CN111362977A - Bimolecular polar compound and synthesis and application thereof - Google Patents
Bimolecular polar compound and synthesis and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 206010034972 Photosensitivity reaction Diseases 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 230000036211 photosensitivity Effects 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 230000021615 conjugation Effects 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 14
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000005577 anthracene group Chemical group 0.000 claims description 3
- ZVFJWYZMQAEBMO-UHFFFAOYSA-N 1h-benzo[h]quinolin-10-one Chemical group C1=CNC2=C3C(=O)C=CC=C3C=CC2=C1 ZVFJWYZMQAEBMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000006552 photochemical reaction Methods 0.000 claims description 2
- 230000003335 steric effect Effects 0.000 claims description 2
- 206010059605 Necrobiosis Diseases 0.000 claims 1
- 208000015906 Necrobiotic disease Diseases 0.000 claims 1
- 230000004900 autophagic degradation Effects 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- 210000004881 tumor cell Anatomy 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- 230000005281 excited state Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 238000002560 therapeutic procedure Methods 0.000 abstract 1
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000002428 photodynamic therapy Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VHHDLIWHHXBLBK-UHFFFAOYSA-N anthracen-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=CC2=C1 VHHDLIWHHXBLBK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- A61K41/008—Two-Photon or Multi-Photon PDT, e.g. with upconverting dyes or photosensitisers
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Abstract
The invention relates to a bimolecular compound which has fluorescence emission wavelength and intensity changed along with the polarity of a solvent, has photosensitivity and can sensitize the generation of singlet oxygen. The invention adopts molecules containing N ^ O bidentate ligand and BF2The functional groups are complexed to obtain a nonpolar chromophore with enhanced conjugation degree, and after the nonpolar chromophore is covalently connected with benzene condensed ring chromophores such as anthracene and the like, the two chromophores are orthogonally connected due to steric hindrance effect to obtain a bimolecular polar compound. When the compound is in an excited state, the compound is sensitive to change of environmental polarity, and the fluorescence emission wavelength and intensity are red-shifted and reduced along with the increase of the polarity of a solvent; at the same time, the compound can reach a triplet state through intersystem crossing in an excited state, and the sensitized oxygen generates singlet oxygen for usePhotodynamic therapy, and the like.
Description
Technical Field
Relates to synthesis and application of bimolecular polar compounds with fluorescence emission wavelength and intensity changed along with the polarity of a solvent, photosensitivity and capability of sensitizing singlet oxygen generation.
Background
Due to the application in the fields of photodynamic therapy, photocatalysis, triplet-triplet annihilation up-conversion, etc., studies on properties of triplet photosensitizers have been receiving attention in recent years, and among them, triplet photosensitizers containing no heavy atom such as a transition metal or a halogen atom have been reported less because of the structural specificity and unpredictability of intersystem crossing. A bimolecular compound having a vertically conjugated system has a long-lived triplet state through intramolecular charge transfer-induced intersystem crossing (see FIG. 1, Dance, Z.E.X.; Mickley, S.M.; Wilson, T.M.; Ricks, A.B.; Scott, A.M.; Ratner, M.A.; Wasielewski, M.R., The Journal of Physical Chemistry A2008, 112,4194-4201.), and is superior in properties, low in price, and predictable and repairable compared to conventional noble metal photosensitizers.
Disclosure of Invention
The invention provides an orthogonally-connected bimolecular compound which is simple and convenient to synthesize, has long service life (200 mu s), has the absorption wavelength of 430nm, and can be used for photosensitization to generate singlet oxygen.
In order to achieve the above purpose of the present invention, the present invention adopts the following technical scheme:
the invention adopts molecules containing N ^ O bidentate ligand and BF2The functional groups are complexed to obtain a nonpolar chromophore with enhanced conjugation degree, the chromophore is covalently connected with benzene condensed ring chromophores such as anthracene and the like, and due to steric effect, the two chromophores are orthogonally connected to obtain the bimolecular polar compound with photosensitivity.
The compounds have the general formula:
general formula I: P-R-BF2，
In the general formula I, P is a benzene fused ring compound which is naphthalene, anthracene, pyrene, anthracene containing methyl or phenyl substituent or naphthalene containing substituent, and the substituent on the naphthalene ring is C1～C20Carbon chain alkyl group of (5), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or hydroxyl (-OH), etc.; r is an organic molecule containing N ^ O bidentate ligand and is used as BF2The complexing center of (1).
When R is 10-hydroxybenzo [ H ] quinoline (HAP), the compound has the general formula:
in the general formula II, R' is a substituent on a benzene ring of HAP and can be hydrogen atom and C1～C20Carbon chain alkyl group of (2), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or hydroxyl (-OH), etc.;
p is a benzene fused ring compound which is naphthalene, anthracene, pyrene, anthracene containing methyl or phenyl substituent or naphthalene containing substituent, and the substituent on the naphthalene ring is C1～C20Carbon chain alkyl group of (5), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or a hydroxyl group (-OH).
When P is anthracene, the compound has the formula:
wherein R' has the same meaning as formula II; r' is a substituent on an anthracene ring and can be a hydrogen atom, a methyl or a phenyl.
When P is pyrene, the compound has the general formula:
wherein R' has the same meaning as in the general formula II.
When P is naphthalene, the compound has the general formula:
wherein R' has the same meaning as formula II; r1Is a substituent on the naphthalene ring, can be a hydrogen atom, C1～C20Carbon chain of (2), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Hydroxyl (-OH), and the like.
When the bimolecular compound of the general formula 1 is in an excited state, the bimolecular compound is sensitive to change of environmental polarity, and the fluorescence emission wavelength and intensity are red-shifted and reduced along with the increase of the polarity of a solvent; meanwhile, the compound can reach a triplet state through intersystem crossing in an excited state, and the sensitized oxygen generates singlet oxygen for application of photodynamic therapy and the like.
When the bimolecular compound shown in the general formula 1 is used for photosensitizing singlet oxygen, the bimolecular compound is characterized in that the general formula I can perform photochemical reaction with oxygen in the environment under the irradiation of light with a specific wavelength range to generate singlet oxygen, and the chemical equation is as follows:
the invention has the beneficial effects that:
the bimolecular compound is simple and convenient to synthesize, does not contain heavy atoms, has good light stability, has the molecular fluorescence emission wavelength and intensity sensitive to the environmental polarity, has the triplet state life of 200 mu s, and can reach the singlet oxygen quantum yield of 0.58 when being used for sensitizing in a solution to generate singlet oxygen.
Drawings
FIG. 1 is a schematic representation of the molecular structure of a compound as set forth in the background;
FIG. 2 is a schematic structural diagram of bimolecular polar compounds HB-An synthesized in example 1;
FIG. 3 fluorescence spectra of the compound HB-An used in example 2 in different polar solvents;
FIG. 4 is a graph showing the change of the absorption spectrum of 1, 3-Diphenylisobenzofuran (DPBF) with time when singlet oxygen generated by sensitization with HB-An, the compound used in example 3, is captured by the DPBF.
Detailed Description
The examples serve to further illustrate the invention, but the invention is not limited to the examples.
Example 1 (synthesis of bimolecular polar compound HB-An):
as shown in FIG. 2, the bimolecular compounds used in the examples have the structures represented by the symbols HB-An, and HB represents 10-hydroxybenzo [ H ]]BF of quinoline (HAP)2Complex, An represents An anthracene group.
Synthesis of HB-An: (1) under the protection of nitrogen, 0.055g of Br-HB,0.053g of 9-anthraceneboronic acid, 0.17g of potassium carbonate and 0.023g of tetrakis (triphenylphosphine) palladium were dissolved in 30mL of a mixed solvent of dioxane and water (volume ratio 2:1), and the solution was raised to 90 ℃ to react for 8 hours. The solvent is distilled off under vacuum, and the obtained solid is purified by column chromatography to obtain the compound HB-An.
1H NMR(400MHz,CDCl3)δ(ppm):9.12(d,1H),8.63(s,1H),8.58(dd,1H),8.13(d,2H),7.93(dd,1H),7.87(d,1H),7.66(d,1H),7.49(m,3H),7.38(m,2H),7.29(m,2H),7.23(d,1H).13C NMR(400MHz,d6-DMSO)δ(ppm):153.70,143.81,143.52,142.63,139.38,138.59,136.08,134.01,133.34,131.51,131.22,129.16,128.08,127.86,127.35,126.80,126.38,125.93,124.00,116.01.19F NMR(40MHz,CDCl3)δ(ppm):-146.43.ESI-HRMS:Calcd[M+NH4]+([C27H20BF2N2O]+),m/z＝437.1631；found,m/z＝437.1648.
Example 2 (fluorescence spectra of HB-An in different polar solvents):
a quartz cuvette was charged with 30. mu. mol of HB-An dissolved in a solvent of different polarity, and the fluorescence spectrum was measured. The fluorescence emission wavelength and intensity as a function of solvent polarity are shown in FIG. 3.
Example 3 (testing of the ability of HB-An to photosensitize to produce singlet oxygen):
a30. mu. mol of HB-An in methylene chloride air saturated solution was put into a quartz cuvette, and DPBF was added to adjust the absorbance at 414nm to about 1.0. The mixed solution was irradiated with light (1.34mA) at 360nm for 20s, shaken, and the absorption spectrum was measured, and the change of the absorption spectrum (after subtracting the absorption of HB-An) with the irradiation time is shown in FIG. 4, which is the DPBF absorption system1O2A graphical representation of the amount change is generated.
FIG. 4 shows the change in the absorption intensity of the system, indicating that HB-An increases with the time of illumination, in An air-saturated solution1O2Increased production of DPBF1O2Capture molecules, the absorption intensity of which decreases; the inset shows a linear fitted curve of the 414nm absorbance with illumination time, the linear regression constant of the linear fitted curve is 0.9991, indicating the quantifiability of the photosensitivity of bimolecular compound HB-An.
Claims (8)
1. A bimolecular polar compound having the formula:
general formula I: P-R-BF2，
In the general formula I, P is a benzene fused ring compound which is naphthalene, anthracene, pyrene, anthracene containing methyl or phenyl substituent or naphthalene containing substituent, and the substituent on the naphthalene ring is C1～C20Carbon chain alkyl group of (5), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or hydroxyl (-OH), etc.; r is an organic molecule containing N ^ O bidentate ligand and is used as BF2The complexing center of (1).
2. The bimolecular polar compound according to claim 1, wherein when R is 10-hydroxybenzo [ H ] quinoline (HAP), the compound has the general formula:
in the general formula II, R' is a substituent on a benzene ring of HAP and can be hydrogen atom and C1～C20Carbon chain alkyl group of (2), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or hydroxyl (-OH), etc.;
p is a benzene fused ring compound which is naphthalene, anthracene, pyrene, anthracene containing methyl or phenyl substituent or naphthalene containing substituent, and the substituent on the naphthalene ring is C1～C20Carbon chain alkyl group of (5), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or a hydroxyl group (-OH).
3. The bimolecular polar compound according to claim 2, wherein when P is anthracene, the compound has the general formula:
wherein R' has the same meaning as formula II; r' is a substituent on an anthracene ring and can be a hydrogen atom, a methyl or a phenyl.
4. The bimolecular polar compound according to claim 2, wherein when P is pyrene, the compound has the general formula:
wherein R' has the same meaning as in the general formula II.
5. The bimolecular polar compound according to claim 2, wherein when P is naphthalene, the compound has the general formula:
wherein R' has the same meaning as formula II; r1Is a substituent on the naphthalene ring, a hydrogen atom, C1～C20Carbon chain alkyl group of (5), halogen atom, nitro group (-NO)2) Amino (-NH-)2) Sulfonic acid group (-SO)3) Or a hydroxyl group (-OH).
6. A process for the synthesis of bimolecular compounds according to claims 1 to 5, characterized in that a molecule containing N ^ O bidentate ligand is used with BF2The functional groups are complexed to obtain a nonpolar chromophore with enhanced conjugation degree, the chromophore is covalently connected with benzene condensed ring chromophores such as anthracene and the like, and due to steric effect, the two chromophores are orthogonally connected to obtain the bimolecular polar compound with photosensitivity.
7. Use of a bimolecular compound according to claims 1-5 for photosensitized singlet oxygen generation.
8. The use of bimolecular polar compounds according to claim 7 for photosensitized singlet oxygen generation, wherein the bimolecular compounds are capable of photochemical reaction with oxygen in the environment under irradiation of light to produce singlet oxygen, which can be used for sterilization or to cause necrobiosis or autophagy of tumor cells.
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