DETAILED ACTION
This action is in response to the RCE with amendments and remarks filed 12/30/2025, in which claims 1 and 6-14 have been amended, and claims 1, 3 and 6-23 are pending and ready for examination.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 12/30/2025 has been entered.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 6 is rejected under 35 U.S.C. 112(b) as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 6 recites the limitation “wherein the method comprises incubating the membrane support between two cells, wherein a first cell comprises zinc nitrate hexahydrate and a second cell comprises 2-methylimidazole, salicylaldoxime and the viscosity enhancer”. This conflicts with the incubating already recited in claim 1 and it is thus not clear if this is the same incubating. It is suggested that it be corrected to “wherein the comprising disposing the membrane support between two cells, wherein a first cell comprises zinc nitrate hexahydrate and a second cell comprises 2-methylimidazole, salicylaldoxime and the viscosity enhancer.”
Claims 12 recites the limitation “comprising a zinc imidazole salicylaldoxime supramolecule (ZIOS) nanosheets”. The “a” makes it unclear if the ZIOS nanosheets are singular or plural. It is suggested that it be corrected to “comprising
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 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, 3, 7-16 and 18-22 are rejected under 35 U.S.C. 103 as being unpatentable over Chunyan Chen, et al., A high absorbent PVDF composite membrane based on β-cyclodextrin and ZIF-8 for rapid removing of heavy metal ions, Separation and Purification Technology, Volume 292, 2022, 120993, ISSN 1383-5866 (hereinafter “Chen”) in view of Bui, N.T., Kang, H., Teat, S.J. et al. A nature-inspired hydrogen-bonded supramolecular complex for selective copper ion removal from water. Nat Commun 11, 3947 (2020). (hereinafter “Bui”) and Abounahia, N.; Qiblawey, H.; Zaidi, S.J. Progress for Co-Incorporation of Polydopamine and Nanoparticles for Improving Membranes Performance. Membranes 2022, 12, 675. (hereinafter “Abounahia”), Xin-ping Wang, Jingwei Hou, Fu-shan Chen, Xiang-min Meng, In-situ growth of metal-organic framework film on a polydopamine-modified flexible substrate for antibacterial and forward osmosis membranes, Separation and Purification Technology, Volume 236, 2020, 116239 (hereinafter “Wang”) and Jing Deng, et al., Morphologically Tunable MOF Nanosheets in Mixed Matrix Membranes for CO2 Separation, Chemistry of Materials 2020 32 (10), 4174-4184, DOI: 10.1021/acs.chemmater.0c00020, (hereinafter “Deng”).
Regarding Claim 1 Chen discloses a method of preparing a metal cation-capturing membrane, the method comprising depositing a heavy metals adsorbent nanoparticle, βCD@ZIF-8, onto a membrane support wherein the membrane support is polyvinylidene fluoride (PVDF); Chen Sec. 2.2.2.; Abstract, Introduction, Secs. 2.2. and 2.3.
Chen does not disclose (1) the adsorbent nanoparticle is a zinc imidazole salicylaldoxime supramolecule (ZIOS), or (2) wherein the membrane support has been coated with polydopamine (PDA) and polyethyleneimine (PEI), or (3) wherein the method comprises incubating the membrane support with zinc nitrate hexahydrate, 2-methylimidazole, salicylaldoxime in one or more solutions, and (4) a viscosity enhancer.
However, with regard to (1) ZIOS, Bui discloses zinc imidazole salicylaldoxime supramolecule (ZIOS) is a known copper and heavy metals adsorbent, which is directly compared to ZIF 8; and exhibits unprecedented rapid adsorption kinetics and a moderately high copper ion adsorption capacity; Bui Abstract, Introduction (pg. 2), Discussion, Methods.
Therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to modify the method of Chen by substituting for the heavy metals adsorbent nanoparticle ZIOS as disclosed by Bui because ZIOS exhibits unprecedented rapid adsorption kinetics and a moderately high copper ion adsorption capacity (Bui Discussion).
With regard to (2) with PDA and PEI, Abounahia discloses it is known to use an intermediate layer of PDA and PEI as a means of immobilizing nanoparticles onto membrane surfaces, including by first coating the membrane in PDA/PEI then depositing the nanoparticles; Sec. 2., 3.1., 3.2.
Therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to modify the method and membrane of Chen in view of Bui by first coating the PVDF membrane with an intermediate layer of PDA and PEI as disclosed by Abounahia because this is a known means of improving the immobilization of nanoparticles on membranes surfaces.
With regard to (3) incubating the membrane support with zinc nitrate hexahydrate, 2-methylimidazole, salicylaldoxime in one or more solutions, Wang discloses using a PDA coating on a membrane in order to attach a ZIF-8 particle layer on the membrane via direct immersion in a single ZIF-8 precursor solution, i.e. an aqueous solution comprising zinc nitrate hexahydrate and 2-methylimidazole; Abstract, 1. Introduction, Secs. 2.2.-2.3., Fig. 1.
Therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to modify the combined method and membrane of Chen in view of Bui and Abounahia by incubating the PDA and PEI coated membrane directly in a singular precursor solution (i.e. for ZIOS) because as disclosed by Wang the PDA coating layer improves nucleation propensity and bonding which allows direct immersion in the precursor solution to form an attached particle layer, and thus avoids the extra steps of first impregnating the membrane with zinc nitrate hexahydrate then drying as in Chen, where the solution(s) may be filtered through the membrane to achieve the deep-permeation of Chen.
Thus resulting in incubating the membrane support with zinc nitrate hexahydrate, 2-methylimidazole, salicylaldoxime and a viscosity enhancer in one solution.
With regard to (4) a viscosity enhancer, Deng discloses forming a ZIF nanoparticles (which are formed in a similar process to ZIOS), wherein 1 wt% PVA was added to the ZIF precursors solution during ZIF formation to control the morphology of the formed ZIF particles, wherein the molecular weight of the additive PVA has a significant influence on the thickness and size of the ZIF nanosheets; Abstract, “ZIF-C Synthesis”, Conclusions.
Therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to modify the method of Chen in view of Bui, Abounahia and Wang by adding 1 wt% PVA to the precursor solution(s) as disclosed by Deng because it would have been obvious to try in order to control the morphology of the ZIOS nanosheets since they are formed in a similar way from similar precursors.
Regarding Claim 3 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 1, wherein the membrane support has a pore size of 0.45; Chen Sec. 2.1.
Regarding Claims 7-8 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 1, wherein Bui discloses the incubation is carried out for 2 h at 53–57 °C (Bui “ZIOS synthesis”). Since the range disclosed overlaps the range claimed, the range recited in the claim is considered prima facie obvious. Overlapping ranges are prima facie evidence of obviousness. It would have been obvious to one having ordinary skill in the art to have selected the portion of the disclosed range that corresponds to the claimed range. See MPEP 2144.05(I).
Regarding Claims 9-10 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 1, wherein the viscosity enhancer is PVA, Deng Abstract, “ZIF-C Synthesis”, Conclusions.
Regarding Claim 11 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 1, wherein the viscosity enhancer is present in one or more solutions at a concentration of 1 wt%; Deng Abstract, “ZIF-C Synthesis”, Conclusions.
Regarding Claim 12 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of preparing a metal cation-capturing membrane as in the rejection of claim 1, which is herein incorporated in this rection of claim 12, and thus the metal cation-capturing membrane formed by said method, which comprises a zinc imidazole salicylaldoxime supramolecule (ZIOS) nanosheet on a membrane support; see the detailed rejection of claim 1 supra. Where in the ZISO is in the form on a nanosheet, because the particles shown have dimension(s) in the nanometer range (Bui Pg. 3, right column, Fig. 2).
Regarding Claim 13 Chen in view of Bui, Abounahia, Wang and Deng discloses the metal cation-capturing membrane of claim 12, wherein the metal cation-capturing membrane is made by controlled growth of ZIOS onto the membrane support; see rejection of claims 1 and 12 supra. Where because the synthesis process of Chen in view of Bui, Abounahia, Wang and Deng is substantially similar to that disclosed in the instant specification, it is asserted, absent evidence to the contrary, that one would reasonably expect that controlled growth of ZIOS nanosheets inherently occurs. See MPEP 2112.01.
Regarding Claim 14 Chen in view of Bui, Abounahia, Wang and Deng discloses the metal cation-capturing membrane of claim 13, wherein the method comprises incubating the membrane support with two precursors solutions (Chen 2.2.2.), and wherein the precursor solution for ZIOS is disclosed to include zinc nitrate hexahydrate, 2-methylimidazole, salicylaldoxime in one solution (Bui “ZIOS synthesis”). Therefore in combination it would have been obvious to deposit the ZIOS nanoparticles on the membrane via incubation with either one solution comprising all the precursors (as in Bui), or alternatively to deposit a first solution of zinc nitrate hexahydrate then a second solution comprising the remaining precursors (as in Chen) (i.e. 2-methylimidazole, salicylaldoxime).
Regarding Claim 15 Chen in view of Bui, Abounahia, Wang and Deng discloses the metal cation-capturing membrane of claim 12, wherein the membrane support is polyvinylidene fluoride (PVDF); Chen Sec. 2.2.2.
Regarding Claim 16 Chen in view of Bui, Abounahia, Wang and Deng discloses the metal cation-capturing membrane of claim 12, wherein the membrane support has a pore size of 0.45; Chen Sec. 2.1.
Regarding Claim 18 Chen in view of Bui, Abounahia, Wang and Deng discloses the metal cation-capturing membrane of claim 12, wherein the ZIOS nano sheet has a hexagonal sheet morphology (Bui Fig. 2 shows some ZIOS sheets that are broadly “hexagonal”).
Regarding Claim 19 Chen in view of Bui, Abounahia, Wang and Deng discloses the metal cation-capturing membrane of claim 12, which is used in a method of removing transition metal ions (i.e. copper) from an aqueous solution (Chen Abstract, 2.3., Bui Title, Abstract, “Adsorption capability of ZIOS”), the method comprising passing the aqueous solution across the metal cation-capturing membrane (Chen 2.3., Fig. 2).
Regarding Claim 20 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 19, wherein the aqueous solution used is a test solution, but Chen discloses the intended use in for removal copper/heavy metals from wastewater (Abstract, Introduction) and similarly Bui discloses the ZIOS material is useful for the adsorptive removal of copper from acid mine drainage-polluted water (pg. 2, right column). Therefore, at the time of filing, it would have been obvious to substitute the test solution for wastewater or mine drainage.
Regarding Claim 21 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 19, wherein the aqueous solution has a pH in a range of about 2 to about 9.; (Chen Sec. 3.2.1., Fig. 8; Bui Fig. 3, Pg. 6 left column). Since the range disclosed overlaps the range claimed, the range recited in the claim is considered prima facie obvious. Overlapping ranges are prima facie evidence of obviousness. It would have been obvious to one having ordinary skill in the art to have selected the portion of the disclosed range that corresponds to the claimed range. See MPEP 2144.05(I).
Regarding Claim 22 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 19, wherein the transition metal ions comprise Cu ions; Chen Abstract, 2.3., Bui Title, Abstract, “Adsorption capability of ZIOS”.
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Chen in view of Bui, Abounahia, Wang and Deng further in view of Bishnu P. Biswal, et al., Selective interfacial synthesis of metal–organic frameworks on a polybenzimidazole hollow fiber membrane for gas separation, (Paper) Nanoscale, 2015, 7, 7291-7298 (hereinafter “Biswal”).
Regarding Claim 6 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 1, but does not disclose wherein the method comprises incubating the membrane support between two cells, wherein the first cell comprises zinc nitrate hexahydrate and the second cell comprises 2-methylimidazole, salicylaldoxime and a viscosity enhancer
However Biswal discloses forming a ZIF nanoparticles (which are formed in a similar process to ZIOS), wherein the method comprises incubating the membrane support between two cells (i.e. the hollow fiber membrane’s lumen/tube side as one cell and the shell side/outside the hollow fiber as a second cell, separated by the membrane); wherein the first cell/tube side comprises zinc nitrate solution and the second cell/shell side comprises 2-methylimidazol solution; Sec. “Fabrication of the ZIF-8@PBI-BuI-In composite”.
Therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to modify the method of Chen in view of Bui, Abounahia, Wang and Deng by incubating the membrane support between two cells, wherein the first cell comprises a zinc nitrate hexahydrate solution and the second cell comprises a 2-methylimidazole solution as disclosed by Biswal because this is a known means to form nanoparticles on a membrane from zinc nitrate hexahydrate and 2-methylimidazole precursor solutions.
Biswal does not address which solution the other materials of the precursor should go in, so it would have been obvious to try placing the addition precursor solution materials (i.e. salicylaldoxime and the viscosity enhancer) in either solution in their respective cells, because this involves choosing from a finite number of identified, predictable solutions, with a reasonable expectation of success.
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Chen in view of Bui, Abounahia, Wang and Deng further in view of Kontos, A.G., et al. (2014), CO2 Captured in Zeolitic Imidazolate Frameworks: Raman Spectroscopic Analysis of Uptake and Host–Guest Interactions. ChemSusChem, 7: 1696-1702. (hereinafter “Kontos”).
Regarding Claim 23 Chen in view of Bui, Abounahia, Wang and Deng discloses the method of claim 22, wherein in-situ Raman analysis is used to differentiate Cu2+ and Ni2+ adsorption mechanisms onto the metal cation-capturing membrane.
However Kontos discloses using in-situ Raman analysis to study CO2 adsorption mechanisms in ZIF-69 including quantifying CO2 uptake, identifying weak host–guest interactions and elucidating CO2 sorption mechanism in ZIFs; Abstract, Conclusions.
Therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to modify the method of Chen in view of Bui, Abounahia, Wang and Deng by using in situ Raman analysis to study the mechanisms of target contaminant absorbance onto the adsorbent (i.e. ZIOS) as disclosed by Kontos because “[i]t not only provides qualitative information related to the contribution of functional groups to sorption, structural changes, framework stability, and nature of binding, but also gives quantitative estimate of the sorption capacity at desired pressures and temperatures”.
As to specifically differentiating Cu2+ and Ni2+ adsorption mechanisms onto the metal cation-capturing membrane, Bui notes that “selective removal of copper from nickel electrolysis anolytes has long been a problem plaguing the global metallurgical industry” (pg. 2 left column), and that “ZIOS may have potential for applications that target more than one toxic cation and/or the selective removal of other metal ions from select mixtures. If the limited selectivity of ZIOS is indeed governed by the salicylaldoxime ligand, this behavior should be tunable by changing the solution pH to a range favorable for more selective copper uptake by this chelator” (pg. 6, left column). And therefore, before the effective filing date, it would have been prima facie obvious to one of ordinary skill in the art to use the in situ Raman analysis to specifically differentiate Cu2+ and Ni2+ adsorption mechanisms onto the metal cation-capturing membrane in order to target conditions which selectively favor adsorption of one over the other.
Response to Arguments
Applicant's arguments filed 12/30/2025 have been fully considered but they are not persuasive.
In response to Applicants’ argument that it would not have been obvious to a person of ordinary skill in the art to substitute ZIOS, the supramolecular copper chelating complex disclosed in Bui, for the ZIP-8 adsorbent utilized in Chen's membrane fabrication method, or otherwise use ZIF synthesis processes to motive creation of a ZIOS membrane; the Examiner disagrees. Applicants argue that the rejections “rest on an impermissible oversimplification of nanomaterials science and an improper analogy across material systems governed by fundamentally different physical and chemical principles”, “[t]herefore, treating nanometer-scale ZIF nanoparticles, micron-scale ZIOS microparticles, and atomically thin ZIOS nanosheets as functionally analogous disregards well-established principles of materials physics. Obviousness cannot be predicated on surface-level similarity when the underlying governing physics differs by orders of magnitude”, and note Bui was employed solely as a benchmark material not because ZIF and ZIOS share structural, chemical and physical similarity.
However, respectfully, Bui is clear that ZIOS is similar to ZIF-8 with some different characteristics, through its many comparisons throughout the disclosure of Bui. ZIOS is also formed from the same precursors as ZIF with the addition of salicylaldoxime:
ZIF-8 is made from reacting: Zinc nitrate and 2-MI (Biu ZIF-8 synthesis) (and in Chen 2.2.1. also cyclodextrin),
ZIOS is made from reacting : Zinc nitrate, 2-MI and salicylaldoxime (Biu ZIOS synthesis).
Therefore, despite differences in size of the formed ZIOS when compared to ZIF, they are both similar heavy metal/copper adsorbents made by remarkably similar synthesis processes. One of skill in the art would not need to understand the more nuanced differences in the underlying synthesis mechanism to find it obvious that they would be obvious to substitute, and that strategies for synthesizing ZIF would be obvious to apply to ZIOS. Particularly because the differences in the synthesis process noted by Applicants appear to be disclosed in the instant specification, which would not have been available to one of skill in the art, and not in Bui. Further, while the ZIOS is shown to be larger, it is still considered a nanoparticles, because some dimension appear to be less than 1 micron, as shown in Bui Fig. 2, and where some of the particle shown in Fig.2 are hexagonal.
In response to applicant's argument that the references fail to show certain features of the invention, it is noted that the features upon which applicant relies (i.e., atomically thin nanosheets, in situ delamination of stacked, three-dimensional ZIOS microparticles into two dimensional nanosheets followed by controlled deposition) are not recited in the rejected claim(s). Although the claims are interpreted in light of the specification, limitations from the specification are not read into the claims. See In re Van Geuns, 988 F.2d 1181, 26 USPQ2d 1057 (Fed. Cir. 1993).
In response to Applicants’ argument that it would not have been obvious to substitute a test solution with wastewater or mine drainage; the Examiner disagrees. Bui discloses the ZIOS material is a “promising candidate for the adsorptive removal of copper from acid mine drainage-polluted water” (pg. 2, right column). And thus to use the membrane comprising ZIOS to treat acid mine drainage-polluted water is clearly obvious from the disclosure of Bui. While the Examiner appreciates that Applicants’ are named authors of Bui, Bui never-the-less is available as prior art and thus the advantages of ZIOS are known to one of skill in the art at the time of filing of the instant invention.
In response to applicant's argument that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971).
In response to Applicants’ argument that it would not have been obvious to include the PVA viscosity enhancer of Deng to control the morphology of ZIOS because Deng is directed to ZIF synthesis, which is a bottom-up process where the ZIOS is a top-down process; the Examiner disagrees. As discussed above, one of skill in the art would see the ZIOS synthesis process as remarkably similar to that of ZIF, and would therefore have been motivated to apply teachings from ZIF synthesis process, such as Deng, to ZIOS. Further, Bui does not appear to disclosed that the synthesis is top-down as opposed to the ZIF being bottom-up, and therefore this information was not available to one of skill in the art at the time of filing. Applicants’ further note that PVA is disclosed merely as one example among several viscosity enhancers. However, it is not clear how this is relevant to the rejection, as the claim limitation are addressed fully by the disclosure of PVA.
In response to Applicants’ argument that “[t]he fact that Raman spectroscopy can be used in one system does not create a reasonable expectation that it would function meaningfully in another” and therefore it would not have been obvious to combine the teachings of Kontos with that of the combined invention; the Examiner disagrees. Applicants appear to argue that there would not have been an expectation of success in applying Raman spectroscopy to the system of Chen in view of Bui, et al. because the system of Kontos does not use the same adsorption process and that “Raman spectroscopy is a known analytical technique, its successful application is highly system and sample dependent”, however this amounts to nothing more than Attorney argument, which is not given weight; see MPEP 2145(I) “assertion of what seems to follow from common experience is just attorney argument and not the kind of factual evidence that is required to rebut a prima facie case of obviousness.” Kontos discloses that it is known to use Raman spectroscopy to identify sorption mechanism in ZIFs, and therefore one of skill in the art would have a reasonable expectation of success in using Raman spectroscopy to identify sorption mechanism in ZIF and other ZIF-like adsorbents such as ZIOS.
Conclusion
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/ERIC J MCCULLOUGH/ Examiner, Art Unit 1773
/BENJAMIN L LEBRON/ Supervisory Patent Examiner, Art Unit 1773