CN111943989B - Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof - Google Patents

Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof Download PDF

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CN111943989B
CN111943989B CN202010699481.5A CN202010699481A CN111943989B CN 111943989 B CN111943989 B CN 111943989B CN 202010699481 A CN202010699481 A CN 202010699481A CN 111943989 B CN111943989 B CN 111943989B
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phthalocyanine
cluster
binary molecule
salt
binary
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CN111943989A (en
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赵澎
梁利花
衣晓燕
吕海金
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Qingdao Spata Analysis Testing Co ltd
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Abstract

The invention discloses a cluster-phthalocyanine binary molecule photosensitizer and a preparation method and application thereof, wherein the cluster-phthalocyanine binary molecule photosensitizer is formed by linking a metal cluster protected by mercaptan and phthalocyanine molecules through chemical bonds, the structural formula is shown in the specification, because of the small-scale nano structure of the cluster, metal atoms in the cluster can generate a strong heavy atom effect, the spin-rail coupling in the phthalocyanine photosensitization process is enhanced, the capability of generating singlet oxygen by the sensitization of the cluster-phthalocyanine binary molecule is improved, meanwhile, the intersystem crossing between excited states is enhanced by the spin-rail coupling, the anti-saturation absorption performance of the phthalocyanine molecules is enhanced, the nanometer phthalocyanine binary molecule can play a good nonlinear absorption role on picosecond to nanosecond pulse laser, and the nanometer phthalocyanine binary molecule photosensitizer can be well applied to laser damage protection, photocatalytic degradation of organic pollutants, photodynamic therapy and sensitized solar cells, and reactants are easy to obtain, and the preparation method is simple.

Description

Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of photosensitizers, in particular to a cluster-phthalocyanine binary molecule photosensitizer and a preparation method and application thereof.
Background
Phthalocyanine compounds are an important photosensitizing molecule, and are widely applied to photochemical related fields including photosensitizing energy conversion, photodynamic therapy, photocatalysis, nonlinear optics and the like, and synthesis and research on various properties of phthalocyanine molecules with novel structures and characteristics are also hot spots. Currently, binary systems composed of large-scale nano materials such as graphene, carbon nano tubes, nano particles and the like and phthalocyanine molecules have the photoelectric characteristics of enhancing charge conduction, separation and the like, and have better photocatalytic performance and the like.
The metal nanocluster scale is typically between a few to tens of nanometers, and is between a molecule and a large-sized nanoparticle, and particularly thiol-protected nickel or palladium cluster molecules are in a crown shape (peara-like), and ring clusters typically containing an even number of metal atoms greater than 6 are better in stability. The application research of palladium-sulfur clusters mainly relates to the action of annular cavities on main and guest bodies of small molecules, electrochemical response performance and the like. In comparison with graphene, carbon nanotubes and the like, thiol-protected metal clusters have no significant electron conjugated system in their molecular structure, and thus their molecules may lack efficient photoelectrochemical properties, thereby limiting their further applications.
However, in the research, it is found that, for the photochemical excited state process, palladium atoms in palladium-sulfur clusters bring about heavy atomic effects, the heavy atomic effects can strengthen spin-orbit coupling effects, and improve the photoexcited state quantum yield and the triplet excited state service life of photosensitizers such as phthalocyanine, so that the photosensitization efficiency of phthalocyanine molecules is enhanced, and in addition, the small-scale nano effect of the clusters can effectively respond to and absorb fs-level ultrashort pulses, so that the palladium-sulfur clusters have potential for being applied as optical limiting materials. Thus, the present patent discloses a novel photosensitizer that links a metal cluster to a phthalocyanine molecule using a chemical bond.
Disclosure of Invention
In view of the above, the invention provides a cluster-phthalocyanine binary molecule photosensitizer, a preparation method thereof and application thereof in protection against laser damage, photocatalytic degradation of organic pollutants, photodynamic therapy and sensitization of solar cells.
The technical scheme adopted by the invention is as follows:
a cluster-phthalocyanine binary molecule photosensitizer formed by linking a thiol-protected metal cluster and a phthalocyanine molecule through a chemical bond, the cluster-phthalocyanine binary molecule photosensitizer having the structural formula:
，
wherein R is CH 2 CH 2 SH or CH 2 CH 2 Ph；
R1 is an ester group, a sulfonate group or a phosphate group;
m' is Pd, ni;
m is Zn, alH or Mn.
Preferably, the ratio of the number of clusters to the number of phthalocyanines in the cluster-phthalocyanine binary molecule photosensitizer is 1:1-4.
Preferably, the number of M' in the structural formula of the cluster-phthalocyanine binary molecule photosensitizer is 4-16.
The preparation method of the cluster-phthalocyanine binary molecule photosensitizer according to any one of the above claims, specifically comprising the following steps:
(1) Adding 4-nitro-substituted phthalonitrile and boron trihalide into n-octanol, keeping the reaction temperature at 150-160 ℃ for reaction for 4 hours under the protection of argon, then adding 4-substituted phthalimide and first metal salt, heating to 150-160 ℃, refluxing for 4-8 hours, and obtaining the corresponding metal phthalocyanine compound after filtration, cleaning and silica gel column chromatography;
(2) Adding first mercaptan and mercaptoethanol into a mixed solvent of triethylamine and acetonitrile, then adding second metal salt, reacting for 24-72 hours at room temperature under the protection of argon, and purifying and separating to obtain a tetrasubstituted mercaptan protected metal cluster;
(3) The molar ratio of tetra-substituted thiol protected metal clusters to mono-carboxyl substituted metal phthalocyanine compounds is 1-3:1, adding the mixture into toluene solvent, adding catalyst and dehydrating agent, reacting at 40-80 ℃ for 2-6 hours, and purifying and separating to obtain the cluster-phthalocyanine binary molecule photosensitizer.
Preferably, the molar ratio of the 4-nitro-substituted phthalonitrile to the boron trihalide is 5:1-3, the boron trihalide being BBr3 or BF3; the molar ratio of the 4-nitro-substituted phthalonitrile to the 4-substituted phthalimide is 9-11:1, and the substituent of the 4-substituted phthalimide is carboxyl, sulfonic acid group or phosphoric acid group, more preferably carboxyl or sulfonic acid group; the molar ratio of the 4-substituted phthalimide to the first metal salt is 1:1-2; when the substituent groups of the 4-substituted phthalimide are carboxyl, sulfonic acid or phosphoric acid groups respectively, the obtained metal phthalocyanine compound is a monocarboxyl substituted metal phthalocyanine compound, a monosulfonic acid substituted metal phthalocyanine compound or a monophosphoric acid substituted metal phthalocyanine compound respectively.
Preferably, the first metal salt in the step (1) is one of zinc salt, aluminum salt or manganese salt; preferably zinc or aluminum salts; the second metal salt in the step (2) is one of palladium salt or nickel salt, preferably palladium nitrate, palladium chloride, nickel acetate, nickel nitrate, more preferably palladium nitrate or nickel acetate.
Preferably, the zinc salt is zinc acetate or zinc chloride, the aluminum salt is aluminum chloride, and the manganese salt is manganese acetate; the zinc salt is more preferably zinc acetate.
Preferably, in the mixed solvent of triethylamine and acetonitrile in the step (2), the volume ratio of triethylamine to acetonitrile is 1:1-3; the mole ratio of the first mercaptan to the mercaptoethanol to the second metal salt is 2-6:1:0.5; the first mercaptan is phenethyl mercaptan or ethanedithiol, more preferably phenethyl mercaptan.
Preferably, the dehydrating agent in the step (3) is N, N' -Dicyclohexylcarbodiimide (DCC), the catalyst is 4-Dimethylaminopyridine (DMAP), and the molar ratio is 1-3:1.
the cluster-phthalocyanine binary molecule photosensitizer is applied to protection of laser damage, photocatalytic degradation of organic pollutants, photodynamic therapy and sensitization of solar cells.
The invention has the beneficial effects that:
1. the cluster-phthalocyanine binary molecule photosensitizer provided by the invention can be effectively dissolved in organic solvents such as dimethyl sulfoxide, dichloromethane and tetrahydrofuran, and is easy to disperse and use. Due to the small-scale nano structure of the cluster, metal atoms such as nickel or palladium can generate a strong heavy atom effect, spin-orbit coupling in the phthalocyanine photosensitization process is enhanced, the capability of generating singlet oxygen by sensitization of the cluster-phthalocyanine binary molecules is improved, meanwhile, intersystem crossing between excited states is enhanced by spin-orbit coupling, the anti-saturation absorption performance of the phthalocyanine molecules is enhanced, and the device can play a good nonlinear absorption role on picosecond to nanosecond pulse laser. The nano-structure of the cluster can effectively scatter picosecond-level laser pulses, and meanwhile, the existence of metal atoms can enable relaxation of an excited state to be improved, and good nonlinear absorption is generated for picosecond-level short pulse lasers, so that the cluster-phthalocyanine binary molecule photosensitizer has good broadband light limiting efficacy.
2. The invention also provides a preparation method of the cluster-phthalocyanine binary molecule photosensitizer, which is easy to obtain reactants and simple in preparation method, and is favorable for mass production of the cluster-phthalocyanine binary molecule photosensitizer.
3. The invention also provides application of the cluster-phthalocyanine binary molecule photosensitizer in protection of laser damage, photocatalytic degradation of organic pollutants, photodynamic therapy and sensitization of solar cells.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof so that those skilled in the art can better understand the present invention.
Example 1
The preparation method of the cluster-phthalocyanine binary molecule photosensitizer comprises the following specific steps:
(1) 8.6g (0.05 mol) of 4-nitrophthalonitrile and 0.67g (0.01 mol) of BF 3 (previously dissolved in 20ml of diethyl ether) was added to 100ml of n-octanol, and after the reaction was carried out for 4 hours at 150 to 160℃under the protection of argon, 0.87g (0.0045 mol) of 4-carboxyphthalimide and 0.825g (0.0045 mol) of zinc acetate were added, and the mixture was heated to 150℃and reacted under reflux for 4 hours, and then filtered, and the filter cake was washed with acetone at a volume ratio of 1:1 as eluent, collecting main bluish violet component after silica gel column chromatography, removing solvent to obtain 7.2g of bluish violet solid powder, namely alpha, -trinitro, alpha-carboxyl, zinc phthalocyanine, wherein the molecular formula is as follows: znPc (NO) 2 ) 3 COOH, yield about 55%;
(2) The volume ratio at 50ml is 1:1, adding 2.76g (0.02 mol) of phenethyl mercaptan and 0.78g (0.01 mol) of mercaptoethanol into a mixed solvent of triethylamine and acetonitrile, then adding 1.24g (0.005 mol) of nickel acetate, stirring at room temperature under the protection of argon gas for reaction for 48 hours, then carrying out recrystallization purification separation on a product by using a mixed solution of methanol and dichloromethane with the volume ratio of 2:1, and separating out 0.8g of light yellow crystals, namely octaphenethyl mercaptan and tetrahydroxyethyl mercaptan protected nickel hexacluster by using dichloromethane as a developing agent by using a method for preparing thin layer chromatography, wherein the molecular formula is as follows: ni (Ni) 6 (SEtPh) 8 (SEtOH) 4 The yield was about 20%;
(3) Mixing 0.002mol of each of the reaction products obtained in the step (1) and the step (2) into 50ml of toluene solution, adding 0.21g (0.001 mol) of N, N' -dicyclohexylcarbodiimide as a dehydrating agent and 0.122g (0.001 mol) of 4-dimethylaminopyridine as a catalyst, reacting for 4 hours at 80 ℃, evaporating the solvent in the reaction products, taking methylene dichloride as a developing agent, collecting a blue-green eluent, and removing the solvent to obtain 3g of cluster-phthalocyanine binary molecule photosensitizer with the molecular formula of: znPcCOO-Ni 6 S 12 The yield is about 60%, and the maximum molecular ion peak is 2502 and the theoretical value is 2503 as determined by MOLDI-TOF mass spectrometry; the structural formula is as follows:
，
wherein R is CH 2 CH 2 Ph。
Example 2
The preparation method of the cluster-phthalocyanine binary molecule photosensitizer comprises the following specific steps:
(1) 8.6g (0.05 mol) of 4-nitrophthalonitrile and 5.00g (0.02 mol) of BBr3 (dissolved in 20ml of diethyl ether in advance) are added to 120ml of n-octanol, after the reaction is carried out for 4 hours under the protection of argon and the reaction temperature is kept between 150 and 160 ℃, 1.49g (0.005 mol) of 4-sulfopotassium-group phthalimide and 1.00g (0.0075 mol) of anhydrous aluminum chloride are added, the mixture is heated to 150 ℃ and refluxed for 4 hours, and then filtered, and the filter cake is washed with acetone and cold dilute hydrochloric acid according to the volume ratio of 1:1 dichloromethylThe mixed solution of alkane and methanol is used as eluent, after silica gel column chromatography, the main blue-violet component is collected, and the solvent is removed to obtain 6.3g of blue-violet solid powder, namely alpha, alpha-trinitro, alpha-sulfonic acid group, aluminum phthalocyanine, the molecular formula of which is AlHPc (NO) 2 ) 3 SO 3 H, yield about 45%.
(2) Adding 3.96g (0.004 mol) of ethanedithiol and 0.78g (0.01 mol) of mercaptoethanol into 50ml of a mixed solvent of triethylamine and acetonitrile with the volume ratio of 1:2, then adding 1.24g (0.005 mol) of nickel acetate, stirring at room temperature under the protection of argon for reaction for 72 hours, then carrying out recrystallization, purification and separation on the product by using a mixed solution of methanol and dichloromethane with the volume ratio of 2:1, and then separating out 0.4g of light yellow crystals, namely octaethanethiol and tetrahydroxyethanethiol protected nickel six clusters with the molecular formula of Ni by using dichloromethane as a developing agent by using a method of preparing thin layer chromatography 6 (SEtSH) 8 (SEtOH) 4 The yield was about 10%.
(3) Mixing 0.002mol of each of the reaction products obtained in the step (1) and the step (2) into 50ml of toluene solution, adding 0.42g (0.002 mol) of N, N' -dicyclohexylcarbodiimide as a dehydrating agent and 0.122g (0.001 mol) of 4-dimethylaminopyridine as a catalyst, reacting for 6 hours at 60 ℃, evaporating the solvent in the reaction products, taking methylene dichloride as a developing agent, collecting a blue eluent, and removing the solvent to obtain 2.2g of cluster-phthalocyanine binary molecule photosensitizer, wherein the molecular formula is as follows: alHPcSO 3 -Ni 6 S 12 The yield was about 45%, the maximum molecular ion peak was 2148 as determined by MOLDI-TOF mass spectrometry, and the theoretical value was 2150; the structural formula is as follows:
wherein R is CH 2 CH 2 SH。
Example 3
The preparation method of the cluster-phthalocyanine binary molecule photosensitizer comprises the following specific steps:
(1) 8.6g (0.05 mol) of 4-nitrophthalonitrile and 2.01g (0.03 mol) of BF 3 (pre-dissolved in 20ml diethyl ether) to 100ml of n-butyl acetateIn octanol, under the protection of argon, after keeping the reaction temperature between 150 and 160 ℃ for 4 hours, adding 1.32g (0.0055 mol)) of 4-phosphate group phthalimide and 1.90g (0.011 mol) of manganese acetate, heating to 150 ℃, carrying out reflux reaction for 4 hours, filtering, washing a filter cake with acetone, and mixing the materials according to the volume ratio of 1:1 as eluent, collecting main blue-violet component after silica gel column chromatography, removing solvent to obtain 7.2g of blue solid powder, namely alpha, alpha-trinitro, alpha-phosphate, and manganese phthalocyanine, wherein the molecular formula is as follows: mnPc (NO) 2 ) 3 PO 3 H 2 The yield was about 55%.
(2) The volume ratio at 50ml is 1:3, adding 8.28g (0.006 mol) of phenethyl mercaptan and 0.78g (0.01 mol) of mercaptoethanol into a mixed solvent of triethylamine and acetonitrile, then adding 1.15g (0.005 mol) of palladium nitrate dihydrate, stirring at room temperature under the protection of argon gas for reaction for 36 hours, then carrying out recrystallization purification separation on the product by using a mixed solution of methanol and dichloromethane with the volume ratio of 2:1, and separating 0.9g of light yellow crystals, namely octaphenethyl mercaptan and tetrahydroxyethyl mercaptan protected palladium six clusters with the molecular formula Pd by using dichloromethane as a developing agent by using a method of preparing thin layer chromatography 6 (SEtPh) 8 (SEtOH) 4 The yield was about 30%.
(3) Mixing 0.002mol of each of the reaction products obtained in the step (1) and the step (2) into 50ml of toluene solution, adding 0.56g (0.003 mol) of N, N' -dicyclohexylcarbodiimide as a dehydrating agent and 0.122g (0.001 mol) of 4-dimethylaminopyridine as a catalyst, reacting for 6 hours at 60 ℃, evaporating the solvent in the reaction products, taking methylene dichloride as a developing agent, collecting a blue-green eluent, removing the solvent to obtain 2.6g of cluster-phthalocyanine binary molecule photosensitizer with a molecular formula of MnPcPO 3 -Pd 6 S 12 The yield is about 50%, and the maximum molecular ion peak is 2844 and the theoretical value is 2846 as determined by MOLDI-TOF mass spectrometry; the structural formula is as follows:
wherein R is CH 2 CH 2 Ph。
Example 4
(1) In example 3, step (2), after separating the palladium hexacluster with methylene chloride as a developing agent, a pale yellow band immediately above the palladium hexacluster band, namely, palladium octacluster, was observed on the thin layer chromatography plate, and the molecular formula was Pd 8 (SEtPh) 12 (SEtOH) 4 The pale yellow crystals (0.2 g) were obtained by separation and crystallization, and the yield was about 7%.
(2) Mixing 0.001mol of the reaction product obtained in the step (1) of the present example and the step (1) of the example 1 into 30ml of toluene solution, adding 0.56g (0.003 mol) of N, N' -dicyclohexylcarbodiimide as a dehydrating agent and 0.122g (0.001 mol) of 4-dimethylaminopyridine as a catalyst, reacting at 60 ℃ for 4 hours, evaporating the solvent in the reaction product, using methylene dichloride as a developing agent, collecting a blue-green eluent, removing the solvent to obtain 2.6g of cluster-phthalocyanine binary molecule photosensitizer with a molecular formula of ZnPcCOO-Pd 8 S 16 The yield is about 50%, and the maximum molecular ion peak is 3543 and the theoretical value is 3544 as determined by MOLDI-TOF mass spectrometry; the structural formula is as follows:
wherein R is CH 2 CH 2 Ph。
Example 5
The synthesized cluster-phthalocyanine binary molecule photosensitizer is subjected to singlet oxygen quantum yield test, and the obtained results are shown in table 1:
table 1 comparison of photophysical and photosensitizing properties of the cluster-phthalocyanine binary molecules provided by the present invention with existing phthalocyanine molecules.
As can be seen from Table 1, compared with the conventional common phthalocyanine molecules, the cluster-phthalocyanine binary molecule photosensitizer provided by the invention has the advantages of reduced fluorescence quantum yield, stronger singlet oxygen sensitization capability and equivalent photostability, and is a novel high-efficiency photosensitizer. The method is characterized in that heavy atomic effects are generated by metal atoms such as nickel or palladium in the nano structure of the cluster, so that spin-orbit coupling is enhanced, transition probability from a singlet state to a triplet state is increased, fluorescence emission is reduced, and the generation efficiency of oxygen in the triplet state and the singlet state is enhanced.
Example 6
The synthesized cluster-phthalocyanine binary molecule photosensitizer of examples 1-4 was subjected to a nonlinear optical property test, and its optical limiting properties were tested in dimethyl sulfoxide solution by using a nonlinear optical z-scan test method, and the results are shown in table 2:
table 2 optical limiting test data for the cluster-phthalocyanine binary photosensitizers of example 1 and example 3
It can be seen from Table 2 that the cluster-phthalocyanine binary molecules prepared in example 1 and example 3 have a certain optical clipping capability for both 150fs short pulse and 25ns long pulse lasers. The nano structure of the cluster molecule can absorb and scatter 150fs short pulse laser, and the phthalocyanine molecule can generate strong reverse saturation absorption for 25ns long pulse laser due to the existence of heavy atom effect of the cluster, which proves that the cluster-phthalocyanine binary molecule prepared by the invention is a good wide pulse light limiting material.
The cluster-phthalocyanine binary molecule photosensitizer provided by the invention and the preparation method and application thereof are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in the understanding of the methods and central concepts of the present invention. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (8)

1. The cluster-phthalocyanine binary molecule photosensitizer is characterized in that the cluster-phthalocyanine binary molecule photosensitizer is formed by linking a metal cluster protected by mercaptan and a phthalocyanine molecule through a chemical bond, and has the structural formula:
，
wherein R is CH 2 CH 2 SH or CH 2 CH 2 Ph；
R1 is an ester group, a sulfonate group or a phosphate group;
m' is Pd, ni;
m is Zn, alH or Mn.
2. The method for preparing the cluster-phthalocyanine binary molecule photosensitizer according to claim 1, which is characterized by comprising the following steps:
(1) Adding 4-nitro-substituted phthalonitrile and boron trihalide into n-octanol, keeping the reaction temperature at 150-160 ℃ for reaction for 4 hours under the protection of argon, then adding 4-substituted phthalimide and first metal salt, heating to 150-160 ℃, refluxing for 4-8 hours, and obtaining the corresponding metal phthalocyanine compound after filtration, cleaning and silica gel column chromatography;
(2) Adding first mercaptan and mercaptoethanol into a mixed solvent of triethylamine and acetonitrile, then adding second metal salt, reacting for 24-72 hours at room temperature under the protection of argon, and purifying and separating to obtain a tetrasubstituted mercaptan protected metal cluster;
(3) The molar ratio of the tetra-substituted thiol-protected metal clusters to the metal phthalocyanine compound is 1-3:1, adding the mixture into toluene solvent, adding catalyst and dehydrating agent, reacting at 40-80 ℃ for 2-6 hours, and purifying and separating to obtain the cluster-phthalocyanine binary molecule photosensitizer.
3. The method for preparing a cluster-phthalocyanine binary molecule photosensitizer according to claim 2, wherein the 4-nitro substitutionThe molar ratio of phthalonitrile to boron trihalide is 5:1-3, and the boron trihalide is BBr 3 Or BF 3 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of the 4-nitro-substituted phthalonitrile to the 4-substituted phthalimide is 9-11:1, and the substituent of the 4-substituted phthalimide is carboxyl, sulfonic group or phosphoric group; the molar ratio of the 4-substituted phthalimide to the first metal salt is 1:1-2.
4. The method for preparing a cluster-phthalocyanine binary molecule photosensitizer according to claim 2, wherein the first metal salt is one of zinc salt, aluminum salt or manganese salt; the second metal salt is one of palladium salt or nickel salt.
5. The method for preparing a cluster-phthalocyanine binary molecule photosensitizer according to claim 4, wherein the zinc salt is zinc acetate or zinc chloride, the aluminum salt is aluminum chloride, and the manganese salt is manganese acetate.
6. The preparation method of the cluster-phthalocyanine binary molecule photosensitizer according to claim 2, wherein the volume ratio of triethylamine to acetonitrile in the mixed solvent of triethylamine and acetonitrile is 1:1-3; the mole ratio of the first mercaptan to the mercaptoethanol to the second metal salt is 2-6:1:0.5; the first mercaptan is phenethyl mercaptan or ethanedithiol.
7. The method for preparing a cluster-phthalocyanine binary molecule photosensitizer according to claim 2, wherein the dehydrating agent is N, N' -dicyclohexylcarbodiimide, the catalyst is 4-dimethylaminopyridine, and the molar ratio of the dehydrating agent to the catalyst is 1-3:1.
8. the use of a cluster-phthalocyanine binary molecule photosensitizer in protection from laser damage, sensitized solar cells according to claim 1.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN101182362A (en) * 2007-12-06 2008-05-21 浙江理工大学 Method for preparing cyclodextrin-phthalocyanine binary combination

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Title
羟基硫醇保护钯纳米团簇对羧基取代锌酞菁光物理性质的影响;赵澎等;《中国感光学会2017年学术年会暨第九届五次理事会论文集》;20171231;第73页 *

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