CN108072636A - A kind of single annular polymeric molecule spreads the measuring method of information in solid/liquid interfaces - Google Patents

A kind of single annular polymeric molecule spreads the measuring method of information in solid/liquid interfaces Download PDF

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CN108072636A
CN108072636A CN201611023738.5A CN201611023738A CN108072636A CN 108072636 A CN108072636 A CN 108072636A CN 201611023738 A CN201611023738 A CN 201611023738A CN 108072636 A CN108072636 A CN 108072636A
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annular
fluorescence
solid
annular polymeric
liquid interfaces
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叶少勇
郑锴锴
杨京法
赵江
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

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  • Optics & Photonics (AREA)
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Abstract

The invention discloses the measuring methods that a kind of single annular polymeric molecule spreads information in solid/liquid interfaces.This method comprises the following steps:(1) annular polymeric to be measured is marked with fluorescent molecular probe, obtains the annular polymeric of fluorescent marker;(2) annular polymer solution of fluorescent marker is prepared, solution is fixed on exciting light optical window, forms solid/liquid interfaces;Laser irradiates solid/liquid interfaces, is measured using fluorescence correlation spectroscopy measuring system, you can obtains diffusion information;Optical microphotograph unit in fluorescence correlation spectroscopy measuring system is using inverted fluorescence microscope, including a micro objective, a dichroscope, a transmitting light high-pass filtering piece, an exciting light band pass filter, a pin hole, a beam splitter and a condenser lens.The method of the present invention can realize that single annular polymeric molecule spreads the measurement of information in solid/liquid interfaces, have high spatial resolution, measure the surface and interface concentration of sample up to the level per the several molecules of square micron.

Description

A kind of single annular polymeric molecule spreads the measurement of information in solid/liquid interfaces Method
Technical field
The invention belongs to Polymer Physics basic research fields, are related specifically to a kind of single annular polymeric molecule and exist The measuring method of information is spread in solid/liquid interfaces.
Background technology
The interface kinetics behavior of macromolecular (including large biological molecule, synthetic polymer) with ring topology is Basic process in biological phenomena, the inhereditary material in life system are replicated with playing particularly important work in transport process With.At the same time, dispersal behavior of the annular macromolecular on surface and interface on synthesis is not only an important basic physics Problem, it may have huge practical value (exploitation of Novel adhesive etc.), while its relevant achievement in research will also be to rubbing The development for wiping the subjects such as, biology and polymer Neo-Confucianism generates important impetus.Therefore, introduce and develop to The technology of dispersal behavior of the annular macromolecular chain of research on surface and interface is very necessary.
Traditional linear polymeric is different from, annular macromolecule is without molecule chain end, and this give a series of its spies Different physical property, for example, smaller mean square radius of gyration and hydrodynamic radius, relatively low melting and solution viscosity and compared with High crystallization temperature etc..In the research field of conventional polymer chain diffusion, chain end is considered playing a crucial role.Example Such as:In the snakelike theory of classics of description conventional linear macromolecular chain dispersal behavior, the movement of chain is defined as opening from its end Begin what is carried out.Dispersal behavior research accordingly, with respect to the annular macromolecular chain uniqueness for not possessing no chain end receives in recent years Theoretical and experiment scholar very big concern.
In terms of theoretical research, for the special topological structure of annular macromolecule, corresponding amoeba model is developed and has retouched State its dispersal behavior;In terms of experimental study, Michael Rubinstein etc. have successfully obtained annular with rheology means Modulus-slack time the curve of macromolecule in the melt, so infer its spread relaxation information (Michael Kapnistos, Michael Lang,Dimitris Vlassopoulos,Wim Pyckhout-Hintzen,Dieter Richter, Donghyun Cho,Taihyun Chang and Michael Rubinstein.Unexpected power-law stress Relaxation of entangled ring polymers, Nature Materials, 2008,7:997-1002), Yushu Matsushita etc. has successfully been obtained with dynamic Secondary Ion Mass Spectrometry combination neutron reflection technology in annular high molecular film Molecule counterdiffusion information (Daisuke Kawaguchi, Keisuke Masuoka, Atsushi Takano, Keiji Tanaka, Toshihiko Nagamura,Naoya Torikai,Robert M.Dalgliesh,Sean Langridge,and Yushu Matsushita.Comparison of interdiffusion behavior between cyclic and linear Polystyrenes with high molecular weights, Macromolecules, 2006,39:5180-5182), The annular that Dieter Richter etc. have successfully obtained different molecular weight with neutron scattering combination neutron spin echo technique is high Whole chain diffusion and segment diffusion information (Ana R.Bras, Rossana Pasquino, Thanasis of the molecule in its melt Koukoulas,Georgia Tsolou,Olaf Holderer,Aurel Radulescu,Jurgen Allgaier,Vlasis G.Mavrantzas,Wim Pyckhout-Hintzen,Andreas Wischnewski,Dimitris Vlassopoulos And Dieter Richter, Soft Matter, 2011,7:11169-11176).However, these conventional polymers test skill Art and the ability without spatial discrimination, it is impossible to be used in the characterization of single annular polymeric surface and interface kinetic property.Therefore, mesh It is preceding not had been reported that also for dispersal behavior research of the single annular macromolecule on surface and interface.Although Michael J.Skaug etc. Once the method tracked using single molecular fluorescence is used for research (the Michael J.Skaug, Joshua that individual molecule is spread Mabry, and Daniel K.Schwartz, Physical Review Letters, 2013,110:256101), but due to The temporal resolution of the method for single molecular fluorescence tracking is appropriate only for the extremely slow system of molecular interface diffusion, and (molecule is mutual with interface Act on extremely strong), it is not particularly suited for annular macromolecule interfacial diffusion system (molecule and interfacial interaction are weaker).
The content of the invention
The object of the present invention is to provide the measurement sides that a kind of single annular polymeric molecule spreads information in solid/liquid interfaces Method.
A kind of single annular polymeric molecule provided by the invention spreads the measuring method of information in solid/liquid interfaces, bag Include following steps:
(1) annular polymeric to be measured is marked with fluorescent molecular probe, obtains the annular polymeric of fluorescent marker;
(2) annular polymer solution of the fluorescent marker is prepared, the solution is fixed on exciting light optical window, Form the solid/liquid interfaces;Laser irradiates the solid/liquid interfaces, is measured using fluorescence correlation spectroscopy measuring system, you can Obtain the diffusion information;
The fluorescence correlation spectroscopy measuring system includes:
One is used to irradiate the excitation light source unit of the annular polymer solution as exciting light;
One optical microphotograph unit, the optical microphotograph unit are used for the exciting light by excitation light source unit outgoing through institute Exciting light optical window is stated to introduce in the annular polymeric of the fluorescent marker so that the annular polymeric of the fluorescent marker by Excitation generates fluorescence signal, and the fluorescence signal collection of generation is transmitted to a fluorescence correlation spectroscopy measuring unit;The fluorescence Association spectral measurement unit obtains the single annular polymeric molecule in the solid/liquid interfaces for obtaining fluorescence signal Diffusion information;
The optical microphotograph unit uses inverted fluorescence microscope, including a micro objective, a dichroscope, a transmitting Light high-pass filtering piece, an exciting light band pass filter, a pin hole, a beam splitter and a condenser lens, described in exciting light warp Microcobjective is transmitted to the annular polymeric of the fluorescent marker in the sample fixed cell, and the annular through fluorescent marker is gathered The fluorescence for closing object excitation is transmitted to the dichroscope after microcobjective collection, the fluorescence being emitted through the dichroscope Signal is transmitted to beam splitter through the transmitting light high-pass filtering piece and pin hole, and a part of light through beam splitter outgoing is through the focusing Lens are transmitted to the fluorescence correlation spectroscopy measuring unit;The exit end of the excitation light source unit sets the exciting light band logical Filter plate.
Above-mentioned measuring method, in step (1), the structural formula of the annular polymeric is as shown in formula I:
Wherein, n is the integer between 10~250, and R is any one of carboxyl, hydroxyl and amino.
The structural formula of the fluorescent molecular probe is as shown in formula II:
The concentration of the annular polymer solution of the fluorescent marker is less than 10nM, such as 5nM.
The annular polymeric and the molar ratio of the fluorescent molecular probe can be 1:(2~10), such as 1:5.
The mark carries out under conditions of being protected from light, and temperature can be 20~30 DEG C, and the time can be 8~14h.
Above-mentioned measuring method, in step (2), the method is after the solid/liquid interfaces are formed before the measurement Further include the step of solution is replaced with into the solvent of the solution.
The excitation light source unit uses continuous laser or femtosecond pulse;The excitation light source unit include one with The laser of upper different wave length, several speculums, several diaphragms, the first beam expanding lens and the second beam expanding lens, second beam expanding lens Incidence end set a neutral-density filter, the light that the laser is sent is respectively through several speculums and the diaphragm And two-stage is carried out through first beam expanding lens and the second beam expanding lens successively and expand excitation beam enlarged-diameter to ensure its size More than the micro objective light well of the optical microphotograph unit.
The measuring system further includes one second fluorescence correlation spectroscopy measuring unit, a speculum and a condenser lens, warp Another part light of the beam splitter outgoing is reflected into the condenser lens through the speculum, through condenser lens outgoing Light emitting is to the second fluorescence correlation spectroscopy measuring unit;The fluorescence correlation spectroscopy measuring unit includes a single-photon detecting Survey device with a data collecting card, single-photon detector by detect receive fluorescence signal be converted to electric signal through data collecting card A being associated property of computer analysis and the fitting of correlation function are sent to, so as to obtain the single annular polymeric molecule Diffusion information.
The present invention has the advantages that:
The method of the present invention can realize that single annular polymeric molecule spreads the measurement of information in solid/liquid interfaces, have pole High spatial resolution, space exploration horizontal direction size are sub-micrometer scale, have the sensitivity of unimolecule rank, measurement The surface and interface concentration of sample can reach the level of the several molecules of every square micron.
Description of the drawings
Fig. 1 is the structure of polymeric rheology spectrometer and measuring principle schematic diagram.
Fig. 2 is the structure diagram of sample fixed cell in polymeric rheology instrument used.
Fig. 3 is the typical fluorescence correlation curve of the line polymer of annular polymeric and identical molecular weight and fitting knot Fruit, wherein, the fluorescence correlation curve and fitting knot of the high molecular interface diffusion of annular that Fig. 3 (A) is molecular weight 8.5kg/mol Fruit, the fluorescence correlation curve and fitting result of the linear high molecular interface diffusion that Fig. 3 (B) is molecular weight 8.5kg/mol, Fig. 3 (C) the fluorescence correlation curve and fitting result spread for the high molecular interface of annular of molecular weight 14kg/mol, Fig. 3 (D) are point The fluorescence correlation curve and fitting result of the high molecular interface diffusion of linear shape of son amount 14kg/mol.
In figure, each mark is as follows:
1 excitation light source unit, 2 shearings apply single with flow measurement unit, 3 optical microphotograph units, the imaging of 4 single molecular fluorescences Member, 5 single molecular fluorescence emission spectroscopy measurements units, 6 fluorescence correlation spectroscopy measuring units, 31 micro objectives, 32 dichroscopes, The speculum of 33 first speculums~the 3rd, 34 transmitting light high-pass filtering pieces, 35 pin holes, 36 beam splitters, 37 slits, 38 first focus on The condenser lens of lens~the 4th, 39 exciting light band pass filters, I solution inlet port, II taphole, III polytetrafluoroethylene (PTFE) hold wall, IV fluororubber O circle, V quartz plate.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
In following embodiments end group used for the annular polystyrene (PS-COOH) of-COOH structural formula such as 1 institute of formula Show:
Wherein, n 10-250.Wherein, during n=78, molecular weight 8.5kg/mol;During n=131, molecular weight 14kg/ mol。
According to document Lonsdale D.E., Bell C.A., Monteiro M.J.Macromolecules, 2010,43 (7):3331-9.Jia Z.F.,Monteiro M.J.Adv.Polym.Sci.2013:295-327.Eugene D.M., Grayson S.M.Macromolecules,2008,41(14):End group shown in method formula 1 disclosed in 5082-4.) for- The annular polystyrene of COOH, is as follows:
1st, the synthesis of annular polystyrene (CPS)
Using the method for copper catalysis alkynes/nitrine cycloaddition click chemistry (CuAAC) by a series of obtained LPS samples in pole Ring closure reaction is carried out under the conditions of weak solution.Specific preparation process is as follows:
PMDETA is dissolved in 230mL DMF, and mixed liquor is placed in 250mL Schlenk reaction bulbs, rouses nitrogen 1h to remove Remove the oxygen in solution.Above-mentioned solution is transferred in the 1L Schlenk reaction bulbs for filling CuBr with double-ended needle, in 50 DEG C of oil Bath is lower to stir 30min to form CuBr/PMDETA compounds.The linear presoma LPS of annular polystyrene is dissolved in 450mL It in DMF, is placed in another 500mL Schlenk reaction bulb, drum nitrogen 1h is protected to remove the oxygen in solution, by it in nitrogen It is slowly transferred under conditions of shield in the 1L Schlenk reaction bulbs for filling CuBr/PMDETA complex solutions.Final cyclization is molten The concentration of liquid is controlled 10-5M magnitudes are farthest to reduce the possibility of intermolecular coupling.Mixed liquor under 50 DEG C of oil baths, It is strong to stir at least for 24 hours, to ensure the complete generation of ring closure reaction.Then, DMF, obtained solid are removed by being evaporated under reduced pressure Mixture is dissolved in dichloromethane, by alkali alumina with copper removal.Obtained dichloromethane solution is concentrated, is sunk in methyl alcohol Drop 3 times, vacuum drying obtain solid polymer, and settle (THF/ methanol systems) by high molecular weight cyclization by multiple fractionation A small amount of coupling component present in product removes, the final ring-shaped P S (CPS) for physical characterization for obtaining higher degree.
2nd, end group is the synthesis of the annular polystyrene (PS-COOH) of-COOH
End group-the OH of polymer is modified into-COOH, specific synthetic method is as follows:By PS-OH, succinic anhydride, DMAP (molar ratio 1:5:1) it is dissolved in dichloromethane solution, is stirred at room temperature for 24 hours, stops reaction, concentration settles 3 times in methyl alcohol, Vacuum drying obtains solid sample PS-COOH at room temperature.
The structural formula of fluorescence probe used (Bodipy-FL), maximum absorption wave as shown in formula II in following embodiments A length of 503nm.
Embodiment 1, the single annular polymeric molecule of measurement spread information in solid/liquid interfaces
First, measuring system
Using Application No. 201610031083.X, publication No. is 105699344 A of CN, a kind of entitled " acquisition The measuring system single ring of measurement (as shown in Figure 1) disclosed in single fluorescence molecule spectrum and imaging measurement system under shearing field " Diffusion information of the shape polymer molecule in solid/liquid interfaces, difference lies in survey the shearing application in the measuring system and rheology Amount unit replaces with sample fixed cell, and the bottom of the sample fixed cell is exciting light optical window stone in the measuring system English piece, structure are as shown in Figure 2.
2nd, measuring method
In accordance with the following steps in measure annular polystyrene (CPS) single annular polymeric molecule in quartz plate/dichloromethane Diffusion information on alkane interface:
(1) annular polystyrene (CPS) to be measured is marked with fluorescent molecular probe, obtains the annular polymerization of fluorescent marker Object is as follows:
1) it is annular polystyrene (formula), fluorescence molecule Bodipy-FL, the dicyclohexylcarbodiimide of-COOH by end group (DCC) and 4-dimethylaminopyridine (DMAP) is according to 1:2:10:0.4 molar ratio, which is dissolved in the dry THF of 250 μ L, is made dye Colour response solution is stirred under room temperature (25 DEG C), is protected from light (12h) reaction overnight;
2) by the mixture of staining reaction remove after THF by using DMF as mobile phase Aquapak A-440 chromatographic column (SX-1media;Bio-Rad, USA) at least 5 times to remove unreacted free dyestuff, obtain fluorescent marker Annular polymeric sample.
The annular polystyrene sample of different molecular weight and its colouring method all same of linear presoma.
(2) the annular polystyrene of mark is dissolved in dichloromethane wiring solution-forming, and the absorption for being diluted to 5nM is dense Degree;The annular polystyrene (CPS) of single fluorescent marker is carried out at quartz plate/dichloromethane interface two using above-mentioned measuring system The measurement that dimensional expansion dissipates, operating procedure are as follows:
1) excitation beam after opening excitation light source (473nm) and expanding adjusts collimation and makes collimated light beam;
2) water immersion objective is switched to, and 40 μ L ultra-pure waters are added on micro objective, the self-control of quartz plate will be fixed Sample cell is placed on it (shown in Fig. 2);
3) plus sample solution is in adsorbing 5min on quartz plate, then uses dichloromethane pure solvent exchange polymer solution again, It exchanges repeatedly about 10 times, until not detecting fluorescence signal in upper solution;
4) position for adjusting laser spot causes it to be positioned on the interface of Polymer adsorption, and passes through fine tuning detection The fluorescence signal arrived is optimal;
5) open fluorescence correlation spectroscopy measuring unit and obtain invariance curve, and pass through data and be fitted to obtain polymer diffusion letter Breath, as shown in Figure 3.By the fluorescent intensity fluctuation caused by fluorescence molecule passes in and out in two detector recording excitation volumes, lead to The correlation analysis for crossing signal obtains fluorescence correlation curve, is fitted to obtain the diffusion information of molecule according to data.
The measuring method all same of different molecular weight annular polystyrene sample and its linear presoma.

Claims (8)

1. a kind of single annular polymeric molecule spreads the measuring method of information in solid/liquid interfaces, include the following steps:
(1) annular polymeric to be measured is marked with fluorescent molecular probe, obtains the annular polymeric of fluorescent marker;
(2) annular polymer solution of the fluorescent marker is prepared, the solution is fixed on exciting light optical window, is formed The solid/liquid interfaces;Laser irradiates the solid/liquid interfaces, is measured using fluorescence correlation spectroscopy measuring system, you can obtain The diffusion information;
The fluorescence correlation spectroscopy measuring system includes:
One is used to irradiate the excitation light source unit of the annular polymer solution as exciting light;
One optical microphotograph unit, the optical microphotograph unit are used to swash the exciting light of excitation light source unit outgoing through described Luminous optical window is introduced in the annular polymeric of the fluorescent marker so that the annular polymeric of the fluorescent marker is stimulated Fluorescence signal is generated, and the fluorescence signal collection of generation is transmitted to a fluorescence correlation spectroscopy measuring unit;The fluorescence correlation Spectral measurement unit obtains expansion of the single annular polymeric molecule in the solid/liquid interfaces for obtaining fluorescence signal Dissipate information;
The optical microphotograph unit uses inverted fluorescence microscope, high including a micro objective, a dichroscope, a transmitting light Pass filter piece, an exciting light band pass filter, a pin hole, a beam splitter and a condenser lens, the exciting light is through described micro- Object lens are transmitted to the annular polymeric of the fluorescent marker in the sample fixed cell, the annular polymeric through fluorescent marker The fluorescence of excitation is transmitted to the dichroscope after microcobjective collection, the fluorescence signal being emitted through the dichroscope Beam splitter is transmitted to through the transmitting light high-pass filtering piece and pin hole, a part of light through beam splitter outgoing is through the condenser lens It is transmitted to the fluorescence correlation spectroscopy measuring unit;The exit end of the excitation light source unit sets the exciting light bandpass filtering Piece.
2. measuring method according to claim 1, it is characterised in that:In step (1), the structural formula of the annular polymeric As shown in formula I:
Wherein, n is the integer between 10~250, and R is any one of carboxyl, hydroxyl and amino.
3. measuring method according to claim 1 or 2, it is characterised in that:The structural formula of the fluorescent molecular probe such as formula Shown in II:
The concentration of the annular polymer solution of the fluorescent marker is less than 10nM.
4. the measuring method any one of claim 1-3, it is characterised in that:The annular polymeric and the fluorescence point The molar ratio of sub- probe is 1:(2~10).
5. according to the measuring method any one of claim 1-4, it is characterised in that:The mark is under conditions of being protected from light It carries out, temperature is 20~30 DEG C, and the time is 8~14h.
6. according to the measuring method any one of claim 1-5, it is characterised in that:The method formed it is described it is solid/ After liquid interface the step of solution is replaced with into the solvent of the solution is further included before the measurement.
7. according to the measuring method any one of claim 1-6, it is characterised in that:The excitation light source unit is using company Continuous laser or femtosecond pulse;The laser of the excitation light source unit including more than one different wave length, several speculums, Several diaphragms, the first beam expanding lens and the second beam expanding lens, the incidence end of second beam expanding lens set a neutral-density filter, institute It states light that laser is sent and expands successively through several speculums and the diaphragm and through first beam expanding lens and second respectively Beam mirror carries out two-stage and expands excitation beam enlarged-diameter to ensure that its size is more than the microscope object of the optical microphotograph unit Mirror light well.
8. according to the measuring method any one of claim 1-7, it is characterised in that:The measuring system further includes one Two fluorescence correlation spectroscopy measuring units, a speculum and a condenser lens, another part light through beam splitter outgoing is through institute It states speculum and is reflected into the condenser lens, the light emitting being emitted through the condenser lens is surveyed to second fluorescence correlation spectroscopy Measure unit;The fluorescence correlation spectroscopy measuring unit include a single-photon detector with a data collecting card, single-photon detecting The fluorescence signal for detecting reception is converted to electric signal and is sent to a being associated property of computer analysis through data collecting card by survey device And the fitting of correlation function, so as to obtain the diffusion information of the single annular polymeric molecule.
CN201611023738.5A 2016-11-14 2016-11-14 A kind of single annular polymeric molecule spreads the measuring method of information in solid/liquid interfaces Pending CN108072636A (en)

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CN111337469A (en) * 2020-04-27 2020-06-26 中国科学院化学研究所 Method for acquiring microscopic motion information under shear field by utilizing trace light intensity distribution of fluorescent wide-field imaging
CN111610171A (en) * 2020-04-28 2020-09-01 中国科学院化学研究所 Method for obtaining diffusion movement and concentration information of polymer molecules on immiscible liquid interface
CN117214144A (en) * 2023-08-21 2023-12-12 苏州大学 Method for in-situ monitoring photochemical cycloaddition reaction progress by fluorescence spectrum technology

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Publication number Priority date Publication date Assignee Title
CN111337469A (en) * 2020-04-27 2020-06-26 中国科学院化学研究所 Method for acquiring microscopic motion information under shear field by utilizing trace light intensity distribution of fluorescent wide-field imaging
CN111337469B (en) * 2020-04-27 2021-06-08 中国科学院化学研究所 Method for acquiring microscopic motion information under shear field by utilizing fluorescence wide field imaging
CN111610171A (en) * 2020-04-28 2020-09-01 中国科学院化学研究所 Method for obtaining diffusion movement and concentration information of polymer molecules on immiscible liquid interface
CN117214144A (en) * 2023-08-21 2023-12-12 苏州大学 Method for in-situ monitoring photochemical cycloaddition reaction progress by fluorescence spectrum technology

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