CN107759803A - A kind of four sulfydryl porphyrin compounds and its production and use - Google Patents
A kind of four sulfydryl porphyrin compounds and its production and use Download PDFInfo
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- CN107759803A CN107759803A CN201711114753.5A CN201711114753A CN107759803A CN 107759803 A CN107759803 A CN 107759803A CN 201711114753 A CN201711114753 A CN 201711114753A CN 107759803 A CN107759803 A CN 107759803A
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Abstract
The present invention relates to functional complexes field, and in particular to a kind of four sulfydryl porphyrin compounds and its production and use；The sulfydryl porphyrin of kind four prepared by the inventive method has strength coordination ability, by being combined with the frame materials of UiO 66, the porphyrin modified metal-organic framework material of four sulfydryls of preparation（UiO‑66）, i.e. the H of UiO 662TPP‑(SH)4With extraordinary water-soluble, the problem of having showed less soluble Porphyrin Molecule compound present in prior art and water, easy reunion, stability difference is overcome well, is increased substantially quantum yield, fluorescence lifetime, the light sensitive characteristic of the singlet oxygen of Porphyrin and its derivative.
Description
Technical field
The present invention relates to functional complexes field, and in particular to a kind of four sulfydryl porphyrin compounds and preparation method thereof and use
On the way.
Background technology
Porphyrin and its derivative is the pi-conjugated macrocycle molecule of a kind of typical plane, is widely present in nature and life entity
It is interior.Core of the porphyrin ring as compound, it is one formed respectively by methine (- CH=) connection by four pyrrole rings
What individual closing and continuous conjugation porphin ring formed.The periphery of porphyrin ring can be substituted by various functions group, be formed a variety of more
The substitution porphyrin of sample.Porphyrin present in nature is typically to be conjugated porphines ring hydrogen by other functional groups to be substituted, and artificial
Synthesis porphyrin is mainly then that four methines are substituted, i.e., meso- positions (middle position).Due to meso- positions (middle position) modified porphyrin
Compound synthetic yield is high and stability is good, and researcher is often used as research object by the use of such substitution porphyrin compound.Research is found
Porphyrins has unique physiologically active and the affinity with cancer cell, thus is often moved in medical domain as light
The anticancer photosensitizer of power cure (photodynamic therapy, PDT).But due to the knot of Porphyrin and its derivative itself
Structure feature --- the pi-conjugated system of big plane, solubility is extremely low and with aggregate form in aqueous for the big ring porphyrin compound
In the presence of this greatly reduces the quantum yield and fluorescence lifetime of singlet oxygen, reduces its light sensitive characteristic.
To sum up, current Porphyrin and its derivative still have be not readily dissolved in water, easily reunite, stability difference the problems such as these
Problem can have a strong impact on the chemistry and optical property of Porphyrin and its derivative, and therefore, needing badly a kind of can overcome above mentioned problem
A kind of four sulfydryl porphyrin compounds and preparation method thereof.
The content of the invention
For above-mentioned problems of the prior art, it is an object of the invention to provide a kind of four sulfydryl porphyrin compounds
And its production and use, the inventive method prepare four sulfydryl porphyrins there is strength coordination ability, by with UiO-66 frames
Frame material is combined, the porphyrin modified metal-organic framework material (UiO-66) of four sulfydryls of preparation, i.e. UiO-66-H2TPP-
(SH)4, there is extraordinary water-soluble, overcome that to have showed Porphyrin Molecule compound present in prior art less soluble well
With water, easily reunite, stability difference the problem of, make the quantum yield of the singlet oxygen of Porphyrin and its derivative, fluorescence lifetime, photosensitive
Characteristic is increased substantially.
One of the object of the invention is to provide a kind of four sulfydryl porphyrins.
The two of the object of the invention are to provide a kind of preparation method of four sulfydryls porphyrin.
The three of the object of the invention are to provide a kind of metal-organic framework material (UiO-66) preparation method.
The four of the object of the invention are to provide a kind of porphyrin modified UiO-66 of four sulfydryls and prepare UiO-66-H2TPP-(SH)4Side
Method.
The five of the object of the invention are to provide above-mentioned UiO-66-H2TPP-(SH)4Application.
For achieving the above object, specifically, the invention discloses following technical proposals：
First, the invention discloses a kind of four sulfydryl porphyrin compounds, the structural formula of the four sulfydryls porphyrin compound to be：
The four sulfydryls porphyrin compound molecular formula is：H2TPP-(COSC2H4SH)4, it is named as：5,10,15,20- tetra-
(4- (S- ethanethios ester) thiocarbonyl phenyl) porphyrin, referred to as four sulfydryl porphyrin (H2TPP-(SH)4), wherein H2TPP is four benzene
Base porphyrin.
Secondly, the invention discloses a kind of preparation method of four sulfydryls porphyrin, following steps are specifically included：
(1) by H2TPP-(COOH)4It is dissolved in organic solvent, then adds thionyl chloride and reacted, flowed back, backflow knot
Shu Hou, solvent evaporated, dry tetrahydrofuran is added, obtain the first reaction solution；
(2) 1,2- dimercaptoethanes and triethylamine are dissolved in tetrahydrofuran, obtain the second reaction solution；
(3) the second reaction solution is added drop-wise in the first reaction solution, at room temperature 1.5~3h of stirring reaction；
(4) step (3) reaction resulting solution is post-processed to obtain H2TPP-(SH)4。
In step (1), the H2TPP-(COOH)4, organic solvent, thionyl chloride mass volume ratio (mg/mL) be (15
~20)：1：1；
Preferably, the organic solvent is dichloromethane, chloroform, toluene etc..
In step (1), the reaction condition is：Temperature is 40~45 DEG C, and return time is 4~5h.
In step (1), the H2TPP-(COOH)4Mass volume ratio (mg/mL) with tetrahydrofuran is (5~7)：1.
In step (2), the volume ratio of 1, the 2- dimercaptoethanes and triethylamine is (10~20)：1.
In step (2), the volume ratio of 1, the 2- dimercaptoethanes and tetrahydrofuran is (0.02~0.06)：1.
H in step (1)2TPP-(COOH)4Amount ratio with the material of 1,2- dimercaptoethanes in step (2) is 1：(60~
80)。
In step (3), the speed of the dropwise addition is 2~3 seconds/drop, and dropwise addition process is carried out under the conditions of normal temperature, lucifuge.
In step (4), the post processing is：Column chromatography and recrystallization.
Preferably, column chromatography uses silica gel column chromatography, using dichloromethane as eluent；Recrystallization uses dichloromethane and first
Carried out in alcoholic solvent, the volume ratio of dichloromethane and methanol is 1：(100~120).
Again, the invention discloses a kind of metal-organic framework material UiO-66 preparation method, following step is specifically included
Suddenly：
(1) by ZrCl4It is added in DMF (DMF), adds acetic acid, be eventually adding terephthaldehyde
Acid, after ultrasonic disperse is uniform, solvent structure UiO-66 nano materials, it is centrifuged at a high speed to obtain solid product A；
(2) the solid product A in DMF washing steps (1) is used, solid product B is obtained, solid product B is activated, obtained
To white powder UiO-66.
In step (1), the ZrCl4Amount ratio with the material of terephthalic acid (TPA) is 1：1.
In step (1), the ZrCl4Mass volume ratio (mg/mL) with DMF is (4~6)：1.
In step (1), the acetic acid and DMF volume ratio are (0.035~0.075)：1.
In step (1), the condition of the solvent structure UiO-66 nano materials is：Temperature is 90~120 DEG C, insulation
Time is 12~48h, it is preferable that the soaking time is 24h.
In step (2), the activation refers to：1. solid product A is immersed into DMF solvent, stirred under the conditions of 60~85 DEG C
6~10h of immersion is mixed, is 2. centrifuged at a high speed, obtains solid product B；3. continue solid product B being submerged into absolute ethyl alcohol,
7~12h of stirring immersion, is centrifuged at a high speed, obtains solid product C under the conditions of 50~75 DEG C；3. step is repeated 3 times, obtained
Solid product D, and submerged with ether and wash solid D, dried under natural conditions, obtain solid product E, produced of the present invention
Metal-organic framework material UiO-66.
Finally, made using four sulfydryl porphyrins prepared by the present invention and UiO-66 has machine frame as sensitising agent, metal
Frame material, metal-organic framework material UiO-66 is modified with four described sulfydryl porphyrins, it is porphyrin modified to obtain four sulfydryls
UiO-66, i.e. UiO-66-H2TPP-(SH)4, the mass ratio of the UiO-66 and four sulfydryl porphyrins is 11~13.Specifically, institute
State and UiO-66-H is prepared using the porphyrin modified UiO-66 of four sulfydryls2TPP-(SH)4Method comprise the following steps：
(a) four sulfydryl porphyrins are added in organic solvent and dissolved, four sulfydryl porphyrin solution are made；
(b) UiO-66 is added in four sulfydryl porphyrin solution in step (a), ultrasonic disperse, stirring；
(c) mixture for obtaining step (b), is centrifugally separating to obtain solid product, the solid obtained by organic solvent washing
Product, and dried after being activated to solid product, finally obtain four sulfydryls porphyrin modified UiO-66, i.e. UiO-66-H2TPP-
(SH)4。
In step (a), the organic solvent is dry dichloromethane.
In step (a), the substance withdrawl syndrome of the four sulfydryls porphyrin solution is 0.5~3mmolL-1。
In step (b), the mass volume ratio (mg/mL) of the UiO-66 and four sulfydryl porphyrin solution is (2.5~5.0)：
1。
In step (b), the ultrasonic disperse time is 20~25min.
In step (c), the centrifugal speed is 12000~13000 revs/min.
In step (c), the activation refers to solid product being immersed into dichloromethane, and normal temperature soaks side stirring 5 below
~7 hours.
In addition, present invention also offers UiO-66-H prepared by the present invention2TPP-(SH)4Application, the application include use
In Photodynamic therapy (PDT), specifically, a kind of anticancer photosensitizer can be used as.
The present invention overcomes less soluble existing for Porphyrin Molecule in the prior art and water using UiO-66, easily reunited, stability
The problem of poor, its principle are：Artificial synthesized Porphyrin Molecule often substitutes porphyrin for tetraphenyl, and the porphyrin-like compound is that rigidity is common
Yoke macromolecular, it is soluble in organic solvent and is insoluble in water, and often exists in the solution in the form of aggregation；If by Porphyrin Molecule
Combined with other materials that can be stabilized in aqueous single dispersing, then Porphyrin Molecule can be overcome to be insoluble in water and easily aggregation
The problem of；The present invention has synthesized the dimercaptoethane group porphyrin compound H with strong coordination ability2TPP-(SH)4, by its with
Highly stable in aqueous and biological hypotoxicity metal organic frame nano material UiO-66 is combined, and this is to utilize UiO-66
Space surface defect and dimercaptoethane group strong coordination ability, by rear modification synthetic method by H2TPP-(SH)4Modification
Onto UiO-66 surface, nano material UiO-66-H is obtained2TPP-(SH)4；Thus using the four sulfydryl porphyrins of the present invention
H2TPP-(SH)4The UiO-66-H of synthesis is modified afterwards2TPP-(SH)4Both UiO-66 internal framework had been maintained, and water-soluble
There is good dispersiveness and stability in liquid, the light sensitive characteristic of porphyrin is also retains, so as to as a kind of new anticancer
Light-sensitive material is used in PDT.
Compared with prior art, the present invention achieves following beneficial effect：
(1) from test result, the four sulfydryl porphyrin compounds that the present invention obtains are a kind of excellent sensitising agents, and
The Porphyrin Molecule contains the dimercaptoethane group of four strong coordination ability.
(2) from test result, the surface to UiO-66 is modified after the four sulfydryl porphyrin compounds obtained with the present invention
Obtain nano material UiO-66-H2TPP-(SH)4, it had both maintained UiO-66 good dispersivenesses and stability in aqueous,
The light sensitive characteristic of porphyrin is also retains, overcomes the problems such as Porphyrin Molecule is insoluble in water, easily reunion, stability difference, is a kind of excellent
Different anticancer photosensitive nanoparticle material.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 is the four sulfydryl porphyrin H synthesized in embodiment 12TPP-(SH)4High resolution mass spectrum figure.
Fig. 2 is the four sulfydryl porphyrin H synthesized in embodiment 12TPP-(SH)4Nuclear magnetic spectrogram.
Fig. 3 is the four sulfydryl porphyrin H synthesized in embodiment 12TPP-(SH)4Infrared spectrogram.
Fig. 4 is the four sulfydryl porphyrin H synthesized in embodiment 12TPP-(SH)4Uv absorption spectra.
Fig. 5 is UiO-66 and UiO-66-H in embodiment 42TPP-(SH)4SEM (SEM) figure.
Fig. 6 is UiO-66-H in embodiment 42TPP-(SH)4Transmission electron microscope (TEM) figure.
Fig. 7 is UiO-66 and UiO-66-H in embodiment 42TPP-(SH)4Powder diagram (PXRD).
Fig. 8 is UiO-66-H in embodiment 42TPP-(SH)4The powder diagram being immersed in before and after phosphate buffer solution
(PXRD)。
Fig. 9 is UiO-66 and UiO-66-H in embodiment 42TPP-(SH)4Thermogravimetric analysis (TGA).
Figure 10 is UiO-66 and UiO-66-H in embodiment 42TPP-(SH)4Adsorption/desorption curve.
Figure 11 is UiO-66 and UiO-66-H in embodiment 42TPP-(SH)4Pore size distribution map.
Figure 12 is UiO-66, H in embodiment 42TPP-(SH)4And UiO-66-H2TPP-(SH)4Ultra-violet absorption spectrum
(UV-vis)。
Figure 13 is that 1,3 diphenyl isobenzofuran (DPBF) 415nm peak values under 660nm illumination become in embodiment 7
Change situation.
Figure 14 is four sulfydryl porphyrin H in embodiment 72TPP-(SH)4Singlet oxygen production.
Figure 15 is UiO-66-H in embodiment 72TPP-(SH)4Singlet oxygen production.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
It should be noted that in order to obtain superior technique effect, the H used in the present invention2TPP-(COOH)4For voluntarily
Prepare, but existing commercially available H2TPP-(COOH)4Finished product is also applied for the present invention.
As background technology is introduced, existing Porphyrin and its derivative still have it is less soluble with water, easily reunite, it is steady
The problems such as qualitative poor, in order to solve the above problems, the invention provides a kind of four sulfydryl porphyrin compounds and preparation method thereof and
Purposes, with reference to specific embodiment, the present invention is described further.
Embodiment 1
Four sulfydryl porphyrin H2TPP-(SH)4Preparation：
(1)H2TPP-(COOH)4Preparation：
P formylbenzoic acid methyl esters (6.9g, 0.042mol) and 100mL propionic acid are heated to 145 DEG C of reactions, backflow, obtained
To mixed solution, then 20mL propionic acid and pyrroles (3.0mL, 0.043mol) are added drop-wise in above-mentioned mixed liquor, after being added dropwise
Continue the 1h that flows back.Then, room temperature is naturally cooled to, methanol is added and stands 12h.Finally filter, wash filter cake with water and methanol, i.e.,
Obtain purple powder H2TPP-(COOCH3)4, its quality is 1.8g, and the amount of material is 0.0021mol, yield 20%.
By 1g H2TPP-(COOCH3)4, 80mL tetrahydrofurans (THF) and 6mL 10molL-1KOH and 100mL water heats
To 70 DEG C of backflow 6h, room temperature is naturally cooled to.Air-distillation removes THF, filtering.Then by filtrate with salt acid for adjusting pH to 1~
2, filter, wash filter cake with water and methanol, dry to obtain solid H2TPP-(COOH)4；Specifically course of reaction is：
(2)H2TPP-(SH)4Preparation：
By H2TPP-(COOH)4(79mg, 0.10mmol) is dissolved in the dichloromethane of 5mL dryings, then in lucifuge condition
It is lower by SOCl2(5mL, 0.069mol) is slowly added drop-wise in mixed solution, and after 40 DEG C of 5h that flow back, it is unnecessary to be evaporated under normal pressure
SOCl2And dichloromethane, obtain four acyl chlorides phenyl porphyrin H of blackish green solid-state2TPP-(COCl)4.By 84mg H2TPP-
(COCl)4It is dissolved in the dried THF of 15mL, obtains the first reaction solution.
1,2- dimercaptoethanes (672 μ L, 8.0mmol) and triethylamine (40 μ L, 0.29mmol) are dissolved in into 15mL to dry
THF in, obtain the second reaction solution.
Under conditions of normal temperature and lucifuge, above-mentioned first reaction solution is added drop-wise in the second reaction solution, rate of addition
For 2 seconds/drop, rear stirring reaction 3h is added dropwise；Then, solvent evaporated, using dichloromethane as eluent, silica gel column chromatography are rotated
Separate and purify target product.
Finally, recrystallized in dichloromethane and methanol, the volume ratio of dichloromethane and methanol is 1：100, obtain purple
Solid product H2TPP-(SH)4, its quality is 29mg, and the amount of material is 0.026mmol, yield 26%.Course of reaction is：
To obtained H in the present embodiment2TPP-(SH)4Carry out the detection of mass spectrum, nuclear-magnetism, infrared spectrum and ultraviolet spectra, knot
Fruit is as shown in Figures 1 to 4.Wherein, Fig. 1 H2TPP-(SH)4Flight time high resolution mass spectrum figure, MALDI-TOF/MS:m/z
Calculate：C56H46N4O4S8[M+H]+1095.1, it is corresponding with 1095.5 peak in Fig. 1.
Fig. 2 is H2TCCPP-(SH)4Nucleus magnetic hydrogen spectrum,1H-NMR (300MHz, CDCl3)ppm：δ=8.82 (s, 8H, β-
Pyrrole), 8.37-8.40 (d, 8H, phenyl), 8.30-8.33 (d, 8H, phenyl), 3.46-3.51 (m, 8H ,-
CH2CH2-), 2.92-3.11 (m, 8H ,-CH2CH2-), 1.77-1.83 (t, 4H,-SH), -2.82 (s, 2H, NH).
Fig. 3 is H2TPP-(SH)4Infrared spectrogram, IR：3311 (w), 2917 (w), 2545 (w), 1655 (vs), 1597
(m), 1472 (vw), 1396 (w), 1276 (vw), 1204 (s), 1184 (m), 966 (w), 920 (w), 810 (m), 709 (w), 654
(vw)。
H2TPP-(SH)4Ultra-violet absorption spectrum determined in DMF, see Fig. 4, [λmax(nm) (log (ε), M-1cm-1)]:420 (5.02), 516 (3.72), 551 (3.51), 591 (3.31), 646 (3.15).H2TPP-(SH)4Compound exists
There is a strong porphyrin Soret band and absorbed in 420nm, the four free porphins of typical case occurred near 516,551,591 and 646nm
The Q bands of quinoline absorb.
From Fig. 1 to Fig. 4, it is compound H that the present embodiment, which obtains end product,2TPP-(SH)4。
Embodiment 2
Four sulfydryl porphyrin H2TPP-(SH)4Preparation：
(1)H2TPP-(COOH)4Preparation method with embodiment 1.
(2)H2TPP-(SH)4Preparation：
By H2TPP-(COOH)4(90mg, 0.11mmol) is dissolved in the dichloromethane of 6mL dryings, then in lucifuge condition
It is lower by SOCl2(6mL, 0.069mol) is slowly added drop-wise in mixed solution, after 45 DEG C of reactions, backflow 5h, is evaporated under normal pressure more
Remaining SOCl2And dichloromethane, obtain four acyl chlorides phenyl porphyrin H of blackish green solid-state2TPP-(COCl)4.By 93mg H2TPP-
(COCl)4It is dissolved in the dried THF of 15mL, obtains the first reaction solution.
1,2- dimercaptoethanes (672 μ L, 8.0mmol) and triethylamine (40 μ L, 0.29mmol) are dissolved in into 25mL to dry
THF in, obtain the second reaction solution.
The first reaction solution is added drop-wise in the second reaction solution under conditions of normal temperature and lucifuge, rate of addition be 3 seconds/
Drop, is added dropwise rear stirring reaction 1.5h.Then, solvent is evaporated, using dichloromethane as eluent, silica gel column chromatography separation
And purify target product.
Finally, recrystallized in dichloromethane and methanol, the volume ratio of dichloromethane and methanol is 1：120, obtain purple
Solid product H2TPP-(SH)4, its quality is 27mg, and the amount of material is 0.025mmol, yield 23%.
Embodiment 3
Four sulfydryl porphyrin H2TPP-(SH)4Preparation：
(1)H2TPP-(COOH)4Preparation method with embodiment 1.
(2)H2TPP-(SH)4Preparation：
By H2TPP-(COOH)4(79mg, 0.10mmol) is dissolved in the dichloromethane of 4mL dryings, then in lucifuge condition
It is lower by SOCl2(4mL, 0.069mol) is slowly added drop-wise in mixed solution, and after 43 DEG C of 4.5h that flow back, it is unnecessary to be evaporated under normal pressure
SOCl2And dichloromethane, obtain four acyl chlorides phenyl porphyrin H of blackish green solid-state2TPP-(COCl)4.By 83mg H2TPP-
(COCl)4It is dissolved in the dried THF of 15mL, obtains the first reaction solution.
1,2- dimercaptoethanes (504 μ L, 6.0mmol) and triethylamine (40 μ L, 0.29mmol) are dissolved in into 13mL to dry
THF in, obtain the second reaction solution.
The first reaction solution is added drop-wise in the second reaction solution under conditions of normal temperature and lucifuge, rate of addition be 3 seconds/
Drop, is added dropwise rear stirring reaction 2.5h.Then, solvent is evaporated, using dichloromethane as eluent, silica gel column chromatography separation
And purify target product.
Finally, recrystallized in methylene chloride/methanol, the volume ratio of dichloromethane and methanol is 1：110, obtain purple and consolidate
Body product H2TPP-(SH)4, its quality is 26mg, and the amount of material is 0.024mmol, yield 24%.
Embodiment 4
UiO-66-H2TPP-(SH)4Preparation：
(1) metal-organic framework material UiO-66 preparation
Weigh ZrCl4(18.6mg, 0.080mmol), 3.2mL DMF are added to, add 240 μ L acetic acid, add to benzene
Dioctyl phthalate (13.3mg, 0.080mmol), ultrasound is completely dissolved it, is fitted into 20mL reactors, permanent under conditions of 120 DEG C
Warm 24h, room temperature is down to through 2h, is centrifuged at a high speed to obtain solid product A, solid product A is immersed in DMF, 80 DEG C of conditions
Lower stirring immersion 6h, is centrifuged at a high speed to obtain solid product B.Solid product C is submerged into absolute ethyl alcohol, under the conditions of 70 DEG C
Stirring immersion 10h, is centrifuged at a high speed, obtains solid product D.Continue solid product D being submerged into absolute ethyl alcohol, 65 DEG C of bars
Stirring immersion 8h, is centrifuged at a high speed, obtains solid product E under part.Finally submerged with ether and wash solid E, natural conditions
Under dry, it is UiO-66 to obtain white powder F, and its quality is 14mg, and the amount of material is 0.0084mmol, yield 63%.
(2)UiO-66-H2TPP-(SH)4Preparation
Weigh H made from embodiment 12TPP-(SH)4, configure 1.0mmolL-1H2TPP-(SH)4Dichloromethane solution,
By 20mg UiO-66 ultrasonic disperses in the above-mentioned dichloromethane solutions of 7.4mL, 24h is stirred under conditions of 25 DEG C.High speed centrifugation
Isolated solid product G, centrifugal speed are 12500 revs/min, and solid product G is washed with dichloromethane after centrifugation, then will be solid
Body product G is immersed in dichloromethane, and normal temperature soaks side stirring 6h below, is centrifuged at a high speed to obtain brown-red solid product
UiO-66-H2TPP-(SH)4。
Characterize and analyze product UiO-66 and UiO-66-H that the present embodiment obtains2TPP-(SH)4, as a result such as Fig. 5 to Figure 12
It is shown.
Fig. 5 is UiO-66 and UiO-66-H2TPP-(SH)4Scanning electron microscope diagram (SEM), can be seen that from left figure
UiO-66 average grain diameter is 200nm, and surface is more smooth, is regular shape of octahedron；Right figure is UiO-66-
H2TCPP-(SH)4, average grain diameter is still 200nm, and surface becomes coarse, can keep shape of octahedron substantially；This explanation utilizes two
Coordination between mercapto ethane group and zirconium cluster, four sulfydryl Porphyrin Molecules can be connected to by the method for rear modification synthesis
On UiO-66 surfaces.UiO-66 maximum diameter of hole is ca.0.7nm, much smaller than ca.1.8nm × 1.8nm of Porphyrin Molecule, it is seen then that
The method of the rear modification synthesis is only to modify Porphyrin Molecule into UiO-66 frame materials surface rather than inner void.
Pass through UiO-66-H2TPP-(SH)4Transmission electron microscope (TEM) (Fig. 6), it can be seen that four sulfydryl Porphyrin Molecules
It is not attached between nano particle after modification together, is monodispersed octahedra particle.
Fig. 7 is UiO-66 and UiO-66-H2TPP-(SH)4Powder diagram (PXRD), it can be seen that four mercaptos
Nano material UiO-66-H after base is porphyrin modified2TPP-(SH)4Still keep and UiO-66 metal-organic framework materials before modification
Internal structure.
For the porphyrin modified UiO-66-H of further four sulfydryls of test2TPP-(SH)4Stability in aqueous, will
UiO-66-H2TPP-(SH)4It is immersed in pH=7.4 phosphate buffer solution (PBS), after stirring immersion 24h, high speed centrifugation
Separation, solid is washed with substantial amounts of absolute ethyl alcohol and ether, and tests the powder diagram (PXRD) of sample after immersion, such as Fig. 8
It is shown.From figure 8, it is seen that PXRD data are consistent before and after immersion, illustrate the porphyrin modified UiO-66-H of four sulfydryls2TPP-
(SH)4There is good stability in PBS.
In addition, it was found from Fig. 9 thermogravimetic analysis (TGA)s (TGA), UiO-66-H2TPP-(SH)4It is good with having as UiO-66
Heat endurance, its heat endurance reach more than 400 DEG C.
Figure 10 shows UiO-66 and UiO-66-H2TPP-(SH)4Nitrogen adsorption and desorption are tested under 77K, can by result
Know, UiO-66 and UiO-66-H2TPP-(SH)4Absorption to nitrogen belongs to the I types absorption of classics, the absorption of its nitrogen and de-
It is attached be it is reversible, further demonstrate the internal structure integrality that complexation reaction in rear modification does not destroy UiO-66.
UiO-66-H2TPP-(SH)4BET specific surface area be 926m2·g-1, the specific surface area 1361m with UiO-662·g-1Compare, have
A certain degree of reduction, this explanation H2TPP-(SH)4Chemical bond coordination modification is successfully passed to UiO-66 surface.
Figure 11 is UiO-66 and UiO-66-H2TPP-(SH)4Pore-size distribution, it can be seen that four sulfydryls are porphyrin modified
UiO-66-H2TPP-(SH)4Pore size beWithWith UiO-66 pore-size distributionWithKeep
Unanimously, modification synthetic method is only surface modification rather than H after this further explanation2TPP-(SH)4Encapsulate or be connected to UiO-66
Aperture inside.
Free Porphyrin Molecule has stronger Soret band characteristic absorption characteristics in 420nm or so, for measure Porphyrin Molecule
Success is modified onto UiO-66 nano materials, and UiO-66, H are determined by solvent of DMF2TPP-(SH)4And UiO-66-H2TPP-
(SH)4Ultra-violet absorption spectrum (UV-vis), as shown in figure 12.It can be recognized from fig. 12 that UiO-66 characteristic absorption peak is
265nm, H2TPP-(SH)4Soret band characteristic absorption peaks be 419nm, and the nano material UiO-66- that four sulfydryls are porphyrin modified
H2TPP-(SH)4Not only retain original UiO-66 nano materials outside 265nm characteristic absorption peak, also add the four of 419nm
The characteristic absorption peak of sulfydryl porphyrin.Thus, H can be further illustrated2TPP-(SH)4By successful modification receiving to UiO-66
On rice material.To determine the content of sulfydryl porphyrin, UiO-66-H is further determined2TPP-(SH)4C, H, N, S element of sample
Analysis, is shown in Table 1, can UiO-66-H2TPP-(SH)4The molecular formula of compound is represented by [8.1 (C48H28O32Zr6)·
(C56H45N4O4S8)]。
The UiO-66-H of table 12TPP-(SH)4Elemental analysis data result
| N | C | H | S | |
| UiO-66-H2TPP-(SH)4 | 0.34 | 32.08 | 2.2 | 2.685 |
To sum up analysis can obtain, using four sulfydryl porphyrin H made from the embodiment of the present invention 12TPP-(SH)4UiO-66 is modified, can
Four sulfydryl Porphyrin Molecules are connected on UiO-66 surfaces rather than in inner void.And the nano material UiO-66- after modifying
H2TPP-(SH)4The internal structure with UiO-66 metal-organic framework materials before modification is still kept, is had in aqueous preferable
Dispersiveness and stability, and there is preferable heat endurance.Nano material UiO-66-H modify simultaneously after2TPP-(SH)4Retain
The light sensitive characteristic of porphyrin, it can be used for as a kind of new anticancer light-sensitive material in PDT (Photodynamic therapy).
Embodiment 5
(1) metal-organic framework material UiO-66 preparation
Weigh ZrCl4(18.6mg, 0.080mmol), 4.6mL DMF are added to, add 160 μ L acetic acid, add to benzene
Dioctyl phthalate (13.3mg, 0.080mmol), ultrasound is completely dissolved it, is fitted into 20mL reactors, the constant temperature under conditions of 90 DEG C
48h, room temperature is down to through 2h, is centrifuged at a high speed to obtain solid product A, solid product A is immersed in DMF, under the conditions of 60 DEG C
Stirring immersion 10h, is centrifuged at a high speed to obtain solid product B.Then solid product B is immersed in absolute ethyl alcohol, 60 DEG C of bars
Stirring immersion 12h, is centrifuged at a high speed to obtain solid product C under part.Solid product C is submerged into absolute ethyl alcohol, 60 DEG C of bars
Stirring immersion 10h, is centrifuged at a high speed, obtains solid product D under part.Continue solid product D being submerged into absolute ethyl alcohol, 60
Stirring immersion 8h, is centrifuged at a high speed, obtains solid product E under the conditions of DEG C；Finally submerged with ether and wash solid E, it is natural
Under the conditions of dry, it is UiO-66 to obtain white powder F, and its quality is 14mg, and the amount of material is 0.0084mmol, and yield is
63%.
(2)UiO-66-H2TPP-(SH)4Preparation
Weigh H made from embodiment 12TPP-(SH)4, configure 1.0mmolL-1H2TPP-(SH)4Dichloromethane solution,
By 20mg UiO-66 ultrasonic disperses in the above-mentioned dichloromethane solutions of 8mL, 25min is stirred under conditions of 25 DEG C.High speed centrifugation
Isolated solid product G, centrifugal speed are 12000 revs/min, and solid product G is washed with dichloromethane after centrifugation.Then will be solid
Body product G is immersed in dichloromethane, and normal temperature soaks side stirring 5h below, is centrifuged at a high speed to obtain brown-red solid product
UiO-66-H2TPP-(SH)4。
Embodiment 6
(1) metal-organic framework material UiO-66 preparation
Weigh ZrCl4(28mg, 0.12mmol), 5.4mL DMF are added to, add 240 μ L acetic acid, add terephthaldehyde
Sour (20.0mg, 0.12mmol), ultrasound is completely dissolved it, is fitted into 20mL reactors, the constant temperature 12h under conditions of 120 DEG C,
Room temperature is down to through 2h, is centrifuged at a high speed to obtain solid A, solid product A is immersed in DMF, immersion is stirred under the conditions of 85 DEG C
6h, it is centrifuged at a high speed to obtain solid product B, then solid product B is immersed in absolute ethyl alcohol, leaching is stirred under the conditions of 75 DEG C
10h is steeped, is centrifuged at a high speed to obtain solid product C.Solid product C is submerged into absolute ethyl alcohol, leaching is stirred under the conditions of 75 DEG C
8h is steeped, is centrifuged at a high speed, obtains solid product D.Continue solid product D being submerged into absolute ethyl alcohol, stirred under the conditions of 75 DEG C
Immersion 8h is mixed, is centrifuged at a high speed, obtains solid product E；Finally submerged with ether and wash solid E, dried under natural conditions,
It is UiO-66 to obtain white powder F, and its quality is 21mg, and the amount of material is 0.013mmol, yield 65%.
(2)UiO-66-H2TPP-(SH)4Preparation
Weigh H made from embodiment 12TCLPP-(SH)1, configure 1.0mmolL-1H2TCLPP-(SH)1Dichloromethane
Solution, by 30mg UiO-66 ultrasonic disperses in the 6mL solution, 20min is stirred under conditions of 25 DEG C.It is centrifuged at a high speed
Solid product G is obtained, centrifugal speed is 13000 revs/min, and solid product G is washed with dichloromethane after centrifugation.Then solid is produced
Thing G is immersed in dichloromethane, and normal temperature soaks side stirring 7h below, is centrifuged at a high speed to obtain brown-red solid product UiO-
66-H2TCLPP-(SH)1。
Embodiment 7
Tested caused by singlet oxygen
In test caused by singlet oxygen, using DMF as solvent, 1,3- diphenyl isobenzofuran (DPBF) is used as single line
The agent for capturing of state oxygen, it is 60 μm of olL to take concentration-1DPBF and 5 μm of olL-1Sample H2TPP-(SH)4Mixed solution is placed
In quartz colorimetric utensil, wavelength is used as 660nm, optical intensity density 20mW/cm2Laser be irradiated, per 20s be one
Changes of the time interval measurement DPBF in the absorbance of 415nm characteristic absorption peak.Due to 415nm after DPBF seizure singlet oxygens
The absworption peak at place disappears, therefore can be according to the content of DPBF singlet oxygens in the mutation analysis detection solution of 415nm peak intensities.
In addition, take 60 μm of olL-1DPBF be placed in quartz colorimetric utensil, be irradiated under the same conditions with laser, observe
The change of the absorbance of its characteristic absorption peak, as reference.Before the ultra-violet absorption spectrum detection of the sample containing porphyrin is surveyed, use
The sample of same concentrations deducts the influence of the UV absorption of porphyrin as background.
Figure 13 shows DPBF under the illumination of same test condition, and the peak intensity at 415nm varies less.Figure 14 shows,
Add H2TPP-(SH)4Peak intensities of the DPBF at 415nm reduces ground clearly afterwards, illustrates that the four sulfydryls porphyrin compound is
A kind of excellent sensitising agent.
Similarly, it is 60 μm of olL to take concentration-1DPBF and 5 μm of olL-1(according to UiO-66-H2TPP-(SH)4Point
Minor calculate Porphyrin Molecule amount of substance concentration) sample UiO-66-H2TPP-(SH)4It is placed in quartz colorimetric utensil, in phase
It is irradiated with conditions of with laser, the change of the absorbance of its characteristic absorption peak is observed, as reference.Contain porphin in survey
Before the ultra-violet absorption spectrum detection of the sample of quinoline, by the use of the sample of same concentrations as background, the shadow of the UV absorption of porphyrin is deducted
Ring.As a result as shown in figure 15, it can be seen that adding UiO-66-H2TPP-(SH)4Peak intensities of the DPBF at 415nm reduces afterwards
Ground is very fast, illustrates UiO-66-H2TPP-(SH)4With having light sensitive characteristic as four sulfydryl porphyrins.And the material overcomes porphin
Quinoline molecule is insoluble in the problems such as water, easily reunion, stability difference, is a kind of excellent anticancer photosensitive nanoparticle material.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for those skilled in the art
For member, the application can have various modifications and variations.All any modifications within spirit herein and principle, made,
Equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. one kind prepares UiO-66-H using the porphyrin modified UiO-66 of four sulfydryls2TPP-(SH)4Method, it is characterised in that：Including
Following steps：
(a) four sulfydryl porphyrins are added in organic solvent and dissolved, four sulfydryl porphyrin solution are made；
(b) UiO-66 is added in four sulfydryl porphyrin solution in step (a), ultrasonic disperse, stirring；
(c) mixture for obtaining step (b), is centrifugally separating to obtain solid product, the solid product obtained by organic solvent washing,
And dried after being activated to solid product, finally obtain four sulfydryls porphyrin modified UiO-66, i.e. UiO-66-H2TPP-(SH)4；
In step (c), the activation refers to solid product being immersed into dichloromethane, and it is small that normal temperature soaks side stirring 5~7 below
When.
2. the method as described in claim 1, it is characterised in that：In step (a), the organic solvent is dichloromethane, trichlorine
Methane, toluene；
In step (a), the substance withdrawl syndrome of the four sulfydryls porphyrin solution is 1mmolL-1；
In step (b), the mass volume ratio (mg/mL) of the UiO-66 and four sulfydryl porphyrin solution is (2.5~5.0)：1；
In step (b), the ultrasonic disperse time is 20~25min；
In step (c), the centrifugal speed is 12000~13000 revs/min.
A kind of 3. preparation method of four sulfydryls porphyrin as claimed in claim 1 or 2, it is characterised in that：Specifically include following step
Suddenly：
(1) by H2TPP-(COOH)4It is dissolved in organic solvent, then adds thionyl chloride and flowed back, after backflow terminates, is evaporated
Solvent, dry tetrahydrofuran is added, obtain the first reaction solution；
(2) 1,2- dimercaptoethanes and triethylamine are dissolved in tetrahydrofuran, obtain the second reaction solution；
(3) the second reaction solution is added drop-wise in the first reaction solution, at room temperature 1.5~3h of stirring reaction；
(4) step (3) reaction resulting solution is post-processed to obtain H2TPP-(SH)4。
4. preparation method as claimed in claim 3, it is characterised in that：In step (1), the H2TPP-(COOH)4, You Jirong
Agent, the mass volume ratio (mg/mL) of thionyl chloride are (15~20)：1：1；
In step (1), the organic solvent is dichloromethane；
In step (1), the condition of the backflow is：Temperature is 40~45 DEG C, and return time is 4~5h；
In step (1), the H2TPP-(COOH)4Mass volume ratio (mg/mL) with tetrahydrofuran is (5~7)：1；
In step (2), the volume ratio of 1, the 2- dimercaptoethanes and triethylamine is (10~20)：1；
In step (2), the volume ratio of 1, the 2- dimercaptoethanes and tetrahydrofuran is (0.02~0.06)：1；
H in step (1)2TPP-(COOH)4Amount ratio with the material of 1,2- dimercaptoethanes in step (2) is 1：(60~80)；
In step (3), the speed of the dropwise addition is 2~3 seconds/drop, and dropwise addition process is carried out under the conditions of normal temperature, lucifuge；
In step (4), the post processing is：Column chromatography and recrystallization.
5. method as claimed in claim 4, it is characterised in that：The column chromatography uses silica gel column chromatography, using dichloromethane as
Eluent；Recrystallization uses to be carried out in dichloromethane and methanol solvate, and the volume ratio of dichloromethane and methanol is 1：(100~
120)。
A kind of 6. metal-organic framework material UiO-66 as claimed in claim 1 preparation method, it is characterised in that：Specific bag
Include following steps：
(1) by ZrCl4It is added in DMF (DMF), adds acetic acid, is eventually adding terephthalic acid (TPA), ultrasound
After being uniformly dispersed, solvent structure UiO-66 nano materials, it is centrifuged at a high speed to obtain solid product A；
(2) the solid product A in DMF washing steps (1) is used, solid product B is obtained, solid product B is activated, obtain white
Color powder UiO-66.
7. metal-organic framework material UiO-66 as claimed in claim 6 preparation method, it is characterised in that：In step (2),
The activation refers to：1. solid product A is immersed into DMF solvent, 6~10h of stirring immersion under the conditions of 60~85 DEG C, 2. at a high speed
Centrifuge, obtain solid product B；3. continuing solid product B being submerged into absolute ethyl alcohol, leaching is stirred under the conditions of 50~75 DEG C
7~12h is steeped, is centrifuged at a high speed, obtains solid product C；3. step is repeated 3 times, obtain solid product D, and soaked with ether
Not and solid D is washed, dried under natural conditions, obtain solid product E, as metal-organic framework material UiO-66.
8. metal-organic framework material UiO-66 as claimed in claim 6 preparation method, it is characterised in that：In step (1),
The ZrCl4Amount ratio with the material of terephthalic acid (TPA) is 1：1；
In step (1), the ZrCl4Mass volume ratio (mg/mL) with DMF is (4~6)：1；
In step (1), the acetic acid and DMF volume ratio are (0.035~0.075)：1；
In step (1), the condition of the solvent structure UiO-66 nano materials is：Temperature is 90~120 DEG C, soaking time
For 12~48h；Preferably described soaking time is 24h.
A kind of 9. four sulfydryl porphyrins that as claimed in claim 3 prepared by method, it is characterised in that：The four sulfydryls porphyrin compound
Structural formula be：
The four sulfydryls porphyrin compound molecular formula is：H2TPP-(COSC2H4SH)4, it is named as：(4- (the S- of 5,10,15,20- tetra-
Ethanethio ester) thiocarbonyl phenyl) porphyrin, referred to as four sulfydryl porphyrin (H2TPP-(SH)4), wherein H2TPP is tetraphenyl porphin
Quinoline.
10. method as claimed in claim 1 or 2 and its UiO-66-H of preparation2TPP-(SH)4, such as claim 4-7 it is any
The application in Photodynamic therapy of described method, four sulfydryls porphyrin as claimed in claim 8；Preferably as one kind
Anticancer photosensitizer.
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