# US 5,705,620 A · Sensors for detecting calcium with calix ›4! arene compounds

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- Number: US 5,705,620 A
- Document ID: US5705620A
- Status: Granted
- Kind: A
- Application number: 08/571,840
- Filed: 1996-04-08
- Granted: 1998-01-06
- Earliest claimed: 1993-06-23
- Assignees: Radiometer Medical A/S
- Inventors: Allan Milton Byrnard; Rocco Ungaro; Andrea Pochini
- Web page: https://patentgrep.com/patent/US5705620A

## CPC

- C07C 245/10: with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems
- G01N 33/84: involving inorganic compounds or pH
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)

## Abstract

A calix›4!arene compound, application of the compound as an active component in a calcium sensitive sensor, and a calcium sensitive sensor containing the compound. The sensor is not very sensitive to sodium and potassium ions.

## Claims

### Claim 1

A sensor for detecting the presence of calcium in a sample, said sensor containing as an active ingredient a compound of the following formula: ##STR10## wherein X is selected from the group consisting of --OH, --OR.sup.1, --NR.sup.2.sub.2, and morpholino,
wherein R.sup.1 is straight chain or branched alkyl of 1-22 C-atoms and R.sup.2 is straight chain or branched alkyl of 1-12 C-atoms, and Z is selected from the group consisting of --N.dbd.N--Ar, --CH.dbd.CH--Ar, --CH.dbd.CZ.sup.1 Z.sup.2 and ##STR11## wherein either of Z.sup.1 and Z.sup.2 are selected from the group consisting of --H, --NO.sub.2, --CN, --CF.sub.3, --SOR.sup.3, --SO.sub.2 R.sup.3, --SO.sub.2 OR.sup.3, --SO.sub.2 NHR.sup.3, --SO.sub.3 H, --COOR.sup.3, --COONR.sup.3.sub.2, --COONHR.sup.3, --COOH, --CHO, --COR.sup.3, --F, --Cl and --Br, R.sup.3 is straight chain or branched alkyl of 1-4 C-atoms and both of Z.sup.1 and Z.sup.2 are not --H;
either of Y.sup.1 and Y.sup.2 are selected from .dbd.O, .dbd.N--CN and .dbd.C(CN).sub.2 ; and
Ar is ##STR12## and R.sup.4, R.sup.5, . . . R.sup.22 are each selected from the group consisting of --H, --NO.sub.2, --CN, --CF.sub.3, --F, --Cl , --Br, --SOR.sup.24, --SO.sub.2 R.sup.24, --SO.sub.2 CH.sub.2 CH.sub.2 OR.sup.25, --SO.sub.2 OR.sup.24, --SO.sub.2 NHR.sup.24, --SO.sub.3 H, --COOR.sup.24, --CONR.sup.24.sub.2, --CONHR.sup.24, --COOH, --CHO and --COR.sup.24, wherein R.sup.24 is straight chain or branched alkyl of 1-4 C-atoms, and R.sup.25 is --H, --SO.sub.3 H, --SO.sub.3 Li, --SO.sub.3 Na or --SO.sub.3 K, with the proviso that when Z is --CH.dbd.CHAr and Ar is phenyl, at least one of the substituents R.sup.4, R.sup.5, . . . R.sup.8 of the phenyl group must be different from H, and when Z is --CH.dbd.CHAr and Ar is 1-naphthyl, at least one of the substituents R.sup.9, R.sup.10, . . . R.sup.15 of the 1-naphthyl group must be different from H, and when Z is --CH.dbd.CHAr and Ar is 2-naphthyl, at least one of the substituents R.sup.16,R.sup.17, . . . R.sup.22 of the 2-naphthyl group must be different from H.

### Claim 2 (depends on 1)

The sensor according to claim 1, wherein the compound is immobilized in a polymeric membrane.

### Claim 3 (depends on 1)

The sensor according to claim 1 wherein the polymeric membrane is hydrophilic.

### Claim 4 (depends on 2)

The sensor according to claim 2, wherein the polymeric membrane is selected from the group consisting of celluloseacetate, cellophane, cuprophane, polyvinylacetate, polyhydroxyethyimethacrylate and another hydrogel.

### Claim 5 (depends on 1)

The sensor according to claim 1, wherein the sensor has a calcium permeable membrane constituting an outer surface of the sensor and the compound is located adjacent to the membrane.

### Claim 6

A membrane for a sensor for detecting the presence of calcium in a sample, said membrane containing as an active ingredient a compound immobilized in said membrane, said compound having the formula: ##STR13## wherein X is selected from the group consisting of --OH, --OR.sup.1, NR.sup.2.sub.2, and morpholino,
wherein R.sup.1 is straight chain or branched alkyl of 1-22 C-atoms and R.sup.2 is straight chain or branched alkyl of 1-12 C-atoms, and Z is selected from the group consisting of --N.dbd.N--Ar, --CH.dbd.CH--Ar, --CH.dbd.CZ.sup.1 Z.sup.2 and ##STR14## wherein either of Z.sup.1 and Z.sup.2 are selected from the group consisting of --H, --NO.sub.2, --CN, CF.sub.3, --SOR.sup.3, --SO.sub.2 R.sup.3, --SO.sub.2 OR.sup.3, --SO.sub.2 NR.sup.3, --SO.sub.3 H, --COOR.sup.3, --COONR.sup.3.sub.2, --COONHR.sup.3, --COOH, --CHO, --COR.sup.3, --F, --Cl and --Br, R.sup.3 is straight chain or branched alkyl of 1-4 C-atoms, and both of Z.sup.1 and Z.sup.2 are not --H;
either of Y.sup.1 and Y.sup.2 are selected from the group consisting of .dbd.O, .dbd.N--CN and .dbd.C(CN).sub.2 ; and
Ar is ##STR15## and R.sup.4,R.sup.5, . . . R.sup.22 are each selected from the group consisting of --H, --NO.sub.2, --CN, CF.sub.3, --F, --Cl, --Br, --SOR.sup.24, --S02.sup.R.sup.24, --SO.sub.2 CH.sub.2 CH.sub.2 OR.sup.25, --SO.sub.2 OR.sup.24, --SO.sub.2 NHR.sup.24, --SO.sub.3 H, --COOR.sup.24, --CONR.sup.24.sub.2, --CONHR.sup.24, --COOH, --CHO and --COR.sup.24, wherein R.sup.24 is straight chain or branched alkyl of 1-4 C-atoms, and R.sup.25 is selected from the group consisting of --H, SO.sub.3 H, --SO.sub.3 Li, --SO.sub.3 Na and --SO.sub.3 K,
with the proviso that when Z is --CH.dbd.CHAr and Ar is phenyl, at least one of the substituents R.sup.4,R.sup.5, . . . R.sup.8 of the phenyl group must be different from H, and when Z is --CH.dbd.CHAr and Ar is 1-naphthyl, at least one of the substituents R.sup.9,R.sup.10, . . . R.sup.15 of the 1-naphthyl group must be different from H, and when Z is --CH.dbd.CHAr and Ar is 2-naphthyl, at least one of the substituents R.sup.16,R.sup.17, . . . R.sup.22 of the 2-naphthyl group must be different from H.

### Claim 7 (depends on 6)

The membrane according to claim 6, wherein the membrane comprises a polymeric material.

### Claim 8 (depends on 7)

The membrane of claim 7 wherein the polymeric material is selected from the group consisting of celluloseacetate, cellophane, cuprophane, polyvinylacetate, polyhydroxyethylmethacrylate or another hydrogel.