CN108715693A - A kind of photochemistry removes oxygen to protect the medium and methods and applications of the triplet excited state of photosensitizer - Google Patents
A kind of photochemistry removes oxygen to protect the medium and methods and applications of the triplet excited state of photosensitizer Download PDFInfo
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- CN108715693A CN108715693A CN201810698756.6A CN201810698756A CN108715693A CN 108715693 A CN108715693 A CN 108715693A CN 201810698756 A CN201810698756 A CN 201810698756A CN 108715693 A CN108715693 A CN 108715693A
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- 0 *c1cccc(C(Cc2cccc(N)c2)c2cc(N=O)ccc2)c1 Chemical compound *c1cccc(C(Cc2cccc(N)c2)c2cc(N=O)ccc2)c1 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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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
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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
- G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
-
- 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"
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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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"
- G01N2021/6432—Quenching
Abstract
The present invention provides a kind of photochemistry and removes oxygen to protect the medium and its methods and applications of the triplet excited state of photosensitizer, the medium be polyvinylpyrrolidone.The method is：PVP, photosensitizer are mixed with solvent, standing forms gel, irradiates the gel using exciting light.The method can simple effective method deprotection phosphorescence do not quenched by the oxygen in air, and applied observation and testing experiment in optical physics and photochemistry, converted in photoetching or T-T annihilation photon etc..
Description
Technical field
The invention belongs to nonlinear optical material field, it is related to a kind of photochemistry and removes oxygen to protect the triple of photosensitizer
The medium and methods and applications of excitation state.
Background technology
Triplet：Photosensitizer molecule in ground state, absorbs the exciting light of specific wavelength, and molecule jumps from ground state absorption energy
Singlet excited is adjourned, later due to the rigidity of molecule itself or molecule and heavy metal coordination, due to depositing for heavy metal effect
Under, intersystem crossing can occur for intermolecular energy, from singlet excited to triplet excited state.If molecule is directly from substance
Emitted energy returns to ground state to excitation state in the form of light, this process is fluorescent emission, and the service life is usually that nanosecond is other, if
Molecule transits to triplet from singlet excited, and from triplet, emitted energy returns to ground state in the form of light, this process is phosphorus
Light emitting.It is to violate spin rule due to transitting to triplet excited state from singlet excited, when this process needs certain
Between, thus the service life of phosphorescence for the service life of fluorescence, can big several orders of magnitude, generally microsecond rank.
Since the service life of phosphorescence can reach microsecond rank, the molecule oxygen in air is on energy level and symmetry and phosphorescence phase
Matching, therefore phosphorescence is easy to be quenched by the oxygen in air, makes the energy transfer of phosphorescent molecules triplet to oxygen, molecule
After oxygen receives the energy excitation of phosphorescence, from triplet transition to singlet state.Creating singlet oxygen is due to energy ratio molecule oxygen
Height, thus it is more unstable, it is easier to and oxidation occurs for organic compound, destroys organic matter.And the energy of phosphorescence is not logical
The form transmitting of light is crossed, but is quenched by oxygen, therefore phosphorescence is not easy to be detected under aerobic conditions.Phosphorescence biology at
Picture, OLED and organic compound identification etc. have boundless application, therefore phosphorescence is protected not quenched very by oxygen
It is significant.
Colloidal particle or macromolecule in colloidal sol or solution interconnect under certain condition, form space net structure,
It (can also be gas in xerogel, xerogel is also referred to as airsetting to be filled in structural void as the liquid of decentralized medium
Glue), such a special dispersion is referred to as gel.There is no mobility.It is internal often to contain big quantity of fluid.Inside gel
There is fine and close reticular structure, the transmission of solvent and molecule oxygen can be limited, therefore gel can be relatively good as one
Medium protects phosphorescence.Preparation process in terms of general gel is used to protect phosphorescence is under vacuum to be added to gelling agent
In solvent containing photosensitizer, by dissolving by heating gelling agent, after temperature cools down, gel is formed.
Conversion refers to that the donor in ground state is in laser or other light sources in spy on T-T annihilation photon
Under the irradiation of standing wave length, energy jump is absorbed to singlet excited, triplet excited state, Zhi Houyu are reached by intersystem crossing later
Acceptor molecule in ground state carries out energy transfer by collision, is given in triplet excited state in ground state by absorption is known from experience
The energy of body, from ground state transition to triplet excited state, the triplet excited state molecule of two receptors can collide with each other acceptor molecule
Realize energy transfer, it is possible to cause one of receptor to transit to singlet excited from triplet excited state, swash later from substance
Hair state sends out fluorescence and returns to ground state, another molecule for being in the receptor of triplet excited state is returned directly to after energy transmission is complete
Ground state.Here it sends out receptor and sends out the wavelength of fluorescence and be less than the wavelength of incident light.Due to the energy density of required exciting light
Low (usually less than 100mW/cm2), the advantages that absorbing ability is strong, upper conversion quantum yield is high, excitation-emission Wavelength tunable, TTA
Upper conversion is in field of solar energy utilization, three-dimensional mangement, fluorescent molecular biomarker and the high-tech areas such as photodynamics is for cancer
Show good application prospect and high additive value.
Invention content
For the technical problems in the prior art, a kind of photochemistry of present invention offer removes oxygen to protect photosensitizer
Triplet excited state medium and methods and applications, the method can simple effective method deprotect phosphorescence not by air
In oxygen quenching, and applied observation and testing experiment in optical physics and photochemistry, photoetching or triplet-three
Converted on weight state annihilation photon etc..
In order to achieve the above objectives, the present invention uses following technical scheme：
Oxygen is removed it is an object of the present invention to provide a kind of photochemistry to protect Jie of the triplet excited state of photosensitizer
Matter, which is characterized in that the medium is polyvinylpyrrolidone.
As currently preferred technical solution, the number-average molecular weight of the polyvinylpyrrolidone is 8000~60000,
Such as 8000,9000,10000,15000,20000,30000,40000,50000 or 60000, it is not limited to cited
Numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Oxygen is removed the second purpose of the present invention is to provide a kind of photochemistry to protect the side of the triplet excited state of photosensitizer
Method, which is characterized in that the method is：PVP, photosensitizer are mixed with solvent, standing forms gel, irradiates institute using exciting light
State gel.
Specifically, photosensitizer is added in solvent first and is configured to solution, solid state medium PVP is added to solution later
Among, by stirring, the means such as ultrasound promote PVP to dissolve into solution, form thick fluid, place later aside,
It allows solvent to volatilize naturally or can promote the volatilization of solvent, by taking dichloromethane as an example, the item that volatilizees naturally by infrared drying oven
Under part the figurate gel of tool can be formed in or so 12 hours.The time of plastic and the type of solvent, local ring
The humidity and temperature in border and whether using other supplementary means accelerate volatilization it is related.
As currently preferred technical solution, the solvent include water, alcohols solvent, amine solvent, carboxylic acids solvent,
In lactams solvent, ketones solvent, esters solvent, halogenated hydrocarbon solvent or nitroparaffin hydrocarbon solvent any one or at least
Two kinds of combination, the combination is typical but non-limiting examples have：Combination, alcohols solvent and the amine solvent of water and alcohols solvent
Combination, the combination of amine solvent and carboxylic acids solvent, the combination of carboxylic acids solvent and lactams solvent, lactams solvent
The combination of combination, ketones solvent and esters solvent with ketones solvent, the combination of halogenated hydrocarbon solvent and nitroparaffin hydrocarbon solvent
Or the combination etc. of water, alcohols solvent and amine solvent.
Preferably, the alcohols solvent includes any one in methanol, ethyl alcohol, normal propyl alcohol or isopropanol or at least two
Combination, the combination is typical but non-limiting examples have：The combination of methanol and ethyl alcohol, the combination of ethyl alcohol and isopropanol, isopropyl
The combination or methanol of alcohol and normal propyl alcohol, the combination etc. of ethyl alcohol and isopropanol.
Preferably, the amine solvent include in butylamine, cyclohexylamine or aniline any one or at least two combination,
The combination is typical but non-limiting examples have：The combination of butylamine and cyclohexylamine, the combination of cyclohexylamine and aniline, aniline and butylamine
Combination or butylamine, cyclohexylamine and aniline combination etc..
Preferably, the carboxylic acids solvent include in formic acid, acetic acid or propionic acid any one or at least two combination,
The combination is typical but non-limiting examples have：Combination of formic acid and acetic acid etc., combination of acetic acid and propionic acid etc., propionic acid and formic acid
Combination or formic acid, acetic acid and propionic acid combination etc..
Preferably, the halogenated hydrocarbon solvent includes dichloromethane and/or chloroform.
Wherein, the solvent that the present invention uses is not limited in above-mentioned cited solvent, can be with polyethylene dissolving pyrrolidines
The ketone and solvent for forming gel all can be used in the method for the invention.
As currently preferred technical solution, the photosensitizer includes Porphyrin-Based Sensitizer, phthalocyanines photosensitizer, metal
Complexing Polypyridine class photosensitizer, metal acetylene class photosensitizer, ring metal complex species photosensitizer and fluorine boron pyrylium dyes spread out
In biological species photosensitizer any one or at least two combination, the combination is typical but non-limiting examples have：Porphyrin
The combination of photosensitizer and phthalocyanines photosensitizer, the combination of phthalocyanines photosensitizer and metal complex Polypyridine class photosensitizer, metal
Combination, metal acetylene class photosensitizer and the ring metal complex species of Polypyridine class photosensitizer and metal acetylene class photosensitizer are complexed
The combination of photosensitizer, the combination of ring metal complex species photosensitizer and fluorine boron pyrylium dyes derivative species photosensitizer or porphyrin light
Quick dose, the combination etc. of phthalocyanines photosensitizer and metal complex Polypyridine class photosensitizer.
Preferably, the Porphyrin-Based Sensitizer includes porphyrin, the porphyrin containing substituent group or the metalloporphyrin complexing of amplification
In object any one or at least two combination, the combination is typical but non-limiting examples have：The porphyrin of amplification and contain
The combination of the porphyrin of substituent group, the combination of the porphyrin containing substituent group and metal porphyrin complex, metal porphyrin complex and expansion
The combination etc. of the porphyrin of combination or the amplification of the porphyrin of increasing, porphyrin and metal porphyrin complex containing substituent group.
Preferably, the phthalocyanines photosensitizer includes phthalocyanine, the phthalocyanine containing substituent group or the metal phthalocyanine complexing of amplification
In object any one or at least two combination, the combination is typical but non-limiting examples have：The phthalocyanine of amplification and contain
The combination of the phthalocyanine of substituent group, the combination of the phthalocyanine containing substituent group and metal phthalocyanine complex, metal phthalocyanine complex and expansion
The combination etc. of the phthalocyanine of combination or the amplification of the phthalocyanine of increasing, phthalocyanine and metal phthalocyanine complex containing substituent group.
Preferably, the metal include Li, Mg, Al, Ti, V, VO, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Pd, Ag, Re,
Os, Ir, Pt, Pb, U or UO2In any one or at least two combination, the combination is typical but non-limiting examples have：
The combination of Li and Mg, the combination of Mg and Al, Al and the combination of Ti, the combination of Ti and V, the combination of V and VO, the combination of Mn and Fe,
The combination of Co and Ni, the combination of Cu and Zn, Ga and the combination of Ru, the combination of Pd and Ag, the combination of Re and Os, Ir and Pt group
It closes, combination, U and the UO of Pb and U2Combination or Mg, Al and Ti combination etc..
The photosensitizer that the present invention uses can be Formulas I~IV compounds represented：
In the present invention, photosensitizer, polyvinylpyrrolidone and solvent are mixed with gel, pass through specific excitation wave
Long irradiation gel, the energy of the triplet excited state of photosensitizer can be transferred to the molecular oxygen in gel, photosensitizer by light energy
Excitation, from ground state reach singlet excited, later by intersystem crossing reach triplet excited state, triplet excited state is by molecular oxygen
Gas quenches, and generates singlet oxygen, and singlet oxygen interacts with polyvinylpyrrolidone, generates irreversible peroxide,
Gradually use up the oxygen in gel.In the case where oxygen content gradually decreases, corresponding phosphorescence is gradually increased in this process, directly
To maximum value of the arrival under the light intensity.
As currently preferred technical solution, a concentration of the 5 × 10 of the photosensitizer-6~1 × 10-4Mol/L, such as 5 ×
10-6、8×10-6、1×10-5、2×10-5、5×10-5、8×10-5Or 1 × 10-4Deng, it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range.
As currently preferred technical solution, the optical energy density of the exciting light is 0.2mW cm-2~50mW cm-2, such as 0.2W cm-2、0.5W cm-2、1W cm-2、2W cm-2、5W cm-2、10W cm-2、15W cm-2、20W cm-2、25W cm-2、30W cm-2、35W cm-2、40W cm-2、45W cm-2Or 50W cm-2Deng it is not limited to cited numerical value, the number
It is equally applicable to be worth other unrequited numerical value in range.
The excitation wavelength of the present invention is to refer to by photosensitizer from ground state transition to excitation state, in preferred implement, institute
The range for the excitation wavelength stated is from 300nm to 1600nm in range.
As currently preferred technical solution, the method is：Water, alcohols solvent, amine solvent, carboxylic acids is molten
Any one in agent, lactams solvent, ketones solvent, esters solvent, halogenated hydrocarbon solvent or nitroparaffin hydrocarbon solvent is molten
The mixed solvent of agent or at least two solvent combinations is mixed with polyvinylpyrrolidone and photosensitizer, and photosensitizer concentration is 5 × 10-6
~1 × 10-4Mol/L, standing obtain gel and the use of optical energy density are 0.2mW cm-2~50mW cm-2Exciting light irradiation
The gel, wherein the photosensitizer be Porphyrin-Based Sensitizer, phthalocyanines photosensitizer, metal complex Polypyridine class photosensitizer,
It is any one in metal acetylene class photosensitizer, ring metal complex species photosensitizer and fluorine boron pyrylium dyes derivative species photosensitizer
Kind or at least two combination.
The three of the object of the invention are to provide the application of the above method, and the method is applied to optical physics and photochemistry
Observation and testing experiment, photoetching or T-T annihilation photon on convert.
As currently preferred technical solution, the observation of the optical physics and photochemistry and testing experiment include
Stern-Volmer curves, time-resolved emission spectrum and transient absorption spectra.
In the present invention, the method that the method for above-mentioned photochemistry deoxygenation is applied to field of lithography is：It is prepared into first
Gel containing photosensitizer irradiates gel more than ten seconds by the excitation wavelength light source of photosensitizer, utilizes the gelator inside gel
Oxygen can be removed, and itself can limit the diffusion of oxygen, it is possible on gel to the position of illumination into
The removal of row oxygen irradiates the transmitting with phosphorescence that can see and cross position in illumination before with light source, has reproduced and worked as again
The historical rudiment of Shi Guangzhao.The gel itself formed by solid state medium is transparent, it is possible to be observed in different angles
The trace that phosphorescence reproduces.The pierced pattern above gel is tightly attached to by illumination to stay in various pattern traces above gel, profit
Phosphorescence, regenerated pattern are excited with illumination.The trace that this illumination pierced pattern leaves, can completely disappear over time, this
When recursive carry out new pattern and scribe and reproduce.The time of pattern loss depend on light application time, PVP molecular weight with
And the concentration of photosensitizer.
In the present invention, when the method for above-mentioned photochemistry deoxygenation is applied to convert on T-T annihilation photon, on
Conversion gel rubber system is made of donor, receptor, solvent and polyvinylpyrrolidone；Donor should meet level-density parameter with receptor, give
The triplet energy level of body is higher than the triplet energy level of receptor；Two times of the triplet energy level of receptor are higher than singlet level, energy level
It is matched with and is conducive to upper conversion.The upper conversion told can directly utilize one under photosensitizer provided by the invention and receptor complex
Determine the laser excitation of intensity, is converted in realization.
In the present invention, the energy density for the exciting light converted on T-T annihilation photon is 0.2~2500mW
cm-2, such as 5W cm-2、10W cm-2、15W cm-2、20W cm-2、100W cm-2、300W cm-2、500W cm-2、800W cm-2、
900W cm-2Or 950W cm-2Deng it is not limited to cited numerical value, other unrequited numerical value are same in the numberical range
Sample is applicable in.
In the upper conversion solution system that the present invention uses, the molar ratio of donor and receptor is 1:1~200, such as 1:1,1:2,
1:5,1:10,1:15,1:20,1:30,1:40,1:50,1:80,1:100,1:120,1:150,1:180 or 1:200 etc., but simultaneously
It is not limited only to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
In the present invention, the receptor used in being converted on T-T annihilation photon into organic dyestuff, be refer to and
Photosensitizer, which acts synergistically, reaches the corresponding organic molecule (receptor) of conversion, is shown in the range of 360nm to 750nm
The compound of fluorescent emission especially shows the fluorescent dye of fluorescent emission in the range of 360nm to 750nm.As DPA (9,
10- diphenylanthrancenes) can and PtOEP form red turn of indigo plant, BPEA can and PtTPBP be formed red turn it is green etc..The concentration one for the receptor told
As be 1 × 10-3mol·dm-3~2 × 10-3mol·dm-3, such as 1 × 10-3mol·dm-3、1.1×10-3mol·dm-3、1.2×
10-3mol·dm-3、1.3×10-3mol·dm-3、1.4×10-3mol·dm-3、1.5×10-3mol·dm-3、1。6×10- 3mol·dm-3、1.7×10-3mol·dm-3、1.8×10-3mol·dm-3、1.9×10-3mol·dm-3Or 2 × 10-3mol·
dm-3Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
In the present invention, the receptor used in being converted on above-mentioned T-T annihilation photon can be such as Formula V and Formula IV
Compound represented：
In the present invention, difference may be implemented by the selection of donor and acceptor compound and the allotment of concentration and ratio
The upper conversion of color, efficiency reach as high as 12%, can be applied to the fields such as photovoltaic and photocatalysis.
In the present invention, the gel that PVP is formed can also be used to observe the process of photochemistry and optical physics, so far as is known,
This is the medium for inherently having efficient deoxygenation by gelator announced for the first time, it is observed that originally under air conditions
Need to remove oxygen just it is observed that the phenomenon that, such as acceptor density increases the process that the service life of donor is gradually reduced, survey
Quenching constant out is similar with the result obtained inside solvent under the conditions of deoxygenation, it was demonstrated that can carry out Stern-Volmer
The test of curve.Other some time-resolved emission spectrums and transient absorption spectra for as above converting, in the solvent of deoxygenation
Face clearly can not be observed and measure, but clearly can measure and show inside gel.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention firstly discloses protect the side of the triplet excited state of photosensitizer by oxygen in illumination removing gel
Method is interacted oxygen depleted with gelator and singlet oxygen so that solvent rouses inert gas deoxygenation without carrying out, also without
It need to be operated in glove box, directly under air conditions, the mistake that phosphorescence gradually increases in a solvent can be observed by illumination
Journey；
(2) present invention firstly discloses the special deoxygenation function of gelator is utilized, transparent gel is prepared and on gel
Pattern is formed by illumination.This pattern can be on gel there are the regular hour, the molecular weight depending on PVP and illumination
Time, intensity, the concentration etc. of photosensitizer form gem-pure pattern, can be for shorthand information, Quick Response Code etc., together
When the reproduction of the information being recorded can be observed in different angles.Pattern can be gradually permanent after some time
It disappears, illumination can not be pattern reproduction, ensure that the crypticity of record information.New pattern can at this time be scribed at this
Above gel, repeat " wiping, write "；
(3) present invention is utilized for the first time is capable of the solid matter of illumination deoxygenation and applies in T-T annihilation photon
Upper conversion art carries out deoxygenation with illumination, avoids conversion component from being contacted with oxygen, solves the three of prior art photosensitizer
The problem of weight state is quenched by oxygen, upper transfer efficiency is up to 12%, and in general upper transfer efficiency in the prior art is less than
10, achieve unexpected technique effect；
(4) disclosed by the invention that conversion is carried out based on solid matter deoxygenation protection triplet, it prepares simply, without complexity
Process, strong applicability can be obtained shining for a variety of upper conversion components, and safety and environmental protection, can be used in air, have real
With value, it is suitable for industrialized production；
(5) gel that the present invention is formed using solid state class medium realizes under air conditions inside to upper converting system
The measurement of Stern-Volmer curves, time-resolved emission spectrum and transient absorption spectra.For time-resolved emission spectrum and
Transient absorption spectra in general will under anaerobic with it is semisolid under the conditions of the test that could carry out, by means of this kind of solidifying
Glue can directly measure in air；
(6) illumination deoxidation method provided by the invention can also be applied in photocatalysis, light therapy, solar cell and temperature
Degree sensor etc. is related to the field of triplet protection.
Description of the drawings
Fig. 1 is uv absorption spectra of the Formula II in PVP dichloromethane gels and persistently swashs in 380nm excitation light sources
The spectrogram that clockwork spring part Formula Il emissive porwer changes over time.
Fig. 2 is ultraviolet-visible absorption spectroscopy figure of the Formulas I (100 μM) inside PVP methanol gels and in 360nm exciting lights
Source continues the spectrogram that Au1 emissive porwers change over time under shooting condition；
Fig. 3 is ultraviolet-visible absorption spectroscopy figure of the Formulas I (100 μM) inside PVP hydrogels and in 360nm excitation light sources
Continue the spectrogram that Au1 emissive porwers change over time under shooting condition；
Fig. 4 is to be repeated under room temperature to same PVP (40000 molecular weight) gel containing PtOEP (10 μM)
Lithography experiments (time difference in figure between every photo is one day)；
Fig. 5 is to be repeated under room temperature to same PVP (10000 molecular weight) gel containing PtOEP (10 μM)
Lithography experiments (time difference in figure between every photo is 1h)；
Fig. 6 is under room temperature aerobic conditions, and PVP dichloromethane gels are issued comprising PtOEP and DPA in laser irradiation condition
Transition diagram in life；
Fig. 7 a be in air, under room temperature, contained with a series of 532nm steady lasers irradiation of different optical power densities
The PVP gels of PtOEP (10 μM) and DPA (2mM), record emissive porwer is with optical power intensity variation diagram；
Fig. 7 b are the integral area pair of air, PtOEP/DPA systems up-conversion fluorescence inside PVP gels under room temperature
Stress light optical power density variation logarithmic plot；
Fig. 8 be in air, under room temperature, contained with a series of 635nm steady lasers irradiation of different optical power densities
The PVP gels of PtTPBP (10 μM) and BPEA (2mM), record emissive porwer is with optical power intensity variation diagram；
Fig. 9 is under the conditions of air at room temperature, PVP gels the inside PtOEP is at 645nm as DPA concentration increases phosphorescent lifetime
The Stern-Volmer coordinate diagrams of decaying；
Figure 10 be in air, under room temperature, PtOEP (10 μM)/DPA (2.0mM) under 532nm pulse laser shooting conditions
Time resolution upconversion emission figure inside PVP gels；
Figure 11 is transient absorption of PtOEP (10 μM)/DPA (1.0mM) systems inside PVP gels under the conditions of air at room temperature
Spectrum, excitation wavelength are that (luminescent lifetime that interior illustration is PtOEP/DPA systems inside the PVP gels at 416nm, is used for 532nm
Correct transient absorption spectra).
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
Solid kind medium PVP is used in the present embodiment, and the transmitting that phosphorescence is protected in photochemistry deoxygenation is carried out using PVP gels.
The method is：The PVP that 6g molecular weight is 40000 is added to enter in the dichloromethane of the Formula II containing photosensitizer, the concentration of photosensitizer
It is 1.0 × 10-5mol·dm-3, stirring promotion PVP, which is completely dissolved, becomes fluid, is placed in dark surrounds the dichloromethane that volatilizees,
It is formed after 12h and has figurate gel, photoactivation spectrum of the photosensitizer Formula II in PVP gels is as shown in Figure 1.
Embodiment 2
This embodiment demonstrates PVP not only can form gel application in photoetching and activation, in first in methylene chloride
Also photoetching and activation can be carried out in alcohol and water.Specific implementation method is (by taking methanol gel as an example)：By 6g PVP (molecular weight
40000) it is added in the methanol solution of 10ml Formulas I containing photosensitizer, a concentration of the 1.0 × 10 of photosensitizer-4mol·dm-3, PVP is complete
After fully dissolved, it is placed on beside infrared drying oven and accelerates methanol volatilization, after 14 hours or so, form gel.By hollow out
Pattern is tightly attached to gel surface, photoetching is carried out with ultraviolet flashlight irradiation gel later, with the lower ultraviolet flashlight of energy density
Cylinder carries out the reproduction of photoengraving pattern, and Fig. 2 illustrates photosensitizer Formulas I and shown in the photoactivation spectrogram and photoengraving pattern of methanol gel
Result.Fig. 3 illustrates the result of photoactivation spectrogram and photoengraving pattern displaying of the photosensitizer Formulas I in hydrogel.
Embodiment 3
This embodiment demonstrates the carry out photoetching that PVP gels can repeat, and is embodied as：6g molecular weight is added
In 40000 PVP to the dichloromethane solution containing photosensitizer 2, a concentration of the 1.0 × 10 of photosensitizer-5mol·dm-3, PVP is complete
After fully dissolved, pours into the culture dish that radius is 6.5cm, 12h is placed under dark condition, gel is formed, later with ultraviolet
Light (365nm) irradiation is attached to pierced pattern about 20s on surface plate, ultraviolet light between pierced pattern at a distance from be 5cm, luminous power
Density is 30mWcm-2.There is the pattern of phosphorescence under being irradiated with Weak ultraviolet source above gel.Same gel is carried out
Repetitious photoetching and erasable, as a result shows in Fig. 4, the photo being separated by here all experienced the disappearance of photoetching trace again
Scribing and showing to new pattern, per pictures, the time interval of shooting is 1 day.
Embodiment 4
This embodiment demonstrates the gel that different molecular weight PVP is formed has shadow for the retention time of photoengraving pattern
It rings, specific embodiment is：Be added in the PVP to the dichloromethane solution containing photosensitizer 2 of 6g molecular weight 10000, photosensitizer it is dense
Degree is 1.0 × 10-5mol·dm-3, after PVP is completely dissolved, pour into the culture dish that radius is 6.5cm, in dark condition
Lower placement 12h forms gel, is attached to the pierced pattern about 20s on surface plate, ultraviolet light with ultraviolet light (365nm) irradiation later
It is 5cm, optical power density 30mWcm at a distance between pierced pattern-2.Occur with the irradiation of Weak ultraviolet source is lower above gel
The pattern of phosphorescence.Repetitious photoetching and erasable has been carried out for same gel, has as a result been shown in Fig. 5, here phase
Every photo all experienced the disappearance of photoetching trace and arrive scribing and showing for new pattern again, per pictures, the time interval of shooting is
1h, it can be seen that the time of pattern loss is considerably longer than the PVP in molecular weight 10000 inside the PVP gels of molecular weight 40000
In gel.
Embodiment 5
This embodiment is demonstrated can carry out upper conversion inside PVP gels, be embodied as donor shown in Formula II
It is dissolved in 10ml dichloromethane with receptor shown in Formula V, the molar ratio of donor and receptor is 1:200, concentration of the donor in NMP
It is 1.0 × 10-5mol·dm-3, receptor is 2.0 × 10-3mol·dm-3, the PVP molecules of 6g molecular weight 40000 are added to dichloro
12h, which is placed, in dichloromethane, in dark forms gel.Using the laser irradiation of 532nm, it is observed that upper conversion within 1s
The phenomenon that, as shown in fig. 6, the determination of the record and threshold value of spectrum is also carried out to the process converted on this simultaneously, such as Fig. 7 a and
Shown in 7b.Formula IV Formula IV is added to according to same condition inside PVP gels, it can be seen that red turn of green upper conversion phenomena,
Specific spectrogram is as shown in Figure 8.
Embodiment 6
This embodiment has carried out the test of Stern-Volmer curves in PVP gels.It is embodied as preparing a system
The dichloromethane solution containing Formula II and Formula V is arranged, the concentration of wherein Formulas I is fixed on 1.0 × 10-5mol·dm-3, the concentration model of formula 5
It is 0~1.6 × 10 to enclose variation-4mol·dm-3, variation scale is 2.0 × 10-5mol·dm-3.It is later 40000 by molecular weight
PVP is added in these dichloromethane solutions, and the dichloromethane of 10ml corresponds to the PVP of 6g.Gel is formed after 12h, in 532nm
Under the excitation of pulse laser, it can be seen that with increasing for 5 concentration of formula, the phosphorescent lifetime of Formulas I is reducing always, meets linear gauge
Rule, the quenching constant finally measured are 5.77 × 108mol-1s-1.As shown in Figure 9
Embodiment 7
This embodiment determines the test that time resolved spectroscopy and transient absorption spectra can be carried out inside PVP gels.
It is embodied as：Be embodied as receptor shown in donor shown in Formula II and Formula V being dissolved in 10ml dichloromethane, donor with by
The molar ratio of body is 1:200, donor in NMP a concentration of 1.0 × 10-5mol·dm-3, receptor is 2.0 × 10-3mol·dm-3, the PVP molecules of 6g molecular weight 40000 are added in dichloromethane solution, placing 12h in dark forms gel.Sample is put
It sets on spectrometer, excites PVP gels using the pulsed light of 532nm, can differentiate and carry out time resolved spectroscopy (Figure 10) and wink
The test (Figure 11) of state absorption spectrum.
It can be seen that these types of solvent can be effectively removed oxygen protection triplet excited state from above table, and
Also it can be suitable for upper converting system, while achieve relatively good efficiency.It can be removed completely with nitrogen on oxygen scavenging ability
Oxygen mutually matches in excellence or beauty.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And the increase of accessory, the selection etc. of concrete mode, it all falls within protection scope of the present invention and the open scope.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of photochemistry removes oxygen to protect the medium of the triplet excited state of photosensitizer, which is characterized in that the medium is
Polyvinylpyrrolidone.
2. medium according to claim 1, which is characterized in that the number-average molecular weight of the polyvinylpyrrolidone is 8000
~60000.
3. a kind of method that photochemistry removes oxygen to protect the triplet excited state of photosensitizer, which is characterized in that the method is：
PVP, photosensitizer are mixed with solvent, standing forms gel, irradiates the gel using exciting light.
4. according to the method described in claim 3, it is characterized in that, the solvent includes water, alcohols solvent, amine solvent, carboxylic
It is arbitrary in acids solvent, lactams solvent, ketones solvent, esters solvent, halogenated hydrocarbon solvent or nitroparaffin hydrocarbon solvent
It is a kind of or at least two combination；
Preferably, the alcohols solvent include in methanol, ethyl alcohol, normal propyl alcohol or isopropanol any one or at least two group
It closes；
Preferably, the amine solvent include in butylamine, cyclohexylamine or aniline any one or at least two combination；
Preferably, the carboxylic acids solvent include in formic acid, acetic acid or propionic acid any one or at least two combination；
Preferably, the halogenated hydrocarbon solvent includes dichloromethane and/or chloroform.
5. method according to claim 3 or 4, which is characterized in that the photosensitizer includes Porphyrin-Based Sensitizer, phthalocyanines
Photosensitizer, metal complex Polypyridine class photosensitizer, metal acetylene class photosensitizer, ring metal complex species photosensitizer and fluorine boron
In pyrylium dyes derivative species photosensitizer any one or at least two combination；
Preferably, the Porphyrin-Based Sensitizer includes in the porphyrin of amplification, porphyrin or metal porphyrin complex containing substituent group
Any one or at least two combination；
Preferably, the phthalocyanines photosensitizer includes in the phthalocyanine of amplification, phthalocyanine or metal phthalocyanine complex containing substituent group
Any one or at least two combination；
Preferably, the metal include Li, Mg, Al, Ti, V, VO, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Pd, Ag, Re, Os,
Ir, Pt, Pb, U or UO2In any one or at least two combination.
6. according to claim 3-5 any one of them methods, which is characterized in that a concentration of the 5 × 10 of the photosensitizer-6~1
×10-4mol/L。
7. according to claim 3-6 any one of them methods, which is characterized in that the optical energy density of the exciting light is 0.2
~500mW cm-2。
8. according to claim 3-7 any one of them methods, which is characterized in that the method is：By water, alcohols solvent, amine
Class solvent, carboxylic acids solvent, lactams solvent, ketones solvent, esters solvent, halogenated hydrocarbon solvent or nitroparaffin hydrocarbon solvent
In any one solvent or the mixed solvents of at least two solvent combinations mixed with polyvinylpyrrolidone and photosensitizer, it is photosensitive
Agent concentration is 5 × 10-6~1 × 10-4Mol/L, standing obtain gel and the use of optical energy density are 0.2~50mW cm-2Swash
Shine the irradiation gel, wherein the photosensitizer is Porphyrin-Based Sensitizer, phthalocyanines photosensitizer, metal complex Polypyridine class
In photosensitizer, metal acetylene class photosensitizer, ring metal complex species photosensitizer and fluorine boron pyrylium dyes derivative species photosensitizer
Any one or at least two combination.
9. a kind of application of any one of claim 3-8 the methods, which is characterized in that the method is applied to optical physics and light
It is converted on the observation of chemical process and testing experiment, photoetching or T-T annihilation photon.
10. application according to claim 9, which is characterized in that the observation and test of the optical physics and photochemistry
Experiment includes Stern-Volmer curves, time-resolved emission spectrum and transient absorption spectra.
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