CN101824139B - Polycarboxyl fluorescent conjugated polyelectrolyte, preparation method and application - Google Patents
Polycarboxyl fluorescent conjugated polyelectrolyte, preparation method and application Download PDFInfo
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Abstract
The invention discloses fluorescent conjugated polyelectrolyte with a plurality of carboxyl functional groups, and a preparation method. Polyphenylene ethynylene is used as a conjugated backbone; each repeating unit comprises fours carboxyl functional groups, and a plurality of carboxyl functional groups carried on the side chain thereof are easily coupled with biological molecules; and the polyelectrolyte has good biological compatibility, and is suitable for various biochemistry analysis experiments. The polycarboxyl fluorescent conjugated polyelectrolyte has the advantages of simple operation method, high water solubility and stable fluorescent characteristic. Compared with the other polyphenylene ethynylene polyelectrolyte, the polycarboxyl fluorescent conjugated polyelectrolyte solves the problem of poor solubility of the polymer, also has the advantages of good fluorescent characteristic, high biocompatibility and the like, is a fluorescent sensing material with high comprehensive performance, can be used for high-sensitivity detection of copper ions, and has high selectivity compared with the other materials. The polycarboxyl fluorescent conjugated polyelectrolyte has a structural formula shown in the specification.
Description
Technical field
The invention belongs to technical fields such as chemistry, material and biochemical sensitive, relate in particular to a kind of fluorescence conjugated polyelectrolyte sensing material that has a plurality of carboxyl functional groups.
Background technology
In recent years; Fluorescent conjugated polymer (Fluorescent Conjugated Polymers; FCPs) rely on attributes such as the unique and superior light of its a series of ten minutes, electricity, magnetic, obtained research and application more and more widely in high-sensitive biology, chemical sensitisation field.Compare with traditional organic fluorescent dye, fluorescent conjugated polymer is because its unique π-π
*The conjugated molecule conductor structure makes that electronics or exciton can free in whole polymer backbone, migrations apace.Thereby a quencher molecule promptly can cause the ultra quencher of fluorescence of the whole piece polymer chain that combines with it, and the fluorescence response signal has obtained hundreds and thousands of times amplification.Just because of the amplification of sort signal, make fluorescent conjugated polymer just receive increasingly extensive concern in the biochemical sensitive field with various structures and function.Especially the fluorescence conjugated polyelectrolyte that has the ionize side chain, because its water miscible characteristics, and aspect biomolecule detection, have very big advantage.But the fluorescence conjugated polyelectrolyte that so far, is used for the biochemical sensitive field still mainly concentrate on have sulfonic group side chain or a quaternary ammonium salt structure gather several types of conjugated polymerss such as fluorenes, polyphenylene vinylene and the support of polyhenylene acetylene.And have the fluorescence conjugated polyelectrolyte of biological affinity groups such as carboxyl; Particularly polyhenylene acetylene supports base polymer (PPE); Then owing to have long rigidity hydrophobic skeleton, the light current of carboxyl leaves character in addition, and water-soluble relatively poor; Fluorescence quantum yield is on the low side and unstable, thereby has limited its research and application in the biochemical sensitive field widely.
Branch-shape polymer also is current just at one type of flourish synthetic macromolecule.Wherein, polyamide-amide (PAMAM) be research at present the most extensively, one of the most deep dendritic macromole.Remove and have outside the denominator (like accurate molecular structure, a large amount of surface functional groups, the controllability of relative molecular mass and monodispersity etc.) of this base polymer; PAMAM also has some characteristics of self concurrently; Like good consistency, lower soltion viscosity, and be easy to modification property or the like.In conjunction with PPE class fluorescent conjugated polymer and PAMAM dendrimer, will be expected to develop a series of novel fluorescence conjugated polyelectrolytes that have a plurality of side chain functionalities, and effectively improve the water-soluble and fluorescent stability of this base polymer.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of polycarboxyl fluorescent conjugated polyelectrolyte with good aqueous solubility and high fluorescent stability is provided, its general structure is following:
Wherein: k is for modifying alkoxy substituted length, and the value of k can be 0,0.5,1,1.5 or 2; N represents the number of repeat unit of polyelectrolyte, is the integer between 1～200.
Another object of the present invention provides the preparation method of said polycarboxyl fluorescent conjugated polyelectrolyte, realizes through following steps:
1) the 10g Resorcinol is dissolved in the dimethyl sulfoxide solution that contains 0.2～0.6mol alkali (100～200mL), add halogen ester (mol ratio of halogen ester and Resorcinol is 2～6) then, and at room temperature stirred 3～10 days; Reaction adds a large amount of cold water after finishing, and with white precipitate filtration, the vacuum-drying of separating out, obtains 1,4-two (oxo ester group) benzene product then;
Wherein, described halogen ester can be chloro (or bromo, iodo)-acetate (or propionic acid, butyric acid, valeric acid, caproic acid) methyl esters (or ethyl ester), 2-methyl chloroacetate for example, 3-ethyl bromide, 4-bromo-butyric acid ethyl ester etc.; Described alkali is Pottasium Hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood or sodium hydrogencarbonate;
2) (the shared volume ratio of the water and the vitriol oil is respectively 1～5% and 4～10% for 80～150mL) adding 10g 1,4-two (oxo ester group) benzene in the ethanolic soln that contains the water and the vitriol oil; After stirring, add the iodine and the Potassium Iodate of equivalent; Reaction mixture stirred 1～3 day down at 60～80 ℃; Reaction finishes after-filtration, and washes repeatedly with a large amount of second alcohol and waters, after the vacuum-drying, obtains the white powder product, is 1,4-two iodo-2,5-two (oxo ester group) benzene;
3) with 10g 1,4-two iodo-2,5-two (oxo ester group) benzene joins in 40～120mL trichloromethane and the 80mL methyl alcohol, after stirring, adds 60～150mL quadrol, and reaction mixture stirred 3～5 days under 20～40 ℃ of conditions; After reaction finishes, in system, add a large amount of ether, the adularescent flocks is separated out, collecting precipitation, washing, and vacuum-drying then obtains having the white powder product of amido functional group;
4) the white powder product (5g) that step 3 is obtained is dissolved in the mixed solution of 60～150mL methyl alcohol and DMSO 99.8MIN. (volume ratio 1～3 of methyl alcohol and DMSO 99.8MIN.), slowly adds the methyl acrylate of 2～6 times of amounts then; Reaction mixture stirred 3～5 days down at 20～40 ℃; In system, add a large amount of zero(ppm) water, vigorous stirring, the adularescent solid is separated out, and filtration, washing, vacuum-drying get the white powder solid, promptly have the polymerization single polymerization monomer of four ester group functional groups;
5) with the polymerization single polymerization monomer (3g) and 1 of step 4 gained, (360～480mg) are dissolved in the mixed solution of 60～120mL trichloromethane, Diisopropylamine and triethylamine (volume ratio 6: 1: 1) the 4-diacetylene-benzene, under oxygen free condition, add palladium catalyst and cuprous iodide; Reaction mixture stirred 3～5 days down at 40～80 ℃; Reaction adds a large amount of ether after finishing, and stirs; Filter; Use a large amount of deionized water rinsings again, vacuum-drying obtains having the polyhenylene acetylene support type fluorescent conjugated polymer of four ester group functional groups.Wherein, described palladium catalyst is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride.
6) (60～100mg) are dissolved in 80～150mL methanol solution with the fluorescent conjugated polymer of step 5 gained; Add alkali aqueous solution after stirring, reaction mixture refluxed after 3～5 days, is added a large amount of anhydrous diethyl ethers; There is faint yellow solid to separate out; Filter, collect this faint yellow solid, vacuum-drying obtains having the fluorescence conjugated polyelectrolyte of many carboxyl functional groups.Wherein, described alkali is Pottasium Hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood or sodium hydrogencarbonate.
A further object of the present invention provides the application of polycarboxyl fluorescent conjugated polyelectrolyte in cupric ion detects.
The step that polycarboxyl fluorescent conjugated polyelectrolyte is used for the cupric ion detection is following:
1) using phosphate buffer soln that polycarboxyl fluorescent conjugated polyelectrolyte is mixed with concentration is 10
-6-10
-5The dilute solution of mol/L;
2) the cupric ion standardized solution with different concns joins in the aforesaid polycarboxyl fluorescent conjugated polyelectrolyte dilute solution, measures its fluorescence emission spectrum, and changes the drawing standard curve according to fluorescence intensity;
3) cupric ion to be measured is mixed with 10
-6-10
-5The solution of mol/L joins in the aforesaid fluorescence conjugated polyelectrolyte solution then, measures its fluorescence emission spectrum, and confirms the concentration of cupric ion in the solution to be measured according to the variation of fluorescence intensity.
The present invention provides a kind of fluorescence conjugated polyelectrolyte that has many carboxyl functional groups and preparation method thereof through combining polyhenylene acetylene support type fluorescent conjugated polymer and two kinds of synthetic routes of polyamide-amide type dendrimer.It is a conjugated backbone with the support of polyhenylene acetylene, and each repeating unit has four carboxyl functional groups.The introducing of many carboxyls makes the water-soluble of this conjugated polyelectrolytes improve greatly, and fluorescent stability strengthens, and is easy to and the biomolecules coupling, therefore also is applicable to the check and analysis of biomolecules more.The side chain functionalities of polycarboxyl fluorescent conjugated polyelectrolyte type of having EDTA structure of the present invention, thereby and metals ion between have stronger complexing action.In phosphate buffer; Metal copper ion has very sensitive fluorescence quenching for this conjugated polyelectrolytes; And with respect to other common metal ion, have high selectivity, can be used as a kind of copper ion fluorescence probe of highly sensitive, high specific.
Description of drawings
Fig. 1 be a kind of polycarboxyl fluorescent conjugated polyelectrolyte provided by the invention (is example with k=1) in phosphate buffer soln (10mM, pH 7.4) by Cu
2+The curve of quencher, excitation wavelength 400nm, the concentration of polycarboxyl fluorescent conjugated polyelectrolyte is 5 μ M.
Fig. 2 be a kind of polycarboxyl fluorescent conjugated polyelectrolyte provided by the invention (is example with k=1) by different metal ionic quencher degree comparison diagram, copper removal ionic concentration is outside the 3 μ M, the concentration of other metals ions is 20 μ M.
Embodiment
In order to understand content of the present invention better, further describe technical scheme of the present invention below in conjunction with accompanying drawing and specific embodiment.But can not limit interest field of the present invention with this, interest field of the present invention should be as the criterion with the elaboration of claims.
The preparation of 1 one kinds of polycarboxyl fluorescent conjugated polyelectrolytes of embodiment (is example with k=1)
1) 22.4g Pottasium Hydroxide is pulverized in the last 170mL of the being dissolved in DMSO 99.8MIN., under oxygen free condition, add the 8.8g Resorcinol rapidly; After stirring, slowly drip 4-bromo-butyric acid ethyl ester 46mL; Stirred 3 days under the reaction mixture room temperature; Reaction finishes back adding 1L frozen water and stirs fast, and the adularescent solid is separated out; Filter the back and use a large amount of distilled water flushings, vacuum-drying obtains 1, and 4-two (4-ketobutyric acid ethyl ester) benzene is seen the compound (1) in the synthetic route.
1H-NMR(CDCl
3，δ
ppm)：1.25(t，6H)，2.08(quintet，4H)，2.50(t，4H)，3.95(t，4H)，4.13(q，4H)，6.80(s，4H)；ESI-TOF?361.3，[M+Na]；FTIR(KBr，cm
-1)：2980，1729，1510，1472，1420，1378，1358，1273，1226，1181，1117，1098，1061，1037，918，881，859，837，807，774，526，466，415，347.
2) in the 250mL three-necked bottle, add 120mL ethanol, the 2mL vitriol oil, 5mL deionized water; Add 9.8g 1 after stirring successively, 4-two (4-ketobutyric acid ethyl ester) benzene, 3.1g Potassium Iodate and 8.0g iodine; Reaction mixture stirred 3 days down at 60 ℃; Reaction finishes postcooling to room temperature, has a large amount of solids to separate out; Filtering back water and ethanol washes repeatedly; Vacuum-drying obtains the pale pink product, and 1,4-two iodo-2,5-two (4-ketobutyric acid ethyl ester) benzene is seen the compound (2) in the synthetic route.
1H-NMR(CDCl
3，δ
ppm)：1.27(t，6H)，2.13(quintet，4H)，2.59(t，4H)，3.99(t，4H)，4.17(q，4H)，7.18(s，2H)；ESI-TOF613.2，[M+Na]；FTIR(KBr，cm
-1)：2985，2944，1730，1491，1462，1421，1388，1373，1354，1342，1263，1224，1216，1203，1176，1095，1057，1027，956，941，870，771，619，440.
3) with 9.44g 1,4-two iodo-2,5-two (4-ketobutyric acid ethyl ester) benzene joins in the 60mL trichloromethane; After stirring, add the mixed solution (8: 10) of 180mL methyl alcohol and quadrol; Reaction mixture at room temperature stirred 5 days; After reaction finishes, in system, add a large amount of ether, the adularescent flocks is separated out; Collecting precipitation, washing, vacuum-drying then obtains having the white powder product of amido functional group, sees the compound (3) in the synthetic route.
1H-NMR(DMSO-d
6，δ
ppm)：1.91(quintet，4H)，2.27(t，4H)，2.57(t，4H)，3.06(q，4H)，3.96(t，4H)，7.32(s，2H)，7.79(t，2H)；ESI-TOF?619.26，[M+H]；FTIR(KBr，cm
-1)：3304，3082，2935，1637，1552，1488，1464，1351，1265，1215，1059，1039，941，846，821，754，586，490，436.
4) the white powder product 2.6g that step 3 is obtained is dissolved in 15mL DMSO 99.8MIN. and the 30mL methyl alcohol, slowly adds the 5mL methyl acrylate then; Reaction mixture at room temperature stirred 5 days; After reaction finishes, in system, add a large amount of zero(ppm) water, vigorous stirring, the adularescent solid is separated out; Filtration, washing, vacuum-drying get the white powder solid, promptly have the polymerization single polymerization monomer of four ester group functional groups, see the compound (4) in the synthetic route.
1H-NMR(CDCl
3，δ
ppm)：2.16(quintet，4H)，2.42(t，8H)，2.48(t，4H)，2.53(br，4H)，2.73(t，8H)，3.34(q，4H)，3.68(s，12H)，4.00(t，4H)，6.57(br，2H)，7.18(s，2H)；ESI-TOF?963.55，[M+H]；FTIR(KBr，cm
-1)：3298，2949，2831，2204，1736，1647，1517，1437，1377，1265，1213，1041，837，721，544.
5) with the polymerization single polymerization monomer (1.6g) and 1 of step 4 gained, 4-diacetylene-benzene (210mg) is dissolved in the 36mL trichloromethane, in 6mL Diisopropylamine and the 6mL triethylamine; Under anaerobic state, add 23.1mg tetrakis triphenylphosphine palladium and 3.8mg cuprous iodide; Reaction mixture stirred 5 days down at 50 ℃; Reaction adds a large amount of ether after finishing, and stirs, and filters, and uses a large amount of deionized water rinsings again; After the vacuum-drying, obtain having the polyhenylene acetylene support type fluorescent conjugated polymer of four ester group functional groups, see the polymkeric substance (5) in the synthetic route.
1H-NMR(CDCl
3，δ
ppm)：2.24(quintet，4H)，2.38(t，8H)，2.51(br，8H)，2.70(t，8H)，3.33(q，4H)，3.63(s，12H)，4.12(t，4H)，6.63(br，2H)，7.03(s，2H)，7.51(d，4H)；FTIR(KBr，cm
-1)：3298，2949，2831，2204，1736，1647，1518，1437，1377，1265，1213，1041，837，721，588，544.
6) the fluorescent conjugated polymer 83.2mg with step 5 gained is dissolved in the 100mL methyl alcohol, and the back that stirs adds the aqueous solution of 0.5g Pottasium Hydroxide; Reaction mixture refluxed after 5 days, is added excessive anhydrous diethyl ether, have yellow solid to separate out; Filter, collect this faint yellow solid, promptly obtain having the fluorescence conjugated polyelectrolyte of many carboxyl functional groups, see the polymkeric substance (6) in the synthetic route.
1H-NMR(CD
3OD，δ
ppm)：2.16(quintet，4H)，2.36(t，8H)，2.51(t，4H)，2.70(t，4H)，2.88(t，8H)，3.37(q，4H)，4.12(t，4H)，7.13(s，2H)，7.54(d，4H).FTIR(KBr，cm
-1)：3421，2945，2725，1631，1402，1215，1124，1009，833，704，633，619.
A kind of synthetic route of polycarboxyl fluorescent conjugated polyelectrolyte of the present invention (is example with k=1)
2 one kinds of polycarboxyl fluorescent conjugated polyelectrolytes of embodiment (is example with k=1) are used for the highly sensitive detection of cupric ion
1) with phosphate buffer soln (10mM, pH 7.4) polycarboxyl fluorescent conjugated polyelectrolyte being mixed with concentration is 5 * 10
-6The dilute solution of M;
2) the cupric ion standardized solution with different concns joins in the aforesaid polycarboxyl fluorescent conjugated polyelectrolyte dilute solution, measures its fluorescence emission spectrum, and according to the variation drawing standard curve of fluorescence intensity.In 0-3 μ M concentration range, the quenching of fluorescence degree of polycarboxyl fluorescent conjugated polyelectrolyte and copper ion concentration linear (referring to Fig. 1), and other most metals ions all do not have obvious interference (referring to Fig. 2).
3) cupric ion to be measured is diluted to 0～3 * 10
-6The solution of M joins in the described polycarboxyl fluorescent conjugated polyelectrolyte solution of step 1 then, measures its fluorescence emission spectrum, and confirms the content of cupric ion in the solution to be measured according to the variation of fluorescence intensity.
Claims (3)
1. polycarboxyl fluorescent conjugated polyelectrolyte, its general structure is:
Wherein: k be alkoxy substituted in-CH
2-CH
2-number, the value of k selects 0,0.5,1,1.5 or 2 for use; N is the number of repeat unit of polyelectrolyte, is the integer between 1～200.
2. the preparation method of a polycarboxyl fluorescent conjugated polyelectrolyte is characterized in that, realizes through following steps:
(1) 22.4g Pottasium Hydroxide is pulverized in the last 170mL of the being dissolved in DMSO 99.8MIN., under oxygen free condition, add the 8.8g Resorcinol rapidly, after stirring; Slowly drip 4-bromo-butyric acid ethyl ester 46mL, stirred 3 days under the reaction mixture room temperature, reaction end back adds 1L frozen water and stirring fast; The adularescent solid is separated out, and filters the back and uses a large amount of distilled water flushings, and vacuum-drying obtains 1; 4-two (4-ketobutyric acid ethyl ester) benzene is seen the compound (1) in the synthetic route;
1H-NMR (CDCl
3, δ
Ppm): 1.25 (t, 6H), 2.08 (quintet, 4H), 2.50 (t, 4H), 3.95 (t, 4H), 4.13 (q, 4H), 6.80 (s, 4H); ESI-TOF 361.3, [M+Na]; FTIR (KBr, cm
-1): 2980,1729,1510,1472,1420,1378,1358,1273,1226,1181,1117,1098,1061,1037,918,881,859,837,807,774,526,466,415,347;
(2) in the 250mL three-necked bottle, add 120mL ethanol, the 2mL vitriol oil, the 5mL deionized water adds 9.8g 1 successively after stirring; 4-two (4-ketobutyric acid ethyl ester) benzene, 3.1g Potassium Iodate and 8.0g iodine, reaction mixture stirred 3 days down at 60 ℃, and reaction finishes postcooling to room temperature; Have a large amount of solids to separate out, filter back water and ethanol and wash repeatedly, vacuum-drying obtains the pale pink product; Be 1,4-two iodo-2,5-two (4-ketobutyric acid ethyl ester) benzene is seen the compound (2) in the synthetic route;
1H-NMR (CDCl
3, δ
Ppm): 1.27 (t, 6H), 2.13 (quintet, 4H), 2.59 (t, 4H), 3.99 (t, 4H), 4.17 (q, 4H), 7.18 (s, 2H); ESI-TOF613.2, [M+Na]; FTIR (KBr, cm
-1): 2985,2944,1730,1491,1462,1421,1388,1373,1354,1342,1263,1224,1216,1203,1176,1095,1057,1027,956,941,870,771,619,440;
(3) with 9.44g 1,4-two iodo-2,5-two (4-ketobutyric acid ethyl ester) benzene joins in the 60mL trichloromethane; After stirring, add the mixed solution of 180mL methyl alcohol and quadrol, wherein the ratio of methyl alcohol and quadrol is 8: 10; Reaction mixture at room temperature stirred 5 days, after reaction finishes, in system, added a large amount of ether; The adularescent flocks is separated out, collecting precipitation, washing, vacuum-drying then; Obtain having the white powder product of amido functional group, see the compound (3) in the synthetic route;
1H-NMR (DMSO-d6, δ
Ppm): 1.91 (quintet, 4H), 2.27 (t, 4H), 2.57 (t, 4H), 3.06 (q, 4H), 3.96 (t, 4H), 7.32 (s, 2H), 7.79 (t, 2H); ESI-TOF 619.26, [M+H]; FTIR (KBr, cm
-1): 3304,3082,2935,1637,1552,1488,1464,1351,1265,1215,1059,1039,941,846,821,754,586,490,436;
(4) the white powder product 2.6g that step (3) is obtained is dissolved in 15mL DMSO 99.8MIN. and the 30mL methyl alcohol, slowly adds the 5mL methyl acrylate then, and reaction mixture at room temperature stirred 5 days; After reaction finishes, in system, add a large amount of zero(ppm) water, vigorous stirring; The adularescent solid is separated out, and filtration, washing, vacuum-drying get the white powder solid; The polymerization single polymerization monomer that promptly has four ester group functional groups is seen the compound (4) in the synthetic route;
1H-NMR (CDCl
3, δ
Ppm): 2.16 (quintet, 4H), 2.42 (t, 8H), 2.48 (t, 4H), 2.53 (br, 4H), 2.73 (t, 8H), 3.34 (q, 4H), 3.68 (s, 12H), 4.00 (t, 4H), 6.57 (br, 2H), 7.18 (s, 2H); ESI-TOF 963.55, [M+H]; FTIR (KBr, cm
-1): 3298,2949,2831,2204,1736,1647,1517,1437,1377,1265,1213,1041,837,721,544;
(5) with the polymerization single polymerization monomer 1.6g and 1 of step (4) gained, 4-diacetylene-benzene 210mg is dissolved in the 36mL trichloromethane, in 6mL Diisopropylamine and the 6mL triethylamine; Under anaerobic state, add 23.1mg tetrakis triphenylphosphine palladium and 3.8mg cuprous iodide, reaction mixture stirred 5 days down at 50 ℃, after reaction finishes; Add a large amount of ether, stir, filter; Use a large amount of deionized water rinsings again; After the vacuum-drying, obtain having the polyhenylene acetylene support type fluorescent conjugated polymer of four ester group functional groups, see the polymkeric substance (5) in the synthetic route;
1H-NMR (CDCl
3, δ
Ppm): 2.24 (quintet, 4H), 2.38 (t, 8H), 2.51 (br, 8H), 2.70 (t, 8H), 3.33 (q, 4H), 3.63 (s, 12H), 4.12 (t, 4H), 6.63 (br, 2H), 7.03 (s, 2H), 7.51 (d, 4H); FTIR (KBr, cm
-1): 3298,2949,2831,2204,1736,1647,1518,1437,1377,1265,1213,1041,837,721,588,544;
(6) the fluorescent conjugated polymer 83.2mg with step (5) gained is dissolved in the 100mL methyl alcohol; Add the aqueous solution of 0.5g Pottasium Hydroxide after stirring, reaction mixture refluxed after 5 days, is added excessive anhydrous diethyl ether; There is yellow solid to separate out; Filter, collect this faint yellow solid, promptly obtain having the fluorescence conjugated polyelectrolyte of many carboxyl functional groups, see the polymkeric substance (6) in the synthetic route;
1H-NMR (CD
3OD, δ
Ppm): 2.16 (quintet, 4H), 2.36 (t, 8H), 2.51 (t, 4H), 2.70 (t, 4H), 2.88 (t, 8H), 3.37 (q, 4H), 4.12 (t, 4H), 7.13 (s, 2H), 7.54 (d, 4H); FTIR (KBr, cm
-1): 3421,2945,2725,1631,1402,1215,1124,1009,833,704,633,619;
Synthetic route:
3. the application of polycarboxyl fluorescent conjugated polyelectrolyte according to claim 1 in cupric ion detects.
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