Rapid visual ammonia detection kit based on gold-silver core-shell nanorods

Abstract

Ammonia dissolved in water has very adverse effects on the environment, human health and other living organisms, especially aquatic organisms. Therefore, ammonia concentration is one of the most important parameters that should be monitored in water. In this regard, various methods such as electrochemical, ion chromatography, capillary electrophoresis, spectrophotometry and fluorimetry have been proposed for ammonia measurement. These methods require skilled operators and complex and expensive devices, which leads to limited for continuous and in-situ monitoring of ammonia. Also, standard ammonia detection methods (Nessler and indophenol blue) contain highly toxic reagents that must be disposed of as hazardous waste. Therefore, the development of a rapid (due to the volatility of ammonia), inexpensive and simple detection method, especially for on-site determination of ammonia, is of great interest. The basis of the colorimetric kit presented in this invention is the interaction of ammonia and silver ions, which activates the inactive silver ion and forms gold-silver core-shell nanorods. As a result, the presence of ammonia leads to rapid (less than a minute) and clear changes in the color and spectroscopic spectrum of the sensor, which allows for qualitative and quantitative detection of ammonia.

Description

Application Registration Date: 24 / 03 / 1402 Application Number: 140250140003001951 PCT Registration Date: Click to type PCT Number: Click to type Priority Date 1: Click to type Priority Number 1: Click to type Priority Date 2: Click to type Priority Number 2: Click to type Title of Invention: Visual and rapid ammonia detection kit based on gold-silver core-shell nanorods #x200fApplicant: #x200f#x200fIranian Agricultural Biotechnology Research Institute and Caspian Sea International Fish Research Institute#x200f Select the tables that have been completed in the report: ☒ Table (1) Search Report ☒ Table (2) Statement of reasons for meeting or not meeting the patent registration requirements ☐ Table (3) Statement of deficiencies in the application documentation that Needs to be amended. ☐ Table (4) Declaration of reasons for lack of unity of invention Application documents: Application documents (sent by the Patent Office) do not need to be amended.The application documentation (sent by the patent office) needs to be corrected (see Table 3). . Decision of the Inquiry Authority: Acceptance of all claims (explanation in Table 2) Acceptance of some claims (explanation in Table 2) Rejection of all claims (explanation in Table 2) Name of the Inquiry Authority reviewing the declaration. Special Task Force for the Development of Nanotechnology. . Table (1). Search report A) International Classification of the Application (IPC is required and can include one or more classes): IPC: A61K38 / 00, C12Q1 / 68, A61K45 / 06, C12N15 / 113 CPC: A61P35 / 00, A61P43 / 00, A61P25 / 00, A61P29 / 00 B) Search fields: The following databases were searched: 1.IRIPO ☒ 2.PATENTSCOPE ☒ 3.ESPACENET ☒ 4.GOOGLE PATENT ☒ 5. LENS ☒ 6. US PATENT ☒ 7.Others ☒ International Classes used in the search: A61K38 / 00, C12Q1 / 68, A61K45 / 06, C12N15 / 113 Keywords searched: Ammonia detection kit, Gold nanorod, core / shell structure, gold-silver, plasmonic nanoparticles, colorimetric detection, Core / shell, Gold nanorod, Silver, Ammonia detection Other technical criteria searched: If a technical criterion other than the above is considered in the search, please mention it in this section. . . c) Related documents found Category* Related document (Addressing should be such that the document can be easily found in a subsequent search.) Number of related claims of the application X 1.The effect of varying the amount of silver nitrate on the structural and optical properties of gold nanorods, 4th International Conference on Nanoscience and Technology Development, 2010 Gold nanorods are an important type of nanoparticles that are of great interest due to their special plasmonic properties. In this paper, gold nanorods were prepared through a two-step synthesis method (preparation of gold nanoparticles and then growth of these nanoparticles as nanorods) with five different amounts of silver nitrate. The effect of varying the amount of silver ions in the growth solution on the optical and structural properties of these samples was investigated. The growth process of gold nanorods was followed by ultraviolet-visible spectroscopy, and by observing two plasmonic peaks related to the two transverse and longitudinal dimensions of these nanorods, and the change in the location of the second plasmonic peak was investigated by varying the amount of silver nitrate. The stability of the samples over a period of 40 days from the day of production was also investigated. Then, through the analysis of transmission electron microscope (TEM) images, the shape, size, and length-to-width ratio of all five samples of prepared gold nanorods were observed and examined.In the studies, it was observed that increasing the amount of silver nitrate in the growth solution resulted in nanorods with a higher average length-to-width ratio. High-Resolution Colorimetric Assay for Rapid Visual Readout of Phosphatase Activity Based on Gold / Silver Core / Shell Nanorod, ACS Appl. Mater. Interfaces 2014, 6, 20, 18243–18250 Herein, we designed a high-resolution colorimetric protocol based on gold / silver core / shell nanorod for visual readout of alkaline phosphatase (ALP) activity by using bare-eyes. The method relied on enzymatic reaction-assisted silver deposition on gold nanorod to generate significant color change, which was strongly dependent on ALP activity.Upon target ALP introduction into the substrate, the ascorbic acid 2-phosphate was hydrolyzed to form ascorbic acid, and then, the generated ascorbic acid reduced silver ion to metal silver and coated on the gold nanorod, thereby resulting in the blue shift of longitudinal localized surface plasmon resonance peak of gold nanorod accompanying a perceptible color change from red to orange to yellow to green to cyan to blue and to violet. Synthesis of gold nanorod and the effect of silver nitrate on optical properties and morphology of nanorods were reported. Claim 2 The mechanism of determination of phosphate solution through core-shell nanorod by naked eye method is similar to the application and claims 1 and 3 do not have inventive and novel steps. X 3. Construction of silica-encapsulated gold-silver core-shell nanorod: Atomic facets enrichment and plasmon enhanced catalytic activity with high stability and reusability, Materials & Design, Volume 177, 5 September 2019, 107837 2.1.Preparation of gold nanorods (AuNRs) and gold nanospheres (AuNSs) Gold nanorods (AuNRs) and gold nanospheres (AuNSs) were prepared utilizing a recently reported seed-mediated growth method with minor modification [41,42]. Reagents and more experimental details were included in the Supporting Information. Based on the obtained AuNR (or AuNS), nanocatalysts were prepared as following sections of 2.2 Preparation of Au-Ag core-shell nanorods (Au@AgNRs), 2.3 Preparation of mesoporous silica-coated Au@AgNR (Au@AgNR@mSiO, 2.4 Pre-treatment to Au@AgNR@mSiO. 2.2. Preparation of Au-Ag core-shell nanorods (Au@AgNRs) Au@AgNRs were prepared using a previous procedure with some modifications

[17] . Specifically, four growth solution stocks were prepared, and each stock contained 10 mL Au NR solution. Afterward, various amounts (125, 250, 500 and 1000 μL) of 0.02 M AgNO 3 were added to the Au NR solutions, followed by the addition of 0.1 M AA solutions.The volume of the AA solution was equal to the AgNO 3 solution. The resulting solutions were kept in an air bath at 333 K and gently shaken for 4.5 h. Eventually, Au@AgNRs were centrifuged and re-dispersed in 20 mL of CTAB solution (1.5 mM) for the subsequent silica coating. The as-prepared Au@AgNRs were denoted as Ns-Ag (s = 1, 2, 3, 4), respectively. The preparation of gold nanorods using the seed-mediated growth method and the reduction of silver ions with ascorbic acid and its growth on gold cores was reported. Claims 2 and 3 X 4. Highly sensitive colorimetric detection of NH 3 based on Au@Ag@AgCl core-shell nanoparticles, Chinese Chemical Letters, Volume 32, Issue 9, September 2021, Pages 2807-2811 Herein, we have synthesized Au@Ag@AgCl core-shell nanoparticles (NPs) by oxidative etching and precipitating Au@Ag core-shell NPs using FeCl 3 and further used them as optical probes for the colorimetric detection of NH 3 .The sensing mechanism is based on the fact that the etching of NH 3 on AgCl and Ag shell leads to the variations of ingredients and core-to-shell ratio of the Au@Ag@AgCl NPs, thereby inducing noticeable spectral and color changes. By replacing the outmost layer of Ag with AgCl, not only is the stability of the sensor against oxygen significantly enhanced, but also is the sensitivity of the method improved. The method exhibits good linear relationship for the detection of NH 3 from 0 to 5000 μmol / L with the limit of detection of 6.4 μmol / L. This method was successfully applied to the detection of simulated air polluted by NH 3 , indicating its practical applicability for environmental monitoring. This method shows great potential for on-site NH 3 detection particularly in remote area, where a simple, fast, low-cost, and easy-to-handle method is highly desirable. تعیین رنگ سنجی آمونیاک از طریق ساختار نانوهسته / پوسته طلا-نقره گزارش شده است. ادعاهای 1 و 2 و 3 و 4 و 5 و 6 و 7 X 5.CN113059175 - PREPARATION METHOD OF AU@AG@AGCL NANOPARTICLES AND APPLICATION THEREOF IN COLORIMETRIC DETECTION OF AMMONIA (EN) The invention discloses a preparation method of Au@Ag@AgCl nanoparticles for colorimetric detection of ammonia concentration. The method comprises the following steps: firstly, reducing a HAuCl4 solution in a water phase by taking a sodium citrate solution as a reducing agent to prepare Au nanospheres; then reducing an AgNO 3 solution by using ascorbic acid under a weak alkaline condition through an epitaxial growth method, and depositing a layer of silver shell on the prefabricated Au nanospheres; and then depositing a layer of thin AgCl on the Au@Ag nanoparticles through the oxidation etching effect of FeCl 3 on the Ag shell to obtain the Au@Ag@AgCl nanoparticles with a three-layer core-shell structure.A nanoparticle probe is subjected to a specific reaction with ammonia, so that the components and the shell components of the nano probe are changed, and the absorbance of the material is obviously changed; and the nano probe is high in specificity and sensitivity to ammonia response, stable in performance, convenient and fast, and rapid qualitative and semi-quantitative analysis of the ammonia concentration can be realized by naked eyes. Colorimetric determination of ammonia through the gold-silver nanocore / shell structure has been reported. Claims 1, 2, 3, 4, 5, 6, and 7 Select type. *Related categories: X (documents that, alone or in combination with the general knowledge of the relevant art, disprove the inventive step of the claim); Y (documents that, when combined with another document, disprove the inventive step of the claim); A (documents that are relevant to the subject matter and do not disprove the claim); P (documents published before the filing date of the application and after the claimed priority date). . Table (2). Reasons for meeting or not meeting the requirements for the invention (in accordance with the Patent Law) A) Comment (newness in the world, having an inventive step, industrial application) Claim / claims Click to register claim numbers. It is new. Claim / claims 1, 2, 3, 4, 5, 6, and 7 are not new. Claim / claims Click to register claim numbers. It has an inventive step. Claim / claims 1, 2, 3, 4, 5, 6, and 7 do not have an inventive step. Claim / claims 1, 2, 3, 4, 5, 6, and 7 have industrial application. Claim / claims Click to register claim numbers. It does not have industrial application. B) Rejection of claims for the following reasons ☐ Claim / claims Click to register claim numbers. It does not meet the requirements of Article 11 of the Executive Regulations of the Patent Law. (Including the first part of the aforementioned article and paragraphs 2, 3, 4, 6 thereof) ☐ Claim / claims Click to register claim numbers. It has not been effectively disclosed in the application documents. ☐ Claim / Claims Click to register claim number. It is contrary to obvious scientific principles. ☐ Claim / Claims Click to register claim number. According to Article 4 of the Patent Law, it is an exception to the invention. . Table continued (2) C) Statement of reasons and explanations for rejection or approval, taking into account the items and documents mentioned in paragraph A and Table 1: (Completion of this paragraph with complete explanations is mandatory.) The application addresses a visual and rapid ammonia detection kit based on gold-silver core-shell nanorods, which does not constitute an inventive step for the following reasons:  The technical knowledge of synthesizing gold nanorods in accordance with documents 1, 2, and 3 has been previously disclosed and does not constitute an inventive step, and on the other hand, the reduction of silver ions with ascorbic acid and their deposition on gold nanorods with a core / shell array have also been performed, and the effect of various parameters on morphology, dimensions, and plasmonic properties has been evaluated, and claims 1 and 2 do not constitute an inventive step.  The use of gold-silver core-shell nanorods to identify various analytes (glucose, phosphate, etc.) with a mechanism pattern similar to that previously reported in the application, and claim 1 does not constitute an inventive step.Ammonia detection was compared with gold-silver core / shell nanorod probes and probes with a structure protected by silver chloride, and the sensitivity of these two probes was investigated according to the mechanism of etching of the layers by ammonia and the conversion of silver oxide to active silver ions, and the results showed that the probe with a protective layer has a higher sensitivity. According to documents 4 and 5, the technical knowledge of detection in claims 1, 3, 4 and 6 is not innovative, and claim 7 does not express a new technical feature and lacks the necessary inventive step and novelty for registration. . Table (3). Defects in the declaration documents that must be corrected by the applicant. ☐ Title of the invention Click to register the proposed title or the explanation of the title. ☐ Description of the invention (permitted amendments may include corrections of typographical or spelling errors, correction of drawing numbers, and other such amendments that do not change the technical content of the file) Click to register the explanation. ☐ Summary of the description Click to register the explanation. ☐ Claims (the applicant may amend the claims provided that they are supported by the description) Click to register the explanation. ☐ Technical drawings (changes to drawings should not exceed the information provided on the filing date of the application) Click to register the explanation. . Table (4). Lack of unity of invention According to Article 8 of the Patents, Industrial Designs and Trademarks Law of 1386, the unity of the invention has not been observed in the application (in other words, the application includes several separate inventions). Therefore, the applicant must separate the inventions with the following subjects by registering a divisional application: 1- Click to register the subject of the main invention. 2- Click to register the subject of the second (divisional) invention. 3- Click to register the subject of the third (divisional) invention. 4- Click to register the subject of the fourth (divisional) invention. Reasons: Click to state the reasons. Supplementary table Continue table number... Click to type.

Claims

Complaint What is claimed: Claim 1: [A rapid visual ammonia detection kit based on gold-silver core-shell nanorods consists of gold nanorods, ascorbic acid, silver nitrate, sodium hydroxide, and carbonate buffer.] Claim 2: [The carbonate buffer mentioned in claim 1 has a pH of 9.6 and a concentration of 100 mM.]

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