US2014127820A1PendingUtilityA1

Analyte detection using near-infrared fluorophores

49
Assignee: STRONGIN ROBERT MICHAELPriority: Jun 29, 2011Filed: Jun 29, 2012Published: May 8, 2014
Est. expiryJun 29, 2031(~5 yrs left)· nominal 20-yr term from priority
G01N 33/6815C09K 11/06C07D 405/14C09K 2211/1088G01N 33/52C09K 2211/1007C09K 2211/1029G01N 33/582Y10T436/143333C09K 9/02G01N 2800/28C09B 11/24C07D 493/10
49
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Claims

Abstract

Embodiments of compounds for selectively detecting an analyte are disclosed, along with methods and kits for detecting analytes with the compounds. The compounds are bridged viologen conjugates including at least one fluorophore according to the general structure At least one of R 1 /R 2 , R 2 /R 3 , R 3 /R 4 , R 5 /R 6 , R 6 /R 7 , and/or R 7 /R 8 together form a substituted or unsubstituted cycloalkyl or aryl.

Claims

exact text as granted — not AI-modified
1 . A compound according to Formula I, Formula II, or Formula III comprising a bridged viologen backbone and substituents R A  and R B   
       
         
           
           
               
               
           
         
       
       where X −  is any counteranion, R A  and R B  independently are substituted or unsubstituted aliphatic, or substituted or unsubstituted aryl or heteroaryl comprising one or more substituted or unsubstituted aromatic rings and/or heteroaromatic rings, and at least one of R A  and R B  is a fluorophore having a structure according to general formula (i) 
       
         
           
           
               
               
           
         
       
       where each bond depicted as “ ” is a single or double bond as needed to satisfy valence requirements;
 X 1  is O, S, Se, Si(CH 3 ) 2 , Ge(CH 3 ) 2 , Sn(CH 3 ) 2 , CH 2 , C(CH 3 ) 2 , or NH; 
 R 1 , R 2 , R 4  independently are hydrogen, hydroxyl, oxygen, thiol, lower alkyl, carboxyalkyl, amino, substituted amino, alkoxy, halogen, or —NHR c  where R c  is 
 
       
         
           
           
               
               
           
         
         R 5 , R 7 , and R 8  independently are hydrogen, hydroxyl, thiol, lower alkyl, carboxyalkyl, amino, substituted amino, alkoxy, or halogen; 
         R 3  and R 6  independently are hydrogen, hydroxyl, halogen, oxygen, sulfur, thiol, amino, alkyl amino, imino, iminium, alkyl imino, alkyl iminium, cycloalkyl imino or —NHR c ; 
         at least one of R 1  and R 2 , R 2  and R 3 , R 3  and R 4 , R 5  and R 6 , R 6  and R 7 , and/or R 7  and R 8  together form a substituted or unsubstituted cycloalkyl or aryl; 
         R 9 -R 12  independently are hydrogen, alkyl, acyl, carboxyl, nitro, amino, alkyl amino, or —SO 3 H; 
         R 13  is hydrogen, hydroxyl, lower alkyl, lower alkoxy, —SO 3 H or —COOR 14  where R 14  is hydrogen or lower alkyl and the bond depicted as “ ” in ring B is a double bond, or R 13  is one or more atoms forming a ring system with rings B and D and the bond depicted as “ ” in ring B is a single bond; and 
         at least one of R 1 -R 13  is a linker covalently binding the fluorophore to the bridged viologen backbone, 
         wherein if R 3  and R 4  together form a substituted or unsubstituted cycloalkyl or aryl, then at least one of R 1  and R 8  is other than hydrogen, or R 13  is not —COOR 14 , or at least one additional substituted or unsubstituted cycloalkyl or aryl is formed by R 1  and R 2 , R 2  and R 3 , R 5  and R 6 , R 6  and R 7 , and/or R 7  and R 8 . 
       
     
     
         2 . The compound of  claim 1  where at least one of R A  and R B  is a fluorophore having a structure according to general formula (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), or (xi) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       where R 15 -R 22  independently are hydrogen, halogen, hydroxyl, oxygen, thiol, amino, alkyl amino, alkoxy, sulfur, imino, iminium, alkyl imino, alkyl iminium, or —NHR c  where R c  is 
       
         
           
           
               
               
           
         
       
       and
 at least one of R 1 -R 22  is a linker covalently binding the fluorophore to the viologen backbone, 
 wherein if the fluorophore has a structure according to general formula (iii) then at least one of R 1  and R 8  is other than hydrogen or R 13  is not —COOR 14 . 
 
     
     
         3 . The compound of  claim 1  where R 13  is the linker and has the formula —COO—. 
     
     
         4 . The compound of  claim 1  where both R A  and R B  are fluorophores, each fluorophore independently having a structure selected according to general formula (i). 
     
     
         5 . (canceled) 
     
     
         6 . The compound of  claim 1  where one of R A  and R B  is a fluorophore according to general formula (i), and the other of R A  and R B  is a lower alkyl nitrile, lower alkyl substituted phenyl, alkenyl, alkynyl, substituted coumarin, acetal, or carboxylate group. 
     
     
         7 . The compound of  claim 6  where the other of R A  and R B  is 
       
         
           
           
               
               
           
         
       
     
     
         8 . The compound of  claim 1  where X 1  is oxygen. 
     
     
         9 . The compound of  claim 1  where R 13  is —COO— and forms a lactone ring, and at least one of R 1 -R 12  is the linker. 
     
     
         10 . The compound of  claim 2  where R 13  is —COO— and forms a lactone ring, and at least one of R 1 -R 12  or R 15 -R 22  is the linker. 
     
     
         11 - 15 . (canceled) 
     
     
         16 . The compound of  claim 2  where the fluorophore has a structure according to:
 (a) general formula (iii), (iv), (ix), or (x) where X 1  is oxygen and R 18  is halogen, hydroxyl, thiol, amino, alkyl amino, or alkoxy; 
 (b) general formula (iii) where X 1  is oxygen and R 6  and R 16  are —NHR c ; 
 (c) general formula (iv) where X 1  is oxygen and R 16  and R 21  are NHR c ; 
 (d) general formula (iv) where X 1  is oxygen and R 19  is hydroxyl, thiol, oxygen, imino, iminium, alkyl imino, alkyl iminium, amino, or alkyl amino; 
 (e) general formula (iv) where X 1  is oxygen, R 18  is halogen, hydroxyl, thiol, amino, alkyl amino, or alkoxy, and R 19  is hydroxyl, thiol, oxygen, imino, iminium, alkyl imino, alkyl iminium, amino, or alkyl amino; or 
 (f) general formula (vi) where R 17  is halogen, hydroxyl, thiol, amino, alkyl amino, or —NHR c , and R 20  is oxygen, sulfur, imino, iminium, alkyl iminium, or —NHR c . 
 
     
     
         17 - 20 . (canceled) 
     
     
         21 . A method for detecting an analyte, comprising:
 forming a solution by combining a sample comprising an analyte with a compound according to  claim 1 ;   allowing a reaction between the analyte and the compound in the solution to proceed for an effective period of time to a produce a detectable change in the solution's absorbance spectrum, emission spectrum, or both, where the change indicates that the analyte is present; and   detecting the change.   
     
     
         22 . The method of  claim 21  where detecting the change comprises:
 exposing the solution to a light source; and 
 detecting the analyte by detecting fluorescence from the compound at a wavelength corresponding to an emission spectrum maximum of the compound after the reaction has proceeded for the effective period of time. 
 
     
     
         23 - 30 . (canceled) 
     
     
         31 . The method of  claim 21  where the analyte comprises cysteine, homocysteine, glutathione, succinyl-5-amino-4-imidazolecarboxamide riboside, succinyladenosine, or a combination of succinyl-5-amino-4-imidazolecarboxamide riboside and succinyladenosine. 
     
     
         32 . The method of  claim 31  where the compound comprises at least one fluorophore according to general formula (vi) 
       
         
           
           
               
               
           
         
       
       —where:
 R 1 , R 4 , R 5  and R 8  independently are hydrogen, hydroxyl, thiol, lower alkyl, carboxyalkyl, amino, substituted amino, alkoxy, or halogen; 
 R 15 -R 18  independently are hydrogen, halogen, hydroxyl, thiol, amino, alkyl amino, alkoxy or —NHR c ; 
 R 19 -R 22  independently are hydrogen, hydroxyl, thiol, halogen, oxygen, imino, iminium, alkyl imino, alkyl iminium, amino, alkyl amino, or —NHR c ; and 
 at least one of R 1 , R 4 , R 5 , R 8 -R 13 , R 15 , R 16 , R 18 , R 19 , R 21  or R 22  is a linker covalently binding the fluorophore to the viologen backbone. 
 
     
     
         33 . (canceled) 
     
     
         34 . The method of  claim 32  where:
 (a) the analyte is glutathione, R 17  is hydroxyl, amino, or alkyl amino, and R 20  is oxygen, hydroxyl, amino, alkyl amino, imino, or alkyl iminium; or 
 (b) the analyte is succinyl-5-amino-4-imidazolecarboxamide riboside, succinyladenosine, or a combination thereof, at least one of R 17  and R 20  is —NHR c , R 13  is —COOR 14  where R 14  is hydrogen or lower alkyl, and one of R 9 , R 10 , R 11 , or R 12  is the linker. 
 
     
     
         35 . (canceled) 
     
     
         36 . The method of  claim 31  where the analyte is succinyl-5-amino-4-imidazolecarboxamide riboside, succinyladenosine, or a combination thereof, and the compound comprises at least one fluorophore according to:
 (a) general formula (iii): 
 
       
         
           
           
               
               
           
         
         
           where X 1  is oxygen and R 6  and R 16  are —NHR c ; or 
         
         (b) general formula (iv) 
       
       
         
           
           
               
               
           
         
         
           where X 1  is oxygen and R 16  and R 21  are —NHR c . 
         
       
     
     
         37 - 40 . (canceled) 
     
     
         41 . A kit for detecting an analyte, comprising at least one compound according to  claim 1 , wherein the compound when combined with a sample comprising the analyte will undergo a change in its absorbance spectrum and/or emission spectrum compared to the compound in a sample that does not comprise the analyte. 
     
     
         42 . (canceled) 
     
     
         43 . The kit of  claim 41 , further comprising at least one buffer solution in which the compound when combined with a sample comprising the analyte will undergo a change in its absorbance spectrum and/or emission spectrum compared to the compound combined with the buffer solution and a sample that does not comprise the analyte. 
     
     
         44 . The kit of  claim 41 , where the analyte comprises glutathione, cysteine, homocysteine, succinyl-5-amino-4-imidazolecarboxamide riboside, succinyladenosine, or a combination of succinyl-5-amino-4-imidazolecarboxamide riboside and succinyladenosine. 
     
     
         45 . The kit of  claim 44  where the compound comprises at least one fluorophore according to:
 (a) general formula (vi) 
 
       
         
           
           
               
               
           
         
         
           where 
           R 1 , R 4 , R 5  and R 8  independently are hydrogen, hydroxyl, thiol, lower alkyl, carboxyalkyl, amino, substituted amino, alkoxy, or halogen, 
         
         R 15 -R 18  independently are hydrogen, halogen, hydroxyl, thiol, amino, alkyl amino, alkoxy or —NHR c , 
         R 19 -R 22  independently are hydrogen, hydroxyl, thiol, halogen, oxygen, imino, iminium, alkyl imino, alkyl iminium, amino, alkyl amino, or —NHR c , and 
         at least one of R 1 , R 4 , R 5 , R 8 -R 13 , R 15 , R 16 , R 18 , R 19 , R 21  or R 22  is a linker covalently binding the fluorophore to the viologen backbone; 
         (b) general formula (iii) 
       
       
         
           
           
               
               
           
         
         
           where X 1  is oxygen and R 6  and R 16  are —NHR c ; or 
         
         (c) general formula (iv) 
       
       
         
           
           
               
               
           
         
         
           where X 1  is oxygen and R 16  and R 21  are —NHR c . 
         
       
     
     
         46 - 49 . (canceled)

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