CN103864830B - Calixarene boric acid derivatives, preparation method and application thereof - Google Patents
Calixarene boric acid derivatives, preparation method and application thereof Download PDFInfo
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- CN103864830B CN103864830B CN201410114976.1A CN201410114976A CN103864830B CN 103864830 B CN103864830 B CN 103864830B CN 201410114976 A CN201410114976 A CN 201410114976A CN 103864830 B CN103864830 B CN 103864830B
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Abstract
The present invention is calixarene boric acid derivatives, preparation method and application thereof.With 2-formylphenylboronic acid for co-ligand; Be main part with 5,17-, bis--amido-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons.Calixarene boric acid derivatives prepared by the present invention all has keying action and recognition reaction to D-Glucose, D-Fructose, D-MANNOSE and D-semi-lactosi.All have recognition reaction by the known derivative of fluorescent spectrometry to four kinds of monose, wherein minimum to the detection limit of D-Fructose, therefore this derivative is relatively the highest to the selective recognition of D-Fructose.
Description
Technical field
The present invention relates to a kind of calixarene boric acid derivatives, preparation method and and application.
Background technology
Along with the fast development of modern society, the living environment of the mankind there occurs very large change, and associated disease also continues to bring out.Although while scientific and technological and economic development, all kinds of transmissible disease and infectious diseases are effectively controlled, and diabetes have become a kind of lifelong chronic disease, and can cause multiple complications.Existing 3.5 hundred million people in the whole world suffer from diabetes.Detecting blood sugar concentration is diagnosing diabetes main standard, and fluorometry is quick, highly sensitive, selectivity is good and easy etc., and advantage is widely used in trace analysis field to make it, in recent years so seeking efficient, easy blood sugar detecting method is the direction that investigators make great efforts.
Carbohydrate is the important organic compound of the widely distributed class of occurring in nature, is that all life body sustains life the main source of activity institute energy requirement.General elementary composition by carbon, hydrogen and oxygen three kinds, be polyhydric aldehyde or polyhydric ketone.And in human body, carbohydrate is only decomposed into monose and could be absorbed.
Boronate be a class very important realize the group of detection and indentification carbohydrate by generating stable cyclic lactone.
Summary of the invention
The object of the present invention is to provide a kind of to D-Glucose, D-Fructose, D-MANNOSE and D-semi-lactosi have the calixarene boric acid derivatives of recognition capability and binding ability, preparation method and and application, and study this calixarene boric acid derivatives as the possibility of fluorescent probe for sugared content detection and identification.
Object of the present invention can be achieved through the following technical solutions:
A kind of calixarene boric acid derivatives that the present invention proposes, the chemical formula of described derivative is C
42h
40o
8n
2b
2, with 2-formylphenylboronic acid for co-ligand, 5,17-, bis--amido-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons is main part, and its structural formula is as follows:
。
The preparation method of the calixarene boric acid derivatives that the present invention proposes, concrete steps are as follows:
(1) synthesize 5,17-, bis--amido-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons, obtain brick-red powder;
(2) step (1) is processed thick product 0.4870 mmol and 2-formylphenylboronic acid 1.1360 mmol obtained, be dissolved in 63.9 mL anhydrous methanols and Glacial acetic acid, the volume ratio of anhydrous methanol and Glacial acetic acid is 70:1, heating in water bath, temperature controls at 60 ~ 70 ° of C, under agitation reflux after 7 ~ 8 h, rotary evaporation removing methyl alcohol and acetic acid, obtain Red-brown powder;
(3) the whole crude product of step (2) gained is added in three-necked flask, add 75 mL anhydrous methanols and 6 times again to sodium borohydride 2.8237 mmol of desired product, temperature controls at 40 ~ 50 ° of C, stirring and refluxing 6 ~ 7 h, at room temperature stirring reaction 10 h again, take out the first alcohol and water that volatilizees under physical environment, obtain light yellow powder crude product;
(4) step (3) is processed the thick product silica gel column chromatography obtained to be separated, be then spin-dried for eluent, obtain powdery product and be product.
The application of the calixarene boric acid derivatives that the present invention proposes, this derivative has recognition reaction and keying action to D-Glucose, D-Fructose, D-MANNOSE and D-semi-lactosi.
In the present invention, have Enhancement of Fluorescence by fluorescence spectrum to four kinds of monose, the calixarene boric acid derivatives described in explanation can with monose generation keying action.
In the present invention, by calculating the different of derivative and four kinds of monose detectabilities, illustrate that derivative has recognition reaction to four kinds of monose.
In the present invention, by calculating the different of derivative and four kinds of monose detectabilities, illustrate that this derivative is relative the highest to the selective recognition of D-Fructose.
Invention has been hydrogen spectrum (
1h NMR) and electrospray ionization mass spectrum (ES-MS) sign.Fluorescence spectrum means are utilized to have detected the calixarene boric acid derivatives of designed synthesis to four kinds of monose binding abilities and recognition capability.
Beneficial effect of the present invention is:
1. structure is new calixarene boric acid derivatives, its boronate is easy to be combined with carbohydrate generate cyclic lactone; 2. calixarene and boronate bonding with utilize the effect of fluorescence spectrum means discussion calixarene boric acid derivatives and carbohydrate, this kind of research seldom, is therefore enriched and has widened this field; 3. this derivative is different from the detectability of four kinds of monose, and the function having and identify carbohydrate is described; 4. the fluorescent probe of potential highly selective.
Accompanying drawing explanation
Fig. 1 be the present invention obtain in NaCl ion buffer solution, the derivative of different concns and the fluorescence spectrum figure of quantitative D-Glucose effect;
Fig. 2 be the present invention obtain in NaCl ion buffer solution, the fluorescence spectrum figure of the quantitative derivative under different pH value and quantitative D-Glucose effect; (a) reagent blank; The binding substances of (b) derivative and D-Glucose;
Fig. 3 be the present invention obtain in NaCl ion buffer solution, the fluorescence spectrum figure of this derivative and the effect of different concns D-Glucose;
Fig. 4 be the present invention obtain in NaCl ion buffer solution, the fluorescence spectrum figure of this derivative and the effect of different concns D-Fructose;
Fig. 5 be the present invention obtain in NaCl ion buffer solution, the fluorescence spectrum figure of this derivative and the effect of different concns D-MANNOSE;
Fig. 6 be the present invention obtain in NaCl ion buffer solution, the fluorescence spectrum figure of this derivative and the effect of different concns D-semi-lactosi;
Fig. 7 is the histogram of the detectability that this derivative that the present invention obtains is combined with four kinds of monose.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
The synthesis of Calix areneboronic acid derivative
1. in 1000 mL three-necked bottles, add p-tert-butylphenol (50 g, 333 mmol), 5 mL are containing the aqueous solution of 0.6 g NaOH, the formalin (32 mL, 414 mmol) of 36%, heated and stirred, temperature of reaction to accelerate a point water speed, rapid temperature increases, and controls 115 ~ 120 by logical nitrogen
oCleft and right.Reactants dissolved, becomes sticky gradually, constantly has bubble to produce in reaction solution, constantly has moisture to go out in water trap, and after about 1 ~ 1.5h, reaction mixture becomes cellular wax, stops heating.After slightly cold, add the phenyl ether that 500 mL are warm, heating, foam fades away, and logical nitrogen, to separate the water in system as far as possible, can stop logical nitrogen after starting backflow.Reaction solution color deepens gradually, until chocolate.Backflow 2hr, stops heating.Add 500 mL ethyl acetate after being chilled to room temperature, then have solid to separate out.Stirred at ambient temperature 30min, leaves standstill, suction filtration.Precipitation is use water, ethyl acetate, acetic acid washing successively, dries to obtain the thick product of white powder.Thick product re crystallization from toluene, obtains white crystal 30g.Productive rate: 60%.
2. take step (1) product (13.3 g, 20 mmol), phenol (9.02 g, 96 mmol), aluminum trichloride (anhydrous) (14 g, 105 mmol), 125 mL dry toluene add in 500 mL three-necked bottles, logical nitrogen, the whole system of vitriol oil fluid-tight, stirring at room temperature.Reactant slowly becomes clarification by muddiness, and aluminum chloride solid dissolves gradually, mixing liquid color by colourless to yellow and constantly deepen.After reaction for some time, solution becomes muddy again.Stop logical nitrogen after about 1.5h ~ 2.0h, slowly add 0.2 mol/L hydrochloric acid 250 mL and reaction is stopped.Aluminum chloride hydrolysis release large calorimetric when adding hydrochloric acid, and emit white cigarette.Mixed solution proceeds to separating funnel, and layering after concussion, upper organic phase is light yellow, and lower floor's aqueous phase is milky turbidity liquid.Aqueous phase discarded, organic phase washed with water is clarified mutually to institute's wash water.Separate organic phase, anhydrous sodium sulfate drying, filter, rotary evaporation removing toluene, residue adds methyl alcohol, and separate out white solid, suction filtration, oven dry, obtain white solid crude product.Crude product chloroform/methanol recrystallization, obtains white flash solid 6.8 g.Productive rate: 78%.
3. take step (2) product (4.24 g, 10 mmol) and be dissolved in 50 mL pyridines, cool in ice-water bath, add Benzoyl chloride (9.4 mL, 81mmol), stir 1h in ice-water bath, remove ice-water bath, be slowly warming up to room temperature, then stir 1h.Add 300 mL water, stir 10 minutes, leave standstill, suction filtration, solid uses water, methanol wash successively, can obtain white solid crude product.Crude product chloroform/methanol recrystallization, obtains white loose chip solid 6.0 g, productive rate 82%.
4. take step (3) product (7.36 g, 10 mmol) to be dissolved in 100 mL methylene dichloride, add 5 mL Glacial acetic acid, stir lower instillation 1 mL 65% salpeter solution.Mixed solution color from light yellow is deepened gradually until orange.Stirred at ambient temperature 0.5h ~ 1.0h.After reacting completely, reaction solution goes to separating funnel, with dilute NaOH solution, water, dichloromethane layer is washed till neutrality successively.Separate dichloromethane layer, with anhydrous sodium sulfate drying, spend the night.After filtering, namely steaming vibrating dichloromethane obtains crude product, is yellow powder.Crude product methylene chloride/methanol recrystallization, obtains 7.3 g pale yellow powders, productive rate 94 %.
5. take step (4) product (1.56 g, 2 mmol) and SnCl
22H
2o(4.8 g) in 100 mL three-necked bottles, add 50 mL dehydrated alcohols, backflow, TCL follows the tracks of, after reacting completely (about 18h), by reacting liquor while hot impouring ice, stir, be 8 by strong aqua adjust ph, cross and filter pureed solid, and with ethanol, washed with dichloromethane pureed solid.Filtrate and washings merge rear dichloromethane extraction, and organic phase anhydrous sodium sulfate drying, boils off solvent after filtration, obtains pink solid 0.95 g.Productive rate 63%.
6. in the mono-neck bottle of 50 mL, add step (5) product (0.38 g, 0.5mmol), 20 mL are through the methylene dichloride of Vanadium Pentoxide in FLAKES drying treatment, and 0.4 mL triethylamine, cools in ice-water bath, homemade acryloyl chloride 0.5 mL is slowly instilled under stirring, after 0.5h, be slowly warming up to room temperature, add water after reaction 2h stopped reaction.With dilute hydrochloric acid, dilute NaOH solution, water, dichloromethane layer is washed till neutrality successively, separates dichloromethane layer, use anhydrous sodium sulfate drying.Filter, boil off solvent, obtain dark brown oil thick liquid, use sherwood oil efflorescence, obtain thick product.Crude product methylene dichloride/sherwood oil recrystallization, obtains 0.35 g, productive rate 87%.
7. taking step (6) product (1.56 g, 2mmol) is dissolved in 40 mL tetrahydrofuran (THF)s, and solution is orange-yellow, adds the aqueous solution of dehydrated alcohol (or 95% ethanol) 40 mL and 20 mL containing 4g NaOH.After adding alkali lye, solution colour is brown, 70
othe micro-backflow of boiling of C.TLC follows the trail of, and after about 5h reacts completely, rotary evaporation removing volatile solvent, obtains brown solution.Slightly cold, with the neutralization of higher concentration hydrochloric acid, then having tan precipitate to separate out gradually, is that about 2 precipitations are complete to pH value.Leave standstill, filter, with water, washed with diethylether, obtain yellow powder solid.Dry to obtain crude product 0.7 g, productive rate 75%.Product purity is very high, does not need recrystallization to reach and characterize required purity after washed with diethylether.
8. take step (7) product (1.1g, 2.3 mmol) and SnCl
22H
2(6, g) in 100 mL three-necked bottles, add 20 mL dehydrated alcohols, 20mL acetone, 70 to O
oreflux under C, TCL follows the tracks of, and after reacting completely (about 18h), by reacting liquor while hot impouring ice, stirs, separates out sludge.Be neutral by strong aqua adjust ph, cross and filter pureed solid, and with ethanol, washed with dichloromethane pureed solid.Filtrate and washings merge rear dichloromethane extraction, and organic phase is brown color.Extract complete, organic phase anhydrous sodium sulfate drying, boils off solvent after filtration, obtains faint yellow powdery solid.Obtain crude product 0.5g, productive rate 50%.
9. take step (8) and process product (0.2211 g obtained; 0.4870 mmol) and 2-formylphenylboronic acid (0.1704 g; 1.1360 mmol); be dissolved in 63.9 mL anhydrous methanols and Glacial acetic acid, (volume ratio of anhydrous methanol and Glacial acetic acid is 70:1), heating in water bath; temperature controls at 60 ~ 70 ° of C; under agitation reflux after 7 ~ 8 h, rotary evaporation removing methyl alcohol and acetic acid, obtain Red-brown powder.Productive rate about 68%.
10. in three-necked flask, add step (9) gained all thick products, add 75 mL anhydrous methanols and about 6 times again to sodium borohydride (NaBH4) (0.1073 g of desired product, 2.8237 mmol), temperature controls at 40 ~ 50 ° of C, stirring and refluxing 6 ~ 7 h, at room temperature stirring reaction 10 h again, takes out the first alcohol and water that to volatilize under physical environment, obtains light yellow powder crude product.Productive rate about 65%.
Step (10) is processed the thick product silica gel column chromatography obtained by 11. to be separated, and with methanol/ethyl acetate (1:1, v/v) wash-out, collects last red elutriant, is then spin-dried for eluent, can obtain product 0.2140g.Productive rate is 60.8%.
1H-NMR (CDCl
3, TMS, 400 MHz): 9.93(4H, s), 7.09, 6.66(18H, d), 4.46(4H, s), 3.91(2H, s), 3.72(8H, s), 2.21(4H, s) MALDI-MS for a1: calcd. 721.6[M]+, found 744.3[M+Na]+.
。
Embodiment 2
NaCl ion buffer solution: 0.005molNaCl, pH=7.0
General compound method: accurately take 0.2925 g NaCl, dissolves completely with 40 mL distilled water, by the slow adjust ph to 7.0 of diluted sodium hydroxide solution, proceeds to 100 mL volumetric flasks, by methanol constant volume, mixes rear for subsequent use.
Same method, prepares the NaCl ion buffer solution of other different pH value.
The preparation of complex solution:
Accurately take 36.08 mg derivatives, first use the dissolve with methanol of 6 mL, then be settled to 10 mL with distilled water, obtain 5.0 × 10
-3the title complex storing solution of mol/L.
The preparation of sugar soln:
Accurately take 18.0160 mg D-Glucoses, dissolve with distilled water, then be settled to 100 mL with distilled water, obtain 1.0 × 10
-3the D-Glucose storing solution of mol/L.
The fluorescence spectrum optimization experiment of derivative
Instrument: Hitachi FP 7000 fluorophotometer
Instrument parameter: excitation wavelength: 225 nm, slit width: 5.0 nm
Sweep limit: 250-430 nm
The derivative solution adding different concns, in 5 ml volumetric flasks, first adds a certain amount of D-Glucose solution (1.0 × 10
-5mol/L), be then settled to 5 ml with the NaCl ion buffer solution of pH 7.00, shake up.Leave standstill after 6 hours, part solution is transferred in 1cm cuvette, on fluorophotometer, selective exitation and transmitting slit are 5.0 nm, in entering ex=225 nm, enter em=305 nm, measure the fluorescence intensity of derivative and derivative and glucose binding substances, and calculate Δ F(Δ F=F-F
0), shown in its result Fig. 1.
Result shows: when the concentration of D-Glucose is 1.0 × 10
-5during mol/L, the concentration of derivative is 5.0 × 10
-7mol/L-9.0 × 10
-7within the scope of mol/L, the powerful and substantially constant of the fluorescence of system.Therefore, this experiment selects 5.0 × 10
-7mol/L is the concentration of derivative.
When derivatives concentration is 5.0 × 10
-7mol/L, D-Glucose concentration is 1.0 × 10
-5during mol/L, test the fluorescence intensity graph of a relation of derivative and derivative and D-Glucose binding substances under different pH value.PH value is selected as pH=2.00-12.00, shown in its result Fig. 2.
Result shows: when pH=7.00, and the fluorescence intensity change after non-sugaring and sugaring is maximum, therefore experimental selection pH 7.00 is system acidity.
Embodiment 3
NaCl ion buffer solution: 0.005molNaCl, pH=7.0
General compound method: accurately take 0.2925 g NaCl, dissolves completely with 40 mL distilled water, by the slow adjust ph to 7.0 of diluted sodium hydroxide solution, proceeds to 100 mL volumetric flasks, by methanol constant volume, mixes rear for subsequent use.
The preparation of complex solution:
Accurately take 36.08 mg derivatives, first use the dissolve with methanol of 6 mL, then be settled to 10 mL with distilled water, obtain 5.0 × 10
-3the title complex storing solution of mol/L.
The preparation of sugar soln:
Accurately take 18.0160 mg D-Glucoses, dissolve with distilled water, then be settled to 100 mL with distilled water, obtain 1.0 × 10
-3the D-Glucose storing solution of mol/L.
Same method, preparation 1.0 × 10
-3the D-Fructose of mol/L, D-MANNOSE and D-semi-lactosi storing solution.
The fluorescence spectrum experiments of derivative and monose
Instrument: Hitachi FP 7000 fluorophotometer
Instrument parameter: excitation wavelength: 225 nm, slit width: 5.0 nm
Sweep limit: 250-430 nm
Accurately measure the methanol aqueous solution (5.0 × 10 of 5 these derivatives of μ L
-3mol/L) in 5mL volumetric flask, add sugar (D-Glucose, D-Fructose, D-MANNOSE and the D-semi-lactosi) solution of different concns, be settled to 5mL with the NaCl ion buffer solution of pH 7.00, shake up.Leave standstill, get part solution in 1cm cuvette, selective exitation and transmitting slit are 5.0nm, scan fluorescence spectrum, measure the fluorescence intensity of derivative and derivative and glycoconjugate, shown in its result Fig. 3-6 under excitation wavelength is 225 nm.
Result shows: when derivative and four kinds of monose effects, obtain fluorescence intensity and strengthen with the increase of monosaccharide concentration, proves that derivative and four kinds of monose there occurs keying action.
Calculate the detectability of derivative and four kinds of monose respectively.Result shows: this derivative is relatively the highest to the selective recognition of D-Fructose.Illustrate that derivative has recognition capability to four kinds of monose.Shown in its result Fig. 7.
Claims (2)
1. a calixarene boric acid derivatives, is characterized in that, the chemical formula of described derivative is C
42h
40o
8n
2b
2, with 2-formylphenylboronic acid for co-ligand, 5,17-, bis--amino-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons are main part, and its structural formula is as follows:
。
2. a preparation method for calixarene boric acid derivatives as claimed in claim 1, it is characterized in that, concrete steps are as follows:
(1) synthesize 5,17-, bis--amino-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons, obtain brick-red powder;
(2) step (1) is processed thick product 0.4870 mmol and 2-formylphenylboronic acid 1.1360 mmol obtained, be dissolved in 63.9 mL anhydrous methanols and Glacial acetic acid, the volume ratio of anhydrous methanol and Glacial acetic acid is 70:1, heating in water bath, temperature controls at 60 ~ 70 ° of C, under agitation reflux after 7 ~ 8 h, rotary evaporation removing methyl alcohol and acetic acid, obtain Red-brown powder;
(3) the whole crude product of step (2) gained is added in three-necked flask, add 75 mL anhydrous methanols and sodium borohydride 2.8237 mmol again, temperature controls at 40 ~ 50 ° of C, stirring and refluxing 6 ~ 7 h, at room temperature stirring reaction 10 h again, take out the first alcohol and water that volatilizees under physical environment, obtain light yellow powder crude product;
(4) step (3) is processed the thick product silica gel column chromatography obtained to be separated, be then spin-dried for eluent, obtain powdery product and be product.
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| 杯[4]芳烃硼酸与氨基酸配位作用的荧光光谱研究;卢奎等;《高等学校化学学报》;20010430;第22卷(第4期);第581—583页 * |
| 水相中糖识别人工受体;熊雨婷等;《化学进展》;20131225;第26卷(第1期);第48—60页 * |
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