WO2002049967A2 - Novel multidentate sulfur-containing ligands - Google Patents
Novel multidentate sulfur-containing ligands Download PDFInfo
- Publication number
- WO2002049967A2 WO2002049967A2 PCT/US2001/046441 US0146441W WO0249967A2 WO 2002049967 A2 WO2002049967 A2 WO 2002049967A2 US 0146441 W US0146441 W US 0146441W WO 0249967 A2 WO0249967 A2 WO 0249967A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- ligand
- chelate
- chelate ligand
- bound
- Prior art date
Links
- 0 C*C([C@@](CC=C1)NC1C(NC)=O)=O Chemical compound C*C([C@@](CC=C1)NC1C(NC)=O)=O 0.000 description 1
- YGQILMMZHDXGHE-UHFFFAOYSA-N CNC(c1cccc(C(NC)=O)c1)=O Chemical compound CNC(c1cccc(C(NC)=O)c1)=O YGQILMMZHDXGHE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
- C07C323/40—Y being a hydrogen or a carbon atom
- C07C323/42—Y being a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Definitions
- the present invention relates to binding, rendering insoluble, and precipitating a wide range of heavy metals, and more specifically to compounds and methods for multidentate binding or chelation of heavy metals utilizing a novel class of sulfur-containing ligands.
- Heavy metal pollution is an existing and growing worldwide problem.
- federal and state governments have instituted environmental regulations to protect the quality of surface and ground water from heavy metals.
- numerous products have been developed to precipitate heavy metals from surface and ground water, and soil.
- An example of a reagent for precipitating divalent and univalent heavy metals from water is TMT- 55, or 2,4,6-trimercaptotriazine, trisodmm salt nonahydrate, manufactured by Degussa Corporation USA.
- the mode of action, chemistry, and stability of resulting heavy metal- trimercaptotriazine precipitates is unknown.
- There are numerous industrial and environmental situations where ligands capable of binding metals are utilized for remediation purposes. For example, waste water issuing from waste treatment facilities, from the chlor-alkali industry, from the metal finishing industry, and from certain municipal landfills often presents a metal contamination problem.
- Thio-Red® is a chemical reagent used for precipitating divalent heavy metals from water. This product is a complex aqueous solution of sodium (with or without potassium) thiocarbonate, sulfides, and other sulfur species. Thio-Red® ultimately removes Cu, Hg, Pb, and Zn from aqueous solutions through the formation of metal sulfides (i.e. CuS, HgS, PbS, and ZnS) rather than metal thiocarbonates. Sodium and potassium dialkyldithiocarbamates are also widely used as metal precipitants.
- Ligands that lack sufficient binding sites may produce metal precipitates that are unstable over time and under certain pH conditions. Such unstable precipitates may release bound metal back into the environment, thereby proving unsatisfactory as treatment or remediation agents. Further, these compounds may form simple metal sulfides which bacteria are capable of methylating (in the case of Hg, forming the water-soluble and highly toxic cation MeHg + .
- novel sulfur-containing chelate ligands which bind heavy metals resulting in stable ligand-metal precipitates.
- the ligands of the present invention are suitable for binding any metal which is in or is capable of being placed in a positive oxidation state, including cadmium, iron, lead, nickel, zinc, mercury, copper, and the like.
- methods for removal of heavy metals from various substances comprising separating selected heavy metals from selected substances by contacting said substances with an effective amount of said novel sulfur-containing chelate ligands for a sufficient time to form stable ligand-metal precipitates.
- the chelate ligands described herein may be used alone or in varying combinations to achieve the objects of the present invention.
- the ligand-metal precipitates formed by the ligands of the present invention are stable at a range of pH values from about 0 to about 14.
- me present invention relates to cneiate ngan ⁇ s consisting of a ring structure from which depend multiple alkyl chains terminating in sulfur-containing groups.
- the chelate ligands are of the general formula:
- n is an integer from 1-4
- X is any element selected from the elements contained in Group la of the Periodic Table of the Elements, i.e. H, Li, Na, K, Rb, Cs, or Fr.
- the chelate ligands are of the formula:
- n is an integer from 1-4.
- the chelate ligands are of the formula:
- the chelate ligand may be a pyridine-based ligand of the formula C n H 15 N 3 0 2 S 2 , with pendant alkyl-thiol chains located at the 2,6 positions.
- the chelate ligand may be a benzene- based compound of the formula C 12 H 16 N 2 0 2 S 2 , with pendant alkyl-thiol chains located at the 1,3 positions.
- the H group of the terminal thiol groups of the above benzene- and pyridine-based compounds may be replaced with a terminal Na to form the metallated product.
- the stability of the metal complexes formed by use of the compounds of the present invention derive from multiple interactions between the metal and the sulfur- and nitrogen atoms on the ligand, forming a multidentate bonding arrangement around a central metal atom.
- the present invention relates to a method of removing metal ions from a starting material.
- the method of the present invention comprises contacting the starting material of choice with an effective amount of a novel sulfur-containing chelate ligand as described above for a sufficient time to form a stable ligand-metal complex precipitate, said metal remaining essentially irreversibly bound to said ligand at a range of pH values from about 0 to about 14.
- the present invention relates to a method of treating water (e.g.
- the present invention relates to a method of treating aqueous acid mine drainage or water from actual mining processes which contains soft heavy metals, comprising admixing said acid mine drainage or water from mining processes with an effective amount of the sulfur-containing chelate ligand as described above for a sufficient time to form a stable, irreversible ligand-metal complex precipitate, and separating said precipitate from said acid mine drainage.
- the present invention relates to a method of removing soft heavy metals from soils, comprising admixing said soils with an effective amount of the sulfur-containing chelate ligand as described above for a sufficient time to form a stable, irreversible ligand-metal complex precipitate.
- the soils so treated may be left in situ or removed for disposal without concerns regarding leaching of said metals into the environment.
- Figures la and lb show binding and removal of lead from solution by the 1,3 benzene-thiol ligand of the present invention: (a) Removal of lead at pH 4.0 using a 1 : 1 molar ratio of ligand:metal; (b) Removal of lead at pH 6.0 using a 1 : 1 molar concentration of ligand:metal.
- Figures 2a and 2b show binding and removal of mercury from solution of pH 4.0 by the 1,3 benzene-thiol ligand of the present invention: (a) Removal of mercury using a 1:1 molar ratio of ligand:metal; (b) Removal of mercury using 10% in excess of a 1:1 molar ration of ligand:metal.
- Figures 3 a and 3b show binding and removal of mercury from solution at pH 6.0 by the 1,3 benzene-thiol ligand of the present invention: (a) Removal of mercury using a 1:1 molar ratio ligand: metal; (b) Removal of mercury using 10% in excess of a 1:1 molar ration of ligand:metal.
- the present invention relates to novel sulfur- containing chelate ligands which bind heavy metals, resulting in ligand- metal precipitates which remain stable at a wide range of pH values.
- the ligands of the present invention are suitable for binding metals which are in or are capable of being placed in a positive oxidation state, including cadmium, iron, lead, nickel, zinc, mercury, copper, and the like.
- the present invention relates to chelate ligands consisting of a ring structure from which depend multiple alkyl chains terminating in sulfur- containing groups.
- the chelate ligands are of the general formula:
- n is an integer from 1-4
- X is any element selected from the group consisting of H, Li, Na, K, Rb, Cs, and Fr.
- the chelate ligands are of the formula:
- n is an integer from 1-4.
- the chelate ligands are of the formula:
- n is an integer from 1-4.
- novel ligands of the present invention may be adapted to a variety of environmental situations requiring binding and/or removal of heavy metals, such as, e.g. treatment of industrial waste water, treatment of acid mine drainage, soil remediation, and the like.
- the chelate ligands of the present invention may be utilized alone or in varying combinations to achieve the objects of the present invention.
- the present invention relates to a method of removing metal ions from a starting material.
- the method of the present invention comprises contacting the starting material of choice with an effective amount of a novel sulfur-containing chelate ligand as described above for a sufficient time to form a stable ligand-metal complex precipitate.
- Said ligand-metal complex precipitates remain stable at a range of pH values from about 0 to about 14.
- the present invention relates to a method of treating water, such as surface, ground, or waste water, containing soft heavy metals, comprising admixing said water with an effective amount of the sulfur-containing chelate ligand as described above for a sufficient time to form a stable ligand-metal complex precipitate, and separating said precipitate from said water.
- the present invention relates to a method of treating aqueous acid mine drainage or water from actual mining processes containing soft heavy metals, comprising admixing said acid mine drainage or water from actual mining processes with an effective amount of the sulfur-containing chelate ligand as described above for a sufficient time to form a stable ligand-metal complex precipitate, and separating said precipitate from said acid mine drainage.
- the present invention relates to a method of remediation of soils containing soft heavy metals, comprising admixing said soils with an effective amount of the sulfur-containing chelate ligand as described above for a sufficient time to form a stable ligand-metal complex precipitate.
- the soils so treated may then be left in situ or removed for disposal without concerns regarding leaching of said metals into the environment.
- the compositions and methods of the present invention may be accomplished by various means which are illustrated in the examples below. These examples are intended to be illustrative only, as numerous modifications and variations will be apparent to those skilled in the art.
- Example 1 In this example, 3.14 grams of 2-aminoethanethiol hydrochloride was dissolved in chloroform, and 3.88 ml of triethylamine were added. 2.81 grams of isophthaloyl chloride was then dissolved in chloroform under nitrogen. 2-aminoethanethiol hydrochloride and 1,3 -isophthaloyl chloride, prepared as described supra, were then slowly mixed, and the resulting solution was stirred under nitrogen in an ice bath for several hours. The resulting solution was then filtered under nitrogen, and several water/chloroform extractions performed.
- Cadmium (50 ppm in 39%o ethanol/61%» water) and a 2,6 pyridine thiol ligand prepared as described in Example 2 were admixed in a 1 : 1 molar ratio, producing a solution with pH 4.5.
- the experiment was repeated with addition of an acetic acid/sodium acetate buffer to maintain pH at 6.0. Additionally, the experiment was repeated with an 8% increase (above the 1:1 molar ratio) in the amount of pyridine thiol ligand added.
- the ability of a 1,3 benzene thiol ligand to retain bound mercury over time and at various pH ranges was tested.
- the 1,3 benzene thiol ligand synthesized as described in Example 1 was allowed to bind Hg at a 1 : 1 molar ratio.
- Acetic acid/sodium acetate buffer was used to maintain pH of samples at 4.0, 6.0, or 10.0. Samples were tested for Hg leaching by an EPA cold vapor technique as described in Example 9 at 2, 30, and 60 days.
- Example 14 Ability of a 1 ,3 benzene thiol ligand to retain bound iron over time and at various pH ranges was tested.
- the 1,3 benzene thiol ligand synthesized as described in Example 1 was allowed to bind Fe(II) at a 1:1 molar ratio.
- Acetic acid/sodium acetate buffer was used to maintain pH of samples at 0.0 or 4.0.
- Samples were tested for Fe(II) leaching by standard inductively coupled plasma spectrometry as described in Example 8 at 1, 7, and 30 days. Regardless of pH or time of incubation, the 1,3 benzene thiol ligand of the present invention retained at least 94%> of bound Fe(II) over the experimental period (Table V).
- the metal complexes formed by the ligands of the present invention are therefore shown to be stable over time.
- the initial concentration of Fe(II) is based on the original amount of Fe(II)-Ligand complex tested and assumes 100% leached.
- the 1,3 benzene thiol ligand synthesized as described in Example 1 was allowed to bind Fe(II) at a 1 : 1 molar ratio.
- Acetic acid/sodium acetate buffer was used to maintain pH of samples at 0.0 or 4.0 in either deionized water or a 1.0% solution of hydrogen peroxide in deionized water.
- Samples were tested for Fe(II) leaching by standard inductively coupled plasma spectrometry as discussed in Example 8 at 1, 7, and 30 days.
- the 1,3-benzene thiol ligand retained Fe(II) best at pH 4.0 in deionized water (>97% retention; Table VI). However, in no case did Fe(II) retention fall below 86%>, even after 30 days of incubation.
- the metal complexes formed by the ligands of the present invention are therefore shown to remain stable even at varying pH ranges, and in the presence of potentially interfering ions.
- Sample C pH 4.0 in 1.0% Hydrogen Peroxide Solution.
- Samples of acid mine drainage were collected at various stages post- discharge. Samples were collected at the borehole, at two areas of the discharge pipe (3 and 4 inch diameter), at the point discharge site, and downstream of the point discharge site. Collected samples were analyzed for a range of metals by inductively coupled plasma spectrometry before (Table VII) and after (Tables VIII-X) treatment with a 1,3 benzene metallate ligand prepared as described in Example 6. Samples were tested at 1, 6, and 20 hours after addition of an excess of the 1,3 benzene metallate ligand. The ligand bound all metals evaluated which were present at detectable concentrations in acid mine drainage. The ligand was particularly effective in binding Cd, Cu, Fe, Mg, and Mn (Tables VII and VIII). For example, Fe was detected in acid mine drainage at a concentration of 194.2 ppm at the borehole, and 2.703 ppm downstream of the discharge point (Table VII).
- Table VII Metal content of acid mine drainage before treatment with disodium benzene thio ligand (BDETNa 2 ).
- Table VIII Metal content of acid mine drainage after treatment for one hour with BDETNa 2 .
- Table IX Metal content of acid mine drainage after six hours of treatment with BDETNa 2 .
- Table X Metal Content of acid mine drainage after 20 hours of treatment with BDETNa 2 .
- Example 6 The ability of the 1,3 benzene metallate ligand synthesized as described in Example 6 was evaluated on soil samples containing known concentrations of Hg. Each soil sample was treated by admixing with ligand in a 1:1 molar ratio of ligand to Hg at least five times. Results are expressed as percent mercury immobilized by ligand. On average, over 98%o of the Hg contained in soil samples was immobilized by the ligand (Table XI).
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Medicinal Chemistry (AREA)
- Soil Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2003-7007672A KR20040036682A (en) | 2000-12-06 | 2001-12-06 | Novel multidentate sulfur-containing ligands |
JP2002551474A JP2004533990A (en) | 2000-12-06 | 2001-12-06 | New multidentate sulfur-containing ligands |
AU2002245070A AU2002245070A1 (en) | 2000-12-06 | 2001-12-06 | Novel multidentate sulfur-containing ligands |
EP01993216A EP1355883A2 (en) | 2000-12-06 | 2001-12-06 | Novel multidentate sulfur-containing ligands |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/730,622 US6586600B2 (en) | 2000-12-06 | 2000-12-06 | Multidentate sulfur-containing ligands |
US09/730,622 | 2000-12-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002049967A2 true WO2002049967A2 (en) | 2002-06-27 |
WO2002049967A3 WO2002049967A3 (en) | 2002-10-17 |
Family
ID=24936085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/046441 WO2002049967A2 (en) | 2000-12-06 | 2001-12-06 | Novel multidentate sulfur-containing ligands |
Country Status (6)
Country | Link |
---|---|
US (1) | US6586600B2 (en) |
EP (1) | EP1355883A2 (en) |
JP (1) | JP2004533990A (en) |
KR (1) | KR20040036682A (en) |
AU (1) | AU2002245070A1 (en) |
WO (1) | WO2002049967A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10336534A1 (en) * | 2003-08-05 | 2005-02-24 | Stockhausen Gmbh | Process to remove heavy metals from industrial liquid effluent arising from one- or two-stage sulfur dioxide gas washers by admixture of flocculent to sludge |
CN101898824A (en) * | 2010-04-12 | 2010-12-01 | 南京师范大学 | Sulfide heavy metal chelating trapping agent and preparation method thereof |
CN102070235A (en) * | 2010-11-11 | 2011-05-25 | 华南理工大学 | Water-soluble organic thiamine heavy metal chelating agent and preparation method thereof |
EP2606973A1 (en) * | 2011-12-22 | 2013-06-26 | LANXESS Deutschland GmbH | Acrylate resin containing thiol groups |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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US6852369B1 (en) * | 2002-09-05 | 2005-02-08 | University Of Kentucky Research Foundation | Method for prevention of solid dissolution through covalent ligand bonding |
FR2896705B1 (en) * | 2006-01-30 | 2008-12-05 | Commissariat Energie Atomique | PROCESS FOR THE SEPARATION IN AQUEOUS MEDIUM OF AT LEAST ONE ACTINIDE ELEMENT OF LANTHANIDE ELEMENTS BY COMPLEXATION AND MEMBRANE FILTRATION |
US8950583B2 (en) * | 2008-12-06 | 2015-02-10 | Ermes Medical Company Limited | Method to remove heavy metals from a mammal |
US8575218B2 (en) * | 2009-09-28 | 2013-11-05 | The University Of Kentucky Research Foundation | Thiol-containing compounds for the removal of elements from tissues and formulations therefor |
US20110076246A1 (en) * | 2009-09-28 | 2011-03-31 | Haley Boyd E | Thiol-containing compounds for the removal of elements from contaminated milieu and methods of use |
US8426368B2 (en) * | 2010-03-25 | 2013-04-23 | The University Of Kentucky Research Foundation | Method of ameliorating oxidative stress and supplementing the diet |
US20110237776A1 (en) * | 2010-03-25 | 2011-09-29 | Haley Boyd E | Aromatic compounds with sulfur containing ligands |
US8815184B2 (en) | 2010-08-16 | 2014-08-26 | Chevron U.S.A. Inc. | Process for separating and recovering metals |
CN102532372B (en) | 2010-12-17 | 2015-06-10 | 通用电气公司 | Polymer and preparation and using method thereof |
US8834725B2 (en) | 2011-01-31 | 2014-09-16 | Chevron U.S.A. Inc. | Method for treating acid mine drainage |
US9169445B2 (en) * | 2013-03-14 | 2015-10-27 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from oily solids |
GB2524831A (en) * | 2014-04-04 | 2015-10-07 | Ermes Medical Company Ltd | New pharmaceutical use |
GB2526623A (en) | 2014-05-30 | 2015-12-02 | Ermes Medical Company Ltd | New pharmaceutical use |
US9802889B2 (en) | 2014-12-02 | 2017-10-31 | Covalent Research Technologies, LLC | Solid supported trithiol compounds for removing heavy metals from solution, and filtration systems utilizing the compounds |
CA3032858A1 (en) | 2016-08-05 | 2018-02-08 | Emeramed Limited | Use of n,n-bis-2-mercaptoethyl isophthalamide to prevent or treat paracetamol toxicity |
US11174277B2 (en) | 2019-05-29 | 2021-11-16 | Alliance For Sustainable Energy, Llc | Sequestering compositions and materials |
GB202005057D0 (en) | 2020-04-06 | 2020-05-20 | Emeramed Ltd | New Use |
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2000
- 2000-12-06 US US09/730,622 patent/US6586600B2/en not_active Expired - Lifetime
-
2001
- 2001-12-06 WO PCT/US2001/046441 patent/WO2002049967A2/en not_active Application Discontinuation
- 2001-12-06 KR KR10-2003-7007672A patent/KR20040036682A/en not_active Application Discontinuation
- 2001-12-06 EP EP01993216A patent/EP1355883A2/en not_active Withdrawn
- 2001-12-06 AU AU2002245070A patent/AU2002245070A1/en not_active Abandoned
- 2001-12-06 JP JP2002551474A patent/JP2004533990A/en active Pending
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US4751286A (en) * | 1985-11-19 | 1988-06-14 | The Johns Hopkins University | Protein label and drug delivery system |
US5615862A (en) * | 1995-02-02 | 1997-04-01 | Gaudette; Robert M. | Metal precipitation composition for treating spent dry film stripping solution |
Non-Patent Citations (3)
Title |
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CN101898824B (en) * | 2010-04-12 | 2012-10-24 | 南京师范大学 | Sulfide heavy metal chelating trapping agent and preparation method thereof |
CN102070235A (en) * | 2010-11-11 | 2011-05-25 | 华南理工大学 | Water-soluble organic thiamine heavy metal chelating agent and preparation method thereof |
EP2606973A1 (en) * | 2011-12-22 | 2013-06-26 | LANXESS Deutschland GmbH | Acrylate resin containing thiol groups |
WO2013092249A1 (en) * | 2011-12-22 | 2013-06-27 | Lanxess Deutschland Gmbh | Thiol group-containing acrylate resin |
CN103998135A (en) * | 2011-12-22 | 2014-08-20 | 朗盛德国有限责任公司 | Thiol group-containing acrylate resin |
Also Published As
Publication number | Publication date |
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KR20040036682A (en) | 2004-04-30 |
AU2002245070A1 (en) | 2002-07-01 |
EP1355883A2 (en) | 2003-10-29 |
US6586600B2 (en) | 2003-07-01 |
JP2004533990A (en) | 2004-11-11 |
WO2002049967A3 (en) | 2002-10-17 |
US20020100732A1 (en) | 2002-08-01 |
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