The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 7-16 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, 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. In claim 7, the Markush group is improper. The “comprising” language is open while a Markush group must be closed (see claims 10-12 for proper Markush groups). Claims 8-16 depend from claim 7 and fail to correct the problem.
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 1-6 are rejected under 35 U.S.C. 103 as being unpatentable over Sel (Journal of Electronic Materials 2015, newly cited and applied) in view of Xian (Journal of Solid State Chemistry 2019, newly cited and applied). In the paper Sel teaches the preparation of metal-organic frameworks of trimesic acid (TMA = 1,3,5-benzene tricarboxylic acid, see figure 1) and Cu, Co or Ni for potential sensor applications. Metal–organic frameworks (MOFs) have been constructed using trimesic acid (TMA) as organic linker and Co(II), Ni(II) or Cu(II) metal ions from their corresponding aqueous chloride salts at room temperature. The prepared TMA–M (M: Co, Ni, and Cu) MOFs have been characterized in terms of their porosity and optical, thermal, electrical, and structural properties. The prepared MOFs were characterized in terms of their porosity through Brunauer–Emmett–Teller measurements, yielding a value of 330 m2/g for the TMA–Cu MOF. Structural analysis and thermal characterization of the prepared MOFs were done by using Fourier-transform infrared (FT-IR) spectroscopy, x-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA), respectively. The optical properties were analyzed by fluorescence spectroscopy. Additionally, TMA–M MOF disks were prepared and their conductivities determined by room-temperature I–V measurements. The conductivity of the TMA–M MOFs was calculated to be between 7.97 x 10-7 S/cm and 5.39 x 10-9 S/cm. The paragraph bridging pages 136-137 teaches that the recent trend is for production of MOFs with additional properties for use in drug delivery, sensors, and optical devices. The most common, widely used organic linkers with carboxylic acid functionality are benzene 1,4-dicarboxylic (terephthalic) acid, benzene 1,3,5-tricarboxylic acid (TMA, trimesic acid, BTC) and benzene 1,2,4,5-tetracarboxylic acid. The first full paragraph on page 137 teaches that the prepared MOFs have very different properties in terms of their crystal structure, thermal behavior, and surface area. Additionally reported are the florescence spectra, XRD, and conductivity measurements of TMA–M (M: Co, Ni, and Cu) MOF disks, which may provide some insight into their potential use for sensor applications. The MOF preparation is described in the paragraph bridging pages 137-138. Depending on the nature of the metal ion, different colored precipitates, e.g., violet for Co(II) and light green for Ni(II), were observed upon complexing with TMA. The paragraph bridging pages 138-139 teaches that fluorescence measurements were performed using a fluorescence spectrometer by applying an excitation wavelength of 270 nm. The paragraph bridging pages 141-142 teaches that the prepared TMA–M MOFs were colorful; therefore, the optical properties of the TMA–M MOFs were analyzed by fluorescence spectrometry. The normalized fluorescence spectra of the TMA–M MOFs are presented in figure 8. A peak at around 318 nm was observed for the TMA MOF, whereas broader peaks were observed for the TMA–Ni, TMA–Co, and TMA–Cu MOFs at around 337 nm, 340 nm, and 375 nm. Moreover, for the TMA–Cu and TMA–Ni MOFs, an additional peak was observed at around 465 nm. The conclusion paragraph on page 142 teaches that the prepared TMA–M MOFs were colorful and showed different emission wavelengths that could be further exploited in sensor applications due to the color change when in contact with an analyte. They indicated that they were exploring the use of TMA–M MOFs for applications involving various toxic compounds and gas molecules. Sel does not teach a europium doped Ni-BTC MOF.
In the paper Xian teaches an Eu(III) doped zinc metal organic framework material and its sensing detection for nitrobenzene. An Eu(III) doped zinc metal-organic framework (MOF), i.e., Zn3(BTC)2: Eu(III), was synthesized by the solvothermal method. The crystal structure, morphology, compositions and photoluminescence properties of Zn3(BTC)2: Eu(III) were studied by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and optical spectroscopic technique, respectively. The sensing detection for different nitrobenzene concentrations is performed at room temperature. The results show that Zn3(BTC)2: Eu(III) is successfully synthesized, and 4% Eu(III) doped Zn3(BTC)2 exhibits the excellent fluorescence. The photoluminescence properties of activate Zn3(BTC)2: 4% Eu(III) in different solvents have been investigated in detail, and the results show that it has obvious fluorescence quenching behavior towards nitrobenzene (NB) in the range of 0-250 ppm, and the fluorescence intensity decreases exponentially when the NB concentration increases. According to the Stern-Volmer equation, the quenching constant KSV = 0.03873 ppm-1 (i.e., KSV = 3.957 x 103M-1) can be obtained and the limit of detection is 0.97 ppm. The sensing mechanism is also discussed. The MOF sample shows rapid response, high sensitivity, good selectivity, good repeatability to NB, and may be used as a potential NB probe in liquid environment. The paragraph bridging the columns of the first page of the paper teach that metal-organic frameworks (MOFs), due to their unique fluorescent properties, designable pores, and tailored recognized sites, are widely used in the recognition of gas molecules, harmful metal ions, anions, and nitro explosive complexes. Since lanthanide-based MOFs have unique luminescent properties, such as large Stokes’ shifts, high color purity, excellent quantum yields and relatively long luminescence lifetimes, making them can result in promising sensing materials. For example, Eu-MOFs show good luminescence performance and high fluorescence quenching behavior towards Fe3+ (Cr3+) and NB, exhibiting excellent stability and cycling performance. In addition, Eu(III)-MOFs can serve as a fast and recyclable fluorescence sensor for nitroaromatics with low detection limits. However, there had not been a report on Eu(III)-doped MOFs as a sensitive probe for NB. Section 2.2 teaches the synthesis of Eu(III) doped Zn3(BTC)2. In the process, stoichiometric ratios of Zn(NO3)2⋅6H2O and Eu(NO3)3⋅6H2O were dissolved in 10 mL absolute ethanol, and H3BTC was dissolved in 10mL of and ethanol/H2O solution (1:1, v/v). The two solutions were mixed to obtain a uniform mixture after stirring for 10 minutes. The mixture was sealed in a Teflon-lined stainless steel vessel, heated at 120 °C under autogenous pressure for 24 hours, and cooled to room temperature to obtain the Eu(III)-doped Zn3(BTC)2. The white powders were washed with absolute ethanol and dried in air. Section 2.4 teaches that in order to obtain the optimum doping concentration, the fluorescence properties of Zn3(BTC)2 with different Eu(III) doping concentrations were investigated at room temperature. Before sensing detection, Eu(III)-doped Zn3(BTC)2 were activated at 150 °C for 12 hours. The solvent sensing experiments were conducted as follows: 2mg Zn3(BTC)2: 4% Eu(III) were dispersed into different solvents of 2.0 mL, such as methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF), isopropanol (IPA), N,N-dimethylformamide (DMF), dimethylacetamide (DMA), and NB, and treated by ultrasonication for 20 minutes to form stable suspensions before fluorescence measurement. In order to evaluate the quenching properties of the probe, the fluorescence intensity change with different NB concentrations (0-250 ppm) in 2mL of Eu(III) doped Zn3(BTC)2 suspensions was also monitored. Figure 1 gives the different doped structures that were formed. The second full paragraph on page 3 teaches that the emission spectra of pure Zn3(BTC)2 and Zn3(BTC)2: 2-10% Eu(III) samples at room temperature are shown in figures 4 (a) and (b), respectively. As shown in figure 4 (a), the emission peak of pure Zn3(BTC)2 is at 440 nm under 347 nm excitation. As shown in figure 4(b), all Eu(III) doped samples show the same emission peaks under 392 nm excitation. 5D0→7Fn (n =1, 2, 3, 4) transition of Eu(III), respectively, located at 595, 620, 655 and 705 nm. The strongest emission peak is at 620 nm. In addition, Zn3(BTC)2: 4% Eu(III) presents the best luminescence performance. Therefore, Zn3(BTC)2: 4% Eu(III) was chosen to be as the sensing probe in the sensing experiments. The fluorescence spectra are shown in figure 6. Figure 6 (a) shows the overall quenching diagram of the sample (monitoring wavelength at 280 nm), and figure 6 (b) shows the quenching diagram of the monitoring peak at 620 nm. As shown in figure 6 (b), with the increase of the NB concentration, the fluorescence intensity at 620 nm decreases gradually. When 20 ppm of NB is added, the fluorescence intensity is quenched by 43.65%, and when 110 ppm of NB was added, the fluorescence intensity is quenched by more than 80%. When the concentration of NB reaches 250 ppm, the fluorescence is almost completely quenched. This quenching effect is much higher than that of MOFs previously reported for NB detection. These results show that Zn3(BTC)2: 4%Eu(III) can be used as a good fluorescence recognition material for the detection of NB. Figure 7 (a) shows a fitting curve between the fluorescence intensity of the sample and the different NB concentrations. In the range of 0-250 ppm, the fluorescence intensity of the sample decreases exponentially with the increase of the NB concentration. The inset in figure 7 (a) shows that the fluorescence intensity of the sample has a good linear relationship in the range of 0-25 ppm NB. In addition, the limit of detection (LOD) of NB was calculated to be about 0.97 ppm which is lower than reported in most literature. this indicated that Eu(III) doped Zn3(BTC)2 has excellent sensitivity to NB. The paragraph on page 5 teaches that this work provides a good choice to design and synthesize multifunctional fluorescent MOFs as probes for selective detection analytes.
With respect to claims 1 and 6, it would have been obvious to one of ordinary skill in the art at the time the application was filed to modify the Ni-BTC MOF of Sel according to the teachings of Xian by doping it with europium using a solvothermal method in which a nickel salt, an europium salt and trimesic acid are mixed to form a mixture which is heated at 120-160 °C for 18-30 hours to form a europium doped metal-organic framework because of the potential of the Ni-BTC material to serve as a sensing material as taught by Sel and the teaching that doping a metal-organic framework with europium as taught by Xian provides a good choice to design and synthesize multifunctional fluorescent metal-organic frameworks as probes for selective detection analytes. Since Sel and Xian use an aqueous solution to create the MOF and the solvothermal method of Xian falls within the heating temperature and time scope of claim 6 the specifically claimed Ni3(BTC)2 • 12H2O: wt%Eu(III) structure would have been expected to be produced. With respect to claims 2-4, the claimed properties for the material would also have been expected because of the use an aqueous solution by Sel and Xian to create the MOF and because the solvothermal method of Xian falls within the heating temperature and time ranges of claim 6. With respect to claim 5, Because Xian does not use more than 10 wt% of europium to produce the doped MOF, the combination of Sel in view of Xian and in particular the fact that the Zn3(BTC)2: 4%Eu(III) of Xian had the highest fluorescence would point one of ordinary skill in the art to test the same range of europium wt% for the Ni3(BTC)2: wt%Eu(III) metal-organic framework and meet the limitation of claim 5.
Claims 7-16 would be allowable if rewritten to overcome the rejection(s) under 35 U.S.C. 112(b), set forth in this Office action and to include all of the limitations of the base claim and any intervening claims.
The following is a statement of reasons for the indication of allowable subject matter: the art of record points to the metal-organic framework being sensitive to and/or being responsive to some type of analyte such as the NB of Xian. However, there is insufficient disclosure to show that one of ordinary skill in the art would have expected sensitivity to a group consisting of an S-heterocycle, an N-heterocycle and an O-heterocycle.
Applicant’s arguments with respect to the claims have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. The additionally cited material is related to different metal-organic-framework structures.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Arlen Soderquist whose telephone number is (571)272-1265. The examiner can normally be reached 1st week Monday-Thursday, 2nd week Monday-Friday.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Lyle Alexander can be reached at (571)272-1254. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/ARLEN SODERQUIST/Primary Examiner, Art Unit 1797