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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 06/16/2026 has been entered.
DETAILED ACTION
Claims 1-21 of J. T. Hupp, et al., US 18/035,876 (05/08/2023) are pending.
Election/Restrictions
Applicant’s election with traverse of Group 1 in the reply filed on 12/17/2025 is acknowledged. Claims 12-20 drawn to non-elected Groups II-III are withdrawn from consideration pursuant to 37 CFR 1.142(b). The Restriction Requirement is maintained as Final.
Pursuant to the election of species requirement, Applicant elected, without traverse, NU-1000 as the species chemical structure of a metal organic framework molecule, in the reply filed on 12/17/2025, for prosecution on the merits to which the claims shall be restricted if no generic claim is finally held to be allowable. The elected species was searched and determined to be unpatentable as discussed in the 102 rejection below. The provisional species election requirement is in effect and claims 9 and 11 are withdrawn as not reading on the elected species. Claims 1-8, 10 and 21 are under examination on merits.
Priority
Applicant’s claim for the benefit of a prior-filed application under 35 U.S.C. 119(e) or under 35 U.S.C. 120, 121, 365(c), or 386(c) is acknowledged. Applicant has not complied with one or more conditions for receiving the benefit of an earlier filing date under 35 U.S.C. 112(a) as follows:
The later-filed application must be an application for a patent for an invention which is also disclosed in the prior application (the parent or original nonprovisional application or provisional application). The disclosure of the invention in the parent application and in the later-filed application must be sufficient to comply with the requirements of 35 U.S.C. 112(a) or the first paragraph of pre-AIA 35 U.S.C. 112, except for the best mode requirement. See Transco Products, Inc. v. Performance Contracting, Inc., 38 F.3d 551, 32 USPQ2d 1077 (Fed. Cir. 1994).
The disclosure of the prior-filed application, Application No. US63/111,451, fails to provide adequate support or enablement in the manner provided by 35 U.S.C. 112(a) or pre-AIA 35 U.S.C. 112, first paragraph for one or more claims of this application. The publication used for provisional application 63/111,451 discloses information for synthesis, structural characterization of formate-containing NU-1000, formate-free NU-1000 containing chloride, formate-free and Cl-free NU-1000, and nowhere in the provisional application 63/111,451 discloses the concept of “a hydrated metal organic framework comprising a metal organic framework molecule having positively charged ligands on linker unsaturated nodes and a net positive charge, wherein the positively charged ligands account for at least 50 mol% of the ligands on the linker unsaturated nodes”. Further, based on the MOFs disclosed in the provisional application, one ordinary skill in the art would NOT appraised “a hydrated metal organic framework comprising a metal organic framework molecule having positively charged ligands on linker unsaturated nodes and a net positive charge, wherein the positively charged ligands account for at least 50 mol% of the ligands on the linker unsaturated nodes”.
The effective filling date of the instant application is 11/09/2021.
Withdrawal Claim Rejections - 35 USC § 102
Rejection of claims 1-8 and 10 under 35 U.S.C. 102 (a)(1) as being anticipated by P. Deria, et al. 6(9), Chemical science, 5172-5176 (2015)(“Deria”) evidenced with J. E. Mondloch, et al. 135.28, Journal of the American Chemical Society, 10294-10297 (2013)(“Mondloch”) is withdrawn because the limitation of “a metal organic framework molecule having positively charged ligands on linker unsaturated nodes” and “wherein the positively charged ligands account for at least 50 mol% of the ligands on the linker unsaturated nodes” recited by the amended claim 1 cannot be met by the Deria MOF recited in the rejection made in the previous Office action.
Claim Rejections - 35 USC § 102
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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
35 USC § 102 Rejection Over Liu
Claims 1-8, 10, 21 and the elected species are rejected under 35 U.S.C. 102 (a)(1) as being anticipated by J. Liu, et al, 13.19 ACS applied materials & interfaces 22485-22494 (published on 05-07-2021)(“Liu”).
Liu teaches MOF NU-1000-Cl that has a structure and synthesized as indicated below.
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Liu at page 22486, Figure 1.
Liu teaches that the NU-1000-Cl has a node composition of Zr6(μ3-O)4(μ3-OH)4(H2O)812+. Liu at page 22486, left col. the last second paragraph, line 6-7.
Thus, the NU-1000-Cl comprises:
(i). linker unsaturated nodes;
(ii).positively charged ligands on linker unsaturated nodes;
(iii).Cl- that is a charge compensating anions that are not bonded to the linker unsaturated nodes via coordination bonds and have freedom of motion through the pores of the metal organic framework.
Liu teaches that Cl- loading per Zr6 node in the NU-1000-Cl is 3.3 ± 0.3. Liu at page 22487, right col. Materials Synthesis and Characterization, line 25-26. Therefore, the loading of protonated positively ligands is also 3.3 ± 0.3 because Cl- is a compensating anion for H+ in the NU-1000-Cl as indicated above. Liu further teaches that each Zr6 node in 8-connnected NU-1000 can, in principle, bind four non structural, two-oxygen, bridging or chelating ligands. Thus, the positively charged ligands in the NU-1000-Cl account for 82.5% (3.3/4) of the ligands on the linker unsaturated nodes.
Liu teaches that there is physisorbed water in the NU-1000-Cl and the water can be removed by thermal treatment at 120ºC. Liu at page 22488, right col. paragraph 2, line 4-7. Therefore, the Liu NU-1000-Cl is a hydrated MOF. Given the Liu NU-1000-Cl with total pore volume of 1.36cm3/g (See Liu at page 22487, right col. Materials Synthesis and Characterization, the last sentence), there is a reasonable anticipation that the water is physisorbed within the pore of the Liu NU-1000-Cl. Once a reference teaching product appearing to be substantially identical is made the basis of a rejection, and the examiner presents evidence or reasoning to show inherency, the burden of production shifts to the applicant. MPEP § 2112(V) (citing In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433-34 (CCPA 1977). This is a procedural burden shifting. The requirement that the prior art necessarily teaches the alleged inherent (functional) element still remains. MPEP § 2112(IV). However, the burden is shifted to Applicant to demonstrate the alleged inherent element is not necessarily present in the cited prior art.
Regarding the claimed net positive charge, the instant specification discloses that:
A net positive electrical charge may be imparted to a metal organic framework molecule that lacks a net positive electrical charge by reacting pre-existing ligands on the nodes with a salt in an aqueous or non-aqueous solution, whereby the salt dissociates to form a cation that binds to the node and a charge compensating anion that remains unligated. Suitable salts include acids, including inorganic acids, that dissociate into a proton that protonates one or more nodes and an anion. Suitable strong acids include those the provide a halide ion as a charge-compensating anion. These include hydrochloric acid (HCl), hydrobromic acid (HBr), and hydroiodic acid (HI).
Specification at page 5-6, [0025].
Given the NU-1000-Cl is prepared by treating of formate containing NU-1000 with strong acid HCl, therefore, the NU-1000-Cl also comprises a net positive charge that is imparted by protonation of nodes.
Thus, the Liu NU-1000-Cl meets each and every limitation of claims 1-8, 10 and 21, therefore, claims 1-8,10 and 21 are anticipated.
35 USC § 102 Rejection Over Mondloch
Claims 1-8, 10, 21 and the elected species are rejected under 35 U.S.C. 102 (a)(1) as being anticipated by J. E. Mondloch, et al. 135.28, Journal of the American Chemical Society, 10294-10297 (2013)(“Mondloch”). Note: the rejection is adjusted according to claim amendment.
Mondloch teaches a method for preparation of NU-1000 as follows:
Synthesis of NU-1000 in DEF. 70 mg of ZrCl4 (0.30 mmol) and 2700 mg (22 mmol) of benzoic acid were mixed in 8 mL of DEF (in a 6-dram vial) and ultrasonically dissolved. The clear solution was incubated in an oven at 80⁰C for 1h. After cooling down to room temperature 40 mg (0.06 mmol) of H4TBAPy was added to this solution and the mixture was sonicated for 20 min. The yellow suspension was heated in an oven at 120⁰C for 48 h. After cooling down to room temperature, yellow single crystals were present on the vial walls. The sample was washed with DMF and subsequently activated with HCl (see Section S5 below).
Synthesis of NU-1000 in DMF. 70 mg of ZrCl4 (0.30 mmol) and 2700 mg (22 mmol) of benzoic acid were mixed in 8 mL of DMF (in a 6-dram vial) and ultrasonically dissolved. The clear solution was incubated in an oven at 80⁰C for 1h. After cooling down to room temperature 40 mg (0.06 mmol) of H4TBAPy was added to this solution and the mixture was sonicated for 20 min. The yellow suspension was heated in an oven at 120⁰C for 48 h. After cooling down to room temperature, yellow polycrystalline material was isolated by filtration (35 mg of activated material, 54% yield) and washed with DMF and subsequently activated with HCl (see Section S5 below).
S5. Activation procedure for NU-1000.
As synthesized NU-1000 was activated using a slightly modified method previously reported by Feng et al..S1 Approximately 40 mg of solvated (“wet”) material was soaked in 12 ml of DMF and 0.5 ml of 8 M aqueous HCl was added. This mixture was heated in an oven at 100⁰C for 24 h. After cooling to room temperature, the solution was removed and the material was washed twice with DMF to remove HCl impurities. Subsequently the solid residue was washed twice with acetone and soaked in acetone for additional 12h. NU-1000 was filtered, briefly dried on a filter paper and activated at 120⁰C under vacuum for 12h on the preparation station of ASAP 2020 instrument. Shown below, the as synthesized NU-1000 sample was characterized by 1H NMR, N2 adsorption measurements, and DRIFTS. The data are consistent with the removal of benzoic acid from the Zr6 node and the incorporation of -OH groups.
Elemental analysis data for molecular formula Zr6(OH)8(TBAPy)2: C, H, N, Cl Theoretical: 48.7%, 2.4%, 0%, 0%; Experimental: 49.1%, 3.0%, 0.3%, 0.4%. Elemental analysis data for molecular formula {0.75*[Zr6(OH)8(TBAPy)2]+0.25*[Zr6(O)4(OH)4]2(TBAPy)6]}: C, H, N, Cl Theoretical: 51.6%, 2.5%, 0%, 0%; Experimental: 49.1%, 3%, 0.3%, 0.4%.
See Mondloch supporting information S4-S5, emphasis added.
As mentioned in the previous Office action that NU-1000 has a [Zr6(µ3-O)4(µ3-OH)4(-OH)4(-OH2)4]8+ nodes linked by tetra-carboxylate ligands TBAPy, thus, NU-1000 has linker unsaturated nodes.
During the step of activation of the as synthesized NU-1000, the synthesized NU-1000 were soaked in 12 ml of DMF and 0.5 ml of 8 M aqueous HCl at 100⁰C for 24 h. The evidence from the publication used for the provisional application indicated that chloride-containing NU-1000-FF (3) formed as an intermediate during heating of the as synthesized NU-1000 in DMF in the presence of 8 M aqueous HCl as indicated below. See the provisional application Scheme 1 at page 6-7. And the publication concludes that “chloride-containing NU-1000-FF (3) is an intermediate-albeit, a non-isolated one-in the standard activation of as syn-NU-1000”. See the provisional application right col, line 8-11 at page 7.
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The Mondloch chloride-containing NU-1000-FF(3) intermediate is a hydrated metal organic framework because it is formed in presence of water (from the 8 M aqueous HCl). The chloride-containing NU-1000-FF (3) intermediate has a same structure1 as that of the chloride-containing NU-1000-FF disclosed in the specification. See Fig. 2D-2E and Fig.3 of the instant specification. Given the chloride-containing NU-1000-FF (3) intermediate has pores as indicated by Fig. 2C of the instant application, therefore, there is a reasonable anticipation that at least some water is contained in the pores of chloride-containing NU-1000-FF (3) intermediate1. Thus, the Mondloch chloride-containing NU-1000-FF (3) intermediate meets each and every structural limitation of the claimed MOF in claims 1-8, 10 and 21; the elected species and claims 1-8, 10, 21 are anticipated.
Applicant’s Argument
Applicant argues on the ground that:
In contrast, the predominant ligand on the unsaturated linker nodes in an NU-1000-F MOF synthesized by Mondloch are formate ligands (in fact the "F" in NU-1000-F stands for formate). These formate ligands are not positively charged and do not provide the MOF with a net positive charge. Nor would they be expected to be associated with "charge-balancing anions." (Spec. [0026] and FIG. 3.) This is consistent with Mondoch's report of only a trace amount of negatively charged chloride ions in their sample, since charge-balancing anions would be expected to scale with the positive charges on the nodes of the MOFs. Therefore, positively charged ligands do not account for at least 50 mol% of the ligands on the linker unsaturated nodes of the MOFs of Deria, as evidenced by Mondloch. For at least this reason Deria and Mondloch fail to anticipate claim 1, and the withdrawal of the rejection of claims 1-8 and 10 is requested.
Second paragraph at page 7 of the Remarks filed on 06/16/2026.
This argument has been fully considered but not persuasive because while the ligands in the Mondloch synthesized NU-1000-F MOF is not positively charged, however, the evidence from the publication used for the provisional application indicated that chloride-containing NU-1000-FF (3) formed as an intermediate during heating of the synthesized NU-1000 in DMF in the presence of 8 M aqueous HCl. See the provisional application Scheme 1 at page 6-7; and right col, line 8-11 at page 7. As mentioned in the rejection above that the chloride-containing NU-1000-FF (3) intermediate has the same structure as that of the chloride-containing NU-1000-FF disclosed in the specification. See Fig. 2D-2E and Fig.3 of the instant specification, therefore, it meets each and every limitation of the claimed MOF including at least 50 mol% of the ligands on the linker unsaturated nodes are positively charged.
Conclusion
No claims are allowed.
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/FRANK S. HOU/Examiner, Art Unit 1692
/AMY C BONAPARTE/Primary Examiner, Art Unit 1692
1 Once a reference teaching product appearing to be substantially identical is made the basis of a rejection, and the examiner presents evidence or reasoning to show inherency, the burden of production shifts to the applicant. MPEP § 2112(V) (citing In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433-34 (CCPA 1977). This is a procedural burden shifting. The requirement that the prior art necessarily teaches the alleged inherent (functional) element still remains. MPEP § 2112(IV). However, the burden is shifted to Applicant to demonstrate the alleged inherent element is not necessarily present in the cited prior art.
Prosecution Insights