CN1600771A - Usage of photosensitizer of hypocrellin and class of amido group ramification - Google Patents
Usage of photosensitizer of hypocrellin and class of amido group ramification Download PDFInfo
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- CN1600771A CN1600771A CN 03134666 CN03134666A CN1600771A CN 1600771 A CN1600771 A CN 1600771A CN 03134666 CN03134666 CN 03134666 CN 03134666 A CN03134666 A CN 03134666A CN 1600771 A CN1600771 A CN 1600771A
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Abstract
The use of hypocrelline B and amid derivant belong to photosensitizer, hypocrelline B and amid derivant as semiconductor photosensitizer are used in light function material and device. R in above structure general formula is alkenes amid.
Description
Technical field
The invention belongs to the photosensitizers field, particularly the purposes of Hypocrellin B and amido derivative class photosensitizers thereof.
Background technology
Hypocrellin (Hypocrellin) is a kind of parasitical fungi from the arrow bamboo that parasitizes Yunnan Province of China one band---the photosensitizers of a kind of natural pigment class of extracting the red bamboo fungus (Hypocrella bambuase), belong to 3,10-dihydroxyl-4,9-perylene quinone derivative.Natural hypocrellin mainly contains two kinds of components: Hypocrellin A (Hypocrellin A is called for short HA) and Hypocrellin B (Hypocrellin B is called for short HB), and structure and atom numbering are as follows:
The productive rate that extracts hypocrellin from the exsiccant red bamboo fungus can reach 3-5%.Be the first element more than 95% wherein, but under alkaline condition, HA can dewater and be converted into HB.Document " structural changes of Hypocrellin A in alkalescence and neutral solution ", organic chemistry, 1989,9:252, Zhao Kaihong, Jiang Lijin are seen in the extraction of hypocrellin and the conversion from HA to HB.Structure and the existing several pieces of outstanding summaries of character about hypocrellin are delivered, as " structure and the character of the structure of hypocrellin, character, photochemical reaction and reaction mechanism (I)---hypocrellin ", Science Bulletin, 1990,35:1608, Jiang Lijin; " reaction of the structure of hypocrellin, character, photochemical reaction and reaction mechanism (II)-hypocrellin ", Science Bulletin, 1990,35:1681, Jiang Lijin; Lown, J.W.Photochemistry and photobiology ofperylenequinones.Can.J.Chem., 1997,75:99; Diwu, Z.J., Lown, J.W.Hypocrellins and their uses in photosensitization.Photochem.Photobiol., 1990,52:609; Diwu, Z.J.Novel therapeutic and diagnosticapplications of hypocrellins and hypericins.Photochem.Photobiol., 1995,61:529; Jiang Lijin, He Yuying; " optical physics, photochemistry and the photo bio of hypocrellin class photosensitizers " Science Bulletin, 2000,45:2019.Because hypocrellin and derivative thereof can produce a large amount of active oxygen (creating singlet oxygen by using behind irradiation, superoxide anion, hydroxyl radical free radical etc.), many cancer cells are had killing action, so, in the past the research of hypocrellin and derivative thereof mainly all was limited on the drug candidate as phototherapy, as Diwu, Z.J., Lown, J.W.Hypocrellins and their usesin photosensitization.Photochem.Photobiol., 1990,52:609; Diwu, Z.J., Lown, J.W.Phototherapeutic potential of alternativephotosensitizers to porphyrins.Pharmacol.Ther., 1994,63:1-35; Pang, S.Z., Qing, J.F., Yue, J.C., An, J.Y.Photosensitizing damage tomorphology of Hela cells by bromide of hypocrellin B (5-Br-HB) .ActaBiophys.Sin., 1994,10:651; Pleasure adds prosperous, Pang Suzhen, Zhang Manhua etc.The plain modifier of hypocrellin second (thanomin) is studied for the light injury of ascites liver cancer cell.Acta Biophysica Sinica, 1994,10:485-492; Zhang, W.G., Ma, L.P., Wang, S.W., Zhang, M.H., Yang, H.Y., Zhao, H.X., Zhang, Z.Y.Antisense bcl-2 retrovirus vectorincrease the sensitivity of a human gastric adenocarcinoma cell lineto photodynamic therapy.J.Photochem.Photobiol.B:Biol., 1998,44:21; Zhang, J., Cao, E.H., Li, J.F., Zhang, T.C., Ma, W.J.Photodynamiceffects of hypocrellin A on three human malignant cell lines by inducingapoptotic cell death J.Photochem.Photobiol.B:Biol., 1998,43:106.
Summary of the invention
One of purpose of the present invention provides a kind of Hypocrellin B and amido derivative thereof.
Two of purpose of the present invention is that Hypocrellin B and amido derivative thereof are used for optical function material and device as photosensitizers.
Three of purpose of the present invention provides with respect to the parent Hypocrellin B, the evaluation method of the photosensitive property of its amido derivative.
The photoactivated Hypocrellin B class of the semi-conductor photosensitizers that is used for of the present invention comprises that the general structure of substitutive derivative of Hypocrellin B itself and alkanamine base class thereof is as follows:
Wherein, R is an alkylamino radical.
Hypocrellin B of the present invention and amido derivative thereof can be used as semi-conductor and are used for optical function material and device for photosensitive dose.
Semi-conductive photosensitization:
After the semi-conductor extinction, the electronics of valence band can be excited and transit on the conduction band, and positive hole appears in valence band, and electronegative electronics appears in conduction band, so just might form optical function material and device.
General semi-conductor is as inorganic titanium dioxide (TiO
2) and organically polystyrene support (PPV), can only absorb ultraviolet ray; (molar extinction coefficient is 10 and synthetic dyestuff (hereinafter to be referred as dyestuff) or natural pigment (hereinafter to be referred as pigment) have very strong absorption at visible region
4More than).As them as photosensitizers attached to semi-conductive surface, dyestuff or pigment strong absorption visible light and be excited, the photoelectron that produces is injected into semi-conductive conduction band, and the electronics on the semi-conductor valence band can be filled up dyestuff or the pigment positive hole that the back occurs that is excited, dyestuff or pigment are restored, and semi-conductor has then also produced charge separation as itself absorbs ultraviolet ray.Like this, just semi-conductive sensitization scope has been elongated visible light from ultraviolet ray.Here it is semi-conductive dyestuff or pigment photosensitization are referred to as dye sensitization or spectral sensitization again.
The testing method of the photosensitizers photosensitive property of Hypocrellin B of the present invention and amido derivative thereof is characterized in that photosensitizers is coated on the electrically-conductive backing plate, directly measures the relative efficiency that the sensitizing agent photoelectron injects by direct-current biasing on electrically-conductive backing plate.
The test of sensitizing agent photosensitive property as shown in Figure 1, the size in electrode front is as shown in Figure 2.
Photosensitizers thin layer in the coating of the bottom of transparent conductive glass (electrode of photosensitizer layer one side is done on top) plates the electrode of 6 bar aluminum strips as the photosensitizer layer another side in photosensitizers bottom vacuum again.Between two electrodes, connect direct-current biasing and reometer (in case of necessity, can connect and go up sizeable resistance) so that the electric current of being surveyed is in the useful range of reometer.During irradiation, organically photosensitizer layer is not an isolator, though direct-current biasing is arranged in the circuit, does not have galvanic current through reometer yet.When halogen lamp light source during from back side illuminaton to photosensitizer layer, photosensitizers is excited, and can inject photoelectron to conductive glass.Under the direct-current biasing effect, just have the galvanic current reometer of flowing through.And the photosensitive property of sensitizing agent is good more, and under same light intensity, the photoelectron that is injected into conductive glass is just many more, and the photoelectric current under same direct-current biasing is also just big more.
Relative merits of the present invention and positively effect
(1) red bamboo fungus is the special product in China western part, natural pigment wherein-hypocrellin content is abundant, it is convenient to extract, change into the second element and the second element is made amido derivative all than being easier to from Hypocrellin A, be used for semi-conductive photosensitization, with respect to design, synthetic light-sensitive coloring agent, be the photosensitizers that a class is cheap, conveniently be easy to get.
(2) photocell of real dye sensitization is illustrated in Fig. 3.In testing method of the present invention (Fig. 1 and Fig. 2),, directly measure the relative efficiency that various sensitizing agent photoelectrons inject without semiconductor layer.Advantage is to have avoided semi-conductive influence, prepares also more convenient; The limitation part is the absolute efficiency that can not obtain the sensitizing agent photosensitive semiconductor, and can only compare photosensitizers relative efficiency each other.So the parent that the present invention only is suitable for known or a series is a benchmark, the photosensitive relatively efficient of other photosensitizerss or derivative.
Description of drawings
Fig. 1. embodiment of the invention optoelectronic equipment side and test synoptic diagram.
Fig. 2. embodiment of the invention optoelectronic equipment front schematic view.
Fig. 3. traditional photocell synoptic diagram.
Fig. 4. the abosrption spectrogram of embodiment of the invention photosensitizers.
Reference numeral
1. halogen lamp 2. electrode 3. photosensitive dye layer 4. transparent conducting glass of aluminizing
5. direct-current biasing 6. reometers 7. 8. semiconductor layers, 9. ammeters at interval
Embodiment
Embodiment
(1) 2-butylamine base Hypocrellin B (photosensitizers 2) is pressed document Tao Wu, Shangjie Xu, Jianquan Shen, Aimin Song, Shen Chen, Manhua Zhang, Tao Shen.Newpotential photodynamic therapeutic anti-cancer agents:synthesis andcharacterization of demethoxyaminosubstituted hypocrellins.Anti-cancer Drug Design.2000,15, the 287-293 preparation.Reaction formula is as follows:
200 milligrams of Hypocrellin Bs (parent, photosensitizers 1) are dissolved in 250 milliliters of new pyridines that steam, and add 20 milliliters of n-Butyl Amine 99s.Stir under the lucifuge condition, control reaction temperature is between 50-55 degree centigrade, reacts 15 hours.Stopped reaction, the pressure reducing and steaming solvent gets black solid.With the chloroform dissolving, use dilute hydrochloric acid (1%) washing then, be neutral substantially until water layer.Boil off chloroform, get black solid.Use sherwood oil: ethyl acetate: the mixed solvent of ethanol=4: 2: 1 is as developping agent, on the silica-gel plate that soaked with 2% potassium primary phosphate, carry out thin-layer chromatography, obtain n-butylamine-based Hypocrellin B (photosensitizers 2), productive rate (calculating with Hypocrellin B) is 45%.
(2) spectrum property of photosensitizers:
The absorption spectrum of two kinds of photosensitizerss is seen accompanying drawing 4.Among the figure, photosensitizers is made into trichloromethane (chloroform) solution, and concentration is 6 * 10
-5Mol.
Can be summarized as following table from accompanying drawing 4.In the table, λ is a maximum absorption wavelength, and unit is nanometer (nm); Log (ε) is 10 system logarithmic value of molar extinction coefficient.
| Photosensitizers 1 | Photosensitizers 2 | |||||
| ??λ(nm) | 466 | ??548 | ??580 | 463 | ??583 | ??621 |
| ??log(ε) | 4.36 | ??3.70 | ??3.52 | 4.06 | ??4.09 | ??4.10 |
From accompanying drawing 4 and last table as can be seen, replace with alkylamino radical after the methoxyl group of parent, with parent photosensitizers 1 relatively, photosensitizers 2 has been absorbed with significant reinforcement on the long wave direction, this is favourable to the photosensitive property that improves sensitizing agent.
(3) test of sensitizing agent photosensitive property:
Conductive glass is buied from group of SHENZHEN NANBO, and conductive layer is tin indium oxide (ITO).Photosensitizers is made into chloroformic solution, and concentration is 10
-3Mol.
Conductive glass is immersed the chloroformic solution of photosensitizers by height shown in Figure 2,5 minutes for the first time, the hydroxyl that allows the photosensitizers utilization expose fully is adsorbed onto on the metal ion of ITO, after taking out air-dry (about 3 minutes), immerse photosensitizers solution once more, take out air-dryly after about 2 minutes, can form hydrogen bond mutually and adhere to one deck again with hydroxyl and the carbonyl that exposes between the photosensitizers, repeat so again 3 times, amount to 5 times.Situation after finishing can be schematically as follows:
(M+)-(O-HB＝O)…(H-O-HB＝O)…(H-O-HB＝O)…(H-O-HB＝O)…(H-O-HB＝O)
M+ represents the metal ion on the conductive glass conductive layer, and the Hypocrellin B of the first layer (HB) is adsorbed on the metal ion with hydroxyl, exposes outside carbonyl, and with adsorption by hydrogen bond, the rest may be inferred between the hydroxyl of the HB of the second layer and the carbonyl of the first layer.The height of every layer of HB is about 0.12 nanometer, considers intermolecular hydrogen bond action, and total thickness is about 1 nanometer.Carefully clean the dyestuff at the sheet glass back side with wetted absorbent cotton, to absorbent cotton no longer till the staining.
The sheet glass of the good photosensitizers of dip-coating is put into vacuum plating unit, plate as shown in Figure 26 aluminium electrodes by template, thickness is about the 0.1-0.2 micron.Then ready-made sheet glass is put into and shown the test of carrying out photoelectric properties as the device of Fig. 1.The direct-current biasing of test set is adjustable, and data of the present invention are got the current density when being fixed as 0.6 volt, and unit is: microampere/square centimeter.Survey earlier dark current (because of organic dye layer is insulating basically, dark current should be too not big), the measurement of turning on light again deducts the dark current of background, is density of photocurrent value of the present invention.
Each sheet glass sheet should have 6 numerical value (under the individual cases, the aluminium electrode that is plated may with the conductive glass short circuit, dark current at this moment obviously increases, rejection of data need not).At least simultaneously do 3 at every turn,, 18 data should be arranged ideally, can obtain rational data about 15 generally speaking like this for a photosensitizers.Get the photosensitive property data of its arithmetical av as the survey sensitizing agent.
(4) example of sensitizing agent photosensitive property:
In following table first row, which piece sheet glass B represents, and L represents which the bar aluminium electrode on each piece sheet glass.As the data of the 2nd row the 2nd row is exactly to coat on the 1st sheet glass sheet of photosensitizers 1 by the 1st the density of photocurrent numerical value (unit is a microampere/square centimeter) that the aluminium electrode is measured.
The 20th row of form is a number of removing the reasonable numerical value of short circuit, the 21st row be these numerical value adding and, the 22nd row is an arithmetical av, and the 23rd row just last column is that photosensitive property with parent Hypocrellin B (photosensitizers 1) is 100, the relative value of derivative photosensitive property.
| ??B-L | Photosensitizers 1 | |
| ??1-1 | ????6.9 | ????10.7 |
| ??1-2 | ????6.6 | ????10.2 |
| ??1-3 | ????6.2 | ????8.9 |
| ??1-4 | ????7.6 | |
| ??1-5 | ????9.6 | |
| ??1-6 | ????7.4 | ????10.0 |
| ??2-1 | ????7.7 | ????11.1 |
| ??2-2 | ????10.6 | |
| ??2-3 | ????6.3 | |
| ??2-4 | ????7.5 | ????9.9 |
| ??2-5 | ????7.4 | ????10.5 |
| ??2-6 | ????7.6 | ????8.9 |
| ??3-1 | ????6.3 | |
| ??3-2 | ????7.2 | ????10.4 |
| ??3-3 | ????6.8 | ????9.9 |
| ??3-4 | ????7.1 | ????10.3 |
| ??3-5 | ????7.8 | ????10.7 |
| ??3-6 | ????11.0 | |
| Reasonable data number | ????15 | ????15 |
| Add and total value | ????106.4 | ????152.7 |
| Arithmetical av | ????7.1 | ????10.2 |
| Relative photosensitive property | ????100 | ????144 |
As can be known from the above table, photosensitizers 2 (Hypocrellin Bs of 2 last alkylamino radical methoxyl group displacements) is better than parent photosensitizers 1 (Hypocrellin B), reason may be that the electron donation of alkylamino radical is stronger than the methoxyl group of parent, thereby the ability that photoelectron injects is also stronger; Also may be to absorb enhanced results on the long wave direction; Perhaps two kinds of factors have.
Claims (2)
1. the purposes of the substitutive derivative of Hypocrellin B and alkanamine base class thereof, it is characterized in that: described Hypocrellin B and amido derivative thereof are used for optical function material and device for photosensitive dose as semi-conductor.
2. the substitutive derivative of Hypocrellin B as claimed in claim 1 and alkanamine base class thereof is characterized in that: the general structure of the substitutive derivative of described Hypocrellin B and alkanamine base class thereof is as follows:
Wherein, R is an alkylamino radical.
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| CN 03134666 CN1600771A (en) | 2003-09-25 | 2003-09-25 | Usage of photosensitizer of hypocrellin and class of amido group ramification |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007016762A1 (en) * | 2005-08-10 | 2007-02-15 | Quest Pharmatech Inc. | Perylenequinone derivatives and uses thereof |
| US8454991B2 (en) | 2006-07-24 | 2013-06-04 | Quest Pharmatech Inc. | Method and device for photodynamic therapy |
| CN103665050A (en) * | 2013-08-29 | 2014-03-26 | 西北工业大学 | Phenyl imidazole phenanthroline hypocrellin platinum complex and preparation method thereof |
-
2003
- 2003-09-25 CN CN 03134666 patent/CN1600771A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007016762A1 (en) * | 2005-08-10 | 2007-02-15 | Quest Pharmatech Inc. | Perylenequinone derivatives and uses thereof |
| GB2442915A (en) * | 2005-08-10 | 2008-04-16 | Quest Pharmatech Inc | Perylenequinone derivatives and uses thereof |
| JP2009505968A (en) * | 2005-08-10 | 2009-02-12 | クウェスト・ファーマテック・インコーポレイテッド | Perylenequinone derivatives and uses thereof |
| GB2442915B (en) * | 2005-08-10 | 2009-12-16 | Quest Pharmatech Inc | Perylenequinone derivatives and uses thereof |
| US8506931B2 (en) | 2005-08-10 | 2013-08-13 | Quest Pharmatech Inc. | Perylenequinone derivatives and uses thereof |
| US8758725B2 (en) | 2005-08-10 | 2014-06-24 | Quest Pharmatech Inc. | Perylenequinone derivatives and uses thereof |
| US8454991B2 (en) | 2006-07-24 | 2013-06-04 | Quest Pharmatech Inc. | Method and device for photodynamic therapy |
| CN103665050A (en) * | 2013-08-29 | 2014-03-26 | 西北工业大学 | Phenyl imidazole phenanthroline hypocrellin platinum complex and preparation method thereof |
| CN103665050B (en) * | 2013-08-29 | 2016-04-27 | 西北工业大学 | A kind of Phenyl imidazole phenanthroline hypocrellin platinum complex and preparation method thereof |
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