专利摘要:
1. METHOD FOR DETERMINING THE CONCENTRATION OF ALKALI, ALGUM-GROUND METAL IONS AND AMMONIUM IN SOLOGICAL LIQUIDS by; spectroscopic study of the sample, characterized in that, in order to increase the sensitivity of the method, the test sample is reacted with a complex ligaid selected from the group: crown ethers, cryptands or sweats, as well as their derivatives containing chemical bridges or depi with oligo or polyethylene glycol groups, cyclic polypeptide containing tetrahydrofur, ester-sugar macrolide, valine and qing or nonacty, as well as the chromophore, are selected from the group of substances with full-line, quinone , aero-indopolyol, stilbene or cyanine structure, or their lithium, sodium, potassium, ammonium, calcium or magnesium salts, and the chromophore and ligand are taken in a ratio of 1: 1 to 100 or more parts of the sample. CO 2. The method according to claim 1, wherein the test sample is interacted with a complex ligand applied to an absorbent carrier.
公开号:SU1135436A3
申请号:SU792829004
申请日:1979-10-01
公开日:1985-01-15
发明作者:Фегтле Фридрих;Петер Дикс Иоханнес;Яворек Дитер
申请人:Берингер Маннхайм Гмбх (Фирма);
IPC主号:
专利说明:

The invention relates to clinical biochemistry, in particular, to a method for determining the concentration of alkali, alkaline earth metal and ammonium ions in biological fluids. A method is known for determining the concentration of alkali, alkaline earth metal ions and ammonium ions in biological fluids by spectroscopic study of a CO sample. However, the known method is distinguished by its duration, hard work, low sensitivity, and also requires special TV equipment. The aim of the invention is to increase the sensitivity of the method. The goal is achieved by the method that determines the concentration of alkaline, alkaline earth metal and ammonium ions in biological fluids by spectroscopically studying the sample and interacting with the complex ligand selected from the group: crown ethers, cryptands or sweets, as well as their derivatives containing chemical bridges or chains with single or polyethylene glycol groups, cycles, 4ecKiiM peptide containing tetrahydrofuran, ester-bonded macrolide, valinomycin il and nonaktyn, as well as a chromophore selected from the group of veschevTV, possessing polyenrva, x nona azo-indophenol., stilieno or cyanine structure, or their lithium, sodium, potassium ammonium, calcium or magnesium salts, and ratio of 1: 1 to 100 or more parts of the sample. In addition, the interaction of the test sample with the complex ligand deposited on the absorbent carrier is carried out. The method is carried out as follows. As selective complex ligands, cyclically or acyclic high molecular weight compounds with an average molecular weight are taken, which, in relation to the ion to be detected, act as complexing agents or host molecules in their presence, which are necessary for complex formation or adduct formation. in So, as co-ligands or host molecules, compounds like oligoesters, polyethers, oligoesters, polyesters, oligoamides and polyamides are suitable. For example, crown ethers, cryptands, sweats. or their derivatives, as well as cyclic peptides or peptides, which, in the presence of a detectable ion or a polar substance, adopt a secondary, tertiary or quaternary structure necessary for complexation. In addition, tetrahydrofuran containing ester-linked macrolides and similar compounds are used that can regulate ion transport in biological systems, as well as pure hydrocarbon scaffolds as host molecules (lipophilic voids), cyclodextrins, cyclophanes. Combinations of these compounds are also possible. Derivatives of complex ligands or host molecules may have bridges or chains, which may contain oligo- or polyethylene glycol groups or other heteroatom-containing groups. Covalently, heteropolarly or hydrophobically linked, the chromophore is a dye, a fluorescent dye or a chromogen, the absorption spectrum of which changes due to such interaction as charge displacement and disruption of mersmeria, mainly or in an excited state due to guest particles (polar ions or lipophilic guest molecules). As the dyes used for example, the clock polyene, merihinoidnogo, quinone, azo (as metiloran or methyl red) pirroloBoroj merocyanine, indigo, indofenolovogo, stilbene, azomethine, anthraquinone, naftohiionovogo, cyanine, ftaleinovogo, polymethine, alizarin type. The content in the complex-inclusion or molecular molecule and the chromophore may be an acidic dye or its salt, for example, a lithium, sodium, potassium, ammonium, calcium, alkylammonium or magnesium salt. In this case, the dye preferably contains a carboxylate, sul (lonate, phenol or thiophenol moiety. The detected ions can be cations and anions, primarily ions of alkali metals (lithium, sodium, potassium), ammonium alkaline earth metals (magnesium and calcium) or other metallic ions, e.g. heavy metal ions (iron, zinc, copper, cobalt, nickel, molybdenum and chromium). First of all, organic cations, e.g. oligoalkylammonium ion, phosphonium, guanidine, quinoline, are determined. These anions should be called chloride, bromide, iodide, sulfate, nitrite, nitrate, phosphate, diphosphate, triphosphate, hydrophosphate, bicarbonate ions. Neutral guest are used as neutral polar compounds. Particles, for example, urea, thiourea, guanine, guanidine, uric acid, choline, creatinine, amino acid, sugar, as typical lypophilic guest molecules are steroids (cholesterol and lipids (triglycerides, lecithins). The concentration of cations and anions, as well as the concentration neutral guest particles can be defined as Twain and quantified by the proposed method due to the effects .rastsvetki (photometrically).
moreover, Me can mean, for example, an alkali metal, alkaline earth metal, ammonium or a heavy metal ion, and the basis is the mesomerism system according to formula (I), the weight and energy content of which. in the ground and excited states, as a rule, they are different: Selectivity can be attributed. both to a separate gu, a specific ion or a substance to be detected, and to groups of ions or to a group of substances. For example, chromophores such as dyes with several identical or different complex ligands or host molecules, for example, simple crown densifiers with different void sizes, are applicable, for example, with 1,, t and h preferably meaning 0-4. Further, on the complex ligand or molecular molecule, for example, the croien-ether skeleton, one or more identical or different type of dyes can be placed. The color change can be based, for example, on the following mechanism according to the formula (s) t f - Me -S "... M-f
moreover, in denotes the numbers 0-4.
Chemistry npocTbix covers croenta esters, cryptands and sweeps covered
(ffV multiple binding methods more
Large and medium rings, as well as bi tricyclic systems with (SND) -, aryl - and heteroatom-containing structural elements. Crown ethers (crown ethers), cryptands, and potanda molecules have the ability to form stoichiometric crystalline complexes, as well as selective or specific complexing of, for example, alkali, alkaline earth, ammonium and heavy metals, as well as neutral molecules. A series of aero-, di- and triphenyl methane dyes was obtained from a structural element according to formula (V) (P, -hydrogen, 11 t-3) and formula (/ v On these aero-dyes, depending on the size of the ring, Selective, ion-specific shift of the apparent absorption maximum in a certain direction, which is often associated with a change in molar extinction. Most spectral changes (if,) cause, as optimally, r suitable for a particular ether ring from the corresponding group of the periodic system. relate radius cation. ("V ./- P (The invention also covers the use of complex ligands in the form of a cyclic peptide or peptide, which accepts the necessary secondary, tertiary or quaternary structure in the presence of an ion or polar substance. So, ionic forms of natural substances can be used (nalinomycin, nonaktin, gramaschinschiny and pschobnye peptidal) for the intended according to the invention of ion-selective color reactions or color test. The valinomycin includes the dye salt, for example 2, 4-dinitrophenylhydroazonium chloride, sodium picrate or the like. The valynocymin-dye complex has a different color or different absorption maximum compared with the free dye. In the second stage, saline solution is added to the valinomycin-dye complex, in which the concentration is determined, and potassium-specific valynomycin complexs the potassium ions present in the solution, by which the dye is displaced from the vallinomycin void and the solution again acquires a different color or different absorption spectrum. Thus, potassium valinomycin specificity can be used for the stain test. As a simple dye system that is suitable for incorporation or attachment to valinomycin and subsequent displacement with potassium ions, hydrazine salts with diverse bound mesomeric systems, for example, azo - (}) functions, can be used. Sterically low-demand cations of dyes are used. which form a weak, but fairly stable complex with valinomycin, which can then be quantitatively destroyed using potassium ions, also in insignificant concentrations. Similar experiments with crown ethers, for example crown ether (18) -crone-6, which have a comparable structure (valinomycin and nonactin) allow to establish distinct effects of coloring or changes in longer wavelength absorption of the dye associated with crown ether and in a free state. The use of both the katnon salts of dyes (2,4-dinitrophensh1 hydrazonium ions) and anionic chromophores (picrate ions) makes it possible to choose in accordance with the components used. Example 1. Photometric determination of potassium using an ion-reactive dye that contains a chromophore is covalently linked through a mesome system. The non-reactive dye of formula (IV), where step 1, is dissolved in chloroform and shaken with a solution containing potassium ions. The dye complexed with potassium enters the aqueous phase and can be quantitatively determined at 60 on a photometer, depending on the activity of the potassium ions present. The dye Cz-nitro-1, 3-thiazol-2-azo- (3-) 12-OXY-1,4,7,10-tetraox dodechschl / A-hydroxybenzene is obtained by introducing into the interaction 2-amino-5-nitrothiazole in 85% phosphoric acid with sodium nitrite and follow: the addition of benzo- (15) -crone-5. The suspension is intensely red in color mixed with water and extracted with chloroform. After drying over sodium sulfate and removing the solution, the solids in vacuo are separated on silica gel using column chromatography. Using chloroform, a dye with a closed cycle {5-nitro-1,3-thiazol-2-azo- / 1, 4,7,10,13-pentoxaca / 13 / 3,4 / -benzophane / is obtained first. By adding 5% ethanol to the eluent, an open-chain catalyst of formula (iv) is obtained, where "1. Example 2. To study the properties of ion-selective dye in Example 1, the dye solution is applied by dough to the dye solution by dropping it on the filter sheets and these widths. The strips of paper treated in this way are colored in dark red with the addition of test solutions that contain potassium ions. Along with this qualitative method, colored bands can be quantified in a reflective photometer. Example 3. Selective photometric determination of potassium using a ligand that contains covalently (linked chromophore (compound of the formula (W), where n is 1 and, for 3 h, 2,4-dinitrotoluene is reacted cN- (p-formylphenyl) -a (15) crown-5, with a few drops of piperidine at. The frozen melt is dissolved in a small amount of ethyl acetate, filtered and concentrated in vacuo. Purified by column chromatography on silica gel using an acetic mixture of 5-10% ethanol; Upon concentration, the eluent crystallizes 2, 4-dinitro-4- (4,7,10,13-tetraox-1-azo-cyclopentad-1-yl) stilbene. 7.5 ml of the dye is dissolved in 250 ml of methanol. In addition, 36 O, 1 M is ready solutions of calcium chloride, sodium chloride, potassium chloride, lithium chloride and magnesium chloride in O, 1 M triethanolamine hydrochloride / NaOH buffer with pH 7.0. In addition, a number of solutions are prepared with 0.0010, 1 M concentration of potassium chloride, 0.1 M triethanol1 "hydrochloride / NaOH buffer with pH 7.0. 3 ml of the dye solution are mixed with 0.5 MP of the corresponding test salt solution and at 366 nm the absorption properties of the D photometer are determined. This dye shows a different spectrum with respect to potassium than in the presence of lithium, sodium, calcium, barium and magnesium. Ion concentration. Kali is directly proportional to extinction. Example 4. Photometric determination of calcium and lithium using a heterocyclic crown ether of formula (U). 1, A-Benzoquinone- (4,7,10,13-tetraox-1-azocyclo-pentad-1-yl) phenylimine is obtained by the oxidative combination of M- (4-amino-phenyl) ase (15) iKpoHa-5 with phenol . Silver nitrate is then reacted with sodium chloride and a small amount of starch, sodium carbonate and phenol are added, and a solution of N- (4-aminophenyl) -asa (15) -crone-5 in concentrated hydrochloric acid is added dropwise. After the reaction, it is stirred with ethyl acetate, dried over sodium sulfate and evaporated in vacuo. The residue is crystallized from tetrahydrofuran with ether. ax 538nm Po E, 4.77. The dye is dissolved in chloroform (EJ-JSHM) and mixed with the same volumetric parts of water-saline solution. With lithium and calcium, the color change is measured at 578 nm, the concentration of which is directly proportional to the ions to be detected. Photometry is performed at D 577 nm, 4.41. The use of chromophore cryptandic systems provides, in addition to higher stability of the complexes, better selectivity in aquatic environments. Along with qualitative and quantitative photometric proof of alkali and alkaline earth metal ions, as well as ions
9113543610
ammonium with yomoshchiyu of chromophores; Based on thermography
Ev with different void values can be made visible by taking account of solutions, such as blood or physiological colors, and serum and other fluids, organic concentrations of salts by
niema, they are identifiable by spraying tissue areas
also on media materials. Nearly their prints using ibnoeto, it is possible to use them as selective dyes or fluorescently reagent for ionic chroming agents. Thanks to this
Matherapy using silicone imprints creates the ability to distinguish molasses used in medical logic from healthy tissue.
权利要求:
Claims (2)
[1]
1. METHOD FOR DETERMINING THE CONCENTRATION OF ALKALINE IONS, ALKALINE EARTH METALS AND AMMONIUM IN NULOGIC LIQUIDS by spectroscopic examination of a sample, characterized in that, in order to increase the sensitivity of the method, the sample under study interacts with a complex ligand, crytand and also their derivatives containing chemical bridges or chains with oligo- or polyethylene glycol groups, a cyclic peptide containing tetrahydrofuray, ester-linked poppy an olide, valinomycin or nonactin, as well as a chromophore selected from the group of substances having a polyene, quinone, aero-indophenol, stilbene or cyanine structure, or their lithium, sodium, potassium, ammonium, calcium or magnesium salts, and the chromophore and ligand are taken into 1: 1 ratio per 100 or more parts of the test sample.
[2]
2. The method according to π.I, characterized in that it interacts the test sample with a complex ligand deposited on an absorbent carrier.
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同族专利:
公开号 | 公开日
EP0010615B1|1984-07-25|
AU515023B2|1981-03-12|
EP0010615A1|1980-05-14|
DE2967135D1|1984-08-30|
AU5123379A|1980-04-17|
US4367072A|1983-01-04|
JPS5548643A|1980-04-07|
ZA794814B|1980-10-29|
CA1142841A|1983-03-15|
DE2842862A1|1980-04-10|
JPH0240985B2|1990-09-14|
AT8713T|1984-08-15|
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法律状态:
优先权:
申请号 | 申请日 | 专利标题
DE19782842862|DE2842862A1|1978-10-02|1978-10-02|METHOD FOR DETERMINING ION, POLAR AND / OR LIPOPHILE SUBSTANCES IN LIQUIDS|
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