CN103145777B - Rhodamine carbohydrate and application thereof - Google Patents
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Abstract
The invention relates to rhodamine carbohydrate and an application thereof. The rhodamine carbohydrate is obtained by means of connecting triazole with glycosyl and rhodamine B. The invention discloses an application of the rhodamine carbohydrate, namely an application of the rhodamine carbohydrate provided by the invention in preparation of a fluorescent probe used for detecting lectin and glycoprotein receptors on surfaces of cancer cells. Besides, the invention also provides a fluorescent probe used for detecting lectin and glycoprotein receptors on surfaces of cancer cells, and the fluorescent probe is mainly obtained by Phi-stacking self assembly of the rhodamine carbohydrate provided by the invention and oxidized graphene.
Description
Technical field
The present invention relates to a kind of Rhodamine carbohydrate and its production and use, specifically, relate to and a kind of connected Rhodamine carbohydrate of glycosyl and rhodamine B (Rhodamine B) and its production and use by triazole.
Background technology
Cancer is one of major disease threatening human life now as the global difficult medical problem of a class.Early discovery for cancer cells can facilitate early diagnosis and the healing of cancer.Research shows that cancer cell surfaces contains the special glycoprotein receptor that can be combined with certain sugars material, and the mutual recognition reaction between these sugar-acceptors induce cancer cells subsequently a series of physiological development as cell development and differentiation, cell adhesion and motion, the especially transfer of cancer cells.Sensitive Detection for extraordinary cancer cell surfaces sugar receptor protein can reach the object of early diagnosis of cancer.
But at present bibliographical information is rarely had for the preparation of this quasi-cancer cell sugar bioprobe, meanwhile, the technique means acted between research sugar-acceptor has certain limitation." sugared microarray " technology of such as immediate development needs studied carbohydrate molecule to be modified certain solid materials surface and applies fluorescently-labeled albumen, cell or pathogenic agent to detect its interaction.This kind of means, except needing a large amount of consumptive material, cut-and-try work, also need professional and technical personnel to carry out biological sample mark, and can cause the infringement to its original biological nature for the modification of sample.Therefore, simple and easy, economic, the efficient detection for target cancer cell surface trans-membrane sugar identification receptor albumen is the important problem that current academia faces.
Summary of the invention
Contriver, through further investigation, design and apply efficiently " click chemistry " means, has synthesized the glycosyl rhodamine compound of serial triazole connection with cheapness, high biophase content the rhodamine B possessing long excitation wave for fluorescence dye.These compounds and graphene oxide are carried out π-stacking self-assembly, form the glycosyl rhodamine-graphene nanometer composite making fluorescent quenching based on Fluorescence Resonance Energy trans effect (FRET), and for detecting lectin (sugar identifies albumen) and surperficial " fluorescence recovery formula " containing special sugared identification receptor cancer cells (shielding original FRET effect due to the combination of sugared rhodamine and albumen impels fluorescence to recover).
One object of the present invention is, provide a kind of Rhodamine carbohydrate being connected glycosyl and rhodamine B by triazole, described Rhodamine carbohydrate is compound shown in formula I, or its steric isomer, or its pharmaceutically acceptable salt:
In formula I, R is group shown in formula II,
In formula II, R
1for H or carboxyl (-COOH), R
2the amino (as-NHAc etc.) replaced for hydroxyl (-OH), ethanoyl (Ac) or H, R
3the amino replaced for hydroxyl (-OH), ethanoyl (Ac),
r
4for C
1~ C
3alkyl or the C that replaced by 1 ~ 3 hydroxyl
1~ C
3alkyl.
Preferred R is selected from: a kind of in group shown in formula IIa ~ IIk:
Another object of the present invention is, disclose above-mentioned Rhodamine carbohydrate (compound shown in formula I, or its steric isomer, or its pharmaceutically acceptable salt) a kind of purposes: i.e. Rhodamine carbohydrate provided by the present invention (compound shown in formula I, or its steric isomer, or its pharmaceutically acceptable salt) detect the application in the fluorescent probe (or claim: fluorescence " pass open type " bioprobe) of lectin and cancer cell surfaces glycoprotein receptor in preparation.
A further object of the invention is, a kind of fluorescent probe for detecting lectin and cancer cell surfaces glycoprotein receptor (or claim: fluorescence " pass open type " bioprobe) is provided, described fluorescent probe is primarily of Rhodamine carbohydrate provided by the present invention (compound shown in formula I, or its steric isomer, or its pharmaceutically acceptable salt) carry out π-stacking self-assembly with oxidation state Graphene (GO) and obtain.
In addition, the present invention also provides the method for compound shown in a kind of preparation formula I, and the key step of described method is: exist at cuprous chloride (CuCl), under the condition of room temperature (15 DEG C ~ 35 DEG C) and vigorous stirring, by 1-O-proyl various glucosides (
compound shown in preferred formula IIA ~ formula IIK) with containing rhodamine B compound (compound shown in formula III or its steric isomer of azido-, its preparation method is see Chen, X.et al.Dyes Pigm.2012,94,296) react in organic solvent, product obtains target product (shown in formula I compound) through column separating purification;
Wherein, the synthesis step of compound shown in formula IIA ~ formula IIH is see Shaikh, N.et al.Mol.Divers.2011,15,341-345; The preparation method of compound shown in formula II I see Gan, Z.-H & Roy, R.Can.J.Chem.2002,80,908-916; The preparation method of compound shown in formula IIj and formula IIk is see van Kasteren, S.I.et al.Nature2007,446,1105-1109.
Accompanying drawing explanation
Fig. 1 is the atomic force microscope images of oxidation state Graphene (GO) and sugared rhodamine mixture;
Wherein, a is the atomic force microscope images of GO; B is the atomic force microscope images of mixture GO-IA; C is the atomic force microscope images of mixture GO-IB mixture.
Fig. 2 is the infrared and Raman spectrum of Graphene and sugared rhodamine-graphene complex;
Wherein a is the infrared spectra of GO; B is the infrared spectra of mixture GO-IA mixture; C is the infrared spectra of mixture GO-IB mixture; D is the Raman spectrum of GO; E is the Raman spectrum of mixture GO-IA mixture; F is the Raman spectrum of mixture GO-IB mixture.
Fig. 3 is the ultra-violet absorption spectrum of GO, glycosyl rhodamine and GO-sugar rhodamine mixture;
Fig. 4 shows the fluorescent quenching effect of GO to sugared rhodamine;
Wherein, a is the change adding Compound I A fluorescence intensity after different concns GO; B is the change adding Compound I B fluorescence intensity after different concns GO.
Fig. 5 shows specific agglutination element to the specificity restitution of cancellation type GO-glycosyl rhodamine complex fluorescence and non-specific protein to the non-specific restitution of the glycosyl rhodamine fluorescence of GO cancellation;
Wherein a is the change of soybean agglutinin (SBA) the mixture GO-IA fluorescence intensity afterwards adding different concns 2-acetylamino galactosamine; B is the change of wheat germ agglutinin (WGA) the mixture GO-IB fluorescence intensity afterwards adding different concns 2-acetylglucosamine; C is that after the 10 kinds of albumen adding same concentration, mixture GO-IA fluorescence intensity recovers per-cent; D is that after the 10 kinds of albumen adding same concentration, mixture GO-IB fluorescence intensity recovers per-cent.
Fig. 6 is that under lower concentration lectin exists, the glycosyl rhodamine fluorescence recovery strength of GO cancellation is to the linear relationship of lectin concentration;
Wherein a is after the SBA adding 0.05 ~ 0.3 μM, the change of mixture GO-IA fluorescence intensity; B is after the WGA adding 0.8 ~ 8.0 μM, the change of mixture GO-IB fluorescence intensity.
Fig. 7 is that GO is to sugared rhodamine fluorescent quenching and plain fluorescence curve time of recovery to it of specific agglutination;
Wherein, a is GO to Compound I A fluorescent quenching and SBA to its fluorescence curve time of recovery; B is GO to Compound I B fluorescent quenching and WGA to its fluorescence curve time of recovery;
Fig. 8 be wild-type and ASGP-R1 receptor knockout except Hep-G2 cell respectively the fluorescence of mixture GO-IA is recovered and Compound I A, IB and mixture GO-IA, GO-IA to the cell fluorescence mark photo of Hep-G2.
Wherein a adds the change of the fluorescence intensity of mixture GO-IA after different quantities wild-type Hep-G2 cell; B adds the change of different quantities ASGP-R1 receptor knockout except the fluorescence intensity of mixture GO-IA after Hep-G2 cell; C, d and e are respectively 2 μMs, 20 μMs, 200 μMs Compound I A to the specificity fluorescent mark photo not contaminating core Hep-G2; F, g and h are respectively 2 μMs, 20 μMs, 200 μMs Compound I B to the non-specific fluorescence mark photo not contaminating core Hep-G2; I is that 20 μMs of mixture GO-IA contaminate the specificity fluorescent mark photo of core Hep-G2 to Hoechst; J is that 20 μMs of mixture GO-IB contaminate the non-specific fluorescence mark photo of core Hep-G2 to Hoechst.
Fig. 9 is Compound I A and IB structure, the superimposed form of IA and GO and mixture GO-IA detect schematic diagram for the fluorescence " pass open type " of the Hep-G2 cell shown containing ASGP-R.
Embodiment
By embodiment and Figure of description, the present invention is further elaborated, and its object is only better to understand content of the present invention.Therefore, the cited case does not limit the scope of the invention.
Embodiment 1
The preparation of compound shown in formula IA (referred to as Compound I A, lower same):
(1) preparation of Compound I A:
By Compound II per A(141mg, 0.55mmol) and compound III (355mg, 0.66mmol) be dissolved in 6mLCH
2cl
2in, add acetone (4mL), water (1mL) and CuCl(0.5 equivalent successively), stir under room temperature (15 DEG C ~ 35 DEG C) and spend the night.TLC shows initial thing and substantially disappears.Mixed solution is evaporated to pulpous state, adds 5mL ethanol and continues to be concentrated into pulpous state, in triplicate.Residue by silicagel column chromatographic separation is purified (methylene dichloride: methyl alcohol=15:1, V/V), obtains intense violet color solid (Compound I A, 317mg, 73%), R
f=0.6(methylene dichloride: methyl alcohol=6:1, V/V).
1H NMR(400MHz，DMSO-d
6)δ=8.20(d,J=7.0Hz,1H),8.12(s,1H),8.04(d,J=6.0Hz,1H),7.92(m,1H),7.82(m,1H),7.50(d,J=6.8Hz,1H),7.01(d,J=9.3Hz,2H),7.00(d,J=2.4Hz,2H),6.95(d,J=9.4Hz,2H),5.21(d,J=5.1Hz,1H),4.86(d,J=3.8Hz,1H),4.67(d,J=12.4Hz,1H),4.64(s,1H),4.60(t,J=4.5Hz,2H),4.52(d,J=12.2Hz,1H),4.44(d,J=4.8Hz,1H),4.42(t,J=4.5Hz,2H),4.10-4.04(m,2H),3.63(q,J=8.1Hz,9H),1.77(s,3H),1.21(t,J=7.1Hz,12H);
13C NMR(100MHz,DMSO-d
6):δ=182.9,182.2,170.0,169.9,169.9,167.8,156.9,144.1,135.0,134.2,125.0,123.0,121.2,120.1,85.9,73.6,69.8,67.8,67.2,64.1,61.0,21.1,20.5,19.8,19.7;
HR-ESI-MS:[C
41h
51n
6o
9]
+calcd.for(theoretical value): 771.3712, found(experimental value): 771.3716
Embodiment 2
The preparation of Compound I B:
(1) preparation of Compound I B:
By Compound II per B(108mg, 0.4mmol) and compound III (274mg, 0.5mmol) be dissolved in 6mL CH
2cl
2in, add acetone (4mL), water (1mL) and CuCl(0.5 equivalent successively), stir under room temperature (15 DEG C ~ 35 DEG C) and spend the night.TLC shows initial thing and substantially disappears.Mixed solution is evaporated to pulpous state, adds 5mL ethanol and continues to be concentrated into pulpous state, in triplicate.Residue by silicagel column chromatographic separation is purified (methylene dichloride: methyl alcohol=10:1, V/V), obtains intense violet color solid (Compound I B, 262mg, 78%), R
f=0.5(methylene dichloride: methyl alcohol=6:1, V/V).
1H NMR(400MHz,DMSO-d
6)δ=8.20(d,J=7.4Hz,1H),8.05(s,1H),7.88(m,2H),7.74(m,1H),7.47(d,J=7.1Hz,1H),7.02(d,J=9.2Hz,2H),6.95(m,4H),5.12(s,1H),5.01(d,J=4.0Hz,1H),4.72(d,J=11.1Hz,1H),4.66(s,1H).4.56(s,3H),4.44-4.33(m,3H),3.63(d,J=6.5Hz,8H),3.31(m,1H),3.12-3.04(m,2H),1.71(s,3H),1.22(t,J=6.1Hz,12H);
13C NMR(100MHz,DMSO-d
6)δ170.0,163.9,157.4,157.0,154.9,133.3,133.2,131.0,130.8,130.6,130.4,128.4,114.3,112.9,100.2,95.7,76.9,74.0,70.5,63.4,61.1,60.9,54.9,53.9,48.2,45.1,34.3,34.1,31.0,29.8,29.0,28.7,28.5,28.3,22.9,13.5,12.2;
HR-ESI-MS:calcd.for[C
41H
51N
6O
9]
+771.3712，found771.3709.
Embodiment 3
The preparation of glycosyl rhodamine-graphene complex
(1) by the PBS solution (10 of Compound I A or IB
-3m) with oxidation state Graphene (i.e. GO, it adopts two-step penetration method to prepare, specifically see Kovtyukhova, N.I.et al.Chem.Mater.1999,11,771-778) PBS solution (0.2g/L) mixing, with the PBS constant volume of 0.1M, make mixture GO-IA or mixture GO-IB series mixed solution, make the final concentration of Compound I A or IB be 2 × 10
-6m, GO final concentration be 0 ~ 50mg/L not etc., after the homogeneous system of ultrasonic formation, left at room temperature 20 minutes is for subsequent use.
(2) as shown in Figure 1, application atomic force microscope observe the GO thickness prepared be about 1.1nm (Fig. 1 a), conform to bibliographical information (Song, W., et al.Biosens.Bioelectron.2011,26,3181-3186), and Graphene-sugared rhodamine (GO concentration is 50mg/L, Compound I A(Fig. 1 b) after π-stacking effect or I B(Fig. 1 c) composite nano materials thickness rises to 1.6 ~ 1.8nm, prove to combine closely between the two.
(3) as shown in Figure 2, application fourier-transform infrared characterizes further to matrix material, GO(Fig. 2 b by modifying through Compound I A), through Compound I B modify modify GO(Fig. 2 c) a) compare with unmodified GO(Fig. 2, the former has showed the π-stack effect (2350cm of compound rhodamine and GO
-1), rhodamine phenyl ring skeleton (1580cm
-1) and aryl C-N key (1300cm
-1) infrared signature peak.
Equally as shown in Figure 2, the feature of Raman spectral characterization composite nano materials is applied.In the Raman spectrum of GO, (Fig. 2 d) is 1355 and 1600cm
-1there are standard D, the G bands of a spectrum (Kudin, K.N.et al.Nano lett.2008,8,36-41) of Graphene in place, its strength ratio (I
d/ I
g) for weighing its degree of irregularity and sp
2the standard of-territory mean sizes.For without compound-modified GO(Fig. 2 d), its I
d/ I
gbe 0.88, and through Compound I A(Fig. 2 e) and Compound I B(Fig. 2 f) after modified, its I
d/ I
gratio rises to 0.94 and 0.93 respectively, and the GO comparing unmodified is described, the carbon sp of these mixtures
2-hybridization ratios reduces due to the existence of compound, and degree of irregularity raises.
(4) as shown in Figure 3, apply the GO of ultraviolet-visible spectrum to GO, compound and compound stack to characterize.From Compound I A(Fig. 3 a) and Compound I B(Fig. 3 b) ultra-violet absorption spectrum: its absorption peak is positioned at 561nm place, and after stacking with GO, the absorption peak red shift of compound is to 573nm place.
Embodiment 4
Applications as laminates is to " pass open type " fluorescence sense of lectin and cancer cell surfaces saccharide acceptor
(1) use Varian Cary Eclipse spectrophotofluorometer, carry out fluoroscopic examination to the PBS mixed solution of GO-compound, result as shown in Figure 4.With the increase of GO concentration, the fluorescence intensity of compound weakens gradually until disappear, illustrate the fluorescent quenching due to the FRET effect of GO of sugared rhodamine (in Fig. 4 a, GO concentration is followed successively by 0,0.4,3,6,10,15,20,30,40,50mg/L; In Fig. 4 b, GO concentration is followed successively by 0,0.4,1.6,3,6,10,15,20,30,40,50mg/L).
After fluorescence " closedown ", then in system, add the superimposed effect that sugar identification lectin that concentration raises gradually disturbs sugared rhodamine and GO, the fluorescence of cancellation is recovered gradually.As shown in Figure 5, adding in mixture GO-IA solution can the soybean agglutinin (SBA of specific recognition 2-acetylamino galactosamine, concentration is followed successively by 0,0.1,2.0,8.0,30,100,200,300 μM), its fluorescence intensity returns to 94%(Fig. 5 of original fluorescence intensity a) gradually.Equally, adding in mixture GO-IB solution can the wheat germ agglutinin (WGA of specific recognition 2-acetylglucosamine, concentration is followed successively by 0,1.0,3.0,10,30,100,200,300 μM), its fluorescence intensity returns to 71%(Fig. 5 b of original fluorescence intensity gradually).Above phenomenon illustrates that fluorescent probe can by again " unlatching " after " closedown ".
Subsequently, two probe systems are added respectively to various special or non-specific lectin and the albumen of 15 μMs (GO-IA system, Fig. 5 c) and 30 μMs (GO-IB system, Fig. 5 d), consider its biologic specificity.Find that the fluorescence intensity of Compound I A returns to 30% of its initial strength under the SBA of 15 μMs exists, and the fluorescence of all the other 9 kinds of non-specific protein recovery efficiency is 3 ~ 8%; Under the WGA of 30 μMs exist, the fluorescence intensity of Compound I B returns to 19% of its initial strength, and the fluorescence of all the other 9 kinds of non-specific protein recovery efficiency is 6 ~ 10%.Constructed by above-mentioned examples prove, sugared rhodamine-GO probe possesses good biologic specificity at molecular level, can sensitive region dtex XNOR specific plant lectin.
(2) Fig. 6 is low concentration specific agglutination element when existing, and fluorescence recovery strength is to the linear regression of lectin concentration.Lectin Monitoring lower-cut (the LOD of GO-glycosyl rhodamine probe in prediction on such basis, 3 σ/slope, σ is the standard deviation of blank solution fluorescence intensity, and slope is the slope of regression line, specifically see Zhao, H.M.et al.Chem.Commun.2013,49,234-236) be: LOD(IA)=50nM(Fig. 6 a, SBA concentration is 0.05 ~ 3 μM), LOD(I B)=130nM(Fig. 6 b, WGA concentration is 0.8 ~ 8 μM).
(3) Fig. 7 is that GO is to sugared rhodamine fluorescent quenching and the plain curve to complex fluorescence time of recovery of specific agglutination.As diagram, GO can in 2 minutes the fluorescence of limit cancellation sugar rhodamine, and its fluorescence can recover and tend towards stability by specific sugar identification lectin in 6 minutes, illustrated that this probe system can obtain rapidly fluorescence " pass open type " signal.
(4) apply the liver cancer cell Hep-G2(cell of the superimposed probe in detecting surface of GO-IA containing semi-lactosi specific recognition receptor protein (ASGP-R) to be provided by new medicament screen center, Shanghai institute of materia medica of the Chinese Academy of Sciences), the results are shown in Figure 8.
As shown in Figure 8 a, after add the wild-type Hep-G2 containing 100,000,200,000/mL respectively in the probe system of fluorescent quenching, fluorescence intensity is that concentration dependant formula rises.Induced by verifying that this phenomenon is really combined by the identification of ASGP-R acceptor with between the GalNAc glycosyl of probe I A, that has carried out ASGP-R1 to Hep-G2 cell knocks out experiment (Yang, J.et al.J.ViralHepatitis2006,13,158-165).As Fig. 8 b, when same cell concentration, gene knockout group shows the fluorescence recovery Effects significantly weakened GO-IA probe, infers that above-mentioned fluorescence is recovered phenomenon and is mainly derived from the FRET effect that shielded between sugared rhodamine and GO by the effect of glycosyl specific recognition of cell surface sugar identification receptor thus.
Such GO-glycosyl rhodamine combined probe of further research is to the specific mark ability of Hep-G2.First Compound I A and IB is hatched with wild-type Hep-G2 cell respectively, Fig. 8 c/f, d/g and e/h(note: these figure are that pure compound is not illustrated with the mark of GO compound tense for cell) be respectively concentration when 2 μMs, 20 μMs and 200 μMs IA/IB to the fluorescent mark microphotograph of Hep-G2.As Fig. 8 c, 8d, 8e, improve with concentration, the fluorescent mark of Compound I A to cell significantly strengthens, and possesses cell marking ability hardly containing the Compound I B of non-specific GlcNAc glycosyl.The superimposed probe of GO-glycosyl rhodamine of fluorescence " closedown " is utilized to carry out fluorescence " unlatching " formula mark to cancer cells afterwards, Fig. 8 i be the superimposed probe GO-IA of Graphene under 20 μMs of concentration to Hep-G2(Hoechst contaminate core) fluorescent mark photo, its fluorescence intensity is obviously better than the cell (Fig. 8 j) of having hatched GO-IB probe.Above-mentioned experimental data demonstrates constructed " pass open type " fluorescent probe system and is applicable to the cancer cells of searching surface containing specific sugar identification receptor.
Claims (5)
1. a Rhodamine carbohydrate, is characterized in that, described for Rhodamine carbohydrate be compound shown in formula I, or its steric isomer, or its pharmaceutically acceptable salt:
Wherein, R is group shown in formula II, R
1for H or carboxyl, R
2the amino replaced for hydroxyl, ethanoyl or H,
R
3for hydroxyl, ethanoyl replace amino,
r
4for C
1~ C
3alkyl or the C that replaced by 1 ~ 3 hydroxyl
1~ C
3alkyl.
2. Rhodamine carbohydrate as claimed in claim 1, is characterized in that, wherein R is selected from group shown in formula II a ~ II k a kind of:
3. Rhodamine carbohydrate as claimed in claim 2, it is characterized in that, described Rhodamine carbohydrate is compound shown in formula I A or I B:
4. the Rhodamine carbohydrate as described in claim 1,2 or 3 is preparing the application in the fluorescent probe detecting lectin and cancer cell surfaces glycoprotein receptor.
5. for detecting a fluorescent probe for lectin and cancer cell surfaces glycoprotein receptor, it is characterized in that, described fluorescent probe carries out π-stacking self-assembly primarily of the Rhodamine carbohydrate described in claim 1,2 or 3 and oxidation state Graphene and obtains.
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