WO2023225680A1 - Systèmes et procédés d'émission de lumière ultraviolette - Google Patents

Systèmes et procédés d'émission de lumière ultraviolette Download PDF

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WO2023225680A1
WO2023225680A1 PCT/US2023/067306 US2023067306W WO2023225680A1 WO 2023225680 A1 WO2023225680 A1 WO 2023225680A1 US 2023067306 W US2023067306 W US 2023067306W WO 2023225680 A1 WO2023225680 A1 WO 2023225680A1
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sensitizer
bis
annihilator
light
dbp
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PCT/US2023/067306
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Daniel N. CONGREVE
Tracy SCHLOEMER
Qi Zhou
Danielle MAI
Brendan WIRTZ
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The Board Of Trustees Of The Leland Stanford Junior University
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Publication of WO2023225680A1 publication Critical patent/WO2023225680A1/fr

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Definitions

  • the disclosure is generally directed to systems and methods for localized ultraviolet light emission and more specifically to systems of UV-emitting vesicles and methods of synthesis and use.
  • UV light is high-energy electromagnetic radiation having a wavelength between approximately 10 nm and 400 nm.
  • Short-wave UV light can provide ionizing radiation capable of providing sufficient energy to ionize atoms or molecules by detaching electrons.
  • Long-wave UV light is not considered ionizing radiation but does provide sufficient energy to catalyze a number of chemical and biological reactions. Accordingly, UV radiation is utilized in to provide energy for numerous biological, chemical, and industrial applications.
  • Photon upconversion is a process in which the sequential absorption of two or more photons leads to the emission of light at a shorter wavelength.
  • Various organic and inorganic materials can perform upconversion through various mechanisms.
  • Organic molecules can achieve photon upconversion through triplet-triplet annihilation, which is an energy transfer mechanism between two molecules in their triplet state (Fig. 1 ).
  • a sensitizer and an emitter (annihilator).
  • the sensitizer absorbs the low energy photon and populates its first excited triplet state (T1 ) through intersystem crossing.
  • the sensitizer then transfers the excitation energy to the emitter, resulting in a triplet excited emitter and a ground state sensitizer.
  • Two triplet excited emitters then can undergo triplet-triplet annihilation, and if a singlet excited state (S1 ) of the emitter is populated fluorescence results in an upconverted photon.
  • the system can include an amphiphilic vesicle having an organic core encapsulated by an outer hydrophilic region.
  • the organic core can include a sensitizer and an annihilator for performing triplet-triplet annihilation upconversion to emit UV light.
  • the system can be solubilized in an aqueous solution, an aqueous gel, an aqueous sol, or an aqueous emulsion.
  • a system for localized UV emission can be provided.
  • the system includes a sensitizer and an annihilatorfor performing triplet-triplet annihilation upconversion to emit UV light.
  • Input light can be impinged on the system, photons of the input light are upconverted, resulting in UV emission.
  • the input light can traverse through a medium or a material that is incapable of being traversed by light having the same wavelength of the emitted UV light.
  • a system is for localized UV emission.
  • the system comprises an amphiphilic vesicle having an inner organic core encapsulated by an outer hydrophilic region.
  • the system comprises a sensitizer.
  • the system comprises an annihilator.
  • the sensitizer and annihilator are within the inner organic core of the amphiphilic vesicle.
  • annihilator is capable of releasing photons of UV light when the sensitizer is stimulated with input light
  • the system further comprises : an aqueous solution, an aqueous gel, an aqueous sol, or an aqueous emulsion.
  • the amphiphilic vesicle is solubilized within the solution, the aqueous gel, the aqueous sol, or the aqueous emulsion.
  • the sensitizer is stimulated by light having a wavelength between 400 nm and 1000 nm.
  • a method provides localized UV light.
  • the method comprises providing a UV emitting system comprising.
  • the UV emitting system comprises an amphiphilic vesicle having an inner organic core encapsulated by an outer hydrophilic region, a sensitizer, and an annihilator.
  • the sensitizer and annihilator are within the inner organic core of the amphiphilic vesicle.
  • the amphiphilic vesicle is solubilized within an aqueous solution, an aqueous gel, an aqueous sol, or an aqueous emulsion.
  • the method comprises impinging an input light on the UV emitting system such that photons of the input light come into contact with the inner organic core resulting in emission of UV light.
  • the method further comprises, prior to impinging the input light on the UV emitting system, traversing the input light through a medium that cannot be traversed by UV light having a wavelength equivalent the wavelength emitted by the annihilator.
  • the method further comprises,
  • the input light has a wavelength of between 400 nm and 1000 nm.
  • the input light is infrared light.
  • the amphiphilic vesicle is a micelle that comprises an amphiphilic polymer.
  • the amphiphilic polymer comprises one of: polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), poly /V-isopropyl acrylamide (pNIPAM), polylactic acid (PLA), or a polyamide.
  • PEG polyethylene glycol
  • PVP polyvinyl pyrrolidone
  • pNIPAM poly /V-isopropyl acrylamide
  • PLA polylactic acid
  • the amphiphilic polymer comprises block- poly(ethylene glycol)-b/oc -poly(propylene glycol)-b/oc -poly(ethylene glycol).
  • the amphiphilic polymer comprises F127 polymer.
  • the sensitizer is one of: bis(2- phenylpyridine)(acetylacetonate)iridium(lll), lr(ppy)2(acac) (ppy2); bis(2-(3,5- dimethylphenyl)-4-propylpyridine)(2,2,6,6-tetramethylheptane-3,5-diketonate)iridium(lll), lr(dmppy-pro)2tmd (tmd); tris(2-phenylpyridine)iridium(l II), lr(ppy)s (ppy3); 1 ,2,3,5- Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, 2,4,5,6-tetra(carbazol-9-yl)benzene-1 ,3- dicarbonitrile (4CzlPN); or 3,3'-carbonylbis(7-diethylaminocoumarin) (CBDAC).
  • the sensitizer is one of: bis(2- phenylpyridine)(acetylacetonate)iridium(lll), lr(ppy)2(acac) (ppy2) or bis(2-(3,5- dimethylphenyl)-4-propylpyridine)(2,2,6,6-tetramethylheptane-3,5-diketonate)iridium(lll), lr(dmppy-pro)2tmd (tmd).
  • the annihilator is one of: pyrene; 2,7-di-tert- butylpyrene (DBP); 2,5-Diphenyloxazole (PPO); 1 ,4- bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph); or ([1 ,1'-Biphenyl]-4- ylethynyl)triisopropylsilane (p-TIPS-BP).
  • the sensitizer is tris(2-phenylpyridine)iridium(lll), lr(ppy)s (ppy3) and the annihilator is one of: pyrene; 2,7-di-tert-butylpyrene (DBP); 2,5- Diphenyloxazole (PPO); or 1 ,4-bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph).
  • the sensitizer is bis(2- phenylpyridine)(acetylacetonate)iridium(lll), lr(ppy)2(acac) (ppy2) and the annihilator is one of: pyrene; 2,7-di-tert-butylpyrene (DBP); 2,5-Diphenyloxazole (PPO); 1 ,4- or bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph).
  • the sensitizer is bis(2-(3,5-dimethylphenyl)-4- propylpyridine)(2,2,6,6-tetramethylheptane-3,5-diketonate)iridium(lll), lr(dmppy-pro)2tmd (tmd) and the annihilator is one of: pyrene; 2,7-di-tert-butylpyrene (DBP); 2,5- Diphenyloxazole (PPO); or 1 ,4-bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph).
  • the sensitizer is 1 ,2,3,5-Tetrakis(carbazol-9-yl)-4,6- dicyanobenzene, 2,4,5,6-tetra(carbazol-9-yl)benzene-1 ,3-dicarbonitrile (4CzlPN) and the annihilator is one of: pyrene; 2,7-di-tert-butylpyrene (DBP); 2,5-Diphenyloxazole (PPO); 1 ,4-bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph); or ([1 ,1'-Biphenyl]-4- ylethynyl)triisopropylsilane (p-TIPS-BP).
  • DBP 2,7-di-tert-butylpyrene
  • PPO 2,5-Diphenyloxazole
  • TIPS-Nph 1,4-bis((triisoprop
  • the sensitizer is 3,3'-carbonylbis(7- diethylaminocoumarin) (CBDAC) and the annihilator is one of: pyrene, 2,7-di-tert- butylpyrene (DBP); or 1 ,4-bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph).
  • CBDAC 3,3'-carbonylbis(7- diethylaminocoumarin)
  • DBP 2,7-di-tert- butylpyrene
  • TIPS-Nph 1 ,4-bis((triisopropylsilyl)ethynyl)naphthalene
  • Figure 1 provides a schematic of triplet-triplet annihilation photon upconversion.
  • Figure 2 provides a schematic of a system for localized UV emission.
  • Figure 3 provides molecular structures of sensitizers and annihilators and various combinations of use.
  • Fig. 3 further provides data on mix-and-match sensitizer/annihilator pairings for blue-to-UV upconversion micelles.
  • the UCPL was collected through a 425 nm short pass filter. UC intensities were normalized to each spectrum emission counts at 425 nm (set to be 0.5).
  • the concentrations used for data presented in this figure are summarized in Fig. 17.
  • Figure 4 provides a schematic depicting the ability to provide localized UV emission in a location that cannot be reached by traditional UV emission sources.
  • Figure 5 provides a schematic for generating systems for localized UV emission.
  • FIGS. 6A and 6B provide a mechanism of triplet-triplet annihilation upconversion (TTA-UC) and newly identified iridium-based sensitizers for blue-to-UV upconversion.
  • 6A The process of triplet-triplet annihilation upconversion (TTA-UC): Sensitizers (Sen) absorb lower energy photons and generate triplets via intersystem crossing (ISC). Annihilators (Ann) are promoted to their triplet states through triplet energy transfer (TET) from Sen. Two Ann triplets can annihilate to an excited singlet. The Ann singlet emits a higher energy photon, returning to the ground state.
  • TTA triplet energy transfer
  • Figure 7 provides a data table of solubility of three iridium complexes in organic solvents at room temperature determined by UV-vis absorption spectroscopy.
  • Figure 8 provides a theoretical prediction of the number of molecules per micelle based on concentrations in solutions added for micelle fabrication using a Poisson distribution. In this model, the total number of available molecules are distributed among nanodroplets of TCB according to a Poisson probability distribution. An upper boundary of the number of nanodroplets available is determined by the TCB solution volume (20 pL) used to make micelles (for simplicity, we assume all the chloroform initially added evaporates). In this simulation, we estimate a nanodroplet diameter of 25 nm based on DLS. This is an upper boundary condition, as it is difficult to estimate the true volume of the nanodroplet in the F-127 micelle core.
  • Figures 9A to 9C provide data of screening iridium-based sensitizers reveals versatile TTA-UC pairings with the annihilator DBP in toluene.
  • 9A Normalized upconversion photoluminescence (UCPL) of sensitizer/annihilator pairs ppy3/DBP, ppy2/DBP, and tmd/DBP in toluene under 447 nm laser excitation with different power densities.
  • UCPL was collected through a 425 nm short pass filter.
  • 9B UC quantum yields ( ⁇ i>uc) of ppy3/DBP, ppy2/DBP, and tmd/DBP UC systems in toluene.
  • Figure 10 provides a data table of optimized concentrations of [Sensitizer]/[Annihilator] in bulk solution (toluene) and for TCB/chloroform solutions used to prepare micelles.
  • Figure 11 provides data results of Stern-Volmer quenching tests on the sensitizers. All three sensitizers were kept at the same concentration (100 pM). DBP was used as the annihilator at varying concentration.
  • Figures 12A and 12B provide data of nanoencapsulation of iridium complexes with DBP to form UV-emitting UC micelles.
  • 12A Upconversion (UC) and phosphorescence (Ph) of sensitizers in both micelles and solutions (1 ,2,4- trichlorobenzene (TCB)) under 447 nm excitation. Constant concentrations of UC materials were used to compare TTA-UC in TCB solutions as compared to micelles (i.e. , the same total quantity of UC materials was used and diluted to a constant volume). A 425 nm short pass filter was used when collecting UC emission, and a 475 nm long pass filter was used when collecting sensitizer phosphorescence.
  • the gray dashed line separates UC and phosphorescence.
  • the counts of UC and phosphorescence were scaled to the highest count of ppy3/DBP micelle UC (set to 1.0).
  • 12B A comparison of UC and phosphorescence intensities of the three UV-emitting micelles. The concentrations used for data presented in 12A and 12B are summarized in Fig. 10.
  • Figure 13 provides a data table of representative dynamic light scattering (DLS) data for micelles with different encapsulated species.
  • DLS dynamic light scattering
  • Figure 14 provides a data table of upconversion-to-phosphorescence ratios of [Sensitizer]/[Annihilator] in TCB and micelles.
  • Figure 15 provides data of UV-emitting upconversion micelles exhibit energetic losses to phosphorescence.
  • UC and Ph are separated by the gray dashed line.
  • the counts of UC and Ph are scaled to the highest count of ppy3/DBP micelle UC.
  • Figure 16 provides data of upconversion intensity dependence on incident power for ppy3/DBP, ppy2/DBP, and tmd/DBP upconversion micelles.
  • the optimized sensitizer and annihilator concentrations are summarized in Fig. 10.
  • Figure 17 provides a data table of concentrations of [Sensitizer]/[Annihilator] in TCB/chloroform solutions used to fabricate UV-emitting UC micelles in Fig. 3.
  • Figures 18A to 18F provide data showing blue incident light performs UV photochemistry with ppy2/PPO micelles as demonstrated by photolysis of caged fluorescein.
  • 18A Ortho-nitrobenzyl caged fluorescein is non-fluorescent until UV- triggered photolysis, which produces the uncaged product fluorescein.
  • 18B Schematic demonstrating that caged fluorescein undergoes photolysis upon exposure to a 365 nm LED and displays visible color changes (top), whereas caged fluorescein does not photolyze upon exposure to 470 nm LED (middle).
  • All cuvettes contained 2.5 mL of 0.2 mM caged fluorescein in 1 x phosphate-buffered saline (PBS).
  • 18D, 18E, and 18F UV-vis absorption spectra corresponding to the top, middle, and bottom rows of cuvettes shown in 4C, respectively.
  • the black lines in 18E and 18F are micelle-only controls that do not contain fluorescein.
  • a characteristic fluorescein absorbance peak near 490 nm is evident after photolysis of caged fluorescein with UV light (18D) or blue-to-UV upconversion (18F).
  • Figure 19 provides data of optimizing upconverted PPO emission in micelles.
  • Upconversion photoluminescence (UCPL) measurements with 447 nm laser incident light demonstrate that the maximum upconversion intensity ( ⁇ 425 nm) is achieved with micelles made with 200 mM PPO in chloroform. No distinguishable improvement was observed upon increasing the concentration to 250 mM, so ppy2/PPO upconversion micelles were fabricated with saturated ppy2 in TCB and 200 mM PPO in chloroform.
  • a 425 nm short pass filter was placed in front of an Ocean Optics QE Pro detector, resulting in low intensities between 425 nm and 650 nm and influencing the spectral shape of the sensitizer luminescence above 650 nm.
  • Each micelle UCPL spectrum was scaled by the maximum of the 50 mM spectrum to preserve relative intensity.
  • Figure 20 provides a data table of estimation of 4> uc of the optimized micelles using a relative method.
  • Figure 21 provides data of fluorescence changes of caged fluorescein solutions indicate successful photolysis with incident UV light or blue light with ppy2/PPO micelles. Fluorescence data of samples presented in Fig. 18C. Top: 365 nm UV light (19.7 mW) photolyzed caged fluorescein in solution, as demonstrated by a drastic increase in fluorescence. Middle: 470 nm blue light (50.4 mW) did not photolyze caged fluorescence over a 30-minute interval. Bottom: 470 nm blue light (50.4 mW) photolyzed caged fluorescein when ppy2/PPO upconversion micelles were incorporated in solution.
  • FIG. 22A Schematic of the experimental setup for B: light beam penetration through cuvettes. 22B: UV light (365 nm) attenuates more substantially across a 1 cm cuvette than blue light (470 nm).
  • Both samples contain 0.2 mM caged fluorescein in 1 x PBS, and the sample irradiated by blue light also contained ppy2/PPO upconversion micelles.
  • the UV beam is visualized by fluorescence, whereas the blue beam is visualized by fluorescence, sensitizer luminescence, and annihilator upconversion emissions.
  • Both LED sources were operated at 32 mW.
  • 22C Schematic of the experimental setup for C: light focused with a 50x 0.55 numerical aperture (NA) objective.
  • 22D Photographic images of focused UV light photolysis of caged fluorescein throughout the light path, whereas blue-to-UV upconversion confines photolysis to a voxel deep within the solution.
  • the UV beam is visualized by fluorescence, and the blue beam is visualized by fluorescence and sensitizer luminescence.
  • a fluorescein solution (top) and fluorescein and ppy2/PPO micelles solution (bottom) were irradiated with the same power (2.2 mW) of 365 nm UV LED and 470 nm blue LED, respectively.
  • All cuvettes contained 1 .5 mL of 0.67 mM caged fluorescein.
  • the light was focused by a 50x 0.55 NA objective.
  • the scientific camera was equipped with a 500 nm long pass filter.
  • Figure 23 provides data showing UV and blue light excite uncaged fluorescein. Excitation spectrum of the sample irradiated by 365 nm light for 30 s (Fig. 18C, top row) shows that blue and UV light excite uncaged fluorescein. Emission intensity at 512 nm was monitored, and the displayed spectrum was scaled by the maximum measured emission intensity.
  • Figure 24 provides data of normalized intensity of the incident beams across the quartz cuvettes in Fig. 22B. Imaged was used to split images into blue, green, and red color channels. Then, gray values of the green channel were extracted to quantify the attenuation of incident beams across the quartz cuvettes.
  • Figure 25 provides a schematic of four measurements taken for each sample to calculate the UC quantum yield.
  • localized UV emission is achieved via triplet-triplet annihilation photon upconversion (TTA-UC).
  • TTA-UC triplet-triplet annihilation photon upconversion
  • vesicles comprising TTA-UC sensitizers and annihilators are utilized.
  • a sensitizer-annihilator combination is capable of converting longer wavelength light (e.g., visible light) into UV light.
  • Several embodiments are also directed to methods of using and/or synthesizing systems of localized UV emission.
  • TTA-UC sensitizers and annihilators can be strategically positioned in a location in which longer wavelength light (e.g., visible light), but not UV light, is capable of reaching. The longer wavelength light can be upconverted to higher energy UV light via TTA-UC, providing UV light emission.
  • TTA-UC provides a means for UV light emission in locations that UV light cannot normally reach
  • most TTA-UC sensitizers and annihilators are organic molecules with low solubility in water.
  • organic sensitizers and annihilators are unusable due to their lack of solubility and an inability to achieve high concentrations therein. Accordingly, there is a need for a non-superficial UV-emitting system that is water soluble.
  • a UV light emitting vesicle that comprises organic sensitizers and annihilators encapsulated within the interior portion of the vesicle.
  • the vesicles can be utilized in non-superficial aqueous environments and require less input light, allowing for robust UV emission in locations that are difficult to provide UV energy but are reachable via longer wavelength light.
  • the vesicles unexpectedly allow for mixing and matching of combinations of sensitizers and annihilators for emitting UV light due to their good solubility in the vesicle’s organic solvent-filled core.
  • a system of localized UV light emission comprises an amphiphilic vesicle having an outer hydrophilic region and inner organic core, the outer hydrophilic portion encapsulating the inner organic core.
  • a system of localized UV light emission comprises organic compounds of photon upconversion.
  • the organic compounds of photon upconversion comprise a sensitizer and an annihilator for providing TTA-UC.
  • the exemplary system 201 includes an outer hydrophilic region 203 and an inner hydrophobic organic region 205.
  • Inner organic region 205 includes organic compounds for photon upconversion, such as sensitizers and annihilators for providing TTA-UC.
  • To emit UV light two longer wavelength photons 207 contact organic region 205 resulting in upconversion longer wavelength photons 207 into a UV photon 209 that is emitted.
  • Upconversion can be performed by utilizing the TTA-UC mechanism, as shown in Fig. 1 .
  • amphiphilic vesicle such as (for example) micelles and liposomes.
  • Any molecules capable of forming amphiphilic vesicles can be utilized.
  • molecules used to form amphiphilic vesicles include (but are not limited to) detergents, phospholipids, and polymers.
  • polymers used for forming micelles include (but are not limited to) polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), poly /V-isopropyl acrylamide (pNIPAM), polylactic acid (PLA), and polyamides (e.g., poly L-lysine).
  • an amphiphilic block copolymer is utilized.
  • An example of an amphiphilic block copolymer is b/oc -poly(ethylene glycol)-b/oc -poly(propylene g ⁇ yco ⁇ )-block- poly(ethylene glycol). Any appropriate block lengths can be utilized such that a micelle having an inner organic core and a hydrophilic outer region is formed.
  • the F127 polymer is utilized, comprising the formula b/ock-poly(ethylene glycol)ioi-b/ock-poly(propylene glycol)56-b/oc/c-poly(ethylene glycol)ioi.
  • the overall size of a system of localized UV light emission can be any size, but generally in the nanometer to micrometer range.
  • the diameter of a system of localized UV light emission is less than 1000 nm, is less than 500 nm, is less than 200 nm, is less than 100 nm, or is less than 50 nm.
  • the organic core provides a means to perform photon upconversion.
  • the organic core comprises one or more sensitizers and one or more annihilators; the sensitizer and annihilator are paired to perform photon upconversion via TTA-UC. Accordingly, the sensitizer is capable of receiving longer wave light photons then transferring the energy of the photons to the annihilator such that it emits UV light photons (see Fig. 1).
  • sensitizers that can be utilized within the organic core include (but are not limited to) bis(2-phenylpyridine)(acetylacetonate)iridium(lll), lr(ppy)2(acac) (PPy2); bis(2-(3,5-dimethylphenyl)-4-propylpyridine)(2, 2,6,6- tetramethylheptane-3,5-diketonate)iridium(lll), lr(dmppy-pro)2tmd (tmd); tris(2- phenylpyridine)iridium(lll), lr(ppy)s (ppy3); 1 ,2,3,5-Tetrakis(carbazol-9-yl)-4,6- dicyanobenzene, 2,4,5,6-tetra(carbazol-9-yl)benzene-1 ,3-dicarbonitrile (4CzlPN); and 3,3'-carbonylbis(7-dieth
  • annihilators that can be utilized within the organic core include (but are not limited to) pyrene, 2,7-di-tert-butylpyrene (DBP); 2,5-Diphenyloxazole (PPO); 1 ,4-bis((triisopropylsilyl)ethynyl)naphthalene (TIPS-Nph), and ([1 , 1 '-Biphenyl]-4- ylethynyl)triisopropylsilane (p-TIPS-BP).
  • DBP 2,7-di-tert-butylpyrene
  • PPO 2,5-Diphenyloxazole
  • TIPS-Nph 1,4-bis((triisopropylsilyl)ethynyl)naphthalene
  • p-TIPS-BP 1,3-Biphenyl]-4- ylethynyltriisopropylsilane
  • sensitizer and annihilator capable of receiving longer wave light photons and upconverting into UV light photons can be utilized (see Figs. 3).
  • sensitizer and annihilator which provide good upconversion results, are utilized within the organic core:
  • Many embodiments are directed to an aqueous solution, an aqueous gel, an aqueous sol, or an aqueous emulsion having one or more systems of localized UV light emission solubilized therein.
  • Each system of localized UV light emission can comprise an amphiphilic vesicle having an outer hydrophilic region and inner organic core, the outer hydrophilic portion encapsulating the inner organic core and providing the solubility within the aqueous solution.
  • An aqueous solution, gel, sol, or emulsion can comprise a collection of systems of localized UV light emission in which the collection of systems is dispersed throughout.
  • each system of the collection contains the same sensitizer and annihilator combination such that the solution is capable of producing a particular wavelength of UV light.
  • at least two systems of the collection each contain a unique sensitizer and annihilator combination such that the solution is capable of producing at least two wavelengths of light, or alternatively the solution is capable of producing a particular wavelength of UV light from at least two wavelengths of input light.
  • Several embodiments are directed to producing localized UV emission via a system comprising an amphiphilic vesicle, a sensitizer, and an annihilator.
  • a collection of systems is utilized to produce localized UV emission, in which the collection is provided in an aqueous solution, gel, sol, or emulsion.
  • input light is transmitted to and impinged upon a system where at least two photons of the input light are received by a sensitizer.
  • the sensitizer can transmit the energy of the two photon of the input light to an annihilator, resulting in upconversion and emission of a photon of UV light.
  • the input light has a wavelength longer than emitted UV light wavelength.
  • the input light is visible light. In some embodiments, the input light is infrared light. In some embodiments, the input light has a wavelength of between 400 nm and 1000 nm. In some embodiments, the input light is laser light having a particular wavelength (or short range of wavelengths). In some embodiments, the input light is narrowband, or is broadband, or is multiband. In several embodiments, the selection of input light is determined by the compatibility of the sensitizer and/or the desired UV light emission.
  • a number of embodiments are directed to localized UV emission in locations that are generally unreachable by nonlocalized UV light source. Accordingly, in several embodiments, the input light traverses through a medium or material that cannot be traversed by UV light having a wavelength equivalent the wavelength emitted by the annihilator. In several embodiments, the input light penetrates to a depth within a medium or material that cannot be reached by UV light having a wavelength equivalent to the wavelength emitted by the annihilator. In some these embodiments, UV emitting systems can be provided at a location that is reachable by the input light but not by UV light having a wavelength equivalent the wavelength produced by the emitter, and thus producing the UV light at the unreachable location via the input light and UV emitting systems.
  • FIG. 4 An exemplary schematic showing UV emission at an unreachable location is provided in Fig. 4.
  • UV emission is desired at a particular location 401 that is unreachable by UV light 403 due to the inability of UV light 403 to penetrate and/or traverse medium 405.
  • micelles 407 comprising an organic core with a sensitizer and annihilator are dispersed within location 401 .
  • Visible light 409 is provided to traverse through medium 405 to impinge upon and stimulate the organic core of micelles 407, resulting in UV emission 411 in location 401 .
  • a system of localized UV emission can comprise an amphiphilic vesicle having an organic core and hydrophilic outer region.
  • the organic core can comprise organic molecules for performing photon up conversion.
  • amphiphilic vesicle having an organic core and hydrophilic outer region can be utilized, many of which are known and described in the art.
  • amphiphilic molecules are utilized to form the amphiphilic vesicles and organic compounds are localized to the organic core using an organic solvent. The organic solvent can be removed yielding an amphiphilic vesicle with organic core.
  • Fig. 5 Provided in Fig. 5 is a schematic of an example of a method to generate micelles for localized UV emission.
  • the amphiphilic block copolymer F127 is utilized for formulate micelles by stirring the polymer is water.
  • the generated micelles have an organic core formed of the polypropylene glycol) block encapsulated by a hydrophilic region formed of the polyethylene glycol) blocks.
  • a upconversion mixture comprising the sensitizer and annihilator are provided in the organic solvent mixture of chloroform and trichlorobenzene.
  • the upconversion mixture is mixed with the micelles in their solution, resulting in the upconversion mixture centralizing in the organic core of the micelles. Chloroform is evaporated to yield micelles for localized UV emission.
  • any method for generating micelles with an organic core can be utilized and the various reagents can be exchanged for similar reagents.
  • the trichlorobenzene can be substituted with toluene and the water can be substituted with a buffered solution (e.g., phosphate buffered solution).
  • a buffered solution e.g., phosphate buffered solution
  • any amphiphilic polymer or polymer combinations capable of forming micelles with an organic core can be utilized.
  • TTA-UC triplet-triplet annihilation upconversion
  • Sensitizers absorb low energy photons, generate triplets via spin-orbit coupling, and transfer the triplet states to annihilators through triplet energy transfer.
  • Two annihilator triplet states can then undergo triplet-triplet annihilation to generate one high energy singlet excited state, which can radiatively decay and emit light at a higher energy than the incident photon energy.
  • This process must obey energy conservation laws, where the upconverted emission energy is lower than twice the sensitizer triplet energy.
  • Annihilators for TTA-UC are usually small organic molecules like acenes, whereas sensitizers span a range of materials such as metallic complexes, thermally activated delayed fluorescence (TADF) molecules, and inorganic nanoparticles.
  • TADF thermally activated delayed fluorescence
  • the TTA-UC process is extremely sensitive to the local chemical environment, which has posed major challenges to deploy TTA-UC into aqueous solutions.
  • highly polar solvents tend to facilitate electron transfer reactions, which compete with the desired triplet energy transfers between sensitizers and annihilators for TTA-UC.
  • high local concentrations of materials are required for efficient TTA-UC, but organic TTA- LIC molecules have low solubility in polar solvents. Instead, TTA-UC molecules are most soluble in nonpolar organic solvents.
  • sensitizer and annihilator solubility can be tuned by appending different functional groups (e.g., sulfate, carboxylate for water solubility), this approach requires substantial synthetic efforts for each sensitizer and annihilator pair that could result in undesirable changes to their energetic properties and ultimate UC performance.
  • functional groups e.g., sulfate, carboxylate for water solubility
  • Nanoencapsulation can overcome these challenges to expand the scope of chemical environments for TTA-UC.
  • the chemical compatibility of the resultant nanomaterials with a system dictate the ability to deliver upconverted light, thereby overcoming the limitations of individual molecules.
  • micelles comprised of polypropylene oxide) cores surrounded by polyethylene oxide) coronas can be utilized.
  • the encapsulation of UV-emitting UC materials enhance the spatial control of UV light generation in aqueous solutions.
  • Pluronic F-127 to form self-assembled micelles in water, it was found that the solubility of UC materials in the hydrophobic solvent used during micelle fabrication dictates the accessible upconverted light output.
  • Enhanced UC performance is observed from materials with high solubility in a high-boiling point organic solvent (1 , 2, 4- trichlorobenzene; TCB) due to partitioning into the hydrophobic core environment of F- 127 micelles.
  • Two new iridium-based sensitizers are described for blue-to-UV UC with outstanding solubilities in organic solvents, including toluene and TCB. These iridium- based sensitizers enable the fabrication of bright, UV-emitting micelles. For UC materials with sufficient solubility in the micelle core solvent, this encapsulation method allows facile customization of the excitation wavelengths and UV emission ranges required for different contexts. Specifically, the two newly identified sensitizers are paired with four unique annihilators to generate UV light with wavelengths as low as 350 nm. This greatly expands the accessible UC emission ranges, while the smallest UC emission wavelength in prior reports of TTA-UC nanoparticles is 430 nm (violet).
  • the UC properties of the iridium complexes ppy2 and tmd were characterized with a single annihilator, 2,7-di-tert-butylpyrene (DBP) in toluene, which is a favorable nonpolar solvent for screening TTA-UC.
  • DBP 2,7-di-tert-butylpyrene
  • the UC properties of the ppy3/DBP system were also measured to serve as a reference. All three iridium complexes displayed similar absorption ranges and emission profiles with slightly red-shifted emission peaks from ppy3 to ppy2 to tmd, suggesting that ppy2 and tmd should also possess energetically favorable properties for blue-to-UV UC (Fig. 6B).
  • Fig. 6B the iridium complexes ppy2 and tmd
  • UCPL normalized UC photoluminescence
  • Each sensitizer is paired with DBP in toluene under 447 nm excitation with varying power densities.
  • the sensitizer concentrations in this experiment were optimized to maximize UCPL (Fig. 10), and the DBP concentration was held constant between the three systems to maintain consistency and to minimize self-absorption effects from DBP.
  • All UCPL spectra had identical shapes when compared to photoluminescence of DBP (335 nm excitation, Fig. 6B). The spectral shape of the UC emission remained consistent across excitation power densities.
  • the UC quantum yield (0uc) of these systems was quantified as:
  • TTA-UC efficiency is inherently limited by the requirement to absorb two photons to emit one photon, the maximum achievable ⁇ t>uc is 50%.
  • ⁇ t>uc of ppy3, ppy2, and tmd are 1.4%, 2.0%, and 3.2%, respectively (Fig. 9B), indicating the ppy2/DBP and tmd/DBP systems had higher UC efficiencies than the ppy3/DBP system.
  • Another important TTA-UC metric is the threshold (/#»), or the power density of incident light at which UC intensity transitions from a quadratic regime (inefficient TTA) to a linear regime (efficient TTA).
  • Ith for the ppy3/DBP, ppy2/DBP, and tmd/DBP systems were 156, 51.5, and 115 mW/cm 2 , respectively (Fig. 9C), which means the ppy2/DBP and tmd/DBP systems exhibited lower thresholds to achieve efficient UC than the ppy3/DBP system. It is emphasized that these /?/, were measured at concentrations that maximize upconverted light output. Ith is dependent on sensitizer concentration, and ppy2 and tmd concentrations are adjustable by virtue of their enhanced solubilities compared to ppy3; therefore, Ith in bulk solutions can be further reduced if dictated by an application. In summary, using either ppy2 or tmd as a sensitizer with DBP reduced the threshold values and increased UC quantum yields compared to using ppy3 as a sensitizer.
  • ppy3, ppy2, and tmd were encapsulated with DBP into micelles to compare UC performance of micelles to TCB solutions.
  • toluene is generally a better solvent for solution upconversion due to its low polarity (Figs. 9A to 9C)
  • the core solvent was switched for micelle integration to TCB because it provides better solubility for sensitizers (Fig. 7) and facilitates the formation of more consistent and stable micelles.
  • the encapsulation process is shown schematically in Fig. 5. Freshly fabricated micelles were approximately 25 nm in diameter (Fig.
  • the concentrations of materials used for micelle integration were re-optimized for each system to maximize emitted light: the TTA-UC material concentrations required for efficient micelle fabrication were consistently higher than the optimal concentrations in toluene (Fig. 11 ), indicating the importance of high solubility of the UC materials. More efficient upconverting micelles were produced by ppy2/DBP and tmd/DBP systems instead of ppy3/DBP because ppy2/DBP and tmd/DBP have higher intrinsic UC efficiencies (Fig. 9B) and higher solubilities in the TCB solvent used for micelle integration (Fig. 8). Additionally, when adding the same total quantity of UC materials, the magnitude of UCPL was lower from TCB solution than from micelles (Fig. 12A).
  • Encapsulation also reduced sensitizer phosphorescence (Fig. 12A) and increased the UC-to-phosphorescence ratio by an order of magnitude (Fig. 14).
  • This enhanced performance implies fewer losses from the encapsulated UC system compared to UC in TCB solution.
  • Dramatically reduced phosphorescence has been observed in other nanoencapsulated UC systems, suggesting the generalizability of these findings.
  • This effect is attributed to higher local concentrations of the TTA-UC materials after nanoencapsulation, which reduces the average intermolecular distances between sensitizers and annihilators. The high local concentrations facilitate triplet energy transfer and enhance UC efficiency.
  • phosphorescence is still a significant energetic loss pathway as shown in Fig. 15.
  • Fig. 12B The performance of the three UV-emitting UC micelles is summarized in Fig. 12B, where ppy2/DBP micelles produced the highest UC emissions and tmd/DBP micelles generated the highest UC-to-phosphorescence ratio. Furthermore, l t h of the optimized ppy3/DBP, ppy2/DBP, and tmd/DBP micelles were 664, 787, and 622 mW/cm 2 , respectively, as shown in Fig. 16. Considering TCB is a relatively unfavorable solvent for UC due to its polarity, it is unsurprising that the threshold values are slightly higher in micelles than in toluene bulk solutions.
  • PPO emits photons at wavelengths shorter than 350 nm, which is a particularly attractive range for photochemical reactions.
  • UC emissions from all 20 encapsulated UC systems are shown in Fig. 3, with each spectrum normalized to its emission at 425 nm. All but one of the systems formed successful UV- emitting UC micelles.
  • the only unsuccessful combination of CBDAC and PPO did not show UCPL in the micelle precursor TCB solution nor in toluene. Slightly red-shifted UC emissions were observed from pyrene and TIPS-Nph and are attributed to molecular aggregation.
  • a caged fluorophore with a photocleavable protecting group was selected as a UV upconversion reporter, such that removal of the protecting group using UV photolysis results in visible color changes and measurable absorbance and fluorescence changes.
  • the UV upconversion reporter was fluorescein bis-(5-carboxymethoxy-2-nitrobenzyl) ether, hereafter referred to as caged fluorescein (Fig. 18A). It was hypothesized that blue incident light would photolyze caged fluorescein only when UV upconversion micelles were integrated into the solution (Fig. 18B).
  • ppy2/PPO sensitizer/annihilator pair was selected due to its upconversion emission profile extending deepest into the UV spectrum (Fig. 3), where caged fluorescein has high absorptivity.
  • the fabrication of ppy2/PPO micelles was optimized to maximize upconversion counts (Fig. 19).
  • the visualized 470 nm LED beam was a combination of the beam itself, sensitizer fluorescence, and upconverted UV emission. While the UV light intensity reduced by 50% after penetrating 3 mm deep into the solution, the blue light intensity decreased by less than 5% (Fig. 24). Surprisingly, the presence of absorptive sensitizer molecules did not significantly impact the transmission of a 470 nm beam through the cuvette containing ppy2/PPO upconversion micelles. An apparent benefit of encapsulating upconversion materials is that the overall concentration of absorptive compounds in the path of incident light is minimized, while sufficient concentrations are maintained locally in the micelle core to facilitate upconversion. These images demonstrate the potential for blue-to-UV upconversion to trigger UV photochemistry deeper within media than direct UV excitation.
  • UV photochemistry was further demonstrated in localized volume elements by leveraging the quadratic nature of blue-to-UV TTA-UC. Since upconversion only proceeds efficiently at regions of high intensity, the photolysis of caged fluorescein was localized to the focal point of blue input light in a system with blue-to-UV upconversion micelles (Fig. 22C). Focused UV light photolyzed the caged fluorescein primarily where the beam entered the solution (Fig. 22D, top row), and background-subtracted images revealed minimal photolysis at the focal point (Fig. 22E, top row). In contrast, focused blue light enabled photolysis primarily at the focal point in a solution containing ppy2/PPO micelles (Fig.
  • UV-emitting micelles provide the unique advantage of enhanced penetration depth and spatially confined light generation with low incident powers, which are inaccessible with direct excitation due to absorption and scattering effects.
  • blue light is not the most ideal wavelength for biological applications
  • a recent report demonstrates the use of blue light (405 nm) to penetrate through biological tissues to photolytical ly degrade a hydrogel up to 0.5 cm in animal skin.
  • These upconversion micelles still greatly improve the penetration depth of UV light in biological systems.
  • sensitizers for UV-emitting UC are discovered (such as green-to-UV sensitizers)
  • integrating these systems into micelles is worth further investigation to further increase the input light depth penetration for biological applications.
  • Precise, localized UV light generation at depth with TTA-UC has the potential to revolutionize a myriad of burgeoning fields, such as volumetric 3D printing, spatially controlled drug delivery, and precise optogenetic activation.
  • Tris(2-phenylpyridine)iridium(lll), lr(ppy)3 (ppy3) and 2,4,5,6-tetra(carbazol-9- yl)benzene-1 ,3-dicarbonitrile (4CzlPN) were purchased from Ossila.
  • 2,7-di-tert-butylpyrene (DBP) and 3,3'-carbonylbis(7-diethylaminocoumarin) (CBDAC) were purchased from Tokyo Chemical Industry (TCI).
  • TIPS-Nph 1,4-bis((triisopropylsilyl)ethynyl)naphthalene
  • Fluorescein bis-(5-carboxymethoxy-2-nitrobenzyl) ether, dipotassium salt (CMNB-caged fluorescein) was purchased from ThermoFisher Scientific.
  • This fabrication method can be adapted to different scales. However, stirring speed and stirring time should be adjusted accordingly for different scales to ensure adequate mixing and micelle formation. For example, a 20-mL solution was stirred at 1600 rpm for more than 24 h before filtering. Solutions containing micelles were characterized in quartz cuvettes with lids secured by PTFE sealant tape before removal from the glovebox, unless otherwise specified.
  • Photoluminescence (PL) measurements were collected on a custom setup.
  • a 447 nm laser (MDL-F-447-2W, Dragon Lasers) excited the sample, PL was collected at 90 degrees using a collection lens, and the appropriate filter was used to avoid saturating the spectrometer (425 nm short pass filter for upconversion PL; 475 nm long pass filter for phosphorescence), QE Pro (QEPRO-XR, Ocean Insight).
  • Threshold measurements were collected on a custom setup, where a 447 nm laser was focused on the sample, and UCPL was collected at 90 degrees by the spectrometer with a 425 nm short pass filter.
  • the power of the laser at the focal point was measured using an optical power detector (818-SL, Newport Corporation) threaded with an OD3 attenuator if necessary, and the photocurrent was reported by a Keithley 2400 sourcemeter.
  • the image of the laser spot was captured by a CMOS scientific camera (CS165MU, ThorLabs, Inc.) and analyzed in ImageJ to determine the spot size. Different beam intensities were achieved by attenuating the laser with neutral density filters (NEK01 , ThorLabs, Inc.).
  • the upconversion peak was integrated and plotted against excitation intensity in a log-log plot.
  • the resulting plot was analyzed to find the linear and quadratic regimes, and the intersection between these regimes was used to interpolate the threshold intensity.
  • UC quantum yield measurements were collected on a custom setup where a 447 nm laser excited the sample in an integrating sphere, and the resulting emission spectrum was collected by a spectrometer. Upconversion solutions were loaded into quartz cuvettes with 2 mm path lengths. The integrating sphere was calibrated using a radiometric source (HL-3P-CAL, Ocean Insight), which emits a known power at specific wavelengths. This calibration was used to convert arbitrary counts into absolute irradiance (pW/nm). Four measurements shown below were taken for each sample to calculate the UC quantum yield (Fig. 25, which are modified from PLQY measurements developed by de Mello.
  • UC quantum yield measurement was performed once at a relatively high- power density, denoted as 4> uc .
  • the power density was measured in the same way as described in the threshold measurement section.
  • UC quantum yields (4>[JC) °f other data points were calculated using the following equation by comparing their UCPL intensities and power densities with the known one: power density p Ower density'
  • UV-vis absorption spectra were collected with an Agilent Cary 6000i UVA/is/NIR.
  • Photoluminescence data presented in Fig. 6B were collected with a Horiba FluoroLog Fluorimeter.
  • Caged fluorescein samples were prepared in a glovebox under red light conditions to prevent premature uncaging and degradation.
  • 2 mM caged fluorescein was prepared by suspending caged fluorescein powder in 1 * phosphate-buffered saline (PBS) and stirring for several hours to aid dissolution.
  • Caged fluorescein powder was stored at -20 °C between uses.
  • Pluronic F-127 micelles were suspended in 1 x PBS by adding 1 volume of 10x PBS to 9 volumes of freshly fabricated micelles in DI water.
  • Negative control (Fig. 18C, middle row): 0.2 mM caged fluorescein with sensitizer- only micelles were prepared by tenfold dilution of 2 mM caged fluorescein with nitrogen-sparged sensitizer-only micelles in 1 x PBS. Sensitizer-only micelles were fabricated with saturated ppy2 in TCB and neat chloroform, in lieu of an annihilator solution.
  • UC reporter • UC reporter (Fig. 18C, bottom row): 0.2 mM caged fluorescein with UC micelles were prepared by tenfold dilution of 2 mM caged fluorescein with nitrogen-sparged UC micelles in 1 x PBS. UC micelles were fabricated with saturated ppy2 in TCB and 200 mM PPO in chloroform (see Fig. 19 for concentration optimization).

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Abstract

L'invention concerne des systèmes et des procédés d'émission de lumière ultraviolette. De manière générale, les vésicules amphiphiles contiennent un noyau organique. Le noyau organique peut contenir des composés organiques pour effectuer une conversion ascendante par annihilation triplet-triplet pour émettre une lumière ultraviolette. Par conséquent, la lumière d'entrée est incidente sur la vésicule amphiphile, ce qui conduit à une conversion ascendante des photons de lumière d'entrée en photons de lumière UV.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024122604A1 (fr) * 2022-12-09 2024-06-13 出光興産株式会社 Procédé de production de film organique de conversion ascendante optique, dispositif de production de film organique de conversion ascendante optique et film organique de conversion ascendante optique

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160222286A1 (en) * 2013-09-24 2016-08-04 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Long-term stable photoactive composition, such as phosphorescent composition or tta-photon upconversion composition
US20170236653A1 (en) * 2014-09-09 2017-08-17 The Florida State University Research Foundation, Inc. Molecular photon upconversion using organic-inorganic hybrid interfaces
US20180311353A1 (en) * 2015-07-02 2018-11-01 Children's Medical Center Corporation Triplet-triplet annihilation-based upconversion
US20190169495A1 (en) * 2015-12-02 2019-06-06 Adolphe Merkle Institute, University Of Fribourg Optically upconverting liquid-filled polymeric materials
US20190275151A1 (en) * 2018-03-12 2019-09-12 The Trustees Of Columbia University In The City Of New York Triplet fusion upconversion for infrared-sensitized photoredox chemistry
US20210159438A1 (en) * 2018-04-11 2021-05-27 Nanoco Technologies Ltd. Quantum dot architectures for fluorescence donor-assisted oled devices
US20210228719A1 (en) * 2018-08-21 2021-07-29 The University Of Hong Kong Triplet-triplet energy transfer with light excitation at long wavelengths and methods thereof
WO2021154897A1 (fr) * 2020-01-28 2021-08-05 Quadratic 3D, Inc. Compositions photodurcissables comprenant un composant de conversion ascendante et procédés
US20220025255A1 (en) * 2018-11-27 2022-01-27 President And Fellows Of Harvard College Photon upconversion nanocapsules for 3d printing and other applications

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160222286A1 (en) * 2013-09-24 2016-08-04 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Long-term stable photoactive composition, such as phosphorescent composition or tta-photon upconversion composition
US20170236653A1 (en) * 2014-09-09 2017-08-17 The Florida State University Research Foundation, Inc. Molecular photon upconversion using organic-inorganic hybrid interfaces
US20180311353A1 (en) * 2015-07-02 2018-11-01 Children's Medical Center Corporation Triplet-triplet annihilation-based upconversion
US20190169495A1 (en) * 2015-12-02 2019-06-06 Adolphe Merkle Institute, University Of Fribourg Optically upconverting liquid-filled polymeric materials
US20190275151A1 (en) * 2018-03-12 2019-09-12 The Trustees Of Columbia University In The City Of New York Triplet fusion upconversion for infrared-sensitized photoredox chemistry
US20210159438A1 (en) * 2018-04-11 2021-05-27 Nanoco Technologies Ltd. Quantum dot architectures for fluorescence donor-assisted oled devices
US20210228719A1 (en) * 2018-08-21 2021-07-29 The University Of Hong Kong Triplet-triplet energy transfer with light excitation at long wavelengths and methods thereof
US20220025255A1 (en) * 2018-11-27 2022-01-27 President And Fellows Of Harvard College Photon upconversion nanocapsules for 3d printing and other applications
WO2021154897A1 (fr) * 2020-01-28 2021-08-05 Quadratic 3D, Inc. Compositions photodurcissables comprenant un composant de conversion ascendante et procédés

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024122604A1 (fr) * 2022-12-09 2024-06-13 出光興産株式会社 Procédé de production de film organique de conversion ascendante optique, dispositif de production de film organique de conversion ascendante optique et film organique de conversion ascendante optique

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