DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Response to Amendment
This is an office action in response to applicant’s arguments and remarks filed on May 4, 2026. Claims 1-15 an 23-25 are currently pending in the application and are being examined herein.
Status of Objections and Rejections
The objection to claim 15 is maintained and modified as necessitated by the amendments.
The objection to and rejection of claim 16 is obviated by Applicant’s cancellation.
All other objections to the claims are withdrawn in view of Applicant’s amendment.
All other grounds of rejection from the previous office action are maintained.
New objections to the claims are necessitated by the amendments.
New grounds of rejection under 35 U.S.C. 103 are necessitated by the new claims.
Claim Objections
Claim 15 is objected to because of the following informalities: in lines 2-3, “the crystalline MOF nanoparticles of the plurality of crystalline MOF nanoparticles” should read “the plurality of crystalline MOF nanoparticles”. Appropriate correction is required.
Claim 25 is objected to because of the following informalities:
In line 3, “MOF” should read “metal organic framework (MOF)”.
In lines 4-5, “crystalline MOF nanoparticles of the plurality” should read “the plurality of crystalline MOF nanoparticles”.
Appropriate correction is required.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-13, 15, and 25 are rejected under 35 U.S.C. 103 as being unpatentable over Marshall et al., Size-Dependent Properties of Solution-Processable Conductive MOF Nanocrystals, Journal of the American Chemical Society, Vol. 144, Issue 13, pp. 5784-5794 (2022) (hereinafter "Marshall") (provided in Applicant's IDS filed on September 4, 2024) in view of Gandara et al., Porous, Conductive Metal-Triazolates and Their Structural Elucidation by the Charge-Flipping Method, Chem. Eur. J., Vol. 18, Issue 34, pp. 10595-10601 (2012) (hereinafter "Gandara") (provided in Applicant's IDS filed on September 4, 2024).
Regarding claim 1, Marshall teaches a method, comprising:
exposing an electrochemical anion sensor to a sample (exposing an MOF-based electrochemical device to a TBABF₄/MeCN solvent to detect BF₄⁻ anions, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column), wherein the electrochemical anion sensor comprises an electrode functionalized with a conductive porous film comprising a plurality of crystalline metal organic framework (MOF) nanoparticles (a glassy carbon electrode or a quartz crystal microbalance electrode is functionalized with a conductive porous film comprising a plurality of crystalline MOF nanoparticles which are Fe(TA)₂ nanoparticles, Marshall, abstract, Figs. 1, 5c, & 6b, pg. 5789, left column, last paragraph, right column, last paragraph; TA = 1,2,3-triazolate, Marshall, pg. 5784, right column, last paragraph); and
applying a potential to the electrode (applying a potential to the glassy carbon electrode or quartz crystal microbalance electrode to generate cyclic voltammogram traces, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column).
Marshall teaches that the 16 nm Fe(TA)₂ nanoparticles have a small pore size (Marshall, pg. 5789, left column, last paragraph). Marshall is silent with respect to the value of the small pore size of the Fe(TA)₂ nanoparticles, and therefore fails to teach a pore size ranging from greater than 4.5 Å to less than 10 Å.
Gandara teaches microcrystalline, porous, conductive metal-triazolates (MET) combining 1H-1,2,3-triazole and Fe ions (Gandara, abstract). Gandara teaches precise control of pore apertures to a fraction of an Angstrom in the range 4.5 to 6.1 Å (Gandara, abstract, pg. 10596, left column, first paragraph). Gandara teaches that MET-3 (Fe) has a pore diameter of 4.5 Å and exhibits significant electrical conductivity (Gandara, abstract, pg. 10596, left column, first paragraph, pg. 10598, left column, third paragraph, Table 1, Fig. 4).
It would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to modify the small pore size of the Fe(TA)₂ nanoparticles of Marshall to be 4.5 Å as taught by Gandara in order to yield the predictable result of exhibiting significant electrical conductivity. Generally, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985). MPEP § 2144.05(I).
Regarding claim 2, Modified Marshall teaches measuring a signal produced by one or more anions present in the sample to thereby detect a presence and/or identity of the one or more anions (measuring the voltammetric responses in the TBABF₄ environment to monitor the BF₄⁻ anions, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column).
Regarding claim 3, Modified Marshall teaches wherein the one or more anions independently have a diameter ranging from 1 Å to 10 Å (the BF₄⁻ anion was just below the pore size of the MOF which has a pore size of 4.5 Å, Marshall, pg. 5789, left column, last paragraph, Gandara, abstract, pg. 10596, left column, first paragraph, pg. 10598, left column, third paragraph, Table 1, see modification supra).
Regarding claim 4, Modified Marshall teaches wherein the one or more anions are independently selected from halide anions, perhalogenated anions, oxyanions, nitrile-containing anions, or any combination thereof (the BF₄⁻ anions which are perhalogenated anions, Marshall, pg. 5789, left column, last paragraph, right column, last paragraph).
Regarding claim 5, claim 4 recites "halide anions, perhalogenated anions, oxyanions, nitrile-containing anions, or any combination thereof," and therefore, the limitation "wherein the one or more halide anions are selected from F-, Cl-, I-, Br-, or any combination thereof" of claim 5 is further limiting an optional component of claim 4 and is not further limiting the one or more anions when the one or more anions are perhalogenated anions.
Regarding claim 6, Modified Marshall teaches wherein the one or more perhalogenated anions are selected from BF₄⁻, PF₆⁻, OTf-, CF₃SO₃⁻, CF₃SO₂NH-, or any combination thereof (the BF₄⁻ anions, Marshall, pg. 5789, left column, last paragraph, right column, last paragraph).
Regarding claim 7, claim 4 recites "halide anions, perhalogenated anions, oxyanions, nitrile-containing anions, or any combination thereof," and therefore, the limitation "wherein the one or more nitrile-containing anions are C₂N₃⁻" of claim 7 is further limiting an optional component of claim 4 and is not further limiting the one or more anions when the one or more anions are perhalogenated anions.
Regarding claims 8-9, claim 4 recites "halide anions, perhalogenated anions, oxyanions, nitrile-containing anions, or any combination thereof," and therefore, the limitations "wherein the one or more oxyanions comprise a halogen, sulfate, phosphate, or nitrate" of claim 8 and "wherein the one or more oxyanions are C10₄-" of claim 9 are further limiting an optional component of claim 4 and are not further limiting the one or more anions when the one or more anions are perhalogenated anions.
Regarding claim 10, Modified Marshall teaches wherein the potential is a varying potential and the signal is detected as an intercalation potential (varying potential of the cyclic voltammograms and measuring ion intercalation processes, most notably a sharp, reversible feature at 1.2 V which strongly suggests that this redox event corresponds to ion-coupled charge transport to interior Fe sites enabled by the smaller size of the BF₄⁻ anion, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column, first paragraph, right column, first paragraph).
Regarding claim 11, Modified Marshall teaches wherein the potential is a fixed potential and the signal is detected as a change in current (a sharp increase in current at 1.2 V, Marshall, Fig. 6b, pg. 5790, left column, first paragraph).
Regarding claim 12, Modified Marshall teaches wherein a detected concentration of the one or more anions in the sample ranges from 1 nanomolar to 1 molar (0. M TBABF₄/MeCN, Marshall, Fig. 5c, pg. 5789, left column, last paragraph).
Regarding claim 13, Modified Marshall teaches wherein the one or more anions comprise a first anion species (the BF₄⁻ anions, Marshall, pg. 5789, left column, last paragraph, right column, last paragraph). Modified Marshall teaches a separate experiment using a TBAPF₆ environment for monitoring PF₆⁻ anions (Marshall, Figs. 5b & 6a, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column). Modified Marshall is silent with respect to monitoring the BF₄⁻ anions and the PF₆⁻ anions in a mixture during the same experiment, and therefore fails to teach wherein the one or more anions comprise a second anion species, and wherein the first anion species is different from the second anion species.
However, Marshall teaches that the BF₄⁻ anions and the PF₆⁻ anions have different voltammetric responses with respect to the porous MOF nanoparticles (Marshall, Figs. 5b-5c & 6a-6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column).
It would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to modify the environment of Modified Marshall to include both BF₄⁻ anions and the PF₆⁻ anions because they have different voltammetric responses with respect to the porous MOF nanoparticles and thus can be monitored in the same environment. Furthermore, the claimed limitations are obvious because all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination yielded nothing more than predictable results. MPEP § 2143(I)(A).
Regarding claim 15, Modified Marshall teaches applying a negative voltage (a negative voltage is applied in the CVs, Marshall, Figs. 5c & 6b).
The limitation "to de-intercalate the one or more anions from pores of the crystalline MOF nanoparticles of the plurality of crystalline MOF nanoparticles" is an intended result of a positively recited step, and does not further limit the method or steps. In method claims, the intended result is not given patentable weight when it simply expresses the intended result of a process step positively recited. MPEP 2111.04(I). Furthermore, Modified Marshall teaches the claimed structure, materials, and steps of the claims (see rejections supra), so Modified Marshall is expected to predictably yield the same de-intercalation result as claimed when a negative voltage is applied.
Regarding claim 25, Marshall teaches a method, comprising:
exposing a liquid sample to an electrochemical anion sensor comprising an electrode functionalized with a conductive porous film comprising a plurality of crystalline MOF nanoparticles (exposing an MOF-based electrochemical device to a TBABF₄/MeCN solvent to detect BF₄⁻ anions, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column; the MOF-based electrochemical device comprising a glassy carbon electrode or a quartz crystal microbalance electrode functionalized with a conductive porous film comprising a plurality of crystalline MOF nanoparticles which are Fe(TA)₂ nanoparticles, Marshall, abstract, Figs. 1, 5c, & 6b, pg. 5789, left column, last paragraph, right column, last paragraph; TA = 1,2,3-triazolate, Marshall, pg. 5784, right column, last paragraph).
Marshall teaches that the 16 nm Fe(TA)₂ nanoparticles have a small pore size (Marshall, pg. 5789, left column, last paragraph). Marshall is silent with respect to the value of the small pore size of the Fe(TA)₂ nanoparticles, and therefore fails to teach a pore size greater than 4.5 Å and less than 10 Å, provided that crystalline MOF nanoparticles of the plurality do not comprise Fe(1,2,3-triazolate)2.
Gandara teaches microcrystalline, porous, conductive metal-triazolates (MET) combining 1H-1,2,3-triazole and metal ions such as Mg, Mn, Fe, Co, Cu, and Zn (Gandara, abstract). Gandara teaches precise control of pore apertures to a fraction of an Angstrom in the range 4.5 to 6.1 Å (Gandara, abstract, pg. 10596, left column, first paragraph). Gandara teaches that MET-n includes metals such as Mg, Mn, Fe, Co, Cu, or Zn and each has a pore diameter of 4.50 Å, 6.12 Å, 4.54 Å, 5.16 Å, 4.86 Å, or 5.06 Å, respectively, and exhibit electrical conductivity and permanent porosity (Gandara, abstract, pg. 10595, right column, first paragraph, pg. 10596, left column, first paragraph, pg. 10598, left column, third paragraph, Table 1, Fig. 4).
It would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to substitute the Fe in the Fe(1,2,3-triazolate)₂ nanoparticles of Marshall with Mg, Mn, Co, Cu, or Zn as taught by Gandara in order to yield the predictable result of exhibiting electrical conductivity and permanent porosity with a pore diameter of in the range 4.5 to 6.1 Å. Therefore, Modified Marshall teaches Mg(1,2,3-triazolate)₂, Mn(1,2,3-triazolate)₂, Co(1,2,3-triazolate)₂, Cu(1,2,3-triazolate)₂, or Zn(1,2,3-triazolate)₂ nanoparticles.
Modified Marshall teaches applying a potential to the electrode (applying a potential to the glassy carbon electrode or quartz crystal microbalance electrode to generate cyclic voltammogram traces, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column); and
measuring an electrochemical response to detect one or more anions present in the liquid sample (measuring the voltammetric responses in the TBABF₄ environment to monitor the BF₄⁻ anions, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column).
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Marshall in view of Gandara as applied to claim 13 above, and further in view of Mandal et al., Metal-Organic Frameworks (MOFs) as Functional Supramolecular Architectures for Anion Recognition and Sensing, The Chemical Record, Vol. 18, pp. 154-164 (2018) (hereinafter "Mandal").
Regarding claim 14, Modified Marshall teaches the first anion species and the second anion species (the BF₄⁻ anions and the PF₆⁻ anions, Marshall, pg. 5789, left column, last paragraph, right column, last paragraph, see modification supra). Modified Marshall fails to teach wherein the one or more anions further comprise a third anion species, and wherein the third anion species is different from the first anion species and the second anion species.
Mandal teaches that metal-organic frameworks (MOFs) can act as potential receptors toward different target components along with ionic species for selective and sensitive anion sensing (Mandal, abstract). Mandal teaches that MOFs may selectively capture oxo-anions in the presence of other competing anions such as ClO₄-, NO₃⁻, BF₄-, CF₃SO₃⁻, etc. (Mandal, pg. 159, right column, last paragraph, pg. 160, left column, first paragraph). Mandal teaches that BF4- anions can be exchanged with CIO₄⁻ and NO₃- anions in the void-space of the MOFs (Mandal, pg. 161, left column, second paragraph).
It would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to modify the environment of Modified Marshall to further include additional anions such as ClO₄⁻ or NO₃⁻ as taught by Mandal because they can be exchanged with BF₄⁻ in the void-space of the MOFs for monitoring of the anions. Furthermore, the claimed limitations are obvious because all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination yielded nothing more than predictable results. MPEP § 2143(I)(A).
Claims 23-24 are rejected under 35 U.S.C. 103 as being unpatentable over Marshall in view of Gandara as applied to claim 1 above, and further in view of Dinca et al. (US 2020/0330918 A1).
Regarding claim 23, Modified Marshall teaches the plurality of crystalline MOF nanoparticles which are Fe(TA)₂ nanoparticles (Marshall, abstract, Figs. 1, 5c, & 6b, pg. 5789, left column, last paragraph, right column, last paragraph; TA = 1,2,3-triazolate, Marshall, pg. 5784, right column, last paragraph). Modified Marshall fails to teach wherein the plurality of crystalline MOF nanoparticles comprise Cr(1,2,3-triazolate)2.
Dinca teaches methods for adsorption or uptake of a species (e.g., ammonia, water, a halogen) using metal organic frameworks (MOFs) and determining the amount of the compound incorporated into the MOF after exposure of the MOF to an environment that contains the compound (Dinca, abstract, para. [0002], [0044]). Dinca teaches that the MOFs may comprise any suitable metal ions including Fe or Cr (Dinca, para. [0062]). Dinca also teaches that the metal ions in the MOFs may be linked together by ligands such as 1,2,3-triazolate (Dinca, para. [0063]).
It would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to substitute the Fe in the Fe(1,2,3-triazolate)2 nanoparticles of Modified Marshall with Cr to form Cr(1,2,3-triazolate)2 nanoparticles as taught by Dinca in order to yield the predictable result of MOFs for adsorbing a species to be detected. Simple substitution of one known element for another is likely to be obvious when predictable results are achieved. See KSR International Co. v. Teleflex Inc., 127 S. Ct. 1727, 82 U.S.P.Q.2d 1385 (2007); MPEP § 2143(I)(B). Furthermore, the selection of a known material, which is based upon its suitability for the intended use, is within the ambit of one of ordinary skill in the art. MPEP § 2144.07.
Regarding claim 24, Modified Marshall teaches measuring an intercalation potential associated with intercalation of anions into pores of the Cr(1,2,3-triazolate)2 nanoparticles (measuring the voltammetric responses in the TBABF₄ environment to monitor the BF₄⁻ anions and measuring ion intercalation processes, most notably a sharp, reversible feature at 1.2 V which strongly suggests that this redox event corresponds to ion-coupled charge transport to interior sites of the nanoparticles enabled by the smaller size of the BF₄⁻ anion, Marshall, Figs. 5c & 6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column, first paragraph, right column, first paragraph).
Modified Marshall teaches a separate experiment using a TBAPF₆ environment for monitoring PF₆⁻ anions (Marshall, Figs. 5b & 6a, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column). Modified Marshall is silent with respect to monitoring the BF₄⁻ anions and the PF₆⁻ anions in a mixture during the same experiment, and therefore fails to teach intercalation of two or more anions.
However, Marshall teaches that the BF₄⁻ anions and the PF₆⁻ anions have different voltammetric responses with respect to the porous MOF nanoparticles (Marshall, Figs. 5b-5c & 6a-6b, pg. 5789, left column, last paragraph, right column, last paragraph, pg. 5790, left column).
It would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to modify the environment of Modified Marshall to include both BF₄⁻ anions and the PF₆⁻ anions because they have different voltammetric responses with respect to the porous MOF nanoparticles and thus can be monitored in the same environment. Furthermore, the claimed limitations are obvious because all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination yielded nothing more than predictable results. MPEP § 2143(I)(A).
Response to Arguments
Applicant's arguments filed May 4, 2026 have been fully considered but they are not persuasive.
In the arguments presented on pages 4-7 of the amendment, Applicant argues that one of ordinary skill in the art would not have been motivated to modify Marshall’s iron nanoparticle-containing film with Gandara’s powder materials. Applicant asserts that Gandara is directed to materials that have significantly different physical properties than Marshall's Fe(TA)2 nanoparticles, and neither document provides any reasonable expectation of success that pore sizes disclosed for Gandara's materials could be obtained with Marshall's Fe(TA)2 nanoparticles. Applicant asserts that Gandara is directed to microcrystalline powders and does not teach or suggest any nano-sized materials in the form of a film, and not any nano-sized crystalline particles. Applicant asserts that a pore-aperture value disclosed for Gandara's micro-scaled bulk powder materials cannot be extrapolated to Marshall's Fe(TA)2 nanoparticles while preserving Marshall's nanoparticle size, film-forming behavior, and electrochemical properties.
Examiner respectfully disagrees. In response to applicant's argument that the pore size of Gandara cannot be incorporated into the structure of Marshall, the test for obviousness is not whether the features of a secondary reference may be bodily incorporated into the structure of the primary reference; nor is it that the claimed invention must be expressly suggested in any one or all of the references. Rather, the test is what the combined teachings of the references would have suggested to those of ordinary skill in the art. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981). Claim 1 recites the pore size of the individual MOF nanoparticles. Marshall already teaches that the Fe(TA)₂ nanoparticles have a small pore size (Marshall, pg. 5789, left column, last paragraph). Gandara also teaches pore sizes of individual metal-triazolates (MET) including one where the metal is Fe, and the pore size is in the range 4.5 to 6.1 Å (Gandara, abstract, pg. 10596, left column, first paragraph, pg. 10598, left column, third paragraph, Table 1, Fig. 4). Therefore, it would have been obvious for one having ordinary skill in the art before the effective filing date of the claimed invention to modify the small pore size of the Fe(TA)₂ nanoparticles of Marshall to be 4.5 Å as taught by Gandara in order to yield the predictable result of exhibiting significant electrical conductivity (see rejection and modification supra). The modification only changes the pore size of individual MOF, which both references teach.
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/V.T./ Examiner, Art Unit 1794
/SHIZHI QIAN/ Primary Examiner, Art Unit 1795
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