments of the invention
Liquid phase atom mechanics microscope figure and structural scan curve graph in DMF.
Fig. 5 is to be returned in a typical embodiments of the invention by first step ATRP reaction and second step nucleophilic substitution
The schematic diagram of Terminal fluorescent group is embedded in face planar pattern of filling in a form.
Fig. 6 is dying high-molecular has in an of the invention typical embodiments fluorophor under 356nm excitation light source
Launching light spectrogram.
Fig. 7 a and Fig. 7 b are that second polymer grafted chain is in reset condition and altogether in an of the invention typical embodiments respectively
Valence link closes the fluorescence intensity schematic diagram of adsorbed state after having dying high-molecular.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution, environmental response type intellectual material can autonomous selective polymer grafted chain, customized material substrate is generated, to not
Same environmental condition generates specific response.The technical solution, its implementation process and principle etc. will further be solved as follows
Release explanation.
A kind of environmental response type Intelligent sensing device that the one aspect of the embodiment of the present invention provides comprising:
Patterned substrate, the substrate surface are formed at least two spaced recess, at least two recess
It is interior to fill the first polymer containing initiator and form the planar pattern as sensitive zones in the substrate surface；And
A plurality of second polymer grafted chains, the second polymer grafted chain head end by with first polymer surface
Active function groups are reacted and are covalently bonded in the planar pattern, while the terminal covalent key of the second polymer grafted chain
Conjunction has a dying high-molecular, and the dying high-molecular is selected from short block polymer, the short block polymer have fluorophor with
And the functional group that can be specifically bound with selected small molecule.
Further, when being placed in good solvent, the second polymer grafted chain is rendered as tensional state, and works as quilt
When being placed in poor solvent, the second polymer grafted chain is rendered as collapse state, and the second polymer grafted chain
Length in a stretched state is at least 6~10 times of its length under collapse state.
Further, described when contacting the sensitive zones of the environmental response type Intelligent sensing device and good solvent
A plurality of second polymer grafted chains are stretched and form the bristle-like structure of setting, and when the environmental response type is intelligent
When the sensitive zones and poor solvent of sensing device contact, a plurality of equal collapses of second polymer grafted chain are in substrate surface
And make that there is between each spaced figure clear boundary in the planar pattern.
Further, the head end of the second polymer grafted chain and the active function groups on first polymer surface pass through original
Sub- transition free radical polymerization reaction and covalent bonding, and, the end of the second polymer grafted chain and there is dying high-molecular
Pass through nucleophilic substitution covalent bonding.
Further, the first polymer includes polystyrene, polymethyl methacrylate and poly terephthalic acid second
Any one in diol ester etc. or two or more combinations, but not limited to this.
Further, the second polymer grafted chain and dying high-molecular albumen, enzyme, nucleic acid containing amino etc. are covalent
Bonding, but not limited to this.
Further, the number-average molecular weight of the short block polymer is 300~450.
Further, the short block polymer has the segment containing 15~30 carbon atoms.
Further, the second polymer grafted chain derives from polystyrene, but not limited to this.
Further, the fluorophor that the dying high-molecular has is from compound shown in following formula:
Further, the planar pattern includes more than two bar patterns of parallelly distribute on.
Further, the spacing between the two neighboring bar pattern is 10~2000nm.
The other side of the embodiment of the present invention additionally provides the preparation method of aforesaid environmental response type intelligent sensing device,
It includes the following steps:
(1) patterned substrate is provided, the substrate surface is formed at least two spaced recess；
(2) precursor of the first polymer containing active function groups is backfilled in the recess of the substrate surface, then
Under polymerization temperature, the substrate surface and a planar alignment are pressed, the surface of the plane can be higher than the substrate surface, from
And it is formed in planar pattern of the substrate surface formation as sensitive zones；
(3) active function groups of the head end and first polymer surface that make a plurality of second polymer grafted chains pass through atom
Transition free radical polymerization reaction and covalent bonding；
(4) make the end of the second polymer grafted chain and there is dying high-molecular to pass through nucleophilic substitution covalent bond
It closes.
Further, step (4) includes: to make liquid-phase reaction system and the sensing comprising dying high-molecular and good solvent
Region contact, makes the second polymer grafted chain be rendered as tensional state, and make the end of the second polymer grafted chain
Pass through nucleophilic substitution covalent bonding with there is dying high-molecular.
The other side of the embodiment of the present invention additionally provides a kind of detection method, it is based on aforesaid environmental response type intelligence
Energy sensing device is implemented, and the detection method includes: to make the liquid sample to be measured comprising poor solvent and selected small molecule
With the sensitive zones of the environmental response type Intelligent sensing device, and the fluorescence intensity change of sensitive zones is detected, to realize
Detection to small molecule is selected in liquid sample to be measured.
Further, the detection method specifically includes:
The series of standards liquid sample and the environment for making the selected small molecule comprising poor solvent and various concentration are rung
The sensitive zones of type Intelligent sensing device are answered, and detect the fluorescence intensity of sensitive zones, foundation can reflect selected little molecular concentration
Relational expression F=k between fluorescence intensityλC/S, wherein F is fluorescence intensity, unit a.u., kλFor excitation light source coefficient,
C is the concentration that small molecule is selected in standard liquid sample, and unit mol/L, S are the functional group and inspection that dying high-molecular has
Survey the specific surface area in region；
Make the liquid sample to be measured of the selected small molecule comprising poor solvent and unknown concentration and the environmental response type intelligence
The sensitive zones of energy sensing device, and the fluorescence intensity of sensitive zones is detected, and according to the relational expression, calculate liquid to be measured
Little molecular concentration is selected in sample.
Further, it may also include good solvent in the liquid sample to be measured.Further, the environmental response type intelligence
Energy sensing device can make accurate response for good solvent system and poor solvent system, and the object of detection can be oil
The solution system of liquid layering, or adsorbed different solvents and the solid-state system of uneven distribution is presented, or is complicated raw
Object structure etc..In the present invention, environmental response type Intelligent sensing device utilizes atom transfer radical polymerization by second polymer
The first polymer chemical bonds of grafted chain and patterned substrate filling.Second polymer grafted chain is under difficult environmental conditions
With different swelling effects, feedback is generated to environmental stimulus and metamorphosis occurs, so as to cause changing for its substrate surface structure
Become, realizes the automatic control function under the conditions of environmental response.
Present invention is further described in detail combined with specific embodiments below, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
As shown in Figure 1, in one embodiment of the invention, by polymer-filled technique, active function groups will be contained
Precursor (styrene, divinylbenzene, 4- 1-chloro-4-methyl-benzene ratio are 7:1:2) to be backfilled to length and width be 2cm*2cm, spacing is
The Si substrate of the linear pattern of 500nm.Then under polymerization temperature (110 DEG C), substrate is right with suitable pressure (4MPa)
Standard is simultaneously pressed in another Si plane with higher surface energy.Since Si plane has surface energy more higher than substrate, have
The polymer of active function groups can be easily packed into the latter, be generated flat graphical existing for the alternating of active function groups
Substrate.By changing the concentration of monomer, the density of active initiator can be easily adjusted, so as to raw using ATRP
At the polymer grafted chain of specific region.The polymer grafted chain of the present embodiment is the polystyrene containing 40~100 carbon atoms
Scion grafting chain can generate response to different solvents.
Atom transition free radical polymerization reaction tests process in this example are as follows: is placed in the Si substrate for causing group containing Cl
In styryl reagent, it is added and analyzes pure stannous chloride, copper bromide, 2,2'- bipyridyl (mass ratio 7:1:28), be sufficiently mixed
After be heated to 120 DEG C, generate the Si substrate that polymer grafting chain end is Cl group.As shown in Fig. 2, reaction front and back Si substrate table
Significant change occurs for face, and the Si substrate (Fig. 2 a) of linear pattern is transformed into flat patterned substrate (Fig. 2 b).As Fig. 3 is infrared
Shown in spectrum spectrogram, filled substrate contains Cl group.
These response characteristics can provide basis for the exploitation on " intelligence " surface.Based on the interaction with polymer grafted chain
Property, solvent can be broadly dassified into the poor solvent or good solvent of polymer grafted chain.Since solvent and polymer are grafted
Interaction between chain, polymer grafted chain are always at collapsed state in poor solvent.On the contrary, they are in good solvent
There is the conformation stretched.The thickness of stretching is controlled by the balance between osmotic pressure and tensile stress.As solvent quality is from good
To bad variation, polymer grafted chain is gradually tapered up from stretching state and is finally collapsed.Most polymers grafted chain can expansion
To 6 to 10 times of its contracted state.
Polymer under different solvents is observed using liquid phase atom mechanics microscope (LiquidAFM) and fluorescence microscope to be grafted
The metamorphosis of chain.Although can characterize conventional sample with characterization techniques such as scanning electron microscope and transmission electron microscopes, polymer is connect
The real-time state of branch chain in a solvent needs directly to be studied in a solvent by in-situ study technology.Liquid phase atomic force is aobvious
Micro mirror (Liquid AFM) and fluorescence microscope can carry out in liquid medium/environment, provide substrate surface topographical information.
Inventor detects the polymer scion grafting chain of the present embodiment in dimethylformamide with liquid phase atom mechanics microscope
(DMF) home state and in ethyl alcohol, because not allowing in liquid phase atom mechanics microscope using toluene.DMF is a kind of good molten
Agent, ethyl alcohol are a kind of poor solvents of polymer chain.The conformation change of polymer chain may highly significant in both solvents
(Fig. 4 a- Fig. 4 d).As shown in Fig. 4 a and Fig. 4 c, in ethanol, polymer chain is in collapsed state.Therefore, polymer grafted chain
Height less than 10 nanometers.As shown in Fig. 4 b and Fig. 4 d, in DMF, the polymer grafted chain of the present embodiment shows extension
State reaches about 40 nanometers of height.Meanwhile the width of the polymer grafted chain of the present embodiment also changes.In drying regime
Under, the transverse width of the bristle-like structure of polymer grafted chain is 500nm, greater than the width (about 330nm) under extension state.
The polymer grafted chain of the present embodiment has applications well in bioprotein field to the response characteristic of environment.Such as
Shown in Fig. 5, in an application scheme of the present embodiment, with reference to above, polymer grafted chain is equally anti-with ATRP polymerization first
It should manufacture.Then by biologically active dying high-molecular albumen (such as Alexa Fluor 350) and polymer grafted chain into
Row reaction, reaction process are as follows: the Si substrate that polymer grafting chain end is Cl group is put into DMF reagent, Alexa is added
Fluor 350 is heated to 60 DEG C, and high molecular weight protein is connected to the end of polymer grafted chain.Since high molecular weight protein uses
Fluorophor is dyed, and can very easily be observed using state of the fluorescence microscope to the polymer grafted chain.It should
The fluorophor structure such as following formula that dying high-molecular albumen has, the emission spectrum such as Fig. 6 institute measured at wavelength 356nm
Show.
Under the light source irradiation of 356nm, fluorescence microscope is observed that the fluorescence of polymer grafting chain end transmitting.
This sensing device by the interference of other molecules, does not only generate response to the specific molecular in solution.Fig. 7 a and figure
7b be polymer grafted chain respectively in reset condition and after being covalently bonded with dying high-molecular albumen adsorbed state fluorescence intensity
Schematic diagram.
Therefore, the sensitive zones of the environmental response type Intelligent sensing device of the present embodiment building are put into dissolved with small molecule
Reagent in, it can be observed that being changed with the surface fluorescence of high molecular weight protein graft polymers grafted chain.It is logical
It crosses and measures this variation, can determine the little molecular concentration in solution.
It more specifically, can be to specific small molecule due to the biologically active functional group in high molecular weight protein surface
(such as amino acid, silver ion) carries out specific adsorption, can be with by observing the fluorescence intensity change on polymer grafted chain surface
The number of binding molecule quantity judged.It,, can be in solution by fluorescence intensity after reaching equilibrium state shown in following formula
Specific molecular concentration makes measurement:
F=kλC/S,
Wherein, F is fluorescence intensity, unit a.u., kλFor excitation light source coefficient, c be selected in standard liquid sample it is small
The concentration of molecule, unit mol/L, S are the specific surface area of the dying high-molecular functional group having and detection zone.
In another application scheme of the present embodiment, it can use identical ATRP step and produce polymer grafted chain,
Short block polymer (being such as enclosed with the polystyrene of PdS or CdS) is repaired by the ATRP reaction of similarity condition again later
Adorn the end of polymer grafted chain.
Two step ATRP are used in the application scheme handles polymer grafted chain.Wherein, it is made in first time ATRP step
The long polymer chain made can keep similar solvent swelling state, and short block polymer will not be very big to the generation of long-chain character
Change；Moreover, short block polymer can form the thickness of approaches uniformity.Therefore, the fluorescence observed from microscope will have
There is almost the same intensity, the boundary of polymer chain also can clearly be observed.
In conclusion the polymer of environmental response type Intelligent sensing device of the invention is grafted by above-mentioned technical proposal
Chain has the conformation of stretching, extension in good solvent, has the conformation collapsed in poor solvent, is provided simultaneously with screening specificity
The possibility of molecule, is equivalent to have varying environment condition and automated tos respond to, and provides by changing solvent property and accurately controls
Sensing material substrate, or a possibility that design particular substrate measurement solution molecule characteristic, last-in-chain(LIC) is grafted by adjusting polymer
The material category at end can make sensing device generate response, such as different reagent concentrations, difference to diversified environmental condition
Temperature and humidity, different electric and magnetic fields etc..This provides a new way for design intellectual material, in automatic monitoring neck
Domain has broad application prospects and the important foundation information search unit of Future Data exploitation.
It should be appreciated that the above description is only an embodiment of the present invention, it is not intended to limit the scope of the invention, it is all
Using equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content, it is applied directly or indirectly in other
Relevant technical field, is included within the scope of the present invention.
Claims (10)
1. a kind of environmental response type Intelligent sensing device, characterized by comprising:
Patterned substrate, the substrate surface are formed at least two spaced recess, fill out at least two recess
It fills the first polymer containing initiator and forms the planar pattern as sensitive zones in the substrate surface；And
A plurality of second polymer grafted chains, the second polymer grafted chain head end pass through the activity with first polymer surface
Functional group reactions and be covalently bonded in the planar pattern, while the terminal covalent of the second polymer grafted chain is bonded with
Dying high-molecular, the dying high-molecular are selected from short block polymer, and the short block polymer has fluorophor and energy
Enough functional groups with the specific binding of selected small molecule.
2. environmental response type Intelligent sensing device according to claim 1, it is characterised in that: when being placed in good solvent
When, the second polymer grafted chain is rendered as tensional state, and when being placed in poor solvent, the second polymer connects
Branch chain is rendered as collapse state, and the length of the second polymer grafted chain in a stretched state is at least it in collapse shape
6~10 times of length under state.
3. environmental response type Intelligent sensing device according to claim 2, it is characterised in that: when by the environmental response type
When the sensitive zones and good solvent of Intelligent sensing device contact, a plurality of second polymer grafted chains are stretched and form
The bristle-like structure of setting, and when contacting the sensitive zones of the environmental response type Intelligent sensing device and poor solvent,
A plurality of equal collapses of second polymer grafted chain are in substrate surface and make each spaced figure in the planar pattern
Between have clear boundary.
4. environmental response type Intelligent sensing device according to claim 1, it is characterised in that: the second polymer grafting
The head end of chain and the active function groups on first polymer surface by atom transition free radical polymerization reaction covalent bonding, with
And the end of the second polymer grafted chain and there is dying high-molecular to pass through nucleophilic substitution covalent bonding；
And/or the first polymer includes in polystyrene, polymethyl methacrylate and polyethylene terephthalate
Any one or two or more combinations；
And/or the second polymer grafted chain and the dying high-molecular covalent bonding containing amino；The dying high-molecular packet
Include any one in dying high-molecular albumen, enzyme and nucleic acid or two or more combinations；
And/or the number-average molecular weight of the short block polymer is 300~450；Preferably, the short block polymer has
Segment containing 15~30 carbon atoms.
5. environmental response type Intelligent sensing device according to claim 1, it is characterised in that: the second polymer grafting
Chain derives from polystyrene；And/or the fluorophor that the dying high-molecular has is from compound shown in following formula:
6. environmental response type Intelligent sensing device according to claim 1, it is characterised in that: the planar pattern includes
More than two bar patterns of parallelly distribute on；Preferably, the spacing between the two neighboring bar pattern is 10~2000nm.
7. the preparation method of environmental response type Intelligent sensing device as described in any one of claim 1-6, it is characterised in that packet
Include following steps:
(1) patterned substrate is provided, the substrate surface is formed at least two spaced recess；
(2) precursor of the first polymer containing active function groups is backfilled in the recess of the substrate surface, then polymerize
At a temperature of, the substrate surface and a planar alignment are pressed, the surface of the plane can be higher than the substrate surface, thus shape
Substrate surface described in Cheng Yu forms the planar pattern as sensitive zones；
(3) active function groups of the head end and first polymer surface that make a plurality of second polymer grafted chains pass through atom transfer
Raolical polymerizable and covalent bonding；
(4) make the end of the second polymer grafted chain and there is dying high-molecular to pass through nucleophilic substitution covalent bonding.
8. preparation method as claimed in claim 7, which is characterized in that step (4) includes: to make comprising dying high-molecular and good molten
The liquid-phase reaction system of agent is contacted with the sensitive zones, so that the second polymer grafted chain is rendered as tensional state, and make
The end of the second polymer grafted chain and there is dying high-molecular to pass through nucleophilic substitution covalent bonding.
9. a kind of detection method, it is implemented based on environmental response type Intelligent sensing device described in any one of claim 1-6
, which is characterized in that the detection method includes: to make liquid sample to be measured and institute comprising poor solvent and selected small molecule
The sensitive zones of environmental response type Intelligent sensing device are stated, and detect the fluorescence intensity change of sensitive zones, are treated to realize
It surveys in liquid sample and selectes the detection of small molecule.
10. detection method according to claim 9, it is characterised in that specifically include:
Make the series of standards liquid sample and the environmental response type of the selected small molecule comprising poor solvent and various concentration
Sensitive zones of Intelligent sensing device, and detect the fluorescence intensity of sensitive zones, foundation can reflect select little molecular concentration with it is glimmering
Relational expression F=k between luminous intensityλC/S, wherein F is fluorescence intensity, unit a.u., kλFor excitation light source coefficient, c is
The concentration of small molecule is selected in standard liquid sample, unit mol/L, S are the functional group and detection that dying high-molecular has
The specific surface area in region；
The liquid sample to be measured and the environmental response type for making the selected small molecule comprising poor solvent and unknown concentration intelligently pass
The sensitive zones of induction device, and the fluorescence intensity of sensitive zones is detected, and according to the relational expression, calculate liquid sample to be measured
In select little molecular concentration；
It preferably, further include good solvent in the liquid sample to be measured.
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