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 .
Claim Status
Claims 1-20 were filed on 01/31/2024 in a preliminary amendment. Claims 7-20 have been amended.
Claims 1-20 are currently pending and under examination.
Priority
The instant application is a national stage application of PCT/US2022/037901 filed on 07/21/2022, which claims domestic benefit to provisional application no. 63/228,503 filed on 08/02/2021.
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 01/31/2024 and 03/16/2026 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement has been considered by the examiner.
Drawings
The drawings are objected to because Figures 8A, 8B, 8C, and 17 do not provide a scale for the crystals and the scale is not discussed in the specification for those figures. Furthermore, Figure 10 is blurry. Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. The figure or figure number of an amended drawing should not be labeled as “amended.” If a drawing figure is to be canceled, the appropriate figure must be removed from the replacement sheet, and where necessary, the remaining figures must be renumbered and appropriate changes made to the brief description of the several views of the drawings for consistency. Additional replacement sheets may be necessary to show the renumbering of the remaining figures. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
Claim Objections
Claim 12 is objected to because of the following informalities: The Markush group, as recited in the body of the claim, includes “nickle(II) metal salt” which contains a single letter typo with the “l” and “e” switched. The word “nickle” should be “nickel” and the phrase should be corrected to nickel(II) metal salt. Appropriate correction is required.
Claim Rejections - 35 USC § 112(a)
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claim 20 is rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention. This is a written description rejection.
Claim 20 recites “formula MnXm is present in the solution at a concentration of between 5 nM and 100 nM prior to the reacting, and the modulator is present in the solution at a concentration of between 15 nM and 100 nM prior to reacting”, but the specification lacks a representative number for written description support for reacting nM amounts of modulator and formula MnXm with mM amounts of polytopic organic linker.
MPEP § 2163 states an invention described solely in terms of a method of making and/or its function may lack written descriptive support where there is no described or art-recognized correlation between the disclosed function and the structure(s) responsible for the function.
MPEP § 2163 further states that a “representative number of species” means that the species which are adequately described are representative of the entire genus. Thus, when there is substantial variation within the genus, one must describe a sufficient variety of species to reflect the variation within the genus.
In the absence of a representative number of species, the written description requirement for a claimed genus may be satisfied by disclosure of relevant, identifying characteristics; i.e., structure or other physical and/or chemical properties, by functional characteristics coupled with a known or disclosed correlation between function and structure, or by a combination of such identifying characteristics, sufficient to show the applicant was in possession of the claimed genus. To meet this requirement in the instant case, the specification must describe structural features that the skilled artisan as of the effective filing date would have expected to convey to arrive at the claimed MOFs using the structures and concentrations as claimed.
Scope of the claims
Claim 20, is drawn to a method for synthesizing metal-organic frameworks (MOFs) wherein polytopic organic linkers present in a solution are at a concentration range between 1 mM and 50 mM prior to reacting, one or more metal compound(s) of formula MnXm are present in the solution are at a concentration range between 5 nM and 100 nM prior to reacting, and a modulator is present in the solution at a concentration range of 15 nM and 100 nM.
Description of Representative Species in the Specification
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The specification discloses conditions for synthesizing Co2(dobdc) crystals in accordance with an embodiment of the disclosure with the concentration of the polytopic organic linker being 5 mM, the concentration of the formula MnXm and the modulator being 17.5 mM and 35 mM, respectively (see Fig. 9 and shown below). The specification lists a broad range of concentrations of polytopic organic linkers being from at least 0.1 mM to no more than 800 M (paragraph 0079). The specification lists a broad range of concentrations for some embodiments of the formula MnXm ranging from no lower than 0.1 nM to no higher than 1 M (paragraph 0080). The specification also lists a broad range of concentrations for some embodiments of the modulator ranging from no lower than 0.1 nM to no higher than 1 M (paragraph 0081). The specification includes 5 examples wherein all examples have the polytopic organic linker at a concentration of 5 mM, the formula MnXm compound at a concentration of 17.5 mM, and the modulator at a concentration of 35 mM which does not represent the scope of the concentrations as claimed in claim 20. Furthermore, there is no guidance disclosed on how to achieve the MOF crystals from the concentrations of the reagents. The specification does not disclose any examples of a method of synthesizing MOFs using the concentrations as recited in instant claim 20.
State of the Relevant Art
Abney et al. (full citation included below) teaches the synthesis of MOF-274 with Localized Defects using Salicylic Acid: A vessel containing a sparged solution of 33 mL methanol and 27 mL DMF is charged with 2.328 g (9.08 mmol) Mg(NO3)2-6H2O and 2 g (7.3 mmol) H4DOBPDC. The solution is stirred until full dissolution, then 15 mL of this solution is transferred into each of three 23-mL Teflon-lined autoclaves. To each autoclave 78, 31, or 16 mg salicylic acid (0.25 eq, 0.1 eq, 0.05 eq, respectively) are added and stirred until fully dissolved. The reactors are sealed and heated to 120 °C for 96 hours (see 0148).
In the above synthesis, Abney et al. used H4DOBPDC as an organic linker in a concentration of 121 mM, corresponding to a compound similar to the instant polytopic organic linkers. Abney et al. used Mg(NO3)2-6H2O as a metal salt in a concentration of 151 mM, corresponding to a compound similar to the instant compound of formula MnXm. Lastly, Abney et al. used salicylic acid in varying concentrations as a modulator in concentrations of 1.9, 3.6, and 9.4 mmol, corresponding to a compound similar to the instant modulators.
Vornholt et al. (full citation included below) teaches the synthesis of CPO-27-Ni, large single crystals synthesized following a linker modulation approach. Nickel acetate tetrahydrate (251 mg, 1 mmol) was dissolved in water (30 mL) and added to a Teflon liner (50 mL). 2,5-dihydroxyterephthalic acid (0.5 mmol) and 4,6-dihydroxyterephthalic acid (0.5 mmol) were added to the liner and left to stir for 15 min. The liner was then capped, sealed in an autoclave and placed in the oven for 3 days at 130 °C. Yellow-brown, rectangular rods of CPO-27-Ni, with a yield of 73% (based on nickel salt), were obtained after filtration (see SI Table S2). On the basis of SXRD it can be ruled out significant contribution to the CPO-27-Ni framework by 4,6-dhip. Together with the absence of any irregularities in the thermal and elemental analysis, it can be inferred that the isomeric linker 4,6-dhip has only a modulating effect on the formation of large crystals of CPO-27-Ni and does not contribute to the framework composition (see page 8539).
In the above synthesis, the nickel acetate tetrahydrate has a concentration of 33 mM, corresponding to a compound of instant formula MnXm, the 2,5-dihydroxyterephthalic acid has a concentration of 16.6 mM, corresponding to the instant polytopic organic linker, and the 2,5-dihydroxyterephthalic acid has a concentration of 16.6 mM, corresponding to a compound similar to the instant modulators.
Analysis/Conclusion
Regarding scope of claim 20, recites formula MnXm has a concentration range between 5 nM and 100 nM and the modulator has a concentration range between 15 nM and 100 nM. The claim further recites the organic linkers having a concentration range between 1 mM and 50 mM. Claim 20 depends on claim 1 which recites Markush groups for the formula MnXm and the modulator. Claim 1 also does not further define the polytopic organic linker which includes a broad group of compounds known in the prior art to be organic linkers. Accordingly, the scope of claim 20 includes a broad genus of MOF synthesis with the concentrations of the reactants as recited in claim 20.
The specification discloses no examples are within the scope of claim 20 because the amounts of formula MnXm and the modulator are in mM amounts instead of nM. Furthermore, the specification does not provide guidance to one of ordinary skill in the art on how to achieve MOF crystals using nM amounts of formula MnXm and the modulator. Accordingly, in view of the instant disclosure, one of ordinary skill in the art would be unable to envisage the method to produce MOF crystals using nM amounts of formula MnXm and the modulator.
The prior art highlights that the metals, corresponding to the instant formula MnXm, for MOF synthesis are typically in stoichiometric (1:1 ratios) or above concentrations compared to the polytopic organic linkers. While the prior art teaches modulators are used in stoichiometric or substoichiometric concentrations when compared to the metals and the linkers, the substoichiometric ratios are still both in mM amounts and are comparable. Accordingly, the skilled artisan would be unable to envisage the reaction and crystallization to form MOFs based on the concentrations recited in claim 20.
Based on the analysis described above, claim 20 lacks written description due to a broad scope of reactions recited in the claims while being described by reactant concentrations that one of ordinary skill in the art would not predict to make any MOF of the full scope because the ratio of nM amounts of metal to mM amounts of linker is 1:1,000,000 and that ratio of metal to linker would not be expected to crystallize together in a solution to form a network of metal-linker-metal-etc. bonds due to an overwhelming amount of linker compared to metal. Furthermore, there is no representative species in the specification, and neither the specification nor the prior art disclose nanomolar amounts of a metal and modulator would crystallize with mM amounts of an organic linker to form a MOF.
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1, 6, 12, and 18 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Li et al. (NPL, published 09/13/2018, PTO-892).
Regarding the claim interpretation of instant claim 1, the limitation of “wherein R10 and R11 are not each hydrogen” will be interpreted as both R10 and R11 cannot be hydrogen and therefore, also cannot be the salt form. Specifically, salicylic acid and the salt version of salicylic acid, salicylate are being interpreted as outside of the scope claim 1 and thus, are not being examined for prior art.
Li et al. teaches the synthesis of Zn5-cluster-based MOFs were synthesized by a hydrothermal reaction, and their structures have been fully characterized by X-ray single crystal
diffraction analysis (see section 2.1) Zn5 experimental conditions: A mixture of H2BIPA (123 mg), ZnCl2 (136 mg), and 2-methylimidazole (82 mg) were added to deionized water (10 mL) in a 25 mL Teflon-lined stainless steel vessel. The mixture was heated at 150 °C for 72 h. After the reactive mixture was slowly cooled to room temperature, colorless block crystals of Zn5 were obtained.
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Regarding instant claims 1, Li et al. teaches reacting 2-methylimidazole, a ditopic organic linker, corresponding to the instant polytopic organic linker, with ZnCl2, corresponding to the instant formula MnXm wherein M is cationic Zn, X is a basic anion, n is a positive integer, m is a positive integer, and further reacting ZnCl2 and 2-methlimidazole in the presence of H2BIPA (shown below), corresponding to the instant modulator of formula V wherein R1, R3, R4, R6, and R9 are hydrogen and R5 is a halogen.
Regarding instant claim 6, Li et al. teaches the modulator is H2BIPA, corresponding to the instant modulator of formula V wherein R1 and R9 are hydrogen.
Regarding instant claim 12, Li et al. teaches reacting ZnCl2, corresponding to the instant formula MnXm wherein the instant formula MnXm is a zinc(II) metal salt.
Regarding instant claim 18, Li et al. teaches reacting H2BIPA (123 mg) and 2-methylimidazole (82 mg), corresponding to 0.5 equivalent (0.5 mmol) of instant modulator and 1 equivalent (1 mmol) of instant linker.
Claims 1, 3, 6, 12, 17-20 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Huang et al. (NPL, published 04/17/2014, PTO-892).
Regarding the claim interpretation of instant claim 20, instant claim 20 is rejected under 112(a) for written description due to nM concentrations being recited for the instant formula MnXm and the modulator which is free of prior art. However, in the interest of compact prosecution, claim 20 will be interpretated as mM amounts in view of the examples provided in the instant specification (see 00148-00157).
Huang et al. teaches synthesis of [Zn(L)(ip)]·(H2O)2·(CH3CH2OH) (7). Hydrothermal reaction was performed by using Zn(NO3)2·6H2O (0.1 mmol), L (0.1 mmol), and isophthalic acid (0.1 mmol) as raw materials and ethanol (4 ml) and H2O (1 ml) as solvents at 130 °C for 72 h, which produced crystals of 7 (see bottom of column 1, page 5609). L represents N1,N4-di(pyridin-4-yl)naphthalene-1,4-dicarboxamide (see column 2, page 5608). The structure of MOF (7) was determined by single crystal X-ray diffraction (XRD). The results are shown below in Figure 7 (see page 5616).
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Regarding instant claim 1, Huang et al. teaches reacting N1,N4-di(pyridin-4-yl)naphthalene-1,4-dicarboxamide (a tetratopic organic linker represented by L), corresponding to the instant polytopic organic linker, with Zn(NO3)2·6H2O, corresponding to the instant formula MnXm wherein M is Zn, X is a basic anion, n is a positive integer, and m is a positive integer. Huang et al. further teaches L and Zn(NO3)2·6H2O are reacted with isophthalic acid (shown below), corresponding to the instant modulator having the formula V wherein R1, R3, R4, R5, R6, and R9 are hydrogen, in a solution of water
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and ethanol, corresponding to the instant solution.
Regarding instant claim 3, Huang et al. teaches reacting in the presence of isophthalic acid, corresponding to the instant modulator having the formula V wherein R3, R4, R5, and R6 are hydrogen.
Regarding instant claim 6, Huang et al. teaches reacting in the presence of isophthalic acid, corresponding to the instant modulator having the formula V wherein R1 and R9 are hydrogen.
Regarding instant claim 12, Huang et al. teaches Zn(NO3)2·6H2O, corresponding to the instant formula MnXm wherein to the instant formula MnXm is a Zn(II) metal salt.
Regarding instant claim 15, Huang et al. teaches Zn(NO3)2·6H2O, corresponding to the instant formula MnXm wherein n is 1 and m is 2.
Regarding instant claim 17, Huang teaches Fig. 7b which shows the crystal structure, corresponding to the instant polytopic organic linker in the plurality of polytopic organic linkers is connected to two metal cations in the plurality of metal cations.
Regarding instant claims 18 and 19, Huang et al. teaches reacting L (0.1 mmol) and isophthalic acid (0.1 mmol) which are in a 1:1 equivalence, corresponding to the instant one equivalent of the polytopic organic linker to between 0.5 and 20 equivalents of the modulator in the solution prior to the reacting.
Regarding instant claim 20, Huang et al. teaches Zn(NO3)2·6H2O (0.1 mmol), L (0.1 mmol), and isophthalic acid (0.1 mmol) as raw materials and ethanol (4 ml) and H2O (1 ml) as solvents, corresponding to the instant linker having a concentration of 20 mM, the instant formula MnXm having a concentration of 20 mM, and the instant modulator having a concentration of 20 mM.
Claims 1, 6-7, 12, 14, and 18-20 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026).
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Vornholt et al. teaches Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach (see Title). CPO-27-Ni, large single crystals (50‒100 μm): Synthesized following a linker modulation approach (conditions shown below). Nickel acetate tetrahydrate (251 mg, 1 mmol) was dissolved in water (30 mL) and added to a Teflon liner (50 mL). 2,5-dihydroxyterephthalic acid (0.5 mmol) and 4,6-dihydroxyterephthalic acid (0.5 mmol) were added to the liner and left to stir for 15 min. The liner was then capped, sealed in an autoclave and placed in the oven for 3 days at 130 °C. Yellow-brown, rectangular rods of CPO-27-Ni, with a yield of 73% (based on nickel salt), were obtained after filtration (see supplemental information).
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Regarding instant claim 1, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid (2,5-dhtp, shown below), corresponding to the instant polytopic organic linker, with nickel acetate tetrahydrate, corresponding to the instant formula MnXm wherein M is Ni, X is a basic anion, n is a positive integer, m is a positive integer, and is further reacted in the presence of 4,6-dihydroxyisophthalic acid (shown below, 4,6-dhip), corresponding to the instant modulator having the formula V wherein R1, R3, R5, and R9 are hydrogen and R4 and R6 are hydroxyl.
Regarding instant claim 6, Vornholt et al. teaches reacting 4,6-dihydroxyisophthalic acid, corresponding to the instant modulator having the formula V wherein R1 and R9 are hydrogen.
Regarding instant claim 7, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid, corresponding to the instant polytopic organic linker having a formula of instant claim 7.
Regarding instant claim 12, Vornholt et al. teaches nickel acetate tetrahydrate, corresponding to the instant formula MnXm being a nickel (II) salt.
Regarding instant claim 14, Vornholt et al. teaches nickel acetate tetrahydrate, corresponding to the instant formula MnXm having the basic anion be acetate.
Regarding instant claim 18 and 19, Vornholt et al. teaches 2,5-dihydroxyterephthalic acid (0.5 mmol) and 4,6-dihydroxyterephthalic acid (0.5 mmol) were added, corresponding to the instant linker and instant modulator having an equivalence of 1:1.
Regarding instant claim 20, Vornholt et al. teaches nickel acetate tetrahydrate (251 mg, 1 mmol) was dissolved in water (30 mL) and added 2,5-dihydroxyterephthalic acid (0.5 mmol) and 4,6-dihydroxyterephthalic acid (0.5 mmol), corresponding to the instant linker and modulator having a concentration of 16.7 mM and the instant formula MnXm having a concentration of 33 mM.
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.
Claims 1 and 2 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026) in view of Weiping et al. (CN112708143A, published 04/27/2021, PTO-892).
The teachings of Vornholt et al. were discussed above. Vornholt et al. further teaches a wide field of potential applications for MOFs, including battery materials, catalysis, gas separation and storage, as well as biomedicinal applications (see Introduction section).
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach wherein R3, R4, R5, and R6 are each independently a substituted or unsubstituted linear or branched alkyl having between one and ten carbon atoms.
Weiping et al. teaches a preparation method for MOFs for lithium battery negative electrode material. The preparation method of a new type of MOFs lithium battery anode material includes the following steps: S1. Dissolve phenyl acid and nitrate in water to obtain a mixed solution, and add an alkali reagent to adjust the pH of the mixed solution to 2-5; S2. The mixed solution is added to the reaction kettle to perform a hydrothermal reaction, and after the reaction is cooled to room temperature, MOFs crystals are separated and obtained; S2. The MOFs single crystal is dried and then uniformly ground to obtain the MOFs lithium battery negative electrode material. Preferably, the phenyl acid in S1 includes at least one of benzene dicarboxylic acid, biphthalic acid, mellitic acid (shown below), terephthalic acid, trimesic acid, benzene tetracarboxylic acid, etc.
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(see paragraphs 17-22 of translation provided).
MOFs are composed of inorganic metal clusters connected through organic polydentate linkers which can be modulated by the addition of molecules that compete with, or have a similar structure to, the linkers which are known as modulators. In the case of Vornholt et al., Vornholt et al. teaches when using a combination of 4,6-dhip and 2,5-dhtp to synthesize MOFs, only 2,5-dhtp incorporates into the structure of the MOF but 4,6-dhip influences the shape of the MOF when compared to using 2,5-dhtp alone. Therefore, one of ordinary skill in the art would understand 4,6-dhip to be a modulator because it influenced the shape of the MOF synthesized by competing with 2,5-dhtp to bind to the metal center.
It would have been obvious before the effective filing date of the claimed invention to substitute 4,6-dhip, as taught by Vornholt et al., with the mellitic acid linker of Weiping et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute the 4,6-dhip, as taught by Vornholt et al., with mellitic acid because both Vornholt et al. and Weiping et al. teach the synthesis of MOFs for battery applications. Furthermore, 2,5-dhtp, the linker as taught by Vornholt et al., and the linker of mellitic acid, as taught by Weiping et al., both are aromatic molecules that contain multiple carboxylic acid groups which one of ordinary skill in the art would expect to compete with one another when reacting in the presence of metal. One of ordinary skill in the art would have a reasonable expectation of success because Weiping et al. teaches a successful example of producing MOFs where mellitic acid acts as a linker and therefore, one of ordinary skill in the art would have a reasonable expectation of success that mellitic acid would act as a competitor with 2,5-dhtp, as taught by Vornholt et al., acting as a linker.
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Regarding instant claims 1 and 2, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid (2,5-dhtp), corresponding to the instant polytopic organic linker, with nickel acetate tetrahydrate, corresponding to the instant formula MnXm wherein M is Ni, X is a basic anion, n is a positive integer, m is a positive integer, and is further reacted in the presence of 4,6-dhip as a modulator which is substituted with mellitic acid (shown below), corresponding to the instant modulator having the formulas III and V wherein R3, R4, R5, and R6 are each independently a substituted or unsubstituted linear or branched alkyl having between one and ten carbon atoms as required by instant claims 1 and 2.
Claims 1 and 4 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026) in view of Heidary et al. (NPL, published 04/29/2021, PTO-892).
The teachings of Vornholt et al. were discussed above.
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach wherein the modulator is of Formula IV and R1 and R9 are hydrogen as required by instant claim 4.
Heidary et al. teaches the utilization of metal and covalent organic frameworks (MOFs and COFs) in electrochemical systems is increasingly attracting interest because of the unique capabilities of these
structures. Through selection of the organic linker and metal nodes, the porosity, internal chemistry, conductivity, active site physical and electronic structure can all be chosen to generate the ideal catalyst (see Introduction section). Two MOFs were synthesized in a one-pot solution phase method. 20 mL scintillation vials were filled with 10 mL of DMF, 0.5 mL of water, 136.5 mg of nickel nitrate hexahydrate, and 52 mg of 2,5-dihydroxyterepthalic acid for Ni-MOF-74. For Ni-MOF-74D, 39 mg 2,5-dihydroxyterepthalic acid and 13 mg 2-hydroxyterepthalic acid were used. The solutions were briefly sonicated to dissolve all of the components and placed into an oven at 100oC for 24 hrs. Following the MOF growth, the residual solvent was removed by soaking in methanol at 70oC for 5 days while periodically refreshing the methanol and finally vacuum drying at 80oC for 3 days (see SI). A model was synthesized of MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurfural (HMF) as a model reaction. Consequently, superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency (see Abstract).
It would have been obvious before the effective filing date of the claimed invention to substitute the teachings of Vornholt et al. with the teachings of Heidary et al. by substituting the 4,6-dihydroxyisophthalic acid (4,6-dhip), as taught by Vornholt et al., with 2-hydroxyterephthalic acid, as taught by Heidary et al., to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute the 4,6-dhip with 2-hydroxyterephthalic acid because, as taught by Heidary et al., 2-hydroxyterephthalic acid acts as a modulator in MOFs made with nickel in a similar process to that as taught by Vornholt et al and increases the efficiency of the catalyst for electrocatalysis. Furthermore, both Vornholt et al. and Heidary et al. teach the same purpose of preparing MOFs for catalysis. One of ordinary skill in the art would have a reasonable expectation of success because both references use nickel as the metal center for the MOFs in similar preparation processes and both 2-hydroxyterephthalic acid and 4,6-dhip have similar structures (aromatic molecules with multiple carboxylic acid groups) which would be expected to compete with 2,5-dhtp as a linker when reacting in the presence of a metal.
Regarding instant claims 1 and 4, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid (2,5-dhtp), corresponding to the instant polytopic organic linker, with nickel acetate tetrahydrate, corresponding to the instant formula MnXm wherein M is Ni, X is a basic anion, n is a positive integer, m is a positive integer, and is further reacted in the presence of 4,6-dhip as a modulator which is substituted with 2-hydroxyterepthalic acid, corresponding to the instant modulator having the formula IV wherein R1 and R9 are both hydrogen as required by instant claims 1 and 4.
Claims 1 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026) in view of Wu et al. (NPL, published 02/27/2021, PTO-892).
The teachings of Vornholt et al. were discussed above.
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach wherein each polytopic organic linker in the plurality of polytopic organic linkers has the formula of instant claim 8 wherein R12 and R13 are each independently selected from H, halogen, hydroxyl, methyl, or halogen substituted methyl.
Wu et al. teaches synthesis of M2(m-dobdc) (M = Co, Ni, Mg, Mn), a promising material for industrial hydrogen isotope separation (see Abstract). MCl2·6H2O (3 mmol) and H4(m-dobdc) (4,6-dihydroxyisophthalic acid, 240 mg, 1.2 mmol) were dissolved in a mixture of methanol and N,N-dimethylformamide (DMF). (For Co2(m-dobdc), methanol = 30 mL, DMF = 30 mL, for Ni2(m-dobdc), methanol = 21 mL, DMF = 39 mL). The mixed solution was sealed in a 100 mL Teflon-lined reactor and heated at 120 °C for 18 h. After cooled to room temperature, the powder was collected and soaked in 60 mL DMF at 65 °C for one day. Then filtered the product and immersed it in 60 mL of methanol, heated it at 65 °C for four days and replaced the methanol every 12 h during this period (see SI section S2).
It would have been obvious before the effective filing date of the claimed invention to substitute the linker of Vornholt et al. with the teachings of Wu et al. by substituting 2,5-dihydroxyterephthalic acid (2,5-dhtp), as taught by Vornholt et al., with m-dobdc, as taught by Wu et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute the 2,5-dhtp with m-dobdc because, as taught by Wu et al., m-dobdc acts as a linker in MOFs made with nickel in a similar process and both Vornholt et al. and Wu et al. teach the use of MOFs in gas separation processes. One of ordinary skill in the art would have a reasonable expectation of success because both references use nickel as the metal center for the MOFs in similar preparation processes and 2,5-dhtp and m-dobdc have similar structures (aromatic compounds with multiple carboxylic acid groups) which would be expected to react similarly.
Regarding instant claims 1 and 8, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid (2,5-dhtp) which is substituted with m-dobdc, corresponding to the instant polytopic organic linker having the formula of instant claim 8 wherein R12 and R13 are each hydrogen, with nickel acetate tetrahydrate, corresponding to the instant formula MnXm wherein M is Ni, X is a basic anion, n is a positive integer, m is a positive integer, and is further reacted in the presence of 4,6-dhip as a modulator, corresponding to the instant modulator.
Claims 1 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026) in view of Abney et al. (WO 2021/011111A1, published 01/21/2021, IDS dated 03/16/2026).
The teachings of Vornholt et al. were discussed above.
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach wherein each polytopic organic linker in the plurality of polytopic organic linkers has the formula of instant claim 9 wherein R14, R15, R16, R17, R18, and R19 are each independently selected from H, halogen, hydroxyl, methyl, or halogen substituted methyl.
Abney et al. teaches preparation of the metal-organic framework: MOF-274 with Localized Defects using 3-Hydroxypropionic Acid. The MOFs synthesized show improved gas diffusion in separation processes (see 0007). A vessel containing a sparged solution of 20 mL water, 16 mL THF, and 15.5 mL acetonitrile is charged with 269 mg (1.05 mmol) Mg(NO3)2 *6H2O, 115 mg (0.42 mmol), 4,4'- dihydroxy-[1,1’-biphenyl]-3,3'-dicarboxylic acid (H4DOBPDC), and 971.25 mg (4.2 mmol) 3-(N- Morpholino)propane sulfonic acid sodium salt (Na MOPS). The solution is stirred until full dissolution, then 6 mL is aliquoted into 10-mL Teflon-lined autoclaves. To each autoclave, 2.3 μL (0.05 eq) to 45.4 μL (1 eq) of a 30 mol% 3-hydroxypropionic acid solution is added, producing samples having concentrations (by volume) of 5%, 10%, and 25% of 3-hydroxypropionic acid, respectively. The reactors are sealed and heated at 120 C for 24 hours (see Example 2, 0151).
It would have been obvious before the effective filing date of the claimed invention to substitute the linker of Vornholt et al. with the teachings of Abney et al. by substituting 2,5-dihydroxyterephthalic acid (2,5-dhtp), as taught by Vornholt et al., with H4DOBPC, as taught by Abney et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute the 2,5-dhtp with H4DOBPC because, as taught by Abney et al., H4DOBPC acts as a linker in MOFs made in a similar process. Furthermore, both Vornholt et al. and Abney et al. teach the purpose gas separation for the MOFs synthesized. One of ordinary skill in the art would have a reasonable expectation of success because both references use similar preparation processes and 2,5-dhtp and H4DOBPC have similar structures (aromatic compounds with multiple carboxylic acid groups) which would be expected to react similarly.
Regarding instant claims 1 and 9, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid (2,5-dhtp) which is substituted with H4DOBPC, as taught by Abney et al., corresponding to the instant polytopic organic linker having the formula of instant claim 9 wherein R14, R15, R16, R17, R18, and R19 are each independently selected from H, halogen, hydroxyl, methyl, or halogen substituted methyl, with nickel acetate tetrahydrate, corresponding to the instant formula MnXm wherein M is Ni, X is a basic anion, n is a positive integer, m is a positive integer, and is further reacted in the presence of 4,6-dhip as a modulator, corresponding to the instant modulator.
Claims 1, 10, and 11 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026) in view of Gheorghe et al. (NPL, published 07/21/2021, PTO-892).
The teachings of Vornholt et al. were discussed above.
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach wherein each polytopic organic linker in the plurality of polytopic organic linkers has the formula of instant claim 10 and wherein the linker is 2,5-dioxido-1,4- benzenedicarboxylate (dobdc4-) as required by instant claim 11.
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Gheorghe et al. teaches synthesis of Zn-IRMOF-74 as very promising candidate for applications in asymmetric catalysis (see bottom of column 1, page 12160). Zn(NO3)2·6H2O (0.033 g, 0.109 mmol, 3 eq.) and H4dobpdc (0.010 g, 0.037 mmol, 1 eq.) and a solvent mixture of S : EtOH : H2O (20 : 1 : 1 v : v : v, 5.5 mL, S = DMF, NMP, CHP, NBP) was placed in a 10 mL Teflon screw–capped DuranTM Pyrex tube. The mixture was sonicated, then placed in a preheated oven and kept for 48 h at 120 °C. The reaction mixture was then cooled down to room temperature and the solid crystalline material was filtered and washed two times with synthesis solvent mixture, then it was dried in an oven at 80 °C for 12 h (see general synthetic procedures section). Gheorge et al. further teaches H4DOBC can be used as a linker as well (shown below).
It would have been obvious before the effective filing date of the claimed invention to substitute the linker of Vornholt et al. with the teachings of Gheorge et al. by substituting 2,5-dihydroxyterephthalic acid (2,5-dhtp), as taught by Vornholt et al., with either H4dobdc or H4dobpdc, as taught by Gheorge et al. to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute the 2,5-dhtp with H4dobdc or H4DOBPDC because, as taught by Gheorge et al., H4dobdc and H4DOBPDC acts as a linker in MOFs made in a similar modulation process. Furthermore, both Vornholt et al. and Gheorge et al. teach catalysis as an application for the MOFs synthesized. One of ordinary skill in the art would have a reasonable expectation of success because both references use similar preparation processes and 2,5-dhtp and H4dobdc/H4dobpc have similar structures (aromatic compounds with multiple carboxylic acid groups) which would be expected to react similarly.
Regarding instant claims 1, 10, and 11, Vornholt et al. teaches reacting 2,5-dihydroxyterephthalic acid (2,5-dhtp, shown below) which is substituted with H4DOBPDC or H4dobdc, as taught by Gheorge et al., corresponding to the instant polytopic organic linker having the formula of instant claims 10 and 11, with nickel acetate tetrahydrate, corresponding to the instant formula MnXm wherein M is Ni, X is a basic anion, n is a positive integer, m is a positive integer, and is further reacted in the presence of 4,6-dhip as a modulator, corresponding to the instant modulator.
Claims 1 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026).
The teachings of Vornholt et al. were discussed above. Vornholt et al. further teaches the synthesis of (v) Co-4,6-dhip, single crystal (30‒50 μm): In a Teflon liner (30 mL), cobalt acetate tetrahydrate (1 mmol) and benzoic acid (4 mmol) were dissolved in a water/ethanol solvent mixture (5 mL each). The linker 4,6-dhip (1 mmol) was dissolved in THF (10 mL), slowly added to the salt/modulator mixture, and left to stir for 15 min. The Teflon liner was then capped and left to react for 3 days at 150 °C. Pink single crystals were obtained after filtration (70% yield based on Co).
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach an example of the modulated synthesis of MOFs with a modulator of formulas I-V as recited by instant claim 13.
It would have been obvious before the effective filing date of the claimed invention to substitute the teachings of Vornholt et al. by using cobalt acetate tetrahydrate, as taught by Vornholt et al., in the synthesis of vi, as taught by Vornholt et al., to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to use cobalt (II) acetate in place of nickel (II) acetate because, as taught by Vornholt et al., cobalt (II) salts are used in a similar modulated preparation process with benzoic acid as a modulator. One of ordinary skill in the art would have a reasonable expectation of success because the process conditions are similar.
Claims 1, 15, and 16 are rejected under 35 U.S.C. 103 as being unpatentable over Vornholt et al. (NPL, published 2021, IDS dated 03/16/2026) in view of Seetharaj et al (NPL, published 01/21/2016, PTO-892).
The teachings of Vornholt et al. were discussed above.
The teachings of Vornholt et al. differ from that of the instantly claimed invention in that Vornholt et al. does not teach a pH of the solution is between 7.0 and 8.0 as required by instant claims 15 and 16.
Seetharaj et al. teaches it is well known that the crystallization and growth of inorganic–organic hybrid materials are highly influenced by the acidity/basicity of the reaction media. The deprotonation
extent of an organic ligand and sometimes generation of an OH-ligand in aqueous solution with respect to the pH of the reaction media will favor the connectivity of polycarboxylate ligand to metal ion on the basis of acid-base concept. Some interesting works regarding the influence of pH value on MOF synthesis have been studied by many research groups. pH value of the reaction, as one of the external stimuli, has a remarkable influence on determining the coordination modes of carboxylic acid ligands involved in the synthesis of MOFs. For example recently the synthesis of two MOFs using CdCl2_2.5H2O, 4-carboxy-4,2’,6’,4”-terpyridine and oxalic acid (CTPY) by changing the pH values. Frameworks of the formula [Cd2(CTPY)4]n_2nH2O] and [Cd2(CTPY)2(ox)]n were obtained at pH 7.5 and 5.5 respectively. It is clear that oxalate does not appear in the structure. Here, depending on pH CTPY adopts different coordination modes. The participation of oxalic acid as template agent also depends on pH. Oxalic acid may act as a medium for the formation at higher pH value, 7.5 leading to 3D interpenetrating framework, while it is coordinated with Cd(II) atom in (44) at lower pH value, 5.5. Hence higher pH values have favored the formation of interpenetrating networks and lower pH value tends to form a simple uninterpenetrated 3D framework (see Section 3.2).
It would have been obvious before the effective filing date of the claimed invention to combine the teachings of Vornholt et al. with the teachings of Seetharaj et al. by adjusting the pH of the solution to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to adjust the pH of the solution because, as taught by Seetharaj et al., crystallization and growth of inorganic–organic hybrid materials are highly influenced by the acidity/basicity of the reaction media. One of ordinary skill in the art would have a reasonable expectation of success because adjustment of pH is a part of routine method optimization.
Allowable Subject Matter
Instant claim 5 would be allowable if amended to overcome the 112(b) rejection above.
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The closest prior art is Huang et al. (cited above). Huang et al. teaches the synthesis of MOF Zn(HL)(btc)·(H2O)0.5 using Zn(NO3)2 hexahydrate, corresponding to the instant formula MnXm wherein M is Zn, X is a basic anion, and n and m are positive integers, benzene-1,3,5-tricarboxylic acid (BTC), corresponding to the instant polytopic organic linker, and L (shown above). The crystals are formed in a H2O, corresponding to the instant solution (see 4th paragraph, column 1, page 5609). Huang et al. further teaches In the synthesis of Zn(HL)(btc)·(H2O)0.5, the 2D layer is constructed by the Zn ions and btc3− ligands, and the singly protonated L ligand acts as a decoration while playing a puncturing role (see Abstract). The singly protonated L acting as a decoration and a puncturing agent corresponds to L acting as a modulator for the MOF.
Huang et al. does not teach using a modulator of Formula II wherein R2, R7, and R8 are each hydrogen.
However, it is nonobvious to use a modulator of Formula II wherein R2, R7, and R8 are each hydrogen because the prior art is free of the specific structure of Formula II wherein R2, R7, and R8 are each hydrogen in the synthesis of MOFs. While Huang et al. teaches an amide containing compound similar to that of instant Formula II, one of ordinary skill in the art would not have known to modify the ligand L, as taught by Huang et al., to have the structure of the modulator of instant claim 5 because Huang et al. teaches L to be a designer ligand for the specific synthesis of the acrylamide MOFs synthesized. Furthermore, no prior art exists on modifying modulators containing amide moieties for the synthesis of MOFs. Therefore, claim 5 is free of prior art.
Conclusion
No claim is found allowable.
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/KRISTEN W BRADY/ Examiner, Art Unit 1692
/SCARLETT Y GOON/ Supervisory Patent Examiner, Art Unit 1693
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