Long-afterglow luminescent material

Abstract

Disclosed is a long-afterglow luminescent material, comprising A) at least one light-absorbing agent, B) at least one luminescent agent, and C) at least one photochemical cache agent. The light-absorbing agent and the luminescent agent are compounds having different structures, and the cache agent is selected from one or more compounds of formula (I), (II) and/or (III). ##STR00001## The material has luminescent intensity reaching the level of commercialized inorganic long-afterglow powder SrAl.sub.2O.sub.4:Eu.sup.2+, Dy.sup.3+, and can emit light when the exciting light is turned off with a light emitting time up to 100 ms to 3600 s.

Claims

1. A long-afterglow luminescent material, comprising: A) at least one light-absorbing agent; B) at least one luminescent agent; and C) at least one photochemical cache agent, wherein the light-absorbing agent and the luminescent agent are compounds having different structures, the light-absorbing agent is at least one compound selected from polymethine cyanine dyes, porphyrin and phthalocyanine dyes and complexes thereof, phycoerythrin, hypocrellin, benzophenone compounds, metal-organic frameworks (MOFs), quantum dots (QDs), and derivatives of these compounds, the luminescent agent is at least one compound selected from iridium complexes, rare-earth complexes, polyfluorene compounds, coumarin compounds, naphthalimide compounds, triacene and higher acene compounds, dipyrromethene boron difluoride compounds (BODIPY), pyrazoline compounds, triphenylamine compounds, carbazole compounds, green fluorescent protein, perovskite luminescent nanomaterials, thermally activated delayed fluorescence (TADF) compounds, and derivatives of these compounds, and the light absorbing agent has a relatively large molar coefficient, the luminescent agent has a relatively high luminescent quantum efficiency, and an absorption peak of the light absorbing agent overlaps an emission peak of the luminescent agent as little as possible; wherein the cache agent is selected from one or more compounds of formula (II), phenylthiophene compounds of the following formula (IV), luminol compounds of the following formula (IX), phenylimidazole compounds of the following formula (X), and derivatives of these compounds: ##STR00085## wherein ##STR00086## part is a ##STR00087## substituted or unsubstituted by one or more groups L, or a combination thereof; R.sub.c and R.sub.d are each independently aryl, wherein aryl may be substituted by one or more groups L; and L is selected from hydroxyl, nitro, sulfo, halogen, alkyl having 1 to 50 carbon atoms, alkoxy, alkylamino, or a combination thereof; ##STR00088## wherein groups R.sub.1-8 represent H, amino, halogen, alkyl having 1 to 50 carbon atoms, alkoxy, alkylamino, aryl, or a combination thereof, wherein aryl optionally has one or more substituents L; and L is selected from alkyl having 1 to 50 carbon atoms or alkoxy; and wherein a molar ratio of the light-absorbing agent to the luminescent agent is within a range of 1:1.1 to 1:10000, and wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C), is 0.1% to 80%.

2. The long-afterglow luminescent material according to claim 1, wherein the photochemical cache agent is a non-polymeric compound.

3. The long-afterglow luminescent material according to claim 2, wherein the photochemical cache agent has a molecular weight of less than 2000.

4. The long-afterglow luminescent material according to claim 2, wherein the photochemical cache agent has a molecular weight of less than 1000.

5. The long-afterglow luminescent material according to claim 1, wherein a molar ratio of the light-absorbing agent to the luminescent agent is within a range of 1:10 to 1:8000.

6. The long-afterglow luminescent material according to claim 1, wherein the photochemical cache agent is selected from one or more of the following: ##STR00089## ##STR00090## ##STR00091##

7. The long-afterglow luminescent material according to claim 1, wherein the long-afterglow material further comprises a photochemical storage agent component D) selected from fullerene as shown in the following formula (XI), surface-modified fullerene compounds, polyene oligomers, compounds shown in following formulae (XII-1) to (XII-8) and derivatives of the compounds: ##STR00092## ##STR00093## wherein in the above structures, each substituent R and R.sub.1-11, represents H, hydroxyl, carboxyl, amino, mercapto, ester, an aldehyde group, nitro, sulfo, halogen, alkyl having 1 to 50 carbon atoms, alkenyl, alkynyl, aryl, alkoxy, or alkylamino, and wherein z represents an integer greater than 1; wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and D), is 0.1% to 80%.

8. The long-afterglow luminescent material according to claim 7, wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and D), is 0.3% to 60%.

9. The long-afterglow luminescent material according to claim 7, wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and D), is 0.5% to 40%.

10. The long-afterglow luminescent material according to claim 1, wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C), is 0.3% to 60%.

11. The long-afterglow luminescent material according to claim 1, wherein the long-afterglow material further comprises a carrier medium component E) for dissolving, dispersing or adsorbing the components A) to C).

12. The long-afterglow luminescent material according to claim 11, existing in states or forms of crystal, nanoparticle, powder, film, block, metal-organic framework, composite, organic solvent system, ionic liquid, aqueous solution, aerosol dust, and gel sol.

13. The long-afterglow luminescent material according to claim 11, wherein the carrier medium component E) is selected from an organic solvent, an aqueous phase solvent, a polymeric dispersion medium, a protein, phospholipid liposomes, or adsorptive particles.

14. The long-afterglow luminescent material according to claim 1, comprising, by weight based on a material mixture, no more than 0.1% of rare-earth-doped inorganic luminescent nanoparticles.

15. The long-afterglow luminescent material according to claim 14, comprising, by weight based on a material mixture, no more than 0.01% of the rare-earth-doped inorganic luminescent nanoparticles.

16. The long-afterglow luminescent material according to claim 14, comprising, by weight based on a material mixture, no more than 0.001% of the rare-earth-doped inorganic luminescent nanoparticles.

17. The long-afterglow luminescent material according to claim 14, comprising no rare-earth-doped inorganic luminescent nanoparticles.

18. The long-afterglow luminescent material according to claim 1, wherein L in formula (II) is selected from hydroxyl, sulfo, halogen, nitro, linear or branched alkyl having 1 to 12 carbon atoms, alkoxy, alkylamino, or a combination thereof.

19. The long-afterglow luminescent material according to claim 1, wherein in formula (II) ##STR00094## part is ##STR00095## R.sub.c and R.sub.d are each independently selected from phenyl or naphthyl, wherein phenyl or naphthyl may be substituted by one or more groups L; and L is selected from hydroxyl, sulfo, alkyl having 1 to 12 carbon atoms, alkoxy, alkylamino, or a combination thereof.

20. The long-afterglow luminescent material according to claim 1, wherein in formula (IV) R.sub.1, R.sub.2, R.sub.4 and R.sub.5 are independently H; R.sub.3 is alkoxy having 1 to 18 carbon atoms; R.sub.6 and R.sub.7 are independently alkyl having 1 to 18 carbon atoms; and R.sub.8 is H or alkyl having 1 to 18 carbon atoms.

21. The long-afterglow luminescent material according to claim 1, wherein in formula (IX) R.sub.1 represents H, amino, or alkylamino having 1 to 18 carbon atoms; R.sub.2, R.sub.5 and R.sub.6 represent H; R.sub.3 represents H or alkyl having 1 to 18 carbon atoms; and R.sub.4 represents H or amino.

22. The long-afterglow luminescent material according to claim 1, wherein in formula (X) R.sub.1 represents H; R.sub.2 represents phenyl; R.sub.3 represents alkyl having 1 to 18 carbon atoms, alkoxy having 1 to 18 carbon atoms, or alkylamino; R.sub.4 represents H or amino; R.sub.5 represents H or alkoxy; and R.sub.6, R.sub.7 and R.sub.8 independently represent H or alkyl having 1 to 18 carbon atoms.

23. The long-afterglow luminescent material according to claim 1, wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C), is 0.5% to 40%.

24. The long-afterglow luminescent material according to claim 1, wherein a molar ratio of the light-absorbing agent to the luminescent agent is within a range of 1:50 to 1:6000.

25. The long-afterglow luminescent material according to claim 1, wherein a molar ratio of the light-absorbing agent to the luminescent agent is within a range of 1:100 to 1:4000.

26. A long-afterglow luminescent material, comprising: at least one light-absorbing agent selected from polymethine cyanine dyes, porphyrin and phthalocyanine dyes and complexes thereof, phycoerythrin, hypocrellin, benzophenone compounds, metal-organic frameworks (MOFs), quantum dots (QDs), and derivatives of these compounds; at least one luminescent agent selected iridium complexes, rare-earth complexes, polyfluorene compounds, coumarin compounds, naphthalimide compounds, triacene and higher acene compounds, dipyrromethene boron difluoride compounds (BODIPY), pyrazoline compounds, triphenylamine compounds, carbazole compounds, green fluorescent protein, perovskite luminescent nanomaterials, thermally activated delayed fluorescence (TADF) compounds, and derivatives of these compounds; and at least one photochemical cache agent selected from one of the following compounds: ##STR00096## ##STR00097## wherein the light absorbing agent has a relatively large molar coefficient, the luminescent agent has a relatively high luminescent quantum efficiency, and an absorption peak of the light absorbing agent overlaps an emission peak of the luminescent agent as little as possible.

27. The long-afterglow luminescent material of claim 26, wherein: the light-absorbing agent is selected from one or more of the following compounds: ##STR00098## ##STR00099## graphene quantum dots; carbon quantum dots; CdSe quantum dots; and PbS quantum dots; and the luminescent agent is selected from one of the following compounds: ##STR00100## ##STR00101##

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of a photochemical long-afterglow luminescent material according to the present invention.

(2) FIG. 2 is a luminescent picture of a long-afterglow material, which is taken in the dark after excitation light is turned off. The left side is a material of Example 1 of the present invention, and the right side is a commercialized inorganic long-afterglow powder SrAl.sub.2O.sub.4:Eu.sup.2+, Dy.sup.3+ material.

(3) FIG. 3 is a luminescent decay curve of a long-afterglow material of Example 1.

(4) FIG. 4 is a transmission electron microscope of a long-afterglow luminescent nanomaterial of Example 15.

(5) FIG. 5 is a luminescent spectrogram of a long-afterglow material of Example 16.

EXAMPLE

(6) 1. Performance Test Method

(7) In a long-afterglow luminescent test of the present invention, professional instruments and equipment in the field were used. A wavelength tunable laser (Opolette 355) from Opotek, Inc., USA was used as excitation light source, and the power density of excitation light was maintained at 100 mW cm2. Excitation light of a specific wavelength was used to irradiate a sample for charging, and the irradiating and charging time was 3 s. After charging, the laser was turned off, and the luminescent performance test was initiated. A fluorescence spectrometer (Edinburgh FLS-920) from Edinburgh Instruments was used to test the long-afterglow luminescent intensity, and the temperature was kept at a room temperature of 25 degrees Celsius. A long-afterglow test system (OPT-2003) of Beijing Aobodi Photoelectricity Technology Co., Ltd. was used to test the long-afterglow luminescent time.

(8) The phrase visible to the naked eye used in the invention is a professional term in the field of long-afterglow luminescent materials, which means that the luminescent brightness of the material is greater than or equal to 0.32 mcd m.sup.2 (the unit med refers to millicandela), and visible light is usually visible to the naked eye when being at the radiation level of this brightness or above. The phrase luminescent time used in the invention is a professional term in the field of the long-afterglow luminescent materials, which means the time elapsed before the luminescent brightness of the material decays to a level visible to the naked eye. The phrase blue long-afterglow luminescence used in the invention is the expression of the long-afterglow luminescent color of the material, which means that there is obvious long-afterglow luminescence generated in a blue wavelength interval; and similarly, the description is also accordingly applicable to other colors used in the invention. In actual situations, due to differences in observation methods or influence from individual differences, there may be errors in observation results such as luminescent color or luminescent time.

(9) 2. List of Raw Materials Used

(10) TABLE-US-00001 Component Compound name or number Source or structure A PdPc A PtTPBP A Hemin 0 A PdOEP A Methylene blue (MB-1) A PbS quantum dots (PbS) Suzhou Xingshuo Nanotech Co., Ltd. A Graphene Quantum Dots Jiangsu XFNano Material Tech. Co., Ltd. (GQDs) B Iridium complex (Ir-1) B Terbium complex (Tb-1) B Europium complex (Eu-1) B Iridium complex (Ir-2) B BDP-1 B BDP-2 B BDP-3 B Rhodamine B (RhB) 0 B Perylene B Silicon Rhodamine (Rh-1) C Acridin-1 C Acridin-2 C Luminol compound (Luminol- 1) C Luminol compound (Luminol- 2) C EA-1 C EA-2 C OA-1 C OA-2 0 C BT-1 C BT-2 C CA-1 C CA-2 C CA-3 C CA-4 C PN-1 C MEHPPV used in W02019/027370A1 D PyD-1
3. Preparation of Long-Afterglow Material Compositions

Example 1

(11) All components of the photochemical long-afterglow material were mixed in a toluene solvent according to the ratio shown in Table 1, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 3 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. First, 100 mW cm.sup.2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 1.

Examples 2-4

(12) The operation of Example 1 was repeated, and the only difference was that all the components and their contents listed in Table 1 below were used.

Comparative Examples 1-6

(13) The operation of Example 1 was repeated, and the only difference was that all the components and their contents listed in Table 1 below were used.

Comparative Example 7

(14) All components of the photochemical long-afterglow material were mixed in a toluene solvent according to the ratio as shown in Table 2, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 0 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. First, 100 mW cm.sup.2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 2.

Example 5-10

(15) The operation of Comparative Example 7 was repeated, and the only difference was that all the components and their contents listed in Table 2 below were used.

Comparative Examples 8

(16) The operation of Comparative Example 7 was repeated, and the only difference was that all the components and their contents listed in Table 2 below were used.

Example 11

(17) All components of the photochemical long-afterglow material were mixed in a dichloromethane solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. First, 100 mW cm.sup.2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain blue long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 12

(18) The operation of Example 11 was repeated, and the only difference was that all the components and their contents listed in Table 3 below were used.

Example 13

(19) All components of the photochemical long-afterglow material were mixed in a dichloromethane solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. Then, dichloromethane therein was removed to obtain long-afterglow powder without a solvent medium. First, 100 mW cm.sup.2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 14

(20) All components of the photochemical long-afterglow material were mixed in a toluene solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. Then, methylene bis(4-cyclohexyl isocyanate) and polyester polyol were added according to a mass ratio of 1:2, and the total volume of the two substances added was equal to the volume of the above toluene solution. A mixed liquor was stirred uniformly, toluene and dissolved bubbles therein were removed, then the mixed liquor was placed in an oven at 60 degrees Celsius to be dried and cured in the dark, and then a colorless and transparent polyurethane film was formed. First, 100 mW cm.sup.2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 15

(21) All components of the photochemical long-afterglow material were mixed in a liquid paraffin solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. Subsequently, a ten-fold volume of an aqueous solution containing bovine serum albumin (BSA) was added, wherein the concentration of BSA was 10 mg mL.sup.1. A mixture was pre-emulsified by using ultrasonic waves (Sonics VC750, Sonics & Materials, Inc) at room temperature for 10 minutes, and then a high-pressure nano homogenizer (FB-110Q, LiTu Mechanical equipment Engineering Co., Ltd) was immediately used to continue emulsification for 20 minutes. An emulsion was heated at 90 degrees Celsius for 1 hour. After the emulsion was cooled to the room temperature, gradient centrifugation and filtration were performed to obtain long-afterglow nanoparticles uniformly dispersed in water. First, 100 mW cm.sup.2 635 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain blue long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 16-18

(22) The operation of Example 15 was repeated, and the only difference was that the experimental conditions such as all the components and their contents listed in Table 3 below were used.

Example 19

(23) The long-afterglow nanoparticles uniformly dispersed in water were prepared according to Example 15. Subsequently, sodium silicate was added to the above aqueous solution, standing was performed for one day under the condition of pH 8.0, and a silicone hydrogel was prepared by hydrolysis of sodium silicate to obtain long-afterglow hydrogel. First, 100 mW cm.sup.2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 20

(24) All components of the photochemical long-afterglow material were mixed in deionized water according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 1 mmol L.sup.1, and a concentration of a luminescent agent was 1 mmol L.sup.1. Then, dichloromethane therein was removed to obtain long-afterglow powder without a solvent medium. First, 100 mW cm.sup.2 635 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain yellow long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 21

(25) All components of the photochemical long-afterglow material were mixed in a toluene according to the ratio in Table 4, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.1, and a concentration of a luminescent agent was 2 mmol L.sup.1. First, 100 mW cm.sup.2 635 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 4.

Examples 22-28

(26) The operation of Example 21 was repeated, and the only difference was that the experimental conditions such as all the components and their contents listed in Table 4 below were used.

(27) TABLE-US-00002 TABLE 1 Component Ex 1 Ex 2 Ex 3 Ex 4 C1 C2 C3 C4 C5 C6 A PdPc PdPc PdPc PdPc PdPc PdPc PdPc Ir-1 PdPc RhB B Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 MB-1 Perylene C CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 MEHPPV CA-1 CA-1 CA-1 D None None None None None None None None None None E Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene A/B molar ratio 1:500 1:1500 1:5000 1:8000 2:1 1:15000 1:500 1:500 1:500 Excitation 730 730 730 730 730 730 730 365 730 532 wavelength (nm) Performance Test Luminescent 305870 98370 29080 17530 130 670 220 3410 330 1260 intensity (a.u.) Luminescent 20.1 15.3 10.5 8.2 n.m. n.m. n.m. 1.6 n.m. n.m. time (s) n.m.: not measurable due to too-low brightness

(28) TABLE-US-00003 TABLE 2 Component C7 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 C8 Ex 10 A PdPc PdPc PdPc PdPc PdPc PdPc PdPc PdPc B Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 C None CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 Molar concentration 0 0.5 1 3 5 10 20 3 of C (mmol L.sup.1) D None None None None None None None PyD-1 Content of D (%) 0 0 0 0 0 0 0 0.01 E Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene A/B molar ratio 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 Performance Test Luminescent intensity 0 57170 121520 306230 237690 92460 5530 273580 (a.u.) Luminescent time (s) n.m. 13.0 15.9 20.1 18.3 14.9 2.9 23.6 n.m.: not measurable due to too-low brightness

(29) TABLE-US-00004 TABLE 3 Component Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 Ex 18 Ex 19 Ex 20 A PdPc PdPc PtTPBP PbS PdPc GQDs PdPc PdPc PdPc MB-1 B BDP-1 RhB Ir-1 Tb-1 Perylene Tb-1 BDP-2 Ir-1 Ir-1 RhB C EA-1 Luminol-1 BT-1 CA-1 Acridin-1 CA-1 OA-1 CA-1 CA-1 CA-2 E Dichloro Ethanol Dichloro Polyurethane Nano Nano Nano Nano Hydrogel water methane methane film protein protein protein protein A/B molar ratio 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 Excitation 730 730 635 808 730 532 730 730 730 635 wavelength (nm) Performance Test Luminescent Blue Yellow Green Green Blue Green red Blue Green Yellow color Luminescent 12500 9560 21690 102680 37570 73160 6580 56520 43270 3790 intensity (a.u.) Luminescent 186.5 5.9 68.7 15.2 11.1 14.9 260.2 12.8 11.7 2.1 time (s)

(30) TABLE-US-00005 TABLE 4 Component Ex 21 Ex 22 Ex 23 Ex 24 Ex 25 Ex 26 Ex 27 Ex 28 A PdOEP Hemin PtTPBP PtTPBP PtTPBP PtTPBP PtTPBP PtTPBP B BDP-3 Eu-1 Ir-2 Rh-1 Eu-1 Eu-1 Eu-1 Eu-1 C EA-2 Luminol-2 BT-2 CA-3 Acridin-2 CA-4 OA-2 PN-1 E Toluene Ethanol Dichloro- Dichloro- Dichloro- Dichloro- Dichloro- Dichloro- methane methane methane methane methane methane A/B molar ratio 1:400 1:400 1:400 1:400 1:400 1:400 1:400 1:400 Excitation 532 532 635 635 635 635 635 635 wavelength (nm) Performance Test Luminescent Green Red Blue Red Red Red Red Red color Luminescent 13690 52130 32950 218270 273640 480650 7150 102890 intensity (a.u.) Luminescent 320.1 31.6 81.1 18.4 14.5 21.6 351.9 38.4 time (s)