RELATED APPLICATIONS 0001 This application claims provisional priority to U.S. Provisional Patent Application Serial No. 60/293,150 filed May 23, 2001.

BACKGROUND OF THE INVENTION 0002 1. Field of the Invention 0003 The present invention relates to anionic ion pairing reagents and families of anionic ion pairing reagents, where combustion products of the reagents are volatile and include O atoms or S atoms or halogen atoms or combinations thereof as their only heteroatoms, and where the reagents can be used in conjunction with gas-phase or vapor-phase element-specific detectors. 0004 More particularly, the present invention relates to anionic ion pairing reagents and families of anionic ion pairing reagents including an anion and a counterion, where combustion products of the reagents are volatile and include O atoms or S atoms or halogen atoms or combinations thereof as their only heteroatoms, and where the reagents can be used in conjunction with gas-phase or vapor-phase element-specific detectors (ESDs), such as nitrogen-selective gas-phase chemiluminescence detectors, nitrogen-phosphorus thermoionic detectors, atomic emission plasma detectors, inductively-coupled plasma-mass spectrometric (ICP-MS) detectors, element-specific GC detectors such as nitrogen or phosphorus specific GC detectors, etc. 0005 2. Description of the Related Art 0006 In order to form an anionic ion pairing reagent, an anion with a hydrophobic portion and a counterion, a cation, must be present. Typically, the hydrophobicity of the counterion is low to promote interactions between cationic analytes and the anionic pairing ions. The counterion of the anionic pairing ion can be derived either from strong electrolytes or weak electrolytes. 0007 The typical anionic ion pairing reagents are derived from weak acids (i.e., acids with pKa values in the 2 to 10 range) or strong acids and contain sufficiently hydrophobic alkyl, cycloalkyl, aryl or alkylaryl moieties. Typically, the weak acid-derived anionic pairing ions are carboxylate ions, phenolate ions, phosphate ions, phosphonate ions or boronate ions; while the strong acid-derived anionic pairing ions are sulfonate ions or organic sulfate ions. The counterions are typically alkali metal cations, alkaline earth metal cations, protonated amine cations, quaternary ammonium cations or phosphonium cations. Typically, ion pairing reagent compositions that contain only strong electrolyte ions are preferred, because they do not significantly alter the pH of the solutions that contain them, and because they typically do not participate in acid-base reactions. 0008 Present anionic ion pairing reagents that include protonated amine cations or quaternary ammonium cations are undesirable when used with nitrogen-selective detectors, because they contribute a high background signal level; while alkali metal cations, alkaline earth metal cations or phosphonium cations are undesirable when used with gas-phase ESDs, because the combustion products of these counterions are not sufficiently volatile to leave the gas-phase detector systems as vapors or gases and they tend to contaminate the detector systems. 0009 Thus, there is a need in the art for anionic ion pairing reagents and anionic ion pairing reagent systems whose combustion products do not significantly interfere with post-combustion element-specific detection or detector systems.

SUMMARY OF THE INVENTION 0010 The present invention provides anionic ion pairing reagent compositions, whose combustion products are volatile and include O atoms or S atoms or halogen atoms or combinations thereof as their only heteroatoms, and where the reagents can be used in conjunction with gas-phase or vapor-phase, element-specific detectors (ESDs), such as nitrogen-selective gas-phase chemiluminescence detectors, atomic emission plasma detectors, inductively-coupled plasma mass spectrometric (ICP-MS) detectors, element-specific GC detectors such as nitrogen or phosphorus specific GC detectors, etc. 0011 The present invention also provides qualitative or quantitative analytical applications using the anionic ion pairing reagents of this invention for determination of an analyte including chromatographic, electrophoretic and extractive separation or flow-injection analysis of analytes which contain heteroatoms other than O or S or halogen atoms or their combinations. 0012 The present invention also provides anionic ion pairing reagent compositions including an anion and a counterion, where the anion has a hydrophobic portion and a hydrophilic portion and where combustion products of the anion and the counterion are volatile and have only O or S or halogen atoms or combinations thereof as heteroatoms. 0013 The present invention also provides anionic ion pairing reagent compositions formed in situ from a strong and/or weak acid and a base which react to form an anion and a counterion of this invention, where the anion has a hydrophobic portion and a hydrophilic portion, and where combustion products of the anion and the counterion are volatile and have only O or S or halogen atoms or combinations thereof as heteroatoms. 0014 The present invention also provides an anionic ion pairing reagent system covering a desired hydrophobicity range including a plurality of anionic ion pairing reagents or in situ formed pairing ions of this invention. 0015 The present invention also provides anionic ion pairing reagent compositions including an anion selected from the group consisting of carboxylate ions, phenolate ions, sulfonate ions, organic sulfate ions (ROS(O)2O) and mixtures or combinations thereof having volatile combustion products with only O or S or halogen atoms or combinations thereof as heteroatoms. 0016 The present invention also provides a counterion selected from the group consisting of oxonium ions, sulfonium ions, sulfoxonium ions and mixtures or combinations thereof having volatile combustion products with only O or S or halogen atoms or combinations thereof as heteroatoms. 0017 For in situ formed pairing ions, the acids are selected from the group consisting of the acid forms of carboxylic ions, phenolate ions, sulfonate ions, organic sulfate ions (ROS(O)2OH) and mixtures or combinations thereof having volatile combustion products with only O or S or halogen atoms or combinations thereof as heteroatoms, and the bases are selected from the group consisting of oxonium hydroxides, sulfonium hydroxides, sulfoxonium hydroxides and mixtures or combinations thereof having volatile combustion products with only O or S or halogen atoms or combinations thereof as heteroatoms. 0018 The present invention also provides an analytical system for detecting an analyte, where the system includes a combustion zone in which a sample including at least one analyte and at least one anionic pairing ion of this invention is converted to its corresponding combustion products and a detector capable of detecting at least one of the analyte combustion products. 0019 The present invention also provides a method including the steps of dissolving a sample comprising at least one analyte in a solution comprising at least one anionic ion pairing reagent of this invention, combusting the solution and the sample to their corresponding combustion products and detecting at least one analyte combustion product. 0020 The present invention also provides a method including the steps of dissolving a sample comprising at least one analyte in a solution comprising at least one anionic ion pairing reagent of this invention, combusting the solution and the sample to their corresponding combustion products, converting at least one of the analyte combustion products into a transformate and detecting at least one transformate. 0021 The present invention also provides a method for forming an anionic ion pairing reagent in situ including the steps of dissolving at least one strong and/or weak acid having a hydrophobic portion in a solvent to form a solution, adding a base to the solution to convert the acid into an anionic pairing ion to be used according to the present invention, where combustion products of the acid and base are volatile and have only O or S or halogen atoms or combinations thereof as heteroatoms. 0022 The present invention also provides an analytical system for detecting an analyte including a separation apparatus that separates a sample comprising an analyte or a plurality of analytes and at least one in situ formed anionic pairing ion or anionic ion pairing reagent of this invention, a combustion zone where each constituent is converted to its corresponding combustion products and a detector capable of detecting at least one analyte combustion product. 0023 The present invention also provides an analytical system for detecting an analyte including a separation apparatus that separates a sample comprising an analyte or a plurality of analytes and at least one in situ formed anionic pairing ion or anionic ion pairing reagent of the present invention, a combustion zone where each constituent is converted to its corresponding combustion products, a transformation zone where at least one analyte combustion product is converted into a transformate and a detector capable of detecting at least one transformate. 0024 The present invention also provides an analytical system for detecting an analyte including a separation apparatus that separates a solution comprising an analyte or a plurality of analytes and at least one in situ formed anionic pairing ion or anionic ion pairing reagent of this invention, a combustion zone where each constituent is converted to its corresponding combustion products and a detector capable of detecting at least one analyte combustion product. 0025 The present invention also provides an analytical system for detecting an analyte including a separation apparatus that separates a solution comprising an analyte or a plurality of analytes and at least one in situ formed anionic pairing ion or anionic ion pairing reagent of the present invention, a combustion zone where each constituent is converted to its corresponding combustion products, a transformation zone where at least one analyte combustion product is converted into a transformate and a detector capable of detecting at least one transformate.

DESCRIPTION OF THE DRAWINGS 0026 The invention can be better understood with reference to the following detailed description together with the appended illustrative drawings in which like elements are numbered the same: 0027 FIG. 1 graphically depicts the 300 MHz 1H NMR spectrum of the D2O solution of trimethylsulfonium n-octylsulfonate, a typical, anionic ion pairing reagent composition of the present invention whose combustion products are volatile and free of heteroatoms other than O and S. 0028 FIG. 2 graphically depicts the 75 MHz 13C NMR spectrum of the D2O solution of trimethylsulfonium n-octylsulfonate, atypical, anionic ion pairing reagent composition of the present invention whose combustion products are volatile and free of heteroatoms other than O and S.

DETAILED DESCRIPTION OF THE INVENTION 0029 The inventor has found that a new class of anionic ion pairing reagents and anionic ion pairing reagent systems can be constructed that allow element specific detection of analytes without the typical contamination of the analytes by the combustion products of the anionic ion,pairing reagent components that contain a desired detectable element or lack the needed volatility to pass through the analytical system without fouling the system. The anionic ion pairing reagent compositions that have volatile combustion products and include only O or S or halogen atoms or their combinations as the only heteroatoms make possible the use of ESDs in areas which hitherto have been unaccessible to ESDs, because prior art anionic ion pairing reagent compositions included undesired heteroatoms (e.g., nitrogen atoms in amines and quaternary ammonium compounds), or atoms whose combustion products are nonvolatile and cannot leave the analytical system components such as the ESDs as vapors or gases thereby contaminating the components such as the ESDs (e.g., phosphorus atoms in organophosphate and phosphonium compounds or metals). 0030 The present invention broadly relates to anionic ion pairing reagents and families of anionic ion pairing reagents or in situ formed anionic pairing ions or families of in situ formed anionic pairing ions whose combustion products are volatile and have only O or S or halogen atoms or their combinations as heteroatoms, where the reagents or in situ formed anionic pairing ions can be used in conjunction with gas-phase or vapor-phase element-specific detectors. 0031 Although the reagents are designed for use primarily in aqueous solution, where the solvent in water, the reagents can also be used with non-aqueous or mixed aqueous/non-aqueous solvent systems such as solvent systems including, water, a lower alcohol, a lower carboxylic acid, a lower ether, a lower cycle ether, a lower ester, a lower ketone, a lower haloalkane, and/or a lower hydrocarbon or mixtures and combinations thereof. The term lower means that the compounds contain 10 or fewer carbon atoms, preferably 8 or fewer carbon atoms, and particularly 6 or fewer carbon atoms. All of the solvents for use in this invention must have volatile combustion products with O or S or halogen atoms or combinations thereof as their only heteroatoms. 0032 The present invention also relates to anionic ion pairing reagent systems capable of covering a desired hydrophobicity range comprised of a plurality of anionic ion pairing reagents or families of anionic ion pairing reagents or in situ formed anionic pairing ions of this invention. 0033 The present invention also relates to an analytical system for detecting an analyte including a combustion chamber where an analyte dissolved in a solution comprising at least one anionic ion pairing reagent or in situ formed anionic pairing ion of this invention is converted to its corresponding combustion products and a detector capable of detecting at least one analyte combustion product. 0034 The present invention also relates to a method including the steps of dissolving a sample including at least one analyte in a solution comprising at least one anionic ion pairing reagent or in situ formed anionic pairing ion of this invention, combusting the solution and the sample into their corresponding combustion products and detecting at least one combustion product of the analyte. 0035 The present invention also relates to an analytical system for detecting an analyte including a separation apparatus where a sample comprising at least one analyte dissolved in a solution comprising at least one anionic ion pairing reagent or in situ formed anionic pairing ion of the present invention is separated into its constituents, a combustion chamber where each constituent of the sample is converted to its corresponding combustion products and a detector capable of detecting at least one analyte combustion product. 0036 The anionic ion pairing reagents or reagent systems or in situ formed anionic pairing ions or pairing ion systems of this invention are characterized by at least the following properties: (1) each combustion product of each anionic ion pairing reagent or in situ formed anionic pairing ion is volatile at the operating conditions of the detection system and includes only O or S or halogen atoms or their combinations as heteroatoms; (2) each anionic ion pairing reagent or in situ formed anionic pairing ion includes a hydrophobic portion; (3) each anionic ion pairing reagent or in situ formed anionic pairing ion provides adequate ion pairing ability over its application range; and (4) each anionic ion pairing reagent or in situ formed anionic pairing ion permits variation of the solubility, hydrophobicity and/or electrophoretic mobility of the counterion(s) to match the requirements or constraints of the analytical system used. 0037 An anionic ion pairing reagent of this invention comprises a weak acid-derived anion or a strong acid-derived anion and a strong base-derived cationic counterion. An in situ formed anionic pairing ion is derived from a weak acid and a base or a strong acid and a base. 0038 Suitable anionic pairing ions for use in the construction of the anionic ion pairing reagents of this invention include anions having a hydrophilic portion and a hydrophobic portion, where the hydrophobic portion is sufficient to impart a desired hydrophobicity to the anion and where the anions form volatile combustion products and the combustion products include only O or S or halogen atoms or their combinations as heteroatoms at the operating conditions of the detection system. 0039 Suitable hydrophobic portions or groups include, without limitation, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aromatic groups, halogenated derivatives thereof or combinations and mixtures thereof and suitable hydrophilic portions or groups include, without limitation, one or more carboxylate groups (COO), one or more sulfonate groups (SO3), one or more organic sulfate half ester groups (OSO3) or mixtures or combinations thereof; all having volatile combustion products at the operating conditions of the detection system and where the combustion products include O or S or halogen atoms or combinations thereof as their only heteroatoms. 0040 Exemplary anions for use in the anionic ion pairing reagents of this invention include, without limitation: 0041 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic monocarboxylates; 0042 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic moieties having two or more carboxylate groups, 0043 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic monosulfonates, 0044 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic moieties having two or more sulfonate groups, 0045 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic sulfate half esters, 0046 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic moieties having two or more sulfate half ester groups; 0047 halogenated derivatives thereof or mixtures or combinations thereof, where all anions form volatile combustion products and include only O or S or halogen atoms or their combinations as heteroatoms at the operating conditions of the detection system. 0048 Suitable cationic counterions for use in the construction of anionic pairing ion reagents of this invention include, without limitation, oxonium cations, sulfonium cations, sulfoxonium cations or mixture or combinations thereof, where all counterions form volatile combustion products that include only O or S or halogen atoms or their combinations as heteroatoms at the operating conditions of the detection system. 0049 Exemplary acids for in situ formed anionic pairing ions of this invention include, without limitation: 0050 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic monocarboxylic acids; 0051 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic moieties having two or more carboxylic acid groups, 0052 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic monosulfonic acids, 0053 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic moieties having two or more sulfonic acid groups, 0054 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic sulfate half esters in their acid form, 0055 alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl or aromatic moieties having two or more sulfate half ester groups in their acid forms; 0056 halogenated derivatives thereof or mixtures or combinations thereof, where all anions form volatile combustion products and include only O or S or halogen atoms or their combinations as heteroatoms at the operating conditions of the detection system. 0057 Suitable bases for in situ forming of anionic pairing ions from weak and/or strong acids include, without limitation, oxonium hydroxides, sulfonium hydroxides, sulfoxonium hydroxides or mixture or combinations thereof, where all bases form volatile combustion products that include only O or S or halogen atoms or their combinations as heteroatoms at the operating conditions of the detection system. 0058 Preferred anionic pairing ions for use in the construction of anionic ion pairing reagents of this invention having volatile combustion products with O or S or halogen atoms or their combinations as their only heteroatoms at the operating conditions of the detection system include, without limitation, n-alkylcarboxylate ions, n-alkylsulfonate ions, n-alkylsulfate ions or mixtures or combinations thereof, where the n-alkyl groups have one or more carbon atoms, preferably two or more carbon atoms, particularly three or more carbon atoms, and especially four or more carbon atoms. For in situ formed anionic pairing ions, the corresponding acids are preferred. 0059 Particularly preferred S-containing anionic pairing ions for use in the construction of anionic ion pairing reagents of this invention having volatile combustion products with O or S or halogen atoms or their combinations as their only heteroatoms at the operating conditions of the detection system include, without limitation, n-alkylsulfonate ions or n-alkylsulfate ions or mixtures or combinations thereof where the n-alkyl group has one or more carbon atoms, preferably two or more carbon atoms, particularly three or more carbon atoms, and especially four or more carbon atoms. For in situ formed anionic pairing ions, the corresponding acids are preferred. 0060 Preferred cationic counterions for use in the construction of anionic pairing ion reagents of this invention having volatile combustion products with O or S or halogen atoms or their combinations as their only heteroatoms at the operating conditions of the detection system include, without limitation, aryl pyrillium ions, R1, R2, R3-sulfonium ions, or R1, R2, R3-sulfoxonium ions or mixtures or combinations thereof, where R1, R2 and R3 are the same or different and are an alkyl group, cycloalkyl group, alkylcycloalkyl group, alkylaryl group, cycloalkylaryl group, arylalkyl group, arylcycloalkyl group, aryl group, alkyleneoxide group, alkylenesulfide group or halogenated derivatives thereof. Generally, the Ri groups (i1,2 or 3) have fewer than 20 carbon atoms, preferably, fewer than 10 carbon atoms, particularly, fewer than 5 carbon atoms, and especially, fewer than 2 carbon atoms, where the R1 can be used to adjust the solubility, hydrophobic-hydrophilic balance and/or electrophoretic mobility of the counterion. For in situ formed anionic pairing ions, the corresponding bases are preferred. 0061 Exemplary examples of cationic counterions for use in the construction of anionic ion pairing reagents of this invention having volatile combustion products with O or S or halogen atoms or their combinations as their only heteroatoms at the operating conditions of the detection system include, without limitation, trimethylsulfonium ion, which can be obtained from trimethylsulfonium iodide, diethylmethylsulfonium ion, which can be obtained from its respective alkyl sulfide and methyl iodide, trimethylsulfoxonium ion, which can be obtained from trimethylsulfoxonium iodide, diethylmethylsulfoxonium iodide, which can be prepared from its respective alkyl sulfoxides and methyl iodide. For in situ formed anionic pairing ions, the corresponding bases can be obtained by conversion of the respective iodide salts. 0062 The anionic ion pairing reagents of this invention can be produced in a number of ways, including, without limitation: (1) the reaction of the parent acid of a respective anionic pairing ion with the parent base of a desired counterion; (2) the percolation of the parent acid of a respective anionic pairing ion or its salt through a cation exchange column containing a desired counterion; or (3) the extraction of a respective ion pair with an organic solvent from an aqueous solution that holds a mixture of the parent acid of the respective anionic pairing ion or its salt and the parent base of a desired counterion or its salt. The ion pairing reagents of this invention can be stored and/or used either as solids or solutions. 0063 In situ formed anionic pairing ions of this invention can be produced in a number of ways, including, without limitation: (1) adding one or more desired weak and/or strong acid to a solution containing a desired base and (2) adding a desired base to a solution containing one or more desired weak and/or strong acid. 0064 All references cited herein are incorporated by reference. While this invention has been described fully and completely, it should be understood that the invention may be practiced otherwise than as specifically described. Although the invention has been disclosed with reference to its preferred embodiments, from reading this description those of skill in the art may appreciate changes and modification that may be made which do not depart from the scope and spirit of the invention as described above.