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 .
Election/Restrictions
Applicant’s election without traverse of the species associated with semiconductor nanoparticles (Claims 15-16) in the reply filed on 7/27/26 is acknowledged.
Claim 17 is withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected species, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 7/27/26.
Claim Interpretation
The claim sets forth various functions for parts of the ligand as claimed. The ligand has a linking group, a photoreactive group, and an activation group.
The function of the linking group is clearly set forth in the claim as being a portion that comprises a moiety capable of binding the ligand to the surface of a nanoparticle.
The ‘photoreactive group’ is bonded to the linking and activation group and its further function is not clearly set forth in the claims. The specification, at page 21 as filed, describes the photoreactive group is being photocleavable or may undergo a reduction-oxidation reaction. The claims are examined based on the groups ability to perform such a function. The specification sets forth that this function may be performed by a carbonyl group. Other photoreactive groups known in the art include azo groups, peroxy groups (See evidentiary document to Zhang US20200332181; paragraph 42; corresponds to 11453820 in IDS) and disulfide group (See evidentiary document to Cao NPL; See Abstract and introduction- ‘The disulfide bond is prone to ultraviolet light-induced cleavage’). The inclusion of any of these functional groups is considered to meet the claim limitation of including a photoreactive group.
The activation group is bonded to the photoreactive group and its further function is not clearly set forth in the claims. The specification is unclear about the exact function of the activation group. The specification sets forth that the activation can provide energy to the photocleavable group but also sets forth that this energy can be provided separate from the activation group (See Page 23-24). The description of this feature as claimed does not limit the broadest reasonable interpretation of the claim term to any particular structure or group of structures. Page 26 of the specification sets forth that any group may be used as long as the prescribed function is achieved, but as the specification also sets forth that the activation energy may be externally provided, this function may be performed by any group. Thus the claims as set forth do not limit the composition or structure of the activation group. The specification sets forth that the activation group may comprise a monovalent alkyl or divalent alkylene group comprising a saturated or unsaturated hydrocarbon group, which may be linear, branched, cyclic or acyclic. Other examples include monovalent aromatic groups as provided at page 26.
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.
Claim(s) 1, 5, 8-11, 13, 15-16, 19-21 and 23 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Maloney in US20170269046.
Regarding Claim 1: Maloney teaches a quantum dot modified with a photoactive ligand. Maloney teaches that the quantum dot may be provided as a collection of quantum dots (See paragraph 105). Maloney characterizes the quantum dots as nanocrystals and are shown to be particulate in the Figures. The quantum dots of Maloney are thus nanoparticles as claimed. Maloney thus teaches a collection of surface modified nanoparticles.
The surface modification of Maloney comprises photoactive organic ligands comprising a linking group, an activation group and at least one photoreactive group. Maloney teaches ligands having a structure QD-(-X2-R2-S-S-R1-X1-Y)n, wherein X2 is a linkage that functions to attach the R2 group to the surface of the nanoparticle (quantum dot). The R2 group and S-S group are shown in Exemplary molecules at page 10. The R2 group may comprise an amide functional group RC(=O)NHR, which is a photoreactive group described by applicant. The S-S group is also a photoreactive group known in the art (See Claim interpretation above). The Y group of Maloney is a polycyclic dye that meets the interpretation of the activation group as claimed and set forth above (See Claim interpretation). Each of the linking group and activation group are covalently bonded to the photoreactive group through covalent bonds. The linking group binds the ligand to the particle as claimed (See Page 10).
Regarding Claim 5: Maloney shows the linkage between the X2, R2, S-S, R1, X1 and Y groups at page 10. The activation group includes a monovalent aromatic group based on Rhodamine.
Regarding Claim 8: The quantum dots of Maloney are luminescent nanoparticles (See Paragraph 86).
Regarding Claim 9-10: The quantum dots of Maloney have luminescence shown in Figure 8A or 8B. It is noted that in this graph there are two labels for 550 nm on the x-axis. The first 550 label is considered to be 500 nm and the second label is considered to be 550 nm. The surface modified nanoparticles of Maloney contain green CdSe/ZnS (contributing to the peak around 540 nm) and red Rhodamine dye as a surface modifier (See Example 1A). The examples and these figures show the change in luminescence with increasing bisulfide content. Bisulfide is taught by Maloney to cleave the rhodamine from the quantum dot at the disulfide bond. Quantum dots not having a cleaved bond have the red emission from Rhodamine as shown, and thus correspond to a first luminescent nanoparticle emitting light of a first color (red; 600 nm). Quantum dots having a cleaved bond correspond to a second luminescent nanoparticle that emits light of a second color (green; corresponding only the QD). The green and red emission of each nanoparticle is more than 0.2 eV apart (540 nm corresponding to ~2.3eV and 600 nm corresponding to 2 eV). Thus the second nanoparticle may be considered to have a bandwidth greater by at least 0.2 eV.
Regarding Claim 11: Maloney shows in Figure 10C and 10D that the average particle size is between 5 and 11 nm (the full span of the distribution shown).
Regarding Claim 13: Maloney shows in the Figures that the quantum dot is a generally spherical nanoparticle (See Figure 1-3).
Regarding Claim 15-16: Maloney teaches that the quantum dot may have a composition such as CdSe/ZnS (See Paragraph 87).
Regarding Claim 19-20: Maloney teaches that the sensing agent may further include other ligands that do not contain the photoactive dye as set forth. Maloney teaches that these may be provided as phase transfer coating, ligand exchange coatings, polymer coating, and silanization coatings (See Paragraph 20). Such a coating is shown at Example 1B, wherein a PAA coating is provided based upon octylamine ligands (See Paragraph 104). These ligands are non-photoactive and bound to the surface of the quantum dots through an amine functional group. Octylamine necessarily comprises a butylamine moiety as it has a longer alkyl chain length than butylamine. The use of octylamine as is shown in the examples thus meets the claim limitations as set forth.
Regarding Claim 21: Maloney teaches that the surface modified nanoparticles may be dispersed in a buffer solution (which comprises a solvent and a solute; See Exa,[;es).
Regarding Claim 23: Maloney teaches that the surface modified nanoparticles can be provided as a coating on a substrate such as paper, a polymer, or PDMS (See Paragraph 99).
Claim Rejections - 35 USC § 103
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.
Claim(s) 2-4, 6, 12, 22, and 24 is/are rejected under 35 U.S.C. 103 as being unpatentable over Maloney in US20170269046.
Maloney teaches a quantum dot modified with a photoactive ligand. Maloney teaches that the quantum dot may be provided as a collection of quantum dots (See paragraph 105). Maloney characterizes the quantum dots as nanocrystals and are shown to be particulate in the Figures. The quantum dots of Maloney are thus nanoparticles as claimed. Maloney thus teaches a collection of surface modified nanoparticles.
The surface modification of Maloney comprises photoactive organic ligands comprising a linking group, an activation group and at least one photoreactive group. Maloney teaches ligands having a structure QD-(-X2-R2-S-S-R1-X1-Y)n, wherein X2 is a linkage that functions to attach the R2 group to the surface of the nanoparticle (quantum dot). The R2 group and S-S group are shown in Exemplary molecules at page 10. The R2 group may comprise an amide functional group RC(=O)NHR, which is a photoreactive group described by applicant. The S-S group is also a photoreactive group known in the art (See Claim interpretation above). The Y group of Maloney is a polycyclic dye that meets the interpretation of the activation group as claimed and set forth above (See Claim interpretation). Each of the linking group and activation group are covalently bonded to the photoreactive group through covalent bonds. The linking group binds the ligand to the particle as claimed (See Page 10).
Regarding Claim 2: The photoactive ligands of Maloney are of a composition (X2-R2-S-S-R1-X1-Y), wherein X2 is a linkage that functions to attach the R2 group to the surface of the nanoparticle (quantum dot). This ligand overlaps in composition with the ligand 1a as instantly claimed. The X2 group of Maloney may be chosen from amide linkages or any other chemical moiety that can be used to form an attachment to the quantum dot, such as thiol groups (See Paragraph 80). The X2 group of Maloney corresponds to the T group instantly claimed and may be chosen from an overlapping range of materials such as thiols. The R2 group and S-S group are shown in Exemplary molecules at page 10. The R2 group may comprise an amide functional group RC(=O)NHR (carbonyl group), which is a photoreactive group described by applicant. Maloney describes the R2 group as being a substituted or unsubstituted linear aliphatic group having from 1 to 20 carbon atoms. The R2 group shown at page 10 is a C1 group; however, the use of carbon chains up to 20 atoms long would have been obvious. Thus the chain lengths of Maloney correspond to n=1-20; which overlaps with the instantly claimed range. As is discussed above, Maloney teaches the use of an amide functional group wherein W is O and X is NH. The remainder of the claimed ligand R comprises the dye (Y; activation group) as well as S-S bond, the R1 moiety and X1 moiety.
Thus Maloney teaches an overlapping range of ligands with those that are instantly claimed. Maloney obviates the use of carbonyl groups in conjunction with an overlapping range of chain lengths when providing the R2 structure. Maloney also obviates an overlapping range of linking group T and the use of an activation group as claimed.
Regarding Claim 3: The R group claimed corresponds with the -S-S-R1-X1-Y group of Maloney. This group is directly conjugated to the claimed photocleavable group (carbonyl group).
Regarding Claim 4: The claimed R-X group in the ligand of Maloney is a single moiety that can be seen in scheme 1, wherein this R-X group is an amine terminated rhodamine B compound, wherein the amine is associated with X as claimed.
Regarding Claim 6: As is discussed above, Maloney’s X2 group, which attaches to the quantum dot and corresponds with the claimed component T, may be a thiol group (See Paragraph 80). The photocleavable group may comprise X-C(W) as claimed, wherein W is O, and X is NH and the activation group is a monovalent aromatic group (the rhodamine B derivative shown at page 10) conjugated to the photocleavable group.
Regarding Claim 12: Maloney teaches that the semiconductor nanoparticles may be provided having an average diameter in the range from 5-11 nm (See Figure 10C, 10D). Maloney is silent in terms of providing a first and second semiconductor nanoparticles having a first and second average particle diameter. However, those of ordinary skill in the art would have found it obvious to provide the monomodal distribution shown in Figures 10C or 10D from several different populations of particles having different average particle sizes within the span as set forth. As the span ranges from 5 nm to 11 nm, those of ordinary skill in the art would consider that a first and second population of particles could have a first and second average particle size that differs by up to 6 nm. It is noted that the claim does not set forth attributes of the particle size such that a bimodal distribution or the presence of several peaks in the combined distribution is necessary. As this is the case, providing two or more quantum dot populations such that a monomodal distribution is created would have been obvious.
Regarding Claim 22: Maloney teaches that the quantum dots may be provided in a solution having a molarity of 3.43*10-8 M (See Example 1B, 1C, 1D, 2). Maloney is silent in terms of providing a concentration of nanoparticles between 10 wt% and 60 wt% in such a solution. However, generally differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical (See MPEP 2144.05 (II). Maloney specifically sets forth that the solution having this particular molarity is diluted from a more concentrated solution (See Paragraph 105-106). Those of ordinary skill in the art would have found it obvious to provide such a diluted solution from a concentrated solution having any wt% wherein the quantum dots are stable. The determination of suitable concentrations for storage of stock quantum dot solutions (from which the diluted solutions are created) would be a matter of routine experimentation in the art. Those of ordinary skill in the art would find that storing quantum dots at a high weight percentage in solution would provide for more efficient storage. The determination of suitable concentrations for stock solutions would provide a range of suitable concentrations that would at least overlap the range instantly claimed.
Regarding Claim 24: Maloney teaches that the collection of surface modified nanoparticles may be provided on a substrate such as paper, PDMS, or a polymer in terms of a coating (See Paragraph 99). The coating of Maloney is the basis for the sensor as it contains the collection of surface modified nanoparticles that are capable of sensing the presence of H2S as is discussed. Maloney is silent in terms of the thickness of such a coating; however, those of ordinary skill in the art would find the determination of suitable thicknesses of such a sensor coating to be a matter of routine experimentation in the art. Those of ordinary skill in the art would have found it obvious to determine the range of coating thicknesses that are capable of providing fluorescent data such that the concentration of H2S in contact with the coating is determinable. The conclusion of such experimentation would give those of ordinary skill in the art data in terms of a minimum suitable coating thickness, which would necessarily be less than the maximum coating thickness claimed. Thus it is expected that such routine experimentation would lead those of ordinary skill in the art to a range of thicknesses that at least overlap with those instantly claimed. This is evidenced at least by Figure 3, which shows a sensor, wherein its thickness is several times that of the quantum dot diameter. Maloney teaches that the quantum dots have a size on the order of about 10 nm. Those of ordinary skill would expect a sensor having a thickness of 10’s to 100’s of nm to be functional on the basis of this Figure. Such a thickness would fall within the claimed range.
Claim(s) 14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Maloney as applied to claim 1 above, and further in view of Artemyev in their publication “Efficiency of Energy Transfer from Organic Dye Molecules to CdSe−ZnS Nanocrystals: Nanorods versus Nanodots”.
Maloney teaches a quantum dot modified with a photoactive ligand. Maloney teaches that the quantum dot may be provided as a collection of quantum dots (See paragraph 105). Maloney characterizes the quantum dots as nanocrystals and are shown to be particulate in the Figures. The quantum dots of Maloney are thus nanoparticles as claimed. Maloney thus teaches a collection of surface modified nanoparticles.
The surface modification of Maloney comprises photoactive organic ligands comprising a linking group, an activation group and at least one photoreactive group. Maloney teaches ligands having a structure QD-(-X2-R2-S-S-R1-X1-Y)n, wherein X2 is a linkage that functions to attach the R2 group to the surface of the nanoparticle (quantum dot). The R2 group and S-S group are shown in Exemplary molecules at page 10. The R2 group may comprise an amide functional group RC(=O)NHR, which is a photoreactive group described by applicant. The S-S group is also a photoreactive group known in the art (See Claim interpretation above). The Y group of Maloney is a polycyclic dye that meets the interpretation of the activation group as claimed and set forth above (See Claim interpretation). Each of the linking group and activation group are covalently bonded to the photoreactive group through covalent bonds. The linking group binds the ligand to the particle as claimed (See Page 10).
Maloney teaches the use of quantum dots such as CdSe/ZnS, but is silent in terms of the shape of the quantum dots.
However, Artemyev teaches that CdSe/ZnS in the form of both nanodots and nanorods has similar FRET efficiency when provided with organic dye molecules (See Table 3). On the basis of Artemyev’s teachings, those of ordinary skill in the art would have found it obvious to provide the nanoparticles of Maloney in the forms of spherical nanoparticles or in the form of nanorods. Those of ordinary skill in the art would have been motivated to provide either form of nanoparticles as they are expected to provide similar and beneficial results.
Claim(s) 18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Maloney as applied to claim 1 above, and further in view of PlasmaChem in their publication “Quantum Dots particle Sizes” (2016).
Maloney teaches a quantum dot modified with a photoactive ligand. Maloney teaches that the quantum dot may be provided as a collection of quantum dots (See paragraph 105). Maloney characterizes the quantum dots as nanocrystals and are shown to be particulate in the Figures. The quantum dots of Maloney are thus nanoparticles as claimed. Maloney thus teaches a collection of surface modified nanoparticles.
The surface modification of Maloney comprises photoactive organic ligands comprising a linking group, an activation group and at least one photoreactive group. Maloney teaches ligands having a structure QD-(-X2-R2-S-S-R1-X1-Y)n, wherein X2 is a linkage that functions to attach the R2 group to the surface of the nanoparticle (quantum dot). The R2 group and S-S group are shown in Exemplary molecules at page 10. The R2 group may comprise an amide functional group RC(=O)NHR, which is a photoreactive group described by applicant. The S-S group is also a photoreactive group known in the art (See Claim interpretation above). The Y group of Maloney is a polycyclic dye that meets the interpretation of the activation group as claimed and set forth above (See Claim interpretation). Each of the linking group and activation group are covalently bonded to the photoreactive group through covalent bonds. The linking group binds the ligand to the particle as claimed (See Page 10).
Maloney teaches formula for the photoactive organic ligands, a range of ligands per quantum dot (variable n), and that the quantum dots may be of a composition CdSe/ZnS, but is silent in terms of the weight of the quantum dots relative to said ligand.
However, PlasmaChem teaches that CdSe/ZnS of various size may be provided in order to provide emission of various wavelengths. Particularly, PlasmaChem teaches that the wavelength of light from said QD may be modulated from 530 to 650 nm based on the size of the quantum dots. Those of ordinary skill in the art would have found it obvious to provide any of the quantum dots of Plasmachem having a wavelength less than that of the dye, as the quantum dots in the teachings of Maloney. Maloney particularly teaches that the quantum dot’s emission may be adjusted in such a way explicitly at paragraph 86. On this basis, it would have been obvious to use PL QDN-510 through at least 550 as the quantum dot, as these quantum dots clearly have emission that is of shorter wavelength than the dye. Choosing a quantum dot that has a wavelength of 540 nm, for example, has a molecular weight of 25,000 Da. The ligand shown at page 10 of Maloney’s teachings has a molecular weight of 629 Da. Maloney teaches in their examples that the average number of ligands per QD is 1.3 (See Paragraph 98). Based on this average, the use of PlasmaChem’s PL QDN-550 as the QD in the surface modification of Maloney would provide a ratio of photoactive organic ligand to nanoparticle of 629*(1.3):25000 or 1:30.57. Thus the modified quantum dots of Maloney in view of Plasmachem would have an overlapping range of ratios with the ratios claimed. Those of ordinary skill in the art would have found it obvious to use the quantum dots of PlasmaChem as they are of the same composition and structure as those taught by Maloney. Those of ordinary skill in the art would have been motivated to use the quantum dots of PlasmaChem as they provide quantum dots having various emission wavelengths, which is a modification explicitly suggested by Maloney at paragraph 86.
Allowable Subject Matter
Claim 7 is objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including 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 claim sets forth organic ligands that are not taught or obviated by the prior art of record.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to MATTHEW E HOBAN whose telephone number is (571)270-3585. The examiner can normally be reached M-F 9:30am-6:00pm.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Jonathan Johnson can be reached at 571-272-1177. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/Matthew E. Hoban/Primary Examiner, Art Unit 1734
