WO2011038385A2 - Thiol-containing compounds for the removal of elements from contaminated milieu and methods of use - Google Patents

Thiol-containing compounds for the removal of elements from contaminated milieu and methods of use Download PDF

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Publication number
WO2011038385A2
WO2011038385A2 PCT/US2010/050512 US2010050512W WO2011038385A2 WO 2011038385 A2 WO2011038385 A2 WO 2011038385A2 US 2010050512 W US2010050512 W US 2010050512W WO 2011038385 A2 WO2011038385 A2 WO 2011038385A2
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group
groups
hydrogen
alkyls
aryls
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PCT/US2010/050512
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English (en)
French (fr)
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WO2011038385A9 (en
WO2011038385A3 (en
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Boyd E. Haley
David A. Atwood
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University Of Kentucky Research Foundation
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Priority to AU2010297933A priority Critical patent/AU2010297933A1/en
Priority to US12/892,464 priority patent/US20110076246A1/en
Priority to IN2586DEN2012 priority patent/IN2012DN02586A/en
Priority to RU2012113419/04A priority patent/RU2528396C2/ru
Priority to JP2012531110A priority patent/JP2013505963A/ja
Priority to EP10819637.9A priority patent/EP2483239A4/en
Priority to CN2010800505595A priority patent/CN102612511A/zh
Priority to CA2775397A priority patent/CA2775397A1/en
Priority to US13/041,798 priority patent/US8575218B2/en
Publication of WO2011038385A2 publication Critical patent/WO2011038385A2/en
Publication of WO2011038385A3 publication Critical patent/WO2011038385A3/en
Publication of WO2011038385A9 publication Critical patent/WO2011038385A9/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/30—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
    • A61K31/19—Carboxylic acids, e.g. valproic acid
    • A61K31/195—Carboxylic acids, e.g. valproic acid having an amino group
    • A61K31/197—Carboxylic acids, e.g. valproic acid having an amino group the amino and the carboxyl groups being attached to the same acyclic carbon chain, e.g. gamma-aminobutyric acid [GABA], beta-alanine, epsilon-aminocaproic acid or pantothenic acid
    • A61K31/198—Alpha-amino acids, e.g. alanine or edetic acid [EDTA]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
    • A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
    • A61K31/216—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acids having aromatic rings, e.g. benactizyne, clofibrate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/695—Silicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/795—Polymers containing sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P39/00—General protective or antinoxious agents
    • A61P39/04—Chelating agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • 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
    • 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
    • C07C323/50—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 carboxyl groups bound to the same carbon skeleton
    • C07C323/51—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/57—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C323/58—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
    • C07C323/59—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton with acylated amino groups bound to the carbon skeleton
    • 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
    • C07C323/50—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 carboxyl groups bound to the same carbon skeleton
    • C07C323/51—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the present invention relates to compounds utilized in covalent binding to a wide range of metals and main group elements, and more specifically to sulfur- containing ligands and the utilization of such to remove contaminants from solids, liquids and gases.
  • 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 foiTnation of metal sulfides (i.e. CuS, HgS, PbS, and ZnS), rather than metal thiocarbonates.
  • Sodium and potassium dialkyldithiocarbamates such as HMP-2000®, are also widely used as metal precipitants.
  • DMPS dimercaptopropanesulfonate
  • DMSA dimercaptosuccinic acid
  • binders like DMSA, DMPS and EDTA have a non-specific attraction for all metal ions, including the essential metals Ca 2+ , Mg 2+ , Mn 2+ , etc.
  • the rapid excretion of these binders from the body through the urine can have the negative effect of depleting the body of these essential metals. Deaths have occurred by essential metal depletion by charged binding compounds during a process called chelation therapy, and this medical treatment must therefore be done by an experienced physician.
  • Heavy metals such as mercury are typically lipid-soluble or can pass through the cell membrane via native divalent metal ion earners (e.g. for Ca ⁇ Mg + ) as the M 2 " form, and may therefore concentrate intracellularly and more so in the adipose, or fatty, tissue or in other tissues high in lipid content, including without limitation the central nervous system. Indeed, mercury and other heavy metals preferentially partition to and concentrate in the hydrophobic aspects of mammals, fish, and the like, such as fatty tissues, cell membranes, lipid-containing areas of the interior of a cell, and the like.
  • native divalent metal ion earners e.g. for Ca ⁇ Mg +
  • mercury and other heavy metals preferentially partition to and concentrate in the hydrophobic aspects of mammals, fish, and the like, such as fatty tissues, cell membranes, lipid-containing areas of the interior of a cell, and the like.
  • the currently available, approved heavy metal binders have several disadvantages with regard to their overall chemical nature that could be improved on by the synthesis of better-designed, tme chelators that have safer excretoiy properties such as higher affinity for the metals and/or main group elements and excretion through the feces instead of the urine.
  • Such better-designed, tme chelators would desirably be uncharged, lipid-soluble or hydrophobic compounds, or alternatively convertible from water soluble (for suitability for delivery via the bloodstream) to lipid-soluble compounds in the body, to allow them to partition into the fatty
  • chelators would possess low or, better yet, no observable toxicity to mammals alone in the absence of heavy metal exposures. They would be tme chelators that would bind heavy metals and main group elements exceptionally tightly, preventing toxic effects and also preventing release or concentration in toxic form in any organ of the body. Still further, desirably the chelators would be excreted through the biliaiy transport system of the liver into the feces instead of through the kidneys (a very sensitive organ to heavy metal exposure) and into the urine.
  • chelate ligands are of the general formula:
  • R is selected from a group including benzene, pyridine, pyridin-4-one.
  • R ' is independently selected from a group including hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R J is independently selected from a group including alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X is independently selected from a group including hydrogen, lithium, sodium, potassium, mbidium, cesium, francium, alkyls, aryls, a carboxyl group, carboxylate esters, cysteine, homocysteine, glutathione, lipoic acid, dihydrolipoic acid, thiophosphate, N-acetyl cysteine, mercaptoacetic acid, mercaptopropionic acid, ⁇ -glutamyl cysteine, phytochelatins, thiolsalicylate, organic groups and biological groups
  • n independently equals
  • the present invention relates to methods of removing metals and/or main group elements from a starting material.
  • the methods comprise contacting a starting material with an effective amount of a sulfur-containing chelate ligand as described above for a sufficient time to form a stable ligand-metal and/or ligand-main group element complex(es). said metal and/or main group element complex(es) remaining essentially irreversibly bound to said ligand over a range of acidic and basic pH values.
  • the present invention relates to methods of removing metals and/or main group elements from a lipid-containing tissue in a human and/or animal body.
  • the methods comprise intravenously delivering an amount of a sulfur- containing chelate ligand as described above to a lipid-containing tissue in a body, forming a ligand-metal and/or ligand-main group element complex(es). and excreting the complex(es) from the body.
  • Intravenous (IV) application has the advantage of speed of general delivery and the ability to treat an unconscious patient. Therefore, in the present disclosure, analogs of uncharged, nontoxic chelators are described which may initially be provided as charged, water soluble compounds. These water-soluble compounds are converted in the blood to uncharged lipid soluble compounds which can enter the membranes and other hydrophobic aspects of cells and tissues, and even cross the blood brain barrier.
  • the present disclosure provides uncharged, non-toxic lipid soluble analogs that can be converted by intracellular enzymes once internalized into water soluble chelators. These same compounds can be treated externally with enzymes (esterases) to make them water soluble for IV applications. This may be especially useful if treatment is required that does not enter cells or cross the blood brain barrier and still retain high heavy metal and/or main group element affinity.
  • enzymes enzymes
  • the described chelators are thiol/thiolate compounds including an aromatic ring structure, further including additional functional groups on the organic ring stmcture and/or on the pendent thiol chains.
  • a representative stmcture for the compounds is set forth below.
  • Z and Y may be a variety of combinations of organic, organometallic and inorganic groups, including without limitation OH, COOH, M l . -. HSO 3 , halogens, and the like.
  • X may be one or more of hydrogen, halogens, organic groups providing thioethers and related derivatives, or metals selected without limitation from the Group 1 and 2 elements recited in the Periodic Table of the Elements, or may include charged molecules having a terminal sulfhydryl include without limitation glutathione, cysteine, homocysteine, lipoic acid, dihydrolipoic acid, thiophosphate, N-acetyl cysteine, mercaptoacetic acid, mercaptopropionic acid, ⁇ -glutamyl cysteine, phytochelatins, thiolsalicylate, and the like.
  • the reference character n may represent any integer from 1 -10.
  • Other aromatic groups contemplated include naphthalene, anthracene, phenanthrene, and the like as set forth above.
  • Fig. 1 shows the weight loss results of a thermogravimeteric analysis on Si60 from a temperature range of 30 °C to 1000 °C with a temperature increase of 20 0 C/min and a flow rate of 1 10/55 mmHg (inlet/outlet pressure) performed in air atmosphere;
  • Fig 2 shows the weight loss results of a thermogravimeteric analysis on SiM l ; from a temperature range of 30 0 C to 1000 0 C with a temperature increase of 20 0 C/min and a flow rate of 1 10/55 mmHg (inlet/outlet pressure) performed at air atmosphere;
  • Fig. 3 shows the weight loss results of a thermogravimeteric analysis on SiAB9 produced from a first experimental procedure from a temperature range of 30 0 C to 1000 0 C with a temperature increase of 20 0 C/min and a flow rate of 1 10/55 mmHg (inlet/outlet pressure) performed at air atmosphere;
  • Fig. 4 shows the weight loss results of a thermogravimeteric analysis on SiAB9 produced from a second experimental procedure from a temperature range of 30 0 C to 1000 " C with a temperature increase of 20 0 C/min and a flow rate of 1 10/55 mmHg (inlet/outlet pressure) performed at air atmosphere;
  • FIG. 5 shows the chemical structures of various hydrophobic chelators according to the present invention, which are converted to hydrophilic chelators within the microenvironment; and [0021] Figures 6a and 6b show the chemical structures of various chelators according to the present invention, which may be introduced into a body in a hydrophilic state, reduced to a hydrophobic state in the body for partitioning into lipid-rich areas, and subsequently enzymatically returned to a hydrophilic state in vivo.
  • the present invention relates to novel sulfur-containing chelate ligands which bind metals and/or main group elements resulting in ligand- metal and/or ligand-main group element complex(es) which remain stable at a wide range of pH values.
  • the novel ligands are capable of forming covalent bonds with the metals and/or main group elements that may not be broken under most acidic or basic conditions.
  • the ligands of the present invention are suitable for binding metals and/or main group elements which are in or are capable of being placed in a positive oxidation state, including, but not limited to, yttrium, lanthanum, hafnium, vanadium, chromium, uranium, manganese, iron, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, lead, tin and the like.
  • the ligands of the present invention are also suitable for binding main group elements which are in or are capable of being placed in a positive oxidation state, hereinafter defined as including gallium, indium, thallium, boron, silicon, germanium, arsenic, antimony, selenium, tellurium, polonium, bismuth, molybdenum, thorium, plutonium and the like.
  • the present invention relates to chelate ligands consisting of an organic group from which depends at least one alkyl chain that terminates in a sulfur- containing group.
  • the chelate ligands may be of the general formula:
  • R " may be independently selected from a group comprising alkyls, aiyls, carboxyl groups, carboxylate esters, other organic groups that include, but are not limited to, acyls and amides, and biological groups that include, but are not limited to, proteins and amino acids such as cysteine
  • R " may be independently selected from a group comprising alkyls, aiyls, carboxyl groups, carboxylate esters, other organic groups that include, but are not limited to, acyls and amides, and biological groups that include, but are not limited to, proteins and amino acids such as cysteine
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rabidium, cesium, francium, alkyls, aryls, a carboxyl group, carboxylate esters, cysteine, homocysteine, glutathione, lipoic acid, dihydrolipoic acid, thiophosphate, N-acetyl
  • n may independently equal to 1 -6 or 1 -4.
  • m may equal 1-2 or 4-6, and in certain interesting embodiments, m equals 2.
  • X may be independently selected from a group comprising beryllium, magnesium, calcium, strontium, barium and radium.
  • the stability of the metal and/or main group element complexes formed through utilization of the ligands of the present invention is derived from the multiple interactions between the metal and/or main group element atoms and the sulfur and/or nitrogen atoms on the ligand. Accordingly, it is believed that the sulfur and/or nitrogen atoms form a multidentate bonding arrangement with a metal and/or main group element atom.
  • a metal and/or main group element atom may be bound through interactions with the multiple sulfur and/Or nitrogen atoms of the ligand.
  • a metal and/or main group element atom may be bound through interactions with the sulfur and/or nitrogen atoms of multiple ligands.
  • metal and/or main group element atoms may also be bound by the sulfur and/or nitrogen atoms of several ligands that include multiple alkyl chains.
  • the ligands may form metal and/or main group element complexes though the interactions between the metal and/or main group element atoms and the sulfur and/or nitrogen atoms of a single ligand, as well as form polymeric metal and/or main group element complexes through the interactions between the metal and/or main group element atoms and the sulfur and/or nitrogen atoms of multiple ligands.
  • the compounds may be bonded to supporting material Y at R .
  • Y may comprise filtration beads or be otherwise embedded or impregnated in a filtration medium.
  • Y may comprise polystyrene beads such that the sulfur-containing compounds are supported on the polystyrene beads for the filtration of contaminants.
  • the chelate ligands may be of the general formula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R J may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rubidium, cesium, francium, cysteine and glutathione
  • n independently equals 1-10
  • m 1 -6
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates, with the proviso that when R 1 represents an alkyl group, at least one X cannot simultaneously represent hydrogen.
  • chelate ligands may be of the general fonnula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R ⁇ may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R J may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rubidium, cesium, francium, cysteine and glutathione
  • n independently equals 1 -10
  • m 1 -6
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • the present invention relates to chelate ligands consisting of an organic stmcture from which depend two alkyl chains terminating in sulfur-containing groups.
  • the chelate ligands may be of the general formula:
  • R 1 may be selected from a group comprising benzene, pyridine, pyridin-4-one, naphthalene, anthracene, phenanfhrene and alkyl groups
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R 3 may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rubidium, cesium, francium, cysteine and glutathione
  • n independently equals 1 -10
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates
  • Z may be independently selected from a group comprising hydrogen, alkyls.
  • aryls a carboxyl group, carboxylate esters, a hydroxyl group, NH 2 . HSO 3 , halogens, a carbonyl group, organic groups, biological groups, polymers, silicas and silica supported substrates.
  • the present invention relates to chelate ligands consisting of an organic stmcture from which depend two alkyl chains temiinating in sulfur-containing groups.
  • the two sulfur atoms of the two alkyl chains share one X constituent.
  • the chelate ligands may be of the general formula:
  • R may be selected from a group comprising benzene, pyridine, pyridin-4-one, naphthalene, anthracene, phenanthrene and alkyl groups
  • R may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R J may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be selected from a group comprising beryllium, magnesium, calcium, strontium, barium and radium
  • n independently equals 1 - 10
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates
  • Z may be independently selected from a group comprising hydrogen, alkyls, aryls.
  • the present invention relates to chelate ligands consisting of a ring structure from which depend two alkyl chains terminating in sulfur-containing groups.
  • the chelate ligands may be of the general formula:
  • R ⁇ may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R 3 may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rubidium, cesium, francium, cysteine and glutathione
  • n independently equals 1-10
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • chelate ligands of the above general formula, wherein the R ⁇ 1 groups (as well as the R " groups) comprise hydrogen, both n equal 1 , and both Y comprise hydrogen may be referred to as "B9.”
  • the chelate ligands are of the formula:
  • n independently equals 1 -10.
  • Chelate ligands of this general fomiula may be referred to as “glutathione B9” or abbreviated to “GB9.”
  • the chelate ligand is of the formula:
  • the present invention relates to chelate ligands consisting of a ring stracture from which depend two alkyl chains terminating in sulfur-containing groups.
  • the two sulfur atoms of the two alkyl chains share one X group.
  • the chelate ligands may be of the general formula:
  • R " may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R " ' may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be selected from a group comprising beryllium, magnesium, calcium, strontium, barium and radium
  • n independently equals 1-10
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • the chelate ligands are of the formula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 may be independently selected from a group comprising alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rubidium, cesium, francium, cysteine, and glutathione
  • n independently equals 1 -10
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates. Chelate ligands of these general formulas may be referred to as "acid B9" or abbreviated to "AB9.”
  • the chelate ligands are of the fomiula:
  • R 1 may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • Rr may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising beryllium, magnesium, calcium, strontium, barium and radium
  • n independently equals 1 -10
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • the chelate ligands are of the fomiula:
  • R" may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups, n independently equals 1 -10, and Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • the chelate ligands are of the formula:
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • the chelate ligands are of the
  • R may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups, n independently equals 1 -10. and Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • Chelate ligands of this general formula may be referred to as "glutathione AB9" or abbreviated to "GAB9.” [0039] In one useful embodiment of GAB9, the chelate ligand is of the fomiula:
  • Y may be independently selected from a group comprising hydrogen, polymers, silicas and silica supported substrates.
  • the AB9 may be material supported with a structure of: where PS may be polystyrene or a co-polymer containing polystyrene.
  • PS may be chlorometlrylated polystyrene-co- divinylbenzene (2 % DVB, 200 - 400 mesh).
  • the material supported AB9 may be derivatized prior to the addition of AB9, or its equivalent, providing a structure with the formula:
  • AB9 may be loaded onto amine functionalized silica (Silica- ⁇ I - !.
  • Silica-NE produced by binding y- aminopropyltriethoxysilane on silica-60 (Si60), may be refluxed in a solution of AB9 in ethanol producing a structure of the formula:
  • SiN3 ⁇ 4 may be treated with AB9 in the presence of dicyclohexylcarbodiimide (DCC) to facilitate the coupling of the AB9 to the amine of the PS.
  • DCC dicyclohexylcarbodiimide
  • the chelate ligands are of the formula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, mbidium, cesium, francium, cysteine and glutathione
  • n independently equals 1 -10
  • Y is a methyl group.
  • Chelate ligands of these general fomiulas may be referred to as "methyl ester AB9" or abbreviated to "MEAB9.”
  • the chelate ligands are of the formula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising beryllium, magnesium, calcium, strontium, barium and radium
  • n independently equals 1-10
  • Y is a methyl group.
  • the chelate ligands are of the formula:
  • R " may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups, n independently equals 1 - 10, and Y is a methyl group.
  • the chelate ligands are of the formula:
  • the chelate ligands are of the formula:
  • R ⁇ may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups, n independently equals 1 -10, and Y is a methyl group.
  • Chelate ligands of this general formula may be referred to as "glutathione methyl ester AB9" or abbreviated to "GMEAB9.” [0049] In one useful embodiment of GMEAB9, the chelate ligands are of the fomiula:
  • the chelate ligands are of the fomiula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising hydrogen, lithium, sodium, potassium, rabidium. cesium, francium, cysteine and glutathione, n independently equals 1 -10
  • Y is an ethyl group.
  • Chelate ligands of this general formula may be referred to as "ethyl ester AB9" or abbreviated to "EEAB9.”
  • the chelate ligands are of the formula:
  • R may be selected from a group comprising benzene, pyridine, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • X may be independently selected from a group comprising beryllium, magnesium, calcium, strontium, barium and radium
  • n independently equals 1 - 10
  • Y is an ethyl group.
  • the chelate ligands are of the formula:
  • R 2 may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups, n independently equals 1 -10, and Y is an ethyl group.
  • the chelate ligands are of the formula:
  • the chelate ligands are of the formula:
  • R ⁇ may be independently selected from a group comprising hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups, n independently equals 1 -10, and Y is an ethyl group.
  • Chelate ligands of this general formula may be referred to as "glutathione ethyl ester AB9" or abbreviated to "GEEAB9.”
  • the chelate ligands are of the fonmila:
  • the chelate ligands are of the formula:
  • R is selected from a group including benzene, pyridine, pyridin-4-one, naphthalene, anthracene, phenanthrene and alkyl groups
  • R 2 is independently selected from a group including hydrogen, alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups
  • R' is independently selected from a group including alkyls, aryls, a carboxyl group, carboxylate esters, organic groups and biological groups.
  • X hydrogen.
  • R hydrogen
  • R J a carboxyl group
  • X hydrogen
  • Y hydrogen
  • Z a hydroxyl group as is shown below:
  • aromatic groups other than benzene and pyridine for the introduction of the thiol and thiolate groups.
  • naphthalene, anthracene, phenanthrene, etc. can be used.
  • novel ligands of the present invention may also be adapted to a variety of environmental situations requiring binding and/or removal of metals and/or main group elements, such as, for example, additives in flue gas
  • FGD desulphurization
  • the present disclosure relates to a method of removing metals and/or main group elements from a starting material.
  • the method of the present invention comprises contacting a starting material (gas, liquid or solid) with an effective amount of a novel sulfur-containing chelate ligand as described above for a sufficient time to form at least one stable ligand-metal and/or ligand-main group element complex(es).
  • the ligand-metal and/or ligand-main group element complex(es) may remain stable through a range of acidic and basic pH values.
  • the ligand-metal and/or ligand-main group element complex(es) do not release appreciable amounts of the contaminant element(s) through a range of acidic and basic pH values.
  • the B9-Hg complex precipitate does not release appreciable amounts of mercury within a pH range from about 1 to about 13.
  • ligand-metal and/or ligand-main group element complex(es) do not release appreciable amounts of the contaminant elements within a pH range from about 6 to about 8.
  • the present disclosure relates to a method of treating water, such as surface, ground, or waste water, containing metals and/or main group elements, comprising admixing said water with an effective amount of the sulfur- containing chelate ligand as described above for a sufficient time to form at least one stable ligand-metal and/or ligand-main group element complex(es). and separating said complex(es) from said water.
  • the present disclosure relates to a method of treating aqueous acid mine drainage or water from actual mining processes containing soft heavy metals and/or main group elements, 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 at least one stable ligand-metal and/or ligand-main group element complex(es). and separating said complex(es) from said acid mine drainage.
  • the present disclosure relates to a method of remediation of soil containing soft heavy metals and/or main group elements, comprising admixing said soil with an effective amount of the sulfur-containing chelate ligand as described above for a sufficient time to form at least one stable ligand-metal and/or ligand-main group element complex(es).
  • the soil so treated may then be left in situ or removed for disposal without concerns regarding leaching of said metals and/or main group elements into the environment.
  • the present disclosure relates to a method of treating a gas, such as an emissions gas from a power plant containing soft heavy metals and/or main group elements, comprising passing said gas through a filter utilizing an effective amount of the sulfur-containing chelate ligand as described above to form at least one stable ligand-metal and/or ligand-main group complex(es), therefore filtering said complex from said gas.
  • a gas such as an emissions gas from a power plant containing soft heavy metals and/or main group elements
  • the present disclosure relates to a method of
  • the chelators find use in binding and clearance of a variety of heavy metals and/or main group elements, including without limitation mercury, lead, arsenic, cadmium, tin, bismuth, indium, nickel, copper, thallium, gold, silver, platinum, uranium, iron, molybdenum, thorium, polonium, plutonium. antimony, and the like.
  • the method comprises selecting chelate ligands as described herein and modifying the ligands to the desired state of hydrophilicity or hydrophobicity in accordance with the tissue into which the chelator is desired to partition. Still further, the method described herein contemplates modifying such chelators such that an initially hydrophilic chelator derivative is rendered hydrophobic after administration, to more effectively partition into intracellular areas and lipid-containing tissues. Even further, it is contemplated to provide a chelator derivative which is initially hydrophobic for partitioning into lipid-containing tissues for clearance via a fecal route, and after such partitioning is rendered hydrophilic for clearance via the kidney.
  • glutathione, sulfate for removal through naturally designed systems.
  • a chelate ligand such as those described above may be coupled to a charged molecule having a terminal sulfbydryl group to provide a hydrophilic derivative for delivery. After distribution of the derivative, such as by intravenous delivery, the derivative reverts to the hydrophilic form via a reductive process in the bloodstream, releasing the original hydrophobic chelate ligand and the previously coupled charged molecule.
  • the charged molecule is coupled to the starting chelate ligand compound via disulfide bonds, which are readily reduced in the body to release the chai'ged molecule and the hydrophobic chelate ligand which then partitions into lipid-containing tissue.
  • Such charged compounds should be non-toxic, natural compounds having a free thiol group.
  • the hydrophobic chelate ligand partitions into lipid-containing tissues, existing in close proximity to a majority of the body burden of heavy metals and thereby improving the effectiveness of the chelator by such proximity.
  • a variety of natural and synthetic charged molecules including terminal sulfhydryl groups are contemplated herein (e.g., glutathione, cysteine, homocysteine, lipoic acid, dihydrolipoic acid, thiophosphate, N-acetyl cysteine, mercaptoacetic acid, mercaptopropionic acid, ⁇ -glutamyl cysteine, phytochelatins and thiolsalicylate).
  • 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. Examples 1 -8 are directed to embodiments of the above-detailed chelate ligands, and Examples 9-18 are directed to embodiments of the above-detailed chelate ligands that are material supported.
  • L-cysteine hydrochloride (5.0 mmol) obtained from Sigma-Aldrich® was dissolved in 100 mL deionized water.
  • THF tetrahydrofuran
  • the isophthaloyl chloride dissolved in THF was slowly added to the flask. As the reaction proceeded, the color of the reaction mixture turned to light yellow. The reaction mixture continued stirring for 16-18 hours. At the end of the 16-18 hours, the aqueous layer was extracted utilizing 100 niL of ethyl acetate. The ethyl acetate layer was then dried over sodium sulfate, filtered, and evacuated to dryness. The product was recovered as a light yellow solid. The product was soluble in CHCI3, acetone, ethanol and water.
  • GAB9, GMEAB9 and GEEAB9 may also be synthesized utilizing similar methods.
  • EEAB9 (as detailed in Example 3 above) was injected subcutaneously into rats at levels as high as 1.5 millimoles per kg of body weight. This represented 100 to 1 ,000 times the concentration expected to be used in chelation therapies for heavy metal toxicity. No detectable negative effects were observed as determined by physical activity and weight gain.
  • Rats were injected eveiy three days with the EEAB9 (as detailed in Example 3 above) at 300, 400 and 1 ,500 micromoles per kg body weight with no observable toxic effects or weight loss. This represented an exposure of over 2,700 micromoles per kg body weight over a 10 day period with no observable toxic effect.
  • the chelate ligands were dissolved in dimethyl sulfoxide (DMSO, 0.5 ml) before addition to the flasks.
  • DMSO dimethyl sulfoxide
  • the experimental treatments evaluated are as listed in Table 1 below, and included mercuric acetate, B9, EEAB9, GB9, GEEAB9, and DMSO in the amounts shown in Table 1.
  • B9 and EEAB9 were dissolved in DMSO (0.5 ml) before addition to the water. No precipitate was formed during the dissolution. When mercuric acetate solution in water was added, a precipitate foraied.
  • PS-AB9 loaded polystyrene was attempted by first derivatizmg PS-CH 2 C1. This follows the literature procedure found in Roscoe, S.B., et. al Journal of Polymer Science: Part A: Polymer Chemistry, 2000, 38, 2979-2992. First PS-CHb-NHEt was prepared. [0090] PS beads were stirred with 2.0 M solution of ethylamine in THF for 2 days and then rinsed with water and THF and a series of (v/v) mixtures of water/THF (2: 1 , 1 : 1 , 1 :2) to purify the product which was then dried at about 40 °C. The product was characterized by infrared spectroscopy and found to match the spectrum found in the literature.
  • PS-CF -NHEt was stirred with an ethanol or methanol solution of AB9 for about 24 hours. In the alternative, other solvents such as pyridine could also be used. The beads were washed with ethanol or methanol and dried at about 40 °C. The product was characterized by infrared spectroscopy and elemental analysis.
  • PS-AB9 was prepared by derivatizing polystyrene beads but on a 20 g scale.
  • Polystyrene beads (20 g) were stirred with 120 ml 2.0 M solution of ethylamine in THF for 2 days. After 2 days, the beads were then filtered and rinsed with 200 mL of THF and 200 mL of water and a series of (v/v) mixtures of water/THF (2: 1 , 1 : 1 , 1 :2, 200 mL each) and then dried at about 40 °C.
  • PS-CH 2 -NHEt beads (20 g) where then refluxed with AB9 (30 g) in 300 mL of ethanol for about two days. The beads were filtered and washed about five times with 200 mL of ethanol and dried at about 40 °C. The products from each step were characterized by infrared spectroscopy.
  • PS-C3 ⁇ 4-AB9 (202 mg, 400 mg and 600 mg) was added to HgCL (15ppm) in 25 ml of water and stirred one day at room temperature. After stirring, the beads were isolated by filtering through a 0.2 ⁇ environmental express filter and the solutions were digested for inductively coupled plasma spectrometiy analysis. This was conducted at 1 10 °C by sequentially adding, 10 mL 1 : 1 HN0 3 , 5 mL cone. HNO3, 5 mL H 2 0 2 and 10 mL cone. HCl.
  • a solution of excess AB9 in ethanol could be added to polystyrene beads (chloromethylated polystyrene-co- divinylbenzene (2% DVB) (200-400 mesh). This may ensure that each polystyrene bead reacted with an excess of AB9 to prevent cross-linking of the ligand.
  • the mixture could be stirred for -24 hours with and without heating to drive off HC1. If the resulting solution is acidic, any remaining acid could be neutralized with 5 % NaHC0 3 .
  • ⁇ ' Hh may be added with the ligand solution, without heating, to effect HC1 elimination as [HNEt 3 ]Cl.
  • the beads may then be washed with ethanol and water and dried at ⁇ 40 °C.
  • Infrared characterization could be conducted to observe the PS-attached group, SH, NH and the remaining carboxylate. Elemental analysis could be used to detemiine the amount of AB9 present on the PS beads. Additionally, the PS-AB9 may be treated with dilute HC1 and the AB9 isolated and analyzed.
  • amine-functionalized silica (SiNH?) was produced for AB9 binding. This was conducted following the procedure set forth in: Cai, M. et al. Journal of Molecular Catalysis A: Chemical. 2007, 268, 82 and Jyothi, T. M, et al; Chem. Int. Ed. 2001 , 40, 2881.
  • a suspension of silica-60 (20 g) in toluene (500 mL) was refluxed with y-aminopropyltriethoxysilane (15.70 g, 71.36 mmol) in chloroform (40 mL) at -100 °C for 48 h.
  • SiMe 3 Cl derivatization of unprotected hydroxyl groups.
  • Infrared Spectroscopy (cm "1 ) was used to determine the functionality (- NH 2 , -CH 2 -, -OH) on the silica surface. A broad peak at 3434 and 3050 (-CH 2 -) was observed. It was found that the peak intensity at 3459 was decreased drastically after treatment of silica particles with amine. Elemental analysis of Si-NH 2 (%) produced: C 7.71 ; H 2.42; N 2.72; O 9.37; Si 32.87; S 0.03; (Silica-60: C 0.05: H 1 .26; N 0.01 ; O 7.22; Si 42.60; S ⁇ 0.01). The nitrogen content was found to be 1.94 mmol/of SiNH 2 /u Si60.
  • thermogravimetric analysis was performed on Silica-60 and SiNl 1 . at a temperature range of 30 °C to 1000 °C, a temperature increase of 20 "C/min; and a flow rate of 1 10/55 mmHg (inlet/outlet pressure); all at air atmosphere.
  • the TGA analysis of Silica-60 (Si60), SiM I ⁇ showed that the pattern of weight loss changed significantly when Si60 was treated with ⁇ - aminopropyltriethoxysilane.
  • the initial weight losses in both traces correspond to loss of coordinated water.
  • the Si60 with terminal hydroxyl groups is capable of hydrogen bonding a much larger amount of water than the Si60-NH2. Subsequent heating of Si60 causes condensation of the tenninal hydroxyl groups to eliminate water.
  • the mass loss represents loss of the organic amine from the silica surface.
  • thiol functionalities on the surface of silica particles is characterized by elemental analysis (Cai, 2007), Raman spectroscopy, powder X-ray diffraction and scanning electron microscopy (Nakamura, 2007). Due to strong Raman scattering, the thiol groups are detected by Raman spectroscopy. Elemental analysis provides nitrogen content on the silica particle. X-ray diffraction is used to find out the regularity of particles and the change in particle size was determined by scanning electron microscopy.
  • Infrared spectroscopy (cm "1 ) produced a broad peak at 3440 and very small peak at 3050. Also there was peak at 1538 (-NH). Elemental Analysis (%) produced: C 8.34; H 2.42; N 2.75; O 6.85; Si 34.05; S 0.22; (Si60: C 0.05; H 1.26; N 0.01 ; O 7.22; Si 42.60; S ⁇ 0.01 ). The sulfur content was also found to be 0.034 mmol SiAB9/g of Si60.
  • thermogravimetric analysis was performed on SiM f- treated with AB9 in the presence of DCC at a temperature range of - 30°C to 1000°C, a temperature increase of 20 °C/min; and a flow rate of 1 10/55 mniHg; all at air atmosphere. It was found that there is no significant change in thermogravimetric analysis of SiAB9. This might be due to small amount of AB9 present per g of SiAB9. But the pattern of TGA of SiAB9 synthesized by refluxing in EtOH changed from the TGA of SiNH 2 . This might be due to larger amount of AB9 per g of SiAB9, which is also evident from the ICP analysis data of sulfur.
  • SiAB9 beads 500 mg were digested at 1 10 °C by addition of 10 mL water, 10 mL 1 : 1 HN0 3 , 5 mL cone. HNO 3 , 5 mL H 2 0 2 and 10 mL cone. HC1. After digestion, the solutions were filtered to isolate the beads and the final volume of the sample was 50 mL. The solutions were then analyzed by ICP to determine the sulfur content:
  • thermogravimetric analysis was performed on SiN i l treated with AB9 refluxed in EtOH at a temperature range of 30 °C to 1000 °C, a temperature increase of 20 °C/min; and a flow rate of 1 10/55 mmHg; all at air atmosphere. Furthermore, inductively coupled plasma analysis was performed.
  • SiAB9 beads 500 mg were digested at 1 10°C by addition of 10 mL water, 10 mL 1 : 1 HNO 3 , 5 mL cone. HN0 3 , 5 mL H 2 0 2 and 10 mL cone. HC1. After digestion, the solutions were filtered to isolate the beads and the final volume of sample was 50 mL. The solutions were then analyzed by 1CP to determine the sulfur content:
  • Si60 200 mg and 600 mg was added to HgCl 2 ( ⁇ 5 ppm) in water (50 mL) and stirred for 1 day at room temperature. The pH of the solution was 5.5-6.0 and was monitored by Corning 313 pH meter. After stirring, the beads were isolated by filtration through a 0.2 ⁇ filter (Environmental Express) and the solutions were digested for ICP analysis. This was conducted at 1 10 °C by adding, 10 mL 1 : 1 HNO 3 , 5 mL cone. HNO3, 5 mL H2O2 and 10 mL cone. HC1. The removal of Hg by Si60 was then determined:
  • SiAB9 200 mg and 600 mg was added to HgCl 2 ( ⁇ 5 ppm) in water (50 mL) and stirred for 1 day at room temperature. pH of the solution was 5.5-6.0 and was monitored by Coming 313 pH meter. After stirring, the beads were isolated by filtration through a 0.2 ⁇ filter (Environmental Express) and the solutions were digested for 1CP analysis. This was conducted at 1 10 °C by sequentially adding. 10 mL 1 : 1 UNO .-. 5 mL cone. HN0 3 , 5 niL H 2 0 2 and 10 mL cone. HC1.
  • Si60 200 mg and 600 mg was added to NaAs0 2 (-200 ppb) in water (50 mL) and stirred for 1 day at room temperature. After stirring, the beads were isolated by filtration through a 0.45 ⁇ filter (Environmental Express) and the solutions were digested for inductively coupled plasma spectrometry analysis. This was conducted at 95 °C by adding 2.5 mL cone. HN0 3 .
  • SiAB9 (synthesized by refluxing in EtOH) with NaAs0 2 remediation of As(III)
  • SiAB9 200 mg and 600 mg
  • NaAs0 2 -200 ppb
  • water 50 niL
  • the beads were isolated by filtration through a 0.45 ⁇ filter (Environmental Express) and the solutions were digested for inductively coupled plasma spectrometiy analysis. This was conducted at 95 °C by adding 2.5 mL cone. HNO 3 .
  • the solid sample was taken from the filter frit and washed with ethanol to release any physisorbed Hg(0). Then 2g of the solid sample was digested using the EPA 30-50B method and analyzed on the ICP along with the traps, which did not need to be digested.
  • the Silica-AB9 was able to fill 85% of its binding sites with Hg. There were some Hg(0) vapor to pass. However, doing a smaller PTFF run or a larger sample size for an hour may reach the desired 100% Hg(0) vapor capture.

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