Chemical and biological agents for the control of molluscs

Abstract

Compositions and methods for controlling molluscs, members of the Gastropoda and Bivalvia classes which includes but is not limited to lactones, lactams, carbamates, amides, and/or carboxylic acid containing compounds as active ingredients and/or compounds derived from Pseudomonas and/or Erwinia . Also provided are methods and compositions for increasing the efficacy of chemical and biological control for invasive molluscs in open waters, power plants, and drinking water treatment facilities under coldwater conditions.

1 . An isolated compound having the following characteristics (a) is obtainable from a microorganism; (b) is toxic to a member of a Gastropoda and/or Bivalvia class of molluscs and (c) has a molecular weight selected from the group consisting of: about 540-550, and about 1280-1335 as determined by Liquid Chromatography/Mass Spectroscopy (LC/MS). 
     
     
         2 . The compound according to  claim 1 , wherein said compound is toxic to at least one of mussels, snails and slugs. 
     
     
         3 . The composition according to  claim 1 , wherein said compound has (a) a molecular weight of about 1280-1310 as determined by Liquid Chromatography/Mass Spectroscopy (LC/MS); (b) has  1 H NMR values of δ 9.25, 8.36, 8.06, 7.82, 7.71, 7.52, 7.45, 6.82, 6.36, 6.08, 5.42, 5.39, 5.30, 5.14, 4.68, 4.42, 4.31, 4.16, 4.11, 4.07, 3.95-3.86, 3.83, 3.72, 3.66, 3.53, 3.48, 3.37, 3.17, 3.06, 2.56, 2.53, 2.45, 2.32, 2.21, 2.02, 1.96, 1.84, 1.72, 1.65, 1.61, 1.51, 1.48-1.37, 1.32, 1.12, 0.94, 0.91, 0.68 and (c) has an (High Pressure Liquid Chromatography) (HPLC) retention time of about 50-55 min on a reversed phase C-18 HPLC column using a water:acetonitrile gradient solvent system (0-10 min; 30-40% aqueous CH 3 CN, 10-20 min; 40-60% aqueous CH 3 CN, 20-60 min; 60-80% aqueous CH 3 CN, 60-65 min; 80-100% aqueous CH 3 CN) at 2.5 mL/min flow rate and UV detection of 210 nm. 
     
     
         4 . The compound according to  claim 3 , wherein said compound has a molecular weight of about 1295. 
     
     
         5 . The compound according to  claim 1 , wherein said compound (a) has a molecular weight of about 1310-1335 as determined by LC/MS; (b) has an HPLC retention time of about 55-60 min on a reversed phase C-18 HPLC column using a water:acetonitrile gradient solvent system (0-10 min; 30-40% aqueous CH 3 CN, 10-20 min; 40-60% aqueous CH 3 CN, 20-60 min; 60-80% aqueous CH 3 CN, 60-65 min; 80-100% aqueous CH 3 CN) at 2.5 mL/min flow rate and UV detection of 210 nm. 
     
     
         6 . The compound according to  claim 5 , wherein said compound has a molecular weight of about 1321. 
     
     
         7 . The compound according to  claim 1 , wherein said compound has a molecular weight of about 540-550 as determined by LC/MS; (d) has an HPLC retention time of about 50-55 min on a reversed phase C-18 HPLC column using a water:acetonitrile solvent system (0-10 min; 35-45% aqueous CH 3 CN, 10-20 min; 45-60% aqueous CH 3 CN, 20-50 min; 60-85% aqueous CH 3 CN, 50-60 min; 85-100% aqueous CH 3 CN, 60-70 min; 100% CH 3 CN) at 10 mL/min flow rate and UV detection of 210 nm. 
     
     
         8 . The compound according to  claim 7 , wherein said compound has a molecular weight of about 546. 
     
     
         9 . A composition comprising a water:acetonitrile solvent system (0-10 min; 35-45% aqueous CH 3 CN, 10-20 min; 45-60% aqueous CH 3 CN, 20-50 min; 60-85% aqueous CH 3 CN, 50-60 min; 85-100% aqueous CH 3 CN, 60-70 min; 100% CH 3 CN) at 10 mL/min flow rate and UV detection of 210 nm fraction obtainable from a  Pseudomonas  species cell suspension by HPLC with a retention time of about 45-50 min, said fraction comprising at least two compounds that (a) are toxic to a member of a Gastropoda and/or Bivalvia class; (b) have molecular weights between about 630-660 and between about 970-1000 as determined by LC/MS. 
     
     
         10 . The composition according to  claim 9 , wherein said compounds have molecular weights of about 643 and about 984. 
     
     
         11 . A composition comprising at least one or more substances effective for controlling a member of a Gastropoda and Bivalvia class and an inert material. 
     
     
         12 . The composition according to  claim 11 , wherein said substances are derived from a  Pseudomonas  species or cell suspension derived from a  Pseudomonas  species. 
     
     
         13 . The composition according to  claim 11 , wherein said substances are derived from  Pseudomonas fluorescens  or cell suspension derived from  Pseudomonas fluorescens.    
     
     
         14 . The composition according to  claim 11 , wherein said substances are derived from a  Pseudomonas  strain, having the identifying characteristics of  Pseudomonas  ATCC 55799. 
     
     
         15 . The composition according to  claim 11 , wherein the composition comprises a substance that is a cell suspension comprising cells having the toxin producing characteristics of  Pseudomonas  ATCC 55799. 
     
     
         16 . The composition according to  claim 11 , wherein the substances are one or more toxins derived from a  Pseudomonas  species. 
     
     
         17 . The composition according to  claim 11 , wherein the substances are one or more toxins derived from an organism having the identifying characteristics of  Pseudomonas  ATCC 55799. 
     
     
         18 . The composition according to  claim 11 , wherein said substance effective for controlling  Dreissana  and/or  Biomphalaria  species is a compound having the following characteristics (a) is obtainable from a  Pseudomonas  species; (b) is toxic to a member of a Gastropoda and Bivalvia class and (c) has a molecular weight selected from the group consisting of: about 540-550, and about 1280-1335 as determined by Liquid Chromatography/Mass Spectroscopy (LC/MS). 
     
     
         19 . A method for controlling one or more molluscs in a location where control is desired comprising introducing into said location at least one of (a) a cell suspension or extract derived from  Erwinia  sp. Cells; (b) one or more compounds, wherein said compounds are lactone, lactam, carbamate, carboxylic acid and/or amide compounds or composition comprising said compounds, with the proviso that said compounds are not gamma-octalactone, gamma-nonalactone, gamma-decanolactone, gamma-undecalactone, N-cyclpentylcinnamamide, N-(trans-cinnamoyl)pyrrolidine, N-(trans-Cinnamoyl)piperidine and N-(trans-Cinnamoyl)hexamethyleneimine, 4-hydroxydodecanoic acid and dodecanoic acid and with the proviso that the composition is not a  Pseudomonas  culture, extract or suspension; (c) one or more compounds of  claim 1 ; (d) a composition comprising a water:acetonitrile solvent system (0-10 min; 35-45% aqueous CH 3 CN, 10-20 min; 45-60% aqueous CH 3 CN, 20-50 min; 60-85% aqueous CH 3 CN, 50-60 min; 85-100% aqueous CH 3 CN, 60-70 min; 100% CH 3 CN) at 10 mL/min flow rate and UV detection of 210 nm fraction obtainable from a  Pseudomonas  species cell suspension by HPLC with a retention time of about 45-50 min, said fraction comprising at least two compounds that (i) are toxic to a member of a Gastropoda and Bivalvia class; (ii) have molecular weights between about 630-660 and between about 970-1000 as determined by LC/MS, in amounts effective to control said molluscs. 
     
     
         20 . The method according to  claim 19 , wherein said molluscs species are controlled by inducing death in said molluscs species. 
     
     
         21 . The method according to  claim 19 , wherein said compounds introduced into said location, are lactone, lactam, carbamate, carboxylic acid and/or amide and said compounds are members of a family of compounds selected from the group consisting of:
 (a) family I, wherein a family I compound possesses following chemical structure:   
       
         
           
           
               
               
           
         
         
           Wherein X is carbon; Y is oxygen; A and M are carbon, oxygen, nitrogen, sulfur and n is 1 to 21 
           Wherein (R)z represents number Z of the number of substituents on the group R on the ring wherein R and the substituents on R are selected from the group consisting of hydrogen, hydroxyl, alkyl hydroxyl, alkenyl hydroxyl, alkynyl hydroxyl, alkyloxy, alkenyloxyl, alkynylxoy, cycloalkyl, cycloalkenyl, alkyl, alkenyl, alkynyl, heterocyclyl, heteroaryl, aromatic, aryl group, NH-substituted, and N,N-substituted group; the length of the R chain is from 1 to 25 atoms, and Z is 0, 1, 2, 3; 
         
         (b) family II, wherein a family II compound possesses following chemical structure: 
       
       
         
           
           
               
               
           
         
         
           Wherein X is carbon; Y is oxygen; A, B and M are carbon, oxygen, nitrogen and sulfur; Wherein (R)z represents number Z of the number of substituents on the group R on the ring; R and the substituents on R is selected from the group consisting of a hydrogen, hydroxyl, alkyl hydroxyl, alkenyl hydroxyl, alkynyl hydroxyl, alkyloxy, alkenyloxyl, alkynylxoy, alkyl, alkenyl, alkynyl, heterocyclyl, aromatic, aryl group, NH-substituted, and N,N-substituted group; the length of the R chain is from 1 to 25 atoms, and Z is 0, 1, 2, 3; 
         
         (c) family III, wherein a family III compound possesses following chemical structure: 
       
       
         
           
           
               
               
           
         
         
           Wherein X is carbon, Y is oxygen; Z is hydrogen, hydroxyl, alkenyl hydroxyl, alkynyl hydroxyl, alkyl, alkenyl, alkynyl, heterocyclyl, aromatic, aryl group, NH-substituted, or N,N-substituted group. 
           Wherein R is alkenyl hydroxyl, alkynyl hydroxyl, alkyl, alkenyl, alkynyl, heterocyclyl, aromatic, aryl group, NH-substituted, or N,N-substituted group 1 to 50 atoms in length. 
         
       
     
     
         22 . The method according to  claim 21 , wherein R in family I, II and III compounds are from 7 to 17 atoms in length. 
     
     
         23 . The method according to  claim 21 , wherein said compound has the structure 
       
         
           
           
               
               
           
         
       
       wherein Y and M are oxygen, A and X are carbon and n is 2 or 3, R is a C7 or C8 alkyl and z is 0, wherein when n is 2 and R is a C7 alkyl, R is attached to A. 
     
     
         24 . The method according to  claim 21 , wherein said compound is a sarmentine analog having the following structure: 
       
         
           
           
               
               
           
         
         Wherein R 1  is an alkyl, alkenyl, alkynyl, heterocyclyl, aromatic, aryl group, NH-substituted, or N,N-substituted group, wherein the length of R 1  chain is from 4 to 20 atoms, Wherein R 2  and R 3  are alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aromatic, arylalkyl, heterocyclyl or heteroaryl; or alternatively R 2 +R 3 +N can be an N-containing heterocyclic moiety, 
         Wherein when R 2 +R 3 +N is an N-containing heterocyclic moiety, R1 is an alkyl, alkenyl, alkynyl, heterocyclyl, NH-substituted, or N,N-substituted group. 
       
     
     
         25 . The method according to  claim 24 , wherein the length of R 1  chain is from 6 to 12 atoms. 
     
     
         26 . The method according to  claim 19 , wherein said compound is a lactone and has a hydroxylated unsaturated fatty acid lactone structure comprising at least one lactone moiety which is a 5 membered γ-lactone, at least one unsaturated moiety and at least one alcohol group; a molecular weight from 285 to about 310 in the core structure; at least 15 carbons and at least 3 oxygens. 
     
     
         27 . The method according to  claim 26 , wherein said compound has the structure 
       
         
           
           
               
               
           
         
       
       wherein: X are each independently —O, —NR 1 , or —S, wherein R 1  is —H or C 1 -C 6 alkyl; n=0 to 15, R 2  to R 4  are each independently —H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic, substituted heterocyclic, cycloalkyl, substituted cycloalkyl, alkoxy, substituted alkoxy, thioalkyl, substituted thioalkyl, hydroxy, halogen, amino, amido, carboxyl, —C(O)H, acyl, oxyacyl, carbamate, sulfonyl, sulfonamide, or sulfuryl; m=double bond or triple bond. 
     
     
         28 . The method according to  claim 19 , wherein said compound is has a hydroxylated unsaturated fatty acid structure comprising at least one carboxylic acid moiety, at least one unsaturated moiety and at least one alcohol group; a molecular weight from 285 to about 310 in the core structure; at least 15 carbons and at least 3 oxygens. 
     
     
         29 . The method according to  claim 28 , wherein said compound has the structure 
       
         
           
           
               
               
           
         
       
       wherein: X are each independently —OH, —NR 1 , or —S, wherein R 1  is —H or C 1 -C 6  alkyl; n=0 to 15, R 2  to R 4  are each independently —H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic, substituted heterocyclic, cycloalkyl, substituted cycloalkyl, alkoxy, substituted alkoxy, thioalkyl, substituted thioalkyl, hydroxy, halogen, amino, amido, carboxyl, —C(O)H, acyl, oxyacyl, carbamate, sulfonyl, sulfonamide, or sulfuryl; m=double bond, triple bond. 
     
     
         30 . The method according to  claim 19 , wherein the compound is selected from the group consisting of:
 (a) a compound set forth in  FIG. 1 ;   (b) a lactone selected from the group consisting of gamma-dodecalactone, delta-tridecalactone, piliferolide A and alpha-heptyl-gamma-butyrolactone and   (c) a sarmentine analog selected from the group consisting of N-Cyclopentyldecanamide, N-(Decanoyl)pyrrolidine, N-(Decanoyl)piperidine, N-(Decanoyl)hexamethyleneimine, N-Cyclopentyldecenamide, (N-(Decenoyl)pyrrolidine, N-(Decenoyl)piperidine, N-(Decenoyl)hexamethyleneimine and N-(Decenoyl)piperidine and   (d) 11-hydroxy-12-ene-octadecanoic acid.   
     
     
         31 . A method for controlling one or more molluscs comprising introducing a substance and one or more inert materials in a location where control is desired in amounts effective for controlling said molluscs. 
     
     
         32 . The method according to  claim 31 , wherein said substance for controlling molluscs is present in an amount to result in at least about a 20% mortality of said molluscs relative to untreated control and said inert material is present in an amount sufficient to increase mortality rate of said substance for controlling molluscs at least about 20%. 
     
     
         33 . The method according to  claim 31 , wherein said location is a liquid wherein said liquid is a body of water or paint. 
     
     
         34 . The method according to  claim 31 , wherein said location is a solid surface selected from the group consisting of plastic, concrete, wood, fiberglass, pipes made of iron and polyvinyl chloride, surfaces covered with coating materials and/or paints. 
     
     
         35 . A method for increasing the efficacy of one or more substances for controlling molluscs comprising introducing in a location where control is desired one or more inert materials in amounts effective to increase efficacy of said substance when introduced in said location. 
     
     
         36 . The method according to  claim 35 , wherein said inert materials increases the efficacy of said substances at least about 20%. 
     
     
         37 . The method according to  claim 35 , wherein said inert materials are derived from a clay mineral. 
     
     
         38 . The method according to  claim 35 , wherein said inert materials are kaolinite, smectite, attapulgite or a combination of the foregoing. 
     
     
         39 . A composition for controlling one or more molluscs in a location where control is desired and/or inducing death in one or more molluscs comprising one or more lactones, lactams, carbamates, carboxylic acids and/or amides, again with the proviso that said compound is not gamma-octalactone, gamma-nonalactone, gamma-decanolactone, gamma-undecalactone, N-cyclpentylcinnamamide, N-(trans-cinnamoyl)pyrrolidine, N-(trans-Cinnamoyl)piperidine and N-(trans-Cinnamoyl)hexamethyleneimine, 4-hydroxydecanoic acid and decanoic acid and with the proviso that the composition is not a  Pseudomonas  culture, extract or suspension. 
     
     
         40 . A method for controlling one or more molluscs comprising the steps of:
 (a) preparing a cell suspension or extract derived from  Erwinia  sp. cells; and   (b) introducing said suspension or extract into a location where control is desired in an amount effective to control said molluscs.   
     
     
         41 . An antifouling paint comprising an antivegetative, biocidal effective amount of the composition of  claim 11  in a paint carrier.