Perylene imide compounds, and methods of making and using the same

Abstract

The application discloses a perylene imide compound and a preparation method and application thereof, and belongs to the technical field of photoacid generators. The perylene imide compound is shown as formula I, and acid and CBI molecules can be generated under excitation of visible light (530-605 nm). On one hand, the acid generating property of the perylene imide compound can be utilized to provide a remote and non-invasive controllable pH adjusting method, which can be used for polymerization of thioctic acid ester and the like; on the other hand, the structure of CBI generated by the perylene imide compound can be used as a photosensitizer to generate active oxygen under light conditions for inhibiting bacterial activity. The perylene imide compound has wide application prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photoacid generators, in particular to a perylene imide compound and a preparation method and application thereof. BACKGROUND

[0002] Photoacid generator (PAG) is a compound that can dissociate or undergo chemical reaction to generate acidic photoproduct under light irradiation, and has important application in initiating cationic polymerization.

[0003] Since the mid-1970s, photoacid generators have been widely used in cationic photopolymerization systems. The acid molecules generated thereby serve as active species to initiate cationic polymerization of monomers such as epoxy compounds, vinyl ethers, lactones, acetals and cyclic ethers. With the development of new photoacid generators, the application of photoacid generators has not been limited to traditional cationic polymerization initiation, and has shown great potential in biochemical and medical fields such as photodynamic therapy, light-controlled enzyme activity, targeted delivery and light energy storage.

[0004] However, since the traditional photoacid generator molecules generally need to be excited by ultraviolet light to undergo photochromic reaction, the ultraviolet excitation has the disadvantages of high energy consumption, high damage, poor tissue penetration, high biological toxicity, etc., which limits its application in biomedical and advanced material fields. There have been reports on acid generator molecules based on diarylethylene substitution (T. Nakashima, K. Tsuchie, R. Kanazawa, R. Li, S. Iijima, O. Galangau, H. Nakagawa, K. Mutoh, Y. Kobayashi, J. Abe, T. Kawai, J. Am. Chem. Soc. 2015, 137, 7023-7026.), but the excitation wavelength is still limited to 406 nm light. Therefore, it is of great significance to develop photoacid generators that can be excited by visible light (400-600 nm).

[0005] In addition, the process of photo-initiator generally requires high-efficiency photoacid generators. Previously, there have been some related work to improve the release efficiency of photoacid generators, but none of the PAGs has an acid yield of 99% or higher. SUMMARY

[0006] In view of the above problem in the prior art that there is a lack of photoacid generators that can be excited by visible light (400-600 nm), the present application provides a perylene imide compound that can be used as a photoacid generator and can be excited by visible light of 530-605 nm, having great application prospects.

[0007] The present application discloses a perylene imide compound shown in formula I:

[0008]

[0009] wherein,

[0010] R1and R2are independently C1-C 20 alkyl, C3-C8cycloalkyl, or C6-C 10 aryl;

[0011] R3and R4are independently hydrogen, C1-C3alkoxy, C1-C6alkyl, halogen, cyano, or C6-C 10 aryl;

[0012] X1is S, O, Se, Te, or NH;

[0013] X2and X3are independently N, CHR 8-1 , C(R 8-1 )2, or X2and X3are cyclic to form a benzene ring;

[0014] each R 8-1 is independently C1-C3alkoxy, halogen, cyano, C1-C6alkyl, or C6-C 10 aryl;

[0015] R5is

[0016] R6and R7are independently C1-C6alkyl, or C6-C 10 aryl, said C1-C6alkyl, C6-C 10 aryl optionally substituted with 1-3 halogens or C1-C6alkyl.

[0017] In some of the embodiments, R1and R2are independently C8-C 15 alkyl, preferably C9-C 13 alkyl, more preferably C 11 alkyl, such as n-undecyl.

[0018] In some of the embodiments, R3and R4are hydrogen.

[0019] In some of the embodiments, X1is S.

[0020] In some of the embodiments, X2and X3are cyclic to form a benzene ring.

[0021] In some of the embodiments, R6and R7are independently C1-C4alkyl, phenyl, said phenyl optionally substituted with 1-3 halogens or C1-C4alkyl.

[0022] In some of the embodiments, said R1and R2are linear alkyl. This can increase the solubility of the compound.

[0023] In some of the embodiments, R1 and R2 are the same.

[0024] In some of the embodiments, the C1-C4 alkyl is methyl, ethyl, propyl, butyl, or isopropyl, preferably methyl or ethyl.

[0025] In some of the embodiments, when R6 or R7 is phenyl substituted with halogen or C1-C4 alkyl, the substitution position is one or more of ortho, meta and para, preferably para. The ortho, meta and para are defined with the connecting position of the phenyl to C or S as the starting position.

[0026] In some of the embodiments, the perylene imide compound of Formula I is selected from the following compounds:

[0027]

[0028] The compounds 9-11 above can all release acidic molecules under the excitation of visible light, but compound 11 can achieve the same photo-reaction effect at a lower light power, and has certain advantages.

[0029] It can be understood that the perylene imide compound of Formula I above can be prepared according to conventional methods, such as prepared from perylene imide (CAS: 110590-83-5).

[0030] In another aspect, the present application discloses a preparation method of the perylene imide compound of Formula I above, which is synthesized according to the following route:

[0031]

[0032] wherein R1, R2, R3, R4, R5, X1, X2 and X3 are as described above;

[0033] X is halogen, preferably bromine.

[0034] In another aspect, the present application discloses the use of the perylene imide compound of Formula I above in the preparation of photo-acid generators and / or bacteriostatic agents.

[0035] It can be understood that the perylene imide compound of Formula I above, which can release acid molecules, is suitable for all polymer monomers that are initiated by B acid to polymerize, such as , etc.

[0036] In another aspect, the present application discloses a perylene imide compound of Formula II:

[0037]

[0038] wherein, R1, R2, R3, R4, X1, X2 and X3 are as described above.

[0039] In some of the schemes, the perylene imide compound of formula II is selected from the following compounds:

[0040]

[0041] In another aspect, the application also discloses a preparation method of the perylene imide compound of formula II, which is synthesized according to the following route:

[0042]

[0043] wherein, R1, R2, R3, R4, R5, X1, X2 and X3 are as described above.

[0044] In another aspect, the application also discloses an application of the perylene imide compound of formula II in preparing a bacteriostatic agent, preferably, the bacteriostatic agent is a photosensitive bacteriostatic agent.

[0045] In another aspect, the application also discloses a bacteriostatic agent comprising the perylene imide compound of formula II, and further comprising a PBI@M micelle prepared by the following method:

[0046] The perylene imide compound dissolved in an organic solvent is mixed with a solution of an amphiphilic substance dissolved in an organic solvent to obtain a mixed solution, and the mixed solution is added dropwise into water under stirring to obtain the PBI@M micelle; preferably, the amphiphilic substance is polymer F127.

[0047] The perylene imide compound of formula II is prepared into a micelle to solve the problem of poor water solubility, enhance the biocompatibility and improve the bacteriostatic effect. In particular, polymer F127 is selected, which has low biological toxicity and the polarity of the hydrophobic cavity formed by F127 can better match the working polarity of the perylene imide compound of formula I, thereby enhancing the effect of generating active oxygen.

[0048] It can be understood that the preparation steps and parameter conditions of the PBI@M micelle can be prepared according to the conventional method in the art.

[0049] On the basis of the common sense in the art, the above-mentioned preferred conditions can be combined arbitrarily to obtain each preferred example of the application.

[0050] The reagents and raw materials used in the application are commercially available.

[0051] The positive progress effect of the application is that:

[0052] The perylene imide compound of Formula I is a photoacid generator (PAG) that can generate acid and perylene imide-based photosensitive bacteriostatic agent (CBI molecule) under the excitation of visible light (530-605 nm). On the one hand, its property of generating acid can be used to provide a remote and non-invasive controllable pH adjustment means, such as can be used for the polymerization of thioctic acid ester, etc.; on the other hand, the CBI structure molecule generated thereby can be used as a photosensitizer to generate active oxygen under light conditions for inhibiting bacterial activity. This endows the photoacid molecule of the present application with multifunctionality and atom economy.

[0053] In addition, the perylene imide compound of Formula I can release acid molecules in equivalent amount, and the acid yield thereof can be close to 100%. At the same time, the CBI structure generated thereby can be used as a photosensitizer to generate active oxygen under light conditions for inhibiting bacterial activity. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1 Absorption spectrum of toluene solution of compound 9 irradiated with LED light in Example 5.

[0055] Figure 2 Fluorescence spectrum of toluene solution of compound 9 irradiated with LED light in Example 5.

[0056] Figure 3 Absorption spectrum of toluene solution of compound 10 irradiated with LED light in Example 6.

[0057] Figure 4 Fluorescence spectrum of toluene solution of compound 10 irradiated with LED light in Example 6.

[0058] Figure 5 Absorption spectrum of toluene solution of compound 11 irradiated with LED light in Example 7.

[0059] Figure 6 Fluorescence spectrum of toluene solution of compound 11 irradiated with LED light in Example 7.

[0060] Figure 7 NMR titration spectrum of compound 11 in Example 8.

[0061] Figure 8 Transient absorption spectrum of compound 9 in Example 9.

[0062] Figure 9 Transient absorption spectrum of compound 10 in Example 10.

[0063] Figure 10 Transient absorption spectrum of compound 11 in Example 11.

[0064] Figure 11Schematic diagram of the polymerization of lipoic acid ester for compound 11 in Example 12.

[0065] Figure 12 Schematic diagram of the self-repairing of lipoic acid ester for compound 11 in Example 12.

[0066] Figure 13 Active oxygen test results of CBI in Example 13.

[0067] Figure 14 PBI@M micellar particle size distribution chart in Example 14.

[0068] Figure 15 Active oxygen test results of total PBI@M in Example 15.

[0069] Figure 16 Inhibition of P. aeruginosa under PBI@M photodynamic in Example 16.

[0070] Figure 17 Inhibition of P. aeruginosa under PBI@M photodynamic in Example 16 using PI dye and confocal microscope observation.

[0071] Figure 18 Destructive effect of PBI@M photodynamic on the surface membrane structure of bacteria in Example 16. DETAILED DESCRIPTION

[0072] The present application is further illustrated by the following examples without thereby limiting the present application to the examples described. The experimental methods in the following examples without specific conditions are selected according to the conventional methods and conditions, or according to the product instructions.

[0073] Abbreviation definition:

[0074] n-BuLi: n-butyllithium.

[0075] Pd(dppf)Cl2: 1,1-bis(diphenylphosphino)ferrocene palladium dichloride.

[0076] DCM: dichloromethane.

[0077] PI dye: propidium iodide dye.

[0078] TFA: trifluoroacetic acid.

[0079] DPBF: 1,3-diphenylisobenzofuran.

[0080] Example 1: Preparation of compound 9

[0081] Compound 9 is synthesized according to the following route:

[0082] Compound 9 is synthesized according to the following route:

[0082]

[0083] 1. Synthesis of compound 2

[0084] 100 ml Schlenk tube was charged with benz[b]thiophene (1 g, 7.25 mmol) and 10 ml of super dry tetrahydrofuran, then the Schlenk tube was cooled to -78 °C and 3.3 mL (2.5 M, 8.20 mmol) of n-BuLi hexane solution was added. The milky white solution was continuously cooled at -78 °C for 1 h, 10 mL of I2(2.84 g, 11.18 mmol) in super dry tetrahydrofuran was added. After constant stirring for 1 h, the Schlenk tube was brought to room temperature. The reaction mixture was then washed with 10 mL of saturated NaCl solution three times and then extracted with 2 x 15 mL of dichloromethane. The organic layer was dried over anhydrous MgS04, filtered and dried under reduced pressure. The crude compound 2 (2-iodobenz[b]thiophene) was obtained as a yellow solid (1.9 g, ~100%) and the product was used without further purification.

[0085] 2. Synthesis of compound 3

[0086] The crude product 2-iodobenz[b]thiophene 2 (1.5 g, 5.75 mmol) and CuI (I) (0.37 g, 1.92 mmol) were taken in a dry Schlenk tube under Ar atmosphere. NaOMe in methanol (5.4 M, 3.5 mL) was added by syringe and the mixture was heated at 60 °C, which quickly turned deep blue. After three days, the test tube was brought to room temperature and water was carefully added. The aqueous layer was extracted with petroleum ether and the organics were dried over anhydrous MgS04, filtered and dried under reduced pressure. The crude product was purified by silica gel column chromatography (CH2Cl2: petroleum ether = 1 : 10) to obtain compound 3 (2-methoxybenz[b]thiophene) as a white powder (473 mg, 75%).

[0087] Characterization of compound 3: 1 H NMR (400 MHz, CDC13) δ 7.60 (d, J = 7.9 Hz, 1H), 7.52 (d, J = 7.9 Hz, 1H), 7.26 (s, 1H), 7.17 (s, 1H), 6.34 (s, 1H), 3.98 (s, 3H).

[0088] 3. Synthesis of compound 4

[0089] In a 100 mL three-necked round-bottom flask, 2-methoxybenzo[b]thiophene (250 mg, 1.52 mmol) was added to a 1:1 (20 mL) solution of AcOH:CH2Cl2 and stirred at 0 °C for 10 min. Then, N-bromosuccinimide (243.8 mg, 1.37 mmol) was added to the flask and stirred at room temperature for 3 h. The reaction mixture was washed with 20 mL of saturated brine. The reaction mixture was then extracted twice with 20 mL of CH2Cl2. The organic layer was dried over anhydrous MgSO4, filtered, and dried under reduced pressure. The crude product (n-hexane) was purified by silica gel column chromatography to give compound 4 (3-bromo-2-methoxybenzo[b]thiophene) (315 mg, 85%) as a white solid.

[0090] Characterization of compound 4: 1 H NMR (400MHz, CDCl3) δ7.69-7.67(m,1H),7.66(dd,J=2.7,1.2Hz,1H),7.44(ddd,J=8.3,7.2,1.0Hz,1H),7.34-7.29(m,1H),4.10(s,3H).

[0091] 4. Synthesis of Compound 5

[0092] Compound 4 (230 mg, 0.9473 mmol) and 5 mL of dry tetrahydrofuran were added to 100 mL of dry Shrek tube. The Shrek tube was then cooled to -78 °C, and 0.4 mL (2.5 M, 0.9568 mmol) of n-BuLi hexane solution was added. The pale yellow solution was continuously cooled at -78 °C for 1 h, and then 0.2 mL of 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxoborane was added. After stirring at a constant temperature for 1 h, the Shrek tube was brought to room temperature. The reaction mixture was then washed with 10 mL of saturated sodium chloride solution. Extraction was then performed with 2 × 15 mL of dichloromethane, and the organic layer was dried on anhydrous MgSO4, filtered, and dried under reduced pressure. The crude product (CH2Cl2: petroleum ether = 1:1) was purified by silica gel column chromatography to obtain compound 5 ((2-methoxybenzo[b]thiophene-3-yl)boronic acid ester) (206 mg, 75%) as a colorless oily liquid.

[0093] Characterization of compound 5: 1 H NMR(400MHz,THF-d8)δ8.17-8.10(m,1H),7.64-7.59(m,1H),7.22(ddd,J=8.3 ,7.2,1.2Hz,1H),7.11(td,J=7.7,7.2,1.3Hz,1H),4.01(s,3H),1.33(s,12H).

[0094] 5. Synthesis of compound 6

[0095] Tetra-pyrenyl imide (CAS 110590-83-5) (4.98 g, 7.12 mmol), bromine (62.4 g, 0.39 mol) and CH2Cl2(60 mL) were stirred at room temperature for 12 h. Excess bromine was removed by bubbling air, washed with Na2S2O3and saturated brine, dried over anhydrous MgSO4, and the solvent was removed by rotary evaporation under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography eluted with PE / CH2Cl2= 2:1 to obtain compound 6 as a red solid.

[0096] Characterization of compound 6: 1 H NMR (400 MHz, CDC13) δ 9.80 (d, J = 8.3 Hz, 1H), 8.93 (s, 1H), 8.74-8.60 (m, 5H), 5.24-5.12 (m, 2H), 2.30-2.19 (m, 4H), 1.85-1.80 (m, 4H), 1.27-1.26 (m, 24H), 0.83 0.80 (m, 12H).

[0097] 6. Synthesis of compound 7

[0098] Compound 6 (185 mg, 0.2382 mmol), compound 5 (69.1 mg, 0.2382 mmol), Pd(dppf)Cl2(28.4 mg, 0.036 mmol), K2CO3(aqueous solution 1 mL), ethanol (1 mL) and toluene (5 mL) were added to a 100 ml Schlenk tube, which was sealed and backfilled with Ar three times, and then heated at 80 °C for 12 h. After cooling to room temperature, the reaction mixture was diluted with dichloromethane, washed with saturated brine solution, and dried over anhydrous MgSO4, filtered, and vacuumed. The crude product was purified by silica gel column chromatography (petroleum ether / CH2Cl2= 2 / 1) in the dark to obtain compound 7 (0.38 g, 74%) as a red solid.

[0099] Characterization of compound 7: 1H NMR (400 MHz, CDC13) δ 7.92 - 7.78 (m, 5H), 7.46 (s, 1H), 7.29 (dd, J = 17.2, 8.4 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 6.50 - 6.44 (m, 1H), 6.35 (d, J = 4.1 Hz, 2H), 4.29 (d, J = 26.0 Hz, 2H), 3.15 (s, 3H), 1.37 (s, 4H), 1.03 (s, 4H), 0.45 (d, J = 15.3 Hz, 24H), 0.02 (dd, J = 10.0, 6.5 Hz, 12H).

[0100] 7. Synthesis of compound 8

[0101] In a dry 25 ml two necked round bottom flask, compound 7 (60 mg, 0.070 mmol) was dissolved in dry dichloromethane (5 ml) and BBr3(0.35 mmol, 0.35 mL) was added at -40 °C under argon atmosphere and stirred at room temperature for one day. It was washed with saturated brine three times and extracted with 10 mL of dichloromethane and the organic layer was dried over anhydrous MgS04, filtered and dried under reduced pressure to get compound 8 which was used for the next reaction without further purification.

[0102] 8. Synthesis of compound 9

[0103] The crude product of compound 8 was dissolved in dry dichloromethane 5 mL and injected into a 25 ml two necked flask and then CH3COCI (54.2 mg, 49 μί) and NEt3(69.6 mg, 0.12 mL) were added to this solution at 0 °C. The reaction mixture was removed to warm and stirred for 2 h after which the product was extracted with dichloromethane. The organic layer was dried over anhydrous MgS04, filtered and dried under reduced pressure. The crude product was purified by silica gel column chromatography (n-hexane: dichloromethane = 2: 1) to get compound 9 (PBI-PAG-1) as a red solid (37.3 mg, 60%).

[0104] Characterization of compound 9: 1 H NMR (400 MHz, CDC13) δ 8.71 (d, J = 13.6 Hz, 5H), 8.19 (d, J = 8.4 Hz, 1H), 8.08 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.35 (s, 1H), 7.14 (s, 2H), 5.15 (d, J = 30.0 Hz, 2H), 2.23 (s, 4H), 2.11 (s, 3H), 1.83 (s, 4H), 1.27 (d, J = 11.6 Hz, 24H), 0.82 (d, J = 7.2 Hz, 12H).

[0105] Example 2: Preparation of compound 10.

[0106] Compound 10 was synthesized according to the following route:

[0107]

[0108] The crude product 8 was dissolved in dry dichloromethane (5 mL) and injected into a 25 mL two-necked flask, then C2H5SO2Cl (45 mg, 0.35 mmol) and NEt3 (69.6 mg, 0.12 mL) were added to the solution at 0 °C. After the reaction was raised to room temperature and stirred for 2 h, it was washed with saturated sodium chloride three times and the product was extracted with DCM twice. The organic layer was dried over anhydrous MgSO4, filtered and dried under reduced pressure. The crude product was purified by silica gel column chromatography (n-hexane: dichloromethane = 2: 1) to obtain compound 10 (PBI-PAG-2) (53 mg, 81%).

[0109] Characterization of compound 10: 1 H NMR (400 MHz, CDC13) δ 8.78-8.63 (m, 5H), 8.11 (d, J = 5.7 Hz, 2H), 7.87 (d, J = 8.2 Hz, 1H), 7.41 (ddd, J = 8.2, 5.9, 2.4 Hz, 1H), 7.20-7.13 (m, 2H), 5.15 (d, J = 28.8 Hz, 2H), 3.25 (qd, J = 7.5, 1.6 Hz, 2H), 2.29-2.11 (m, 4H), 1.90-1.76 (m, 4H), 1.61 (s, 3H), 1.27 (d, J = 7.4 Hz, 24H), 0.81 (d, J = 6.7 Hz, 12H).

[0110] Example 3: Preparation of compound 11

[0111] Compound 11 was synthesized according to the following route:

[0112]

[0113] The crude product 8 was dissolved in dry dichloromethane (5 mL) and injected into a 25 mL two-necked flask, then CH3C6H4SO2Cl (133.4 mg, 0.7 mmol) and NEt3 (69.6 mg, 0.12 mL) were added to the solution at 0 °C. After the reaction was raised to room temperature and stirred for 2 h, it was washed with saturated sodium chloride three times and the product was extracted with DCM twice. The organic layer was dried over anhydrous MgSO4, filtered and dried under reduced pressure. The crude product was purified by silica gel column chromatography (n-hexane: dichloromethane = 2: 1) to obtain compound 11 (PBI-PAG-3) (59.4 mg, 85%).

[0114] Characterization of compound 11: 1 H NMR (400 MHz, CDC13) δ 8.78-8.64 (m, 4H), 8.40-8.25 (m, 1H), 7.99 (dd, J = 13.7, 5.4 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.40 (dt, J = 8.3, 4.1 Hz, 1H), 7.17 (d, J = 4.3 Hz, 2H), 6.95 (d, J = 8.1 Hz, 2H), 5.16 (d, J = 28.0 Hz, 2H), 2.19 (s, 7H), 1.83 (s, 4H), 1.25 (t, J = 8.6 Hz, 25H), 0.82 (d, J = 9.3 Hz, 12H).

[0115] Example 4: Preparation of compound 12

[0116] Compound 12 was synthesized according to the following route:

[0117]

[0118] Compound 11 was dissolved in dichloromethane and irradiated under 560 nm light for 30 minutes. Then the solution was diluted with dichloromethane, washed with saturated brine, extracted with DCM. And dried with anhydrous MgS04, filtered, and the solvent was removed in vacuum, and the crude product was separated and purified by silica gel column chromatography (n-hexane: dichloromethane = 2: 1) to obtain compound 12 (CBI).

[0119] Characterization of compound 12: 1 H NMR (600 MHz, CDC13) δ 10.21, 9.30, 9.16, 9.14, 9.12, 9.10, 9.02, 9.01, 8.21, 8.20, 8.19, 8.19, 7.79, 7.79, 7.78, 7.77, 7.77, 7.76, 7.75, 7.75, 7.74, 7.74, 5.36, 5.35, 5.35, 5.34, 2.41, 2.39, 2.37, 2.05, 2.04, 2.03, 2.03, 2.02, 2.01, 1.35, 1.34, 1.33, 1.33, 1.28, 1.27, 1.26, 1.26, 1.25, 0.89, 0.88, 0.87.

[0120] Example 5

[0121] This example tests the photo-reaction performance and fluorescence change of compound 9.

[0122] A solution of 8.88 mg of compound 9 prepared in Example 1 was dissolved in 1000 mL of toluene to obtain a solution with a concentration of 10 μM. 3.5 mL of the solution of compound 9 in toluene was placed in a quartz cuvette and subjected to ultraviolet absorption test (UV-2600, SHIMADZU).

[0123] The solution was irradiated with LED light with a wavelength of 560 nm and a power of 200 mW. The results are shown in Figure 1, in which the red curve is the initial absorption curve at 0 s, the blue curve is the absorption curve after irradiation for 120 s, and the dotted line is the absorption change during the irradiation of 0-120 s. The results show that the absorption peak at 530 nm gradually decreases, while the absorption peaks at 500 nm / 350 nm increase, and the color of the solution gradually changes from red to orange. After 2 min of irradiation, the absorption spectrum no longer changes, reaching a photostationary state. Figure 1

[0124] The absorption spectrum during irradiation is determined by compound 9 and compound 12, and can be calculated by the following formula:

[0125]

[0126] In the region where only compound 9 absorbs (e.g., 530 nm), the ratio of the photostationary state (PSS) to the absorbance of compound 9 is constant. Therefore, the Abs(PSS) / Abs(compound 9) ratio in the constant region can be used to calculate the amount after irradiation, and the conversion rate a can be calculated:

[0127]

[0128] The conversion rate of compound 9 calculated in this example is 96.8%.

[0129] Another 3.5 mL of the solution was placed in a quartz cuvette and subjected to fluorescence test. During the test, the solution was irradiated with LED light with a wavelength of 560 nm and a power of 200 mW. The results are shown in Figure 2, in which the red curve is the initial absorption curve at 0 s, the blue curve is the absorption curve after irradiation for 120 s, and the dotted line is the instantaneous absorption curve during the irradiation of 0-120 s. The results show that the fluorescence emission peak at 600 nm gradually decreases, while the fluorescence emission peak at 530 nm increases, and the fluorescence emission of the compound gradually changes from orange to yellow. After 2 min of irradiation, the fluorescence spectrum no longer changes, reaching a photostationary state. Figure 2 Example 6

[0130] This example tests the photochemical properties and fluorescence changes of compound 10.

[0131]

[0132] ​​The solution preparation and photochromic performance test were carried out according to the method of Example 5, but the solution was irradiated by LED light with wavelength of 560 nm and power of 110 mW. The results are shown in Figure 3 Figure, the red curve is the initial absorption curve at 0 s, the blue curve is the absorption curve after irradiation for 120 s, and the dotted line is the instantaneous absorption curve during 0-120 s. The results show that the photo-reaction performance of compound 10 is similar to that of compound 9. With the irradiation time, the absorption peak at 530 nm gradually decreases, and the absorption peaks at 500 nm / 350 nm increase, and the color of the compound solution gradually changes from red to orange. After 2 min of irradiation, the absorption spectrum no longer changes, reaching a photo-steady state.

[0133] The conversion rate of compound 10 was calculated to be 98.2% according to the method of Example 5.

[0134] The solution preparation and fluorescence change test were carried out according to the method of Example 5, but the solution was irradiated by LED light with wavelength of 560 nm and power of 110 mW. The results are shown in Figure 4 Figure, the red curve is the initial absorption curve at 0 s, the blue curve is the absorption curve after irradiation for 120 s, and the dotted line is the instantaneous absorption curve during 0-120 s. The results show that the photo-reaction performance of compound 10 is similar to that of compound 9. With the irradiation time, the fluorescence emission peak at 600 nm gradually decreases, and the fluorescence emission peak at 530 nm increases, and the fluorescence emission of the compound gradually changes from orange to yellow. After 2 min of irradiation, the fluorescence spectrum no longer changes, reaching a photo-steady state.

[0135] Example 7

[0136] This example tests the photo-reaction performance and fluorescence change of compound 11.

[0137] The solution preparation and photochromic performance test were carried out according to the method of Example 5, but the solution was irradiated by LED light with wavelength of 560 nm and power of 70 mW. The results are shown in Figure 5 Figure, the red curve is the initial absorption curve at 0 s, the blue curve is the absorption curve after irradiation for 120 s, and the dotted line is the instantaneous absorption curve during 0-120 s. The results show that the photo-reaction performance of compound 11 is similar to that of compound 9. With the irradiation time, the absorption peak at 530 nm gradually decreases, and the absorption peaks at 500 nm / 350 nm increase, and the color of the compound solution gradually changes from red to orange. After 2 min of irradiation, the absorption spectrum no longer changes, reaching a photo-steady state.

[0138] The conversion rate of compound 10 was calculated to be 99.2% according to the method of Example 5.

[0139] The solution preparation and fluorescence change test were carried out according to the method of Example 5, but the solution was irradiated with an LED with a wavelength of 560 nm and a power of 70 mW. The results are shown in Figure 6 Figure 8, where the dotted line is the instantaneous absorption curve during 0-120 s. The results show that the photo-reaction performance of compound 10 is similar to that of compound 9, and as the irradiation time increases, the fluorescence emission peak at 600 nm gradually decreases, while the fluorescence emission peak at 530 nm increases, and the fluorescence emission of the compound gradually changes from orange to yellow. After 2 min of irradiation, the fluorescence spectrum no longer changes, reaching a photostationary state.

[0140] The experimental results of Examples 5-7 above show that under the same irradiation conditions, compounds 9-11 use powers of 200 mW, 110 mW and 70 mW respectively, but the absorption spectra obtained are consistent, indicating that compound 11 can achieve the same photo-reaction effect under lower light power.

[0141] Example 8: NMR titration of compound 11

[0142] The solutions of compound 11 before and after irradiation were characterized by NMR using deuterated chloroform as the solvent. The results are shown in Figure 7 Figure 9, where I is the NMR spectrum of compound 11, II is the NMR spectrum of compound 11 after irradiation, and III is the NMR spectrum of compound 12. The results show that the peak value of the methyl group substituted with a p-toluenesulfonyl group on compound 11 at 2.19 ppm gradually decreases, and a new signal appears at 2.32 ppm. II is highly overlapped with III, and the characteristic peak of compound 11 cannot be found in II, indicating that compound 11 is almost completely converted into compound 12 and acid after irradiation, and compound 11 can release acid at a yield close to 100%.

[0143] Example 9: Transient absorption spectroscopy characterization of compound 9

[0144] 8.88 mg of prepared compound 9 was dissolved in 100 mL of toluene solution, and the resulting solution had a concentration of 100 μM. 200 μL of the above solution was placed in a quartz cuvette for transient absorption test (Femto-TA100), and the test conditions were: excitation wavelength 355 nm, test wavelength 550 nm.

[0145] The results are shown in Figure 8 The results show that a new absorption peak appears at 680 nm within 2 ps, corresponding to the photo-cyclization process, and gradually decreases after 500 ps. The absorption peak at 630 nm changes little with time.

[0146] Example 10: Transient absorption spectroscopy characterization of compound 10

[0147] Take 10 mg of the prepared compound 10 and dissolve it in 100 mL of toluene solution, and the concentration of the obtained solution is 100 μM. Take 200 μL of the above solution and place it in a quartz cuvette, and perform transient absorption test (Femto-TA100) under the following conditions: excitation wavelength 355 nm, test wavelength 550 nm.

[0148] The results are shown in Figure 9 The results show that a new absorption peak appears at 680 nm within 2 ps, which corresponds to the photocyclization process, and gradually decreases after 500 ps. The peak at 630 nm gradually increases over time.

[0149] Example 11: Transient absorption spectrum characterization of compound 11

[0150] Take 8.88 mg of the prepared compound 11 and dissolve it in 100 mL of toluene solution, and the concentration of the obtained solution is 100 μM. Take 200 μL of the above solution and place it in a quartz cuvette, and perform transient absorption test (Femto-TA100) under the following conditions: excitation wavelength 355 nm, test wavelength 550 nm.

[0151] The results are shown in Figure 10 The results show that the absorption peak at 630 nm gradually increases over time.

[0152] Example 12: Compound 11 used for polymerization and self-repairing experiment of lipoic acid ester

[0153] 1. Polymerization experiment

[0154] Take 1.76 mg of compound 11 and dissolve it in 10 mL of lipoic acid ester (CAS: 46236-19-5), and take 200 μL of each and place it on a glass sheet, and use 560 nm (200 mW) light to irradiate, with lipoic acid ester without adding compound 11 as a control.

[0155] The results are shown in Figure 11 The results show that after irradiation, the right side of the flowing liquid lipoic acid ester polymerizes to become sticky and adheres to the glass sheet. The left and right liquid spots in the figure are lipoic acid ester without adding compound 11 and the mixture of compound 11 and lipoic acid ester, respectively. The results show that after irradiation, the right side of the flowing liquid lipoic acid ester polymerizes to become sticky and adheres to the glass sheet. The left and right liquid spots in the figure are lipoic acid ester without adding compound 11 and the mixture of compound 11 and lipoic acid ester, respectively.

[0156] 2. Repair experiment

[0157] Another 1 mL of lipoic acid ester added with compound 11 was taken, 0.44 mg of TFA was added and quickly spread on a glass sheet, the liquid lipoic acid ester quickly polymerized on the glass sheet, then the formed glue was destroyed using a putty knife and irradiated with 560 nm light.

[0158] The results are shown in Figure 12 The left photo is after damage, and the right photo is after 10 min irradiation. It can be seen from the figure that the damaged glue is gradually repaired after 10 min.

[0159] Example 13: Active oxygen test of CBI

[0160] 3 ml of toluene solution of compound 11 prepared according to Example 5 was taken, and fluorescent dye DPBF (commercial active oxygen probe) was added, and irradiated with 560 nm light at 110 mW / cm 2 The fluorescent dye DPBF can form internal peroxide and decompose into 1,2-diphenyl benzoyl under the condition of active oxygen, which has fluorescence reduction at 400-425 nm.

[0161] The results are shown in Figure 13 The results show that the fluorescence at 400-425 nm gradually decreases with the increase of irradiation time. It shows that photosensitive molecule 12 can have the ability to convert the surrounding oxygen into active oxygen under the condition of normal temperature and pressure and the presence of oxygen.

[0162] Example 14: Preparation of PBI@M micelles and particle size characterization

[0163] 8.88 mg of compound 11 was dissolved in 1 mL of tetrahydrofuran solution, and the concentration of the obtained solution was 1 mM. In addition, 46 mg of amphiphilic polymer F127 (CAS: 9003-11-6) was dissolved in 900 μL of tetrahydrofuran, then 100 μL of tetrahydrofuran solution of compound 11 was added and mixed uniformly. 200 μL of the above solution was slowly added to 2000 μL of ultrapure water under vigorous stirring to prepare 10 μM micelles (PBI@M), and dialysis was carried out after stirring for 30 min to remove excess tetrahydrofuran. 100 μL of PBI@M solution and 900 μL of water were added to a cuvette, and the particle size was measured, and the results are shown in Figure 14 The results show that the particle size is about 100 nm.

[0164] Example 15: Active oxygen test of PBI@M

[0165] 2.4 mg of fluorescent dye DCFH was dissolved in 12 mL of water, 200 μl of DCFH aqueous solution, 400 μL of PBI@M micellar aqueous solution and 1400 μL of water were taken, and irradiated with 560 nm light at 10 mW / cm 2DCFH is a water-soluble commercially available active oxygen probe. In the presence of active oxygen, DCFH can be oxidized into a fluorescent substance 1,2-dichlorofluorescein (DCF), which has fluorescence enhancement at 525 nm and can be used to detect the generation of active oxygen in an aqueous solvent.

[0166] The results are shown in Figure 15 As shown, the results show that the fluorescence enhancement at 525 nm increases with the increase of irradiation time, indicating that PBI@M can generate active oxygen under light irradiation.

[0167] Example 16: PBI@M photodynamic inhibition of Pseudomonas aeruginosa activity test

[0168] 1. Bacterial survival rate experiment

[0169] Pseudomonas aeruginosa (ATCC 27853) was inoculated in a 37°C shaking medium and cultured to the logarithmic growth phase, and the concentration was diluted to 10 6 CFU / ml. Then 30 μM of PBI@M was added to the bacterial solution, respectively, and incubated in the dark and light conditions for 45 min, and then cultured on solid medium at 37°C overnight. The bacterial survival rate was counted using the colony counting method.

[0170] The results are shown in Figure 16 As shown, the results show that the bacterial survival rate of the group with PBI@M added and light irradiation is about 40%, while that of the other groups is about 100%, indicating that PBI@M has a significant bacteriostatic effect under light irradiation.

[0171] 2. Microscopic observation

[0172] Another part of the bacterial suspension grown to the logarithmic growth phase was added with 30 μM of PBI@M, and incubated in the dark and light conditions for 45 min, and then centrifuged at 10000 rpm for 3 min, and the supernatant was taken out, washed with PBS three times, and then suspended in PBS, and 5 μM of PI (propidium iodide) dye was added for staining in the dark for 15 min. Finally, it was washed with PBS three times and an appropriate volume was placed on a microscope slide and dried at room temperature. A Nikon AIR confocal laser scanning microscope was used for observation, equipped with a 100x oil immersion objective (λ ex = 514 nm; λ ex = 607-715 nm).

[0173] The results are shown in Figure 17 (scale bar 5 μm), and red fluorescence can be observed in the field of view of the group with PBI@M added and light irradiation, indicating that the PI dye has penetrated the cell membrane of dead cells and combined with the cell DNA.

[0174] 3. Observation of bacterial surface membrane structure

[0175] Another 7000 rmp centrifugal 1 min, take out 700 μL of liquid medium, add 100 μM of PBI@M 300 μL, mix and placed in the dark, light conditions respectively incubated for 45 min. 8000 rmp centrifugal 1 min; discard the supernatant, washed with PBS 3 times, add 2.5% glutaraldehyde, mix, 4°C overnight fixation. After overnight 8000 rmp centrifugal 1 min, discard the supernatant, PBS wash three times, according to the volume percentage concentration of 30%, 50%, 70%, 80%, 90% ethanol solution order gradient elution, each time after adding static 15 min, 8000 rmp centrifugal 1 min, finally with 300-600 μL of anhydrous ethanol resuspended for standby. The resuspended bacteria liquid take 7-10 μL drop on the surface of the glass, plastic wrap, oven drying for standby. Using Zeiss Gemini SEM450 SEM pictures.

[0176] The results are shown in Figure 18 (scale 2 μm) as shown, the results show that using PBI@M incubation and light can be observed in the group of bacterial surface membrane structure damage.

Claims

1. Perylene imide compounds represented by Formula I: ， in, R1 and R2 are independently C1-C 20 Alkyl, C3-C8 cycloalkyl, or C6-C 10 Aryl; R3 and R4 are independently hydrogen, C1-C3 alkoxy, C1-C6 alkyl, halogen, cyano, or C6-C 10 Aryl; X1 is S; X2 and X3 cyclize to form a benzene ring; R5 is ,or ; R6 and R7 are independently C1-C6 alkyl groups, or C6-C 10 Aryl, the C1-C6 alkyl, C6-C 10 The aryl group may be optionally substituted with 1-3 halogens or C1-C6 alkyl groups.

2. The perylene imide compound of formula I as described in claim 1, characterized in that, R1 and R2 are independently C8-C 15 alkyl; And / or, R3 and R4 are hydrogen; And / or, R6 and R7 are independently C1-C4 alkyl, phenyl, wherein the phenyl is optionally substituted with 1-3 halogens or C1-C4 alkyl groups.

3. The perylene imide compound of formula I as described in claim 2, characterized in that, R1 and R2 are independently C9-C 13 alkyl.

4. The perylene imide compound of formula I as described in claim 3, characterized in that, R1 and R2 are independently C 11 alkyl.

5. The perylene imide compound of formula I as described in claim 4, characterized in that, R1 and R2 are independently n-undecane.

6. The perylene imide compound of formula I as described in claim 1, characterized in that, R1 and R2 are the same.

7. The perylene imide compound of formula I as described in claim 2, characterized in that, The C1-C4 alkyl group is methyl, ethyl, propyl, butyl, or isopropyl; And / or, when R6 or R7 is a phenyl substituted with a halogen or C1-C4 alkyl group, the substitution position being one or more of the ortho, meta, and para positions.

8. The perylene imide compound of formula I as described in claim 2, characterized in that, The C1-C4 alkyl group is methyl or ethyl; And / or, when R6 or R7 is a phenyl substituted with a halogen or C1-C4 alkyl group, the substitution position is para.

9. The perylene imide compound of formula I as described in claim 1, characterized in that, Selected from the following compounds: 、 、 。 10. A method for preparing the perylene imide compound of formula I as described in any one of claims 1-9, characterized in that, Synthesize according to the following route: ， Wherein, R1, R2, R3, R4, R5, X1, X2 and X3 are as described in any one of claims 1-9; X is a halogen.

11. The method for preparing perylene imide compounds as described in claim 10, characterized in that, X is bromine.

12. The use of the perylene imide compound as described in any one of claims 1-9 in the preparation of photoacid-producing agents and / or photosensitive antibacterial agents; wherein, The bacteria in question are bacteria.

13. A perylene imide compound represented by Formula II: ， in, R1, R2, R3, R4, X1, X2, and X3 are as described in any one of claims 1-9.

14. The perylene imide compound of formula II as described in claim 13, characterized in that, Selected from the following compounds: 。 15. The method for preparing the perylene imide compound of formula II as described in claim 13 or 14, characterized in that, Synthesize according to the following route: ， R1, R2, R3, R4, X1, X2, and X3 are as described in any one of claims 1-9.

16. The use of the perylene imide compound as described in claim 13 or 14 in the preparation of a photosensitive antibacterial agent; wherein, The bacteria in question are bacteria.

17. A photosensitive antibacterial agent, characterized in that, It includes perylene imide compounds of formula II as described in claim 13 or 14; wherein the bacteria are bacteria.

18. A photosensitive antibacterial agent, characterized in that, The antibacterial agent comprises PBI@M micelles, which are prepared by the following method: The perylene imide compound of formula II as described in claim 13 or 14, which is soluble in an organic solvent, is mixed evenly with a polymer F127 solution soluble in an organic solvent to obtain a mixed solution. The mixed solution is then added dropwise to water while stirring to obtain the product; wherein the bacteria are bacteria.

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