Membrane selective for metal ions

• US 5,238,548 A
• Filed: 05/18/1992
• Issued: 08/24/1993
• Est. Priority Date: 05/17/1991
• Status: Expired due to Fees

• Current Assignee: Priva AGRO Holding BV
• Original Assignee: Priva AGRO Holding BV
• Inventors: Honig, Gerardus W. N., Haak, Jan R., van der Wal, Peter D., Verkerk, Udo H., Holterman, Hermanus A. J., Reinhoudt, David N.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): BELL, BRUCE F
• Application Number:
  US07/885,960
• Time in Patent Office: 463 Days
• Field of Search: 204/416, 204/418, 204/296, 568/18, 568/20, 568/74, 568/77, 568/589, 568/36, 568/37, 568/39, 568/44, 568/45, 568/50, 568/56, 568/57
• US Class Current: 204/418
• CPC Class Codes: G01N 27/3335 the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS

Abstract

An ionophore according to the general formula I wherein the substituents are chosen such that the ionophore is either also polymerized in the matrix of a membrane selective for metal ions or interwoven therewith. Thus obtained is a membrane having a long useful life for use in diverse sensors such as ISFET, ion-selective electrode, and the like.

Claims

1. Membrane selective for metal ions comprising an ionophore covalently bonded to the membrane with the general formula:

##STR6## in which;

X represents O, S, or SO;

Y represents S or O;

R₁, R₂, R₃, and R₄ represent (C₁ -C₅)alkyl, polyether, an intramolecular or intermolecular (C₁ -C₁ O)alkyl bridge or polyether bridge;

at least A, B, C, or D is a group with the formula;

space="preserve" listing-type="equation">--(CEF).sub.m --G and the other A, B, C, and D are hydrogen, (C.sub.1 -C.sub.5)alkyl, (C.sub.5 -C.sub.7)aryl, (C.sub.1 -C.sub.5)alkyl(C.sub.5 -C.sub.7)aryl, halogen or (C.sub.5 -C.sub.7)aryl(C.sub.1 -C.sub.5)alkyl,

wherein;

m≧

0;

E and F are equal or different and represent hydrogen, (C₁ -C₅)alkyl, or halogen; and

G is a group for covalent bonding to the membrane;

or A, B, C, and D form a saturated (C₅ -C₇)cycloalkyl group, which group is substituted by the group --(CEF)_m --G, wherein m ≧

0;

or A, B, C, and D form an aromatic (C₅ -C₇)aryl group which is substituted by the group --(CEF)_m --G, wherein m≧

0;

wherein;

E and F are equal or different and represent hydrogen, (C₁ -C₅)alkyl, or halogen; and

G is a group for covalent bonding to a membrane.

2. Membrane as claimed in claim 1, characterized in that the group G covalently bonded to the membrane is derived from:

hydroxyl, halogenide, amine, amide, ketone, aldehyde, enamine, epoxide, carboxylic acid ester, acylhalogen, acid anhydride, allylether, acryl, methacryl, alkenyl, alkynyl, sulphide, sulphonic acid, sulphonic acid ester, silane, or siloxane.

6. Membrane as claimed in claim 1, characterized in that the membrane polymer is prepared by photopolymerization.

7. Sensor having incorporated therein a membrane as claimed in claim 1.

3. Membrane selective for metal ions, comprising a polymer membrane and an ionophore included in the polymer membrane with the general formula I, wherein:

X represents O, S, or SO;

Y represents S or O;

R₁, R₂, R₃, and R₄ represent (C₁ -C₅)alkyl, polyether, an intramolecular or intermolecular (C₁ -C₁ O)alkyl bridge or polyether bridge;

at least A, B, C, or D is a group with the formula;

space="preserve" listing-type="equation">--(CEF).sub.m --G and the other A, B, C, and D are hydrogen, (C.sub.1 -C.sub.5)alkyl, (C.sub.5 -C.sub.7)aryl, (C.sub.1 -C.sub.5)alkyl(C.sub.5 -C.sub.7)aryl;

, halogenide or (C.sub.5 -C.sub.7)aryl(C.sub.1 -C.sub.5)alkyl,

wherein;

m≧

0;

E and F are equal or different and represent hydrogen, (C₁ -C₅)alkyl, or halogen; and

G is a group covalently bonded to an oligomer Q;

A, B, C, and D form a saturated (C₅ -C₇)cycloalkyl group which is substituted by the combination --(CEF)_m --G--Q, wherein m≧

0;

or A, B, C, and D form an aromatic (C₅ -C₇)aryl group which is substituted by the combination --(CEF)_m --G--Q, wherein m≧

0;

wherein;

E and F are equal or different and represent hydrogen, (C₁ -C₅)alkyl, or halogen; and

G is a group covalently bonded to an oligomer Q.

5. Membrane as claimed in claim 3, characterized in that the oligomer Q is an oligomer of a suitable molecular weight related to the membrane polymer.

8. Membrane as claimed in claim 3, characterized in that the membrane polymer is prepared by photopolymerization.

9. Sensor having incorporated therein a membrane as claimed in claim 3.

4. Membrane as claimed in claim 4, characterized in that G is a group derived from hydroxyl, halogenide, amine, amide, ketone, aldehyde, enamine, epoxide, carboxylic acid ester, acylhalogen, acid anhydride, allylether, acryl, methacryl, alkenyl, alkynyl, sulphide, sulphonic acid, or sulphonic acid ester.