Synthesis of Au nanoparticles by the reaction of HAuCl4·nH2O with organoaluminum compounds

Synthesis of Au nanoparticles by the reaction of HAuCl4·nH2O with organoaluminum compounds | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Synthesis of Au nanoparticles by the reaction of HAuCl 4 ·nH 2 O with organoaluminum compounds Lyudmila V. Parfenova, Almira Kh. Bikmeeva, Pavel V. Kovyazin, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5608886/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The reaction of HAuCl 4 . nH 2 O with organoaluminum compounds (HAlBu i 2 or AlR 3, R=Me, Et, Bu i ) in organic solvents, followed by hydrolysis in the presence of a tertiary thiol (5-methylundecane-5-thiol), afforded gold nanoparticles (AuNPs). The proposed method enables the production of AuNPs with particle sizes ranging from 2 to 20 nm. The smallest particle sizes were observed when reducing HAuCl 4 with HAlBu i 2 . Nanoparticles have been characterized by the means of STEM, PCCS, XPS, and UV-Vis spectroscopy. The proposed method may be further utilized for the deposition of metal nanoparticles onto solid supports for applications in catalysis and other fields. Materials Chemistry Au nanoparticles Organoaluminum compounds Alkanethiols Scanning transmission electron microscopy Photon cross-correlation spectroscopy X-ray photoelectron spectroscopy Figures Figure 1 Figure 2 Figure 3 Figure 4 1 Introduction In recent decades, gold nanoparticles (AuNPs) have become the subject of an exponentially growing number of research. The unique combination of physical and chemical properties of AuNPs has facilitated their successful application in biomedicine for disease visualization and diagnosis, selective delivery of therapeutic agents, enhancement of cellular and tissue sensitivity to treatment regimens, monitoring and guidance of surgical procedures, as well as preferential introduction of electromagnetic radiation into disease sites, among other applications [ 1 – 5 ]. Promising and significant areas of AuNP utilization include analytics [ 6 , 7 ], electronics [ 8 ], and nonlinear optical processes [ 9 ]. Considerable attention is being paid to the study of the catalytic properties of AuNPs [ 10 – 12 ], particularly their use as catalysts for the liquid-phase oxidation of polyols, alcohols, and carbohydrates [ 13 ], the formation of C-C bonds [ 14 ], and a wide range of reactions involving alkenes, alkynes, and enamines [ 15 – 17 ]. Among the methods for synthesizing metal nanoparticles, the "bottom-up" approach is considered the most promising. By varying the precursor, reducing agent, conditions, and the nature of the stabilizing ligand, it becomes possible to control the size, shape, stability, and functionality of the resulting nanoparticles. Most methods for producing gold nanoparticles (AuNPs) are based on the chemical reduction of Au(III) salts in solution in the presence of surface stabilizers, which prevent the aggregation of the formed Au particles [ 17 – 21 ]. In particular, Turkevich et al. developed a synthetic method for gold nanoparticles (AuNPs) synthesis in 1951 by treating HAuCl 4 with citric acid in boiling water, where citrate acts as both a reducing and stabilizing agent [ 22 , 23 ]. The strength of the bond between the Au surface and citrate anions used in the Turkevich-Frens method is comparable to that of hydrogen bonds, making it easily replaceable with thiols or amines [ 21 ]. In 1994, Brust and Schiffrin synthesized AuNPs with a size range of 1.5–5 nm. According to their method, the synthesis of organic-soluble, thiol-stabilized AuNPs is carried out in a mixture of toluene and water in the presence of thiol, tetrabutylammonium bromide (TBAB) as a phase transfer reagent, and sodium borohydride (NaBH 4 ) as a reducing agent [ 24 ]. This methodology allows for the production of AuNPs with low polydispersity by varying the reaction conditions (the ratio of [Au] to thiol, reduction rate, reaction temperature) [ 25 , 26 ]. Thiolated AuNPs exhibit greater stability compared to most other AuNPs, can be thoroughly dried, and re-dispersed in solution without any aggregation, making them excellent precursors for further functionalization [ 4 ]. Typically, thiolate ligands on the surface of nanoparticles form self-assembled monolayers that dictate the structure, stability, electrochemical properties, and functionality of the synthesized nanoparticles. Changes in the structure of the surface ligand can lead to the formation of entirely different structures with varying properties. However, the fundamental aspects of the dependence of nanoparticle structure on ligand nature remain a pertinent issue in the field of nanotechnology and materials science [ 27 , 28 ]. Earlier, we developed methods for the synthesis of thiols and thioesters, which included the thermal hydroalumination of terminal alkene dimers, oxidation of organoaluminum compounds, and thiolation of the oxidation product with thiourea, as well as the reaction of the hydroalumination product with dimethyl disulfide. Direct functionalization of dimers using P 2 S 5 in the presence of catalytic amounts of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) resulted in the selective formation of tertiary alkane thiol—a Markovnikov product [ 21 ]. The obtained product, featuring a thiol group and a branched alkyl substituent, is of interest as a new stabilizer for metal nanoparticles. Thus, the aim of the present study was to develop a new method for the synthesis of AuNP via reduction of HAuCl 4 ·nH 2 O by organoaluminum reagents (HAlBu i 2 or AlR 3 , where R = Me, Et, Bui) and to investigate the potential use of S-functionalized 1-hexene dimer as a stabilizer for metal nanoparticles. The obtained AuNP were characterized using electron microscopy, X-ray photoelectron spectroscopy, photon cross-correlation spectroscopy, and UV-vis spectroscopy. 2 Materials and methods All operations for organometallic compounds were performed under argon, according to Schlenk technique. Commercially available HAlBu i 2 (99%, Aldrich), AlMe 3 (97%, Aldrich), AlEt 3 (98%, Merck), AlBu i 3 (95%, Strem), НAuCl 4 ·nH 2 O, n = 3–4 (49% Au), and deionized ultra-filtered water (Merck) were used. Toluene were distilled from triisobutylaluminium immediately prior to use. CH 2 Cl 2 were distilled from P 2 O 5 immediately prior to use. The synthesis of tertiary thiol 1 (5-methylundecane-5-thiol) was carried out according to the methodology described in Ref. [ 29 ]. The microstructure of the samples was studied using field emission scanning electron microscopy (FE-SEM) on a Hitachi Regulus 8230 electron microscope (Japan, 2020). Target-oriented approach was utilized for the optimization of the analytic measurements [ 30 ]. Samples were pre-treated using ultrasound (UZDN-2T, F = 44 kHz, W = 25 W, T = 295 K) in isopropanol. Before measurements the samples were deposited on the 3 mm carbon-coated copper grids from isopropanol suspension. Images were acquired in transmitted electron mode at 30kV or 20 kV accelerating voltage.). The image analysis was conducted using ImageJ Analysis. The particle size distribution was studied by the means of Photon Cross-correlation Spectroscopy (PCCS) implemented in the NanoPhox (Sympatec, Germany). Particle size analysis was performed using the PAQXOS 4.2 program. Each sample was measured three times at 25°C. Nanosphere™ Size Standards (ThermoFisher Scientific) with particle sizes 23 ± 2, 100 and 510 ± 7 nm were examined prior to analysis to verify the accuracy. XPS spectra were obtained using a JEOL JPS 9010MX spectrometer (Japan) equipped with an X-ray source (Mg Kα). The pressure in the analytical chamber during spectrum acquisition was less than 7·10 − 8 Pa. The samples of AuNP solutions were deposited on a titanium plated (Grade 4) in an argon atmosphere, and then dried from the solvent under an argon flow. Spectra were collected from 0 to 1100 eV with a pass energy of 50 eV and a step size of 0.5 eV. Binding energies (BE) were corrected by adjusting the position of the C1s peak to 284.7 eV. The JEOL SpecSurf software was used to determine peak areas, calculate elemental composition from peaks, and fit peaks to high-resolution spectra. Deconvolution of the spectra was performed using the Voigt function with the JEOL SpecSurf v. 1.9.0 software. Reaction of HAuCl 4 . nH 2 O with HAlBu i 2 Under argon, HAlBu i 2 (0.47–1.26 mmol) was added to the reactor containing 4 mL of toluene or dichloromethane and 0.13–0.18 mmol of HAuCl 4 .nH 2 O (molar ratio [Au]:[Al] = 1:(2.6–10)). The mixture was stirred for 16 hours. The solution turned black with a purple tint. Then, upon cooling to 0°C, 4 mL of deionized ultra-filtered water was added, and stirring continued for an additional 16 hours. Subsequently, 0.52–0.90 mmol of thiol 1 was introduced into the reactor, and the reaction mixture was stirred for 8 hours. Reaction of HAuCl 4 . nH 2 O with AlR 3 (R = Me, Et, Bu i ) Under argon, AlR 3 (1.80 mmol) was added to the reactor containing 4 mL of toluene or dichloromethane and 0.18 mmol of HAuCl 4 ·nH 2 O to achieve a molar ratio of [Au]:[Al] = 1:10, and the mixture was stirred for 16 hours. Subsequently, the mixture was cooled to 0°C, and 4 mL of deionized ultra-filtered water was added, followed by stirring for an additional 16 hours at room temperature. Then, 0.9 mmol of thiol 1 was introduced into the biphasic system, and the reaction mixture was stirred for another 8 hours. 3 Results and Discussion In this study, we propose an approach in which HAuCl 4 ·nH 2 O (with w Au = 49%) reacts with organoaluminum compounds (OACs) ‒ HAlBu i 2 or AlR 3 (R = Me, Et, Bu i ), in a toluene or dichloromethane solution, followed by hydrolysis in the presence of alkanethiol 1 . Alkanethiol 1 was obtained through the reaction of vinylidene dimer, synthesized in the Cp 2 ZrCl 2 -HAlBu i 2 -MAO-1-hexene system [ 31 ], with P 2 S 5 in the presence of catalytic amounts of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) (Scheme 1 ) [ 29 ]. The addition of OACs to HAuCl 4 ·nH 2 O in a toluene or dichloromethane solution was carried out while cooling to 0°C, followed by stirring at room temperature for 16 hours. The OAC residues were decomposed with water while cooling and were stirred at room temperature for 16 hours Finally, thiol 1 was introduced into the two-phasic system under vigorous stirring. The results of the synthesis are presented in Table 1 Table 1 The synthesis of AuNP by reducing HAuCl 4 .nH 2 O with organoaluminum compounds (AlMe 3 , AlEt 3 , AlBu i 3 , HAlBu i 2 ) in the presence of thiol 1 . Entry Molar ratio HAuCl 4 .nH 2 O/ OAC/1 ОАС Solvent Particle size (PCCS), nm UV-vis (SPR), nm 1 1:2.6:4 HAlBu i 2 toluene 13; 138 542 2 1:2.6:4 HAlBu i 2 CH 2 Cl 2 38; 47; 477 537 3 1:10:5 HAlBu i 2 toluene 14; 20 a 533 4 1:10:5 HAlBu i 2 CH 2 Cl 2 9; 103 b 525 5 1:10:5 AlMe 3 toluene 24; 265 535 6 1:10:5 AlMe 3 CH 2 Cl 2 24; 45 546 7 1:10:5 AlEt 3 toluene 17; 192 8 1:10:5 AlEt 3 CH 2 Cl 2 96 517 9 1:10:5 AlBu i 3 toluene 72; 852 10 1:10:5 AlBu i 3 CH 2 Cl 2 22; 45 525 а particle sizes evaluated by STEM ‒ 2–20 nm; b particle sizes evaluated by STEM ‒ 2–14 nm. The reduction of HAuCl 4 .nH 2 O by HAlBu i 2 occurred exothermically, with the color of the solutions changing from black at the beginning of the reaction to purple at the end, which was maintained during subsequent treatments with water and thiol. The reaction of HAuCl 4 .nH 2 O with HAlBu i 2 in toluene with following processing with water and thiol, at a mole ratio [Au]:[Al]:[ 1 ] 1:2.6:4, proceeded to yield nanoparticles with bimodal distribution at values of 13 nm and 138 nm, as evidenced by PCCS method (entry 1, Table 1 ). The reaction carried out in methylene chloride was accompanied by the formation of larger particles exhibiting a trimodal distribution (entry 2). The increase in the amounts of OAC and thiol to a ratio of 1:10:5, along with conducting the reaction in toluene, resulted in a more homogeneous distribution and a reduction in the quantity of the fraction with larger sizes (entry 3). Particle size analysis using STEM in this case provided values ranging from 2 to 20 nm (Fig. 1 ). A bimodal distribution was observed by the PCCS method, specifically at sizes of 14 and 20 nm (Fig. 2 ). UV-vis analysis showed peaks in the range of 533–543 nm for the aqueous phase (Fig. 3 ). The use of alternative AOCs as reducing agents yielded larger particle sizes (enties 5–10). In these experiments, the reaction in methylene chloride did not afford the particles exceeding 100 nm (enties 6, 8, 10). Thus, the reaction with AlMe 3 produced particles with sizes of 24 and 265 nm in toluene (entry 5), 24 and 45 nm in dichloromethane (entry 6), which were found in the analysis of the aqueous phase by the PCCS method. In the reaction of HAuCl 4 .nH 2 O with AlEt 3 a bimodal distribution of particles was observed at 17 and 192 nm in toluene (entry 7) and 96 nm in CH 2 Cl 2 (entry 8). In the system HAuCl 4 ·nH 2 O-AlBu i 3 in toluene, the formation of the largest particles with a bimodal distribution of 72 and 852 nm was found (entry 9). When the reaction was carried out in CH 2 Cl 2 , the particle sizes decreased to 22 and 45 nm (entry 10 UV-vis analysis showed surface plasmon resonance (SPR) peaks in the range of 517–546 nm for the aqueous phase (Fig. 3 ), which confirms the formation of nanoparticles with a varied size distribution [ 32 ]. The XPS spectrum of AuNP samples, obtained in the system HAuCl 4 .nH 2 O-HAlBu i 2 - 1 with a ratio of 1:2.6:4, exhibited two doublet signals corresponding to Au4f 7/2 and Au4f 5/2 . Peaks at 83.5 eV and 87.3 eV were assigned to Au 0 [ 24 ], whereas the peaks at 84.8 eV and 88.5 eV probably belong to Au + 1 [ 33 ] (Fig. 4 ), which may be a component of a nanoparticle in the form of [AuX 2 ] − and/or Au n (SR) m clusters [ 26 , 34 ]. Research aimed at optimizing the nanoparticle synthesis process through the variation of reagent ratios, the structure of sulfur containing ligands, and synthesis conditions, as well as comprehensive characterization of the resulting NPs, is currently being conducted by our group. 4 Conclusion A novel method for the synthesis of gold nanoparticles (AuNP) has been developed. The method implies the reduction of HAuCl 4 by organoaluminum compounds (HAlBu i 2 or AlR 3 , where R = Me, Et, Bu i ), followed by hydrolysis in the presence of a tertiary thiol - S-functionalized dimer of 1-hexene. This method allows for the production of AuNP with particle sizes ranging from 2 to 20 nm. The particle size distribution depends on the structure of organoaluminum compound and reaction conditions. This method can be further utilized for the deposition of metal nanoparticles onto solid supports for applications in catalysis and other fields. Declarations Funding This work was financially supported by the Russian Science Foundation, grant number 23-73-00024, https://rscf.ru/project/23-73-00024. Data availability The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request. Conflict of interest The authors declare no competing interests. References Hossain, A.; Rayhan, T.; Mobarak, H.; Rimon I.H.; Hossain, N.; Islam, S.; Al Kafi, A. Advances and significances of gold nanoparticles in cancer treatment: A comprehensive review. Results in Chemistry 2024 , 8 , 101559. https://doi.org/10.1016/j.rechem.2024.101559 Shevtsov, M.; Zhou, Y.; Khachatryan, W.; Multhoff, G.; Gao, H. Recent Advances in Gold Nanoformulations for Cancer Therapy. Curr Drug Metab. 2018 , 19 ( 9 ), 768-780. doi: 10.2174/1389200219666180611080736 Abu-Dief, A.M.; Salaheldeen, M.; El-Dabea, T. Recent Advances in Development of Gold Nanoparticles for Drug Delivery Systems. J. 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Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5608886","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":388010141,"identity":"d6aae356-634b-4bf5-ab49-1802a4da41ed","order_by":0,"name":"Lyudmila V. 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Bikmeeva","email":"","orcid":"","institution":"Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Almira","middleName":"Kh.","lastName":"Bikmeeva","suffix":""},{"id":388035443,"identity":"f1fb2e3e-40a6-4a96-9a86-26d826a5110a","order_by":2,"name":"Pavel V. Kovyazin","email":"","orcid":"","institution":"Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Pavel","middleName":"V.","lastName":"Kovyazin","suffix":""},{"id":388035444,"identity":"cc81ffa7-4464-4953-9692-4f12af3057da","order_by":3,"name":"Eldar R. Palatov","email":"","orcid":"","institution":"Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Eldar","middleName":"R.","lastName":"Palatov","suffix":""},{"id":388035445,"identity":"a9bea96d-7efa-4f1c-8d92-635fd97f5f8e","order_by":4,"name":"Leonard M. Khalilov","email":"","orcid":"","institution":"Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Leonard","middleName":"M.","lastName":"Khalilov","suffix":""},{"id":388035446,"identity":"81da006a-22d6-4c9b-b50b-de2220c80d1c","order_by":5,"name":"Nina M. Ivanova","email":"","orcid":"","institution":"Zelinsky Institute of Organic Chemistry","correspondingAuthor":false,"prefix":"","firstName":"Nina","middleName":"M.","lastName":"Ivanova","suffix":""},{"id":388035447,"identity":"9e7c02a5-41b0-4180-a8a8-ad6b47c42fe5","order_by":6,"name":"Semen N. Sergeev","email":"","orcid":"","institution":"Ufa University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Semen","middleName":"N.","lastName":"Sergeev","suffix":""}],"badges":[],"createdAt":"2024-12-09 12:15:54","currentVersionCode":1,"declarations":{"humanSubjects":false,"vertebrateSubjects":false,"conflictsOfInterestStatement":false,"humanSubjectEthicalGuidelines":false,"humanSubjectConsent":false,"humanSubjectClinicalTrial":false,"humanSubjectCaseReport":false,"vertebrateSubjectEthicalGuidelines":false},"doi":"10.21203/rs.3.rs-5608886/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5608886/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":71162897,"identity":"55e0f5cd-b6e0-4d0b-92a7-caee3180e7e2","added_by":"auto","created_at":"2024-12-11 16:51:29","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":222486,"visible":true,"origin":"","legend":"\u003cp\u003eSTEM of aqueous solutions AuNP obtained in system HAuCl\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e.\u003c/sup\u003enH\u003csub\u003e2\u003c/sub\u003eO-HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e-\u003cstrong\u003e1\u003c/strong\u003e (1:10:5), toluene, Н\u003csub\u003e2\u003c/sub\u003eО (entry 3) (right) and particle size distribution (processed by ImageJ Analysis, left).\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5608886/v1/28dce4aff14272b85b186bb5.png"},{"id":71162900,"identity":"b38f8885-6f43-4b57-8a58-92903079d93f","added_by":"auto","created_at":"2024-12-11 16:51:29","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":49924,"visible":true,"origin":"","legend":"\u003cp\u003eParticle size distribution estimated by PCCS of AuNP aqueous solutions obtained in system HAuCl\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e.\u003c/sup\u003enH\u003csub\u003e2\u003c/sub\u003eO-HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e-\u003cstrong\u003e1\u003c/strong\u003e (1:10:5), toluene, Н\u003csub\u003e2\u003c/sub\u003eО (entry 3).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5608886/v1/60c320b59653a1aab02c9d43.png"},{"id":71162507,"identity":"5894a5a9-ea5c-40ac-9201-98b51adc0668","added_by":"auto","created_at":"2024-12-11 16:43:29","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":215623,"visible":true,"origin":"","legend":"\u003cp\u003eUV-Vis spectra of aqueous solutions of AuNPs obtained in the system HAuCl\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e.\u003c/sup\u003enH\u003csub\u003e2\u003c/sub\u003eO-OAC-\u003cstrong\u003e1\u003c/strong\u003e: a) HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e, ratio 1:2.6:4, reaction in toluene; b) HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e, ratio 1:10:5, reaction in toluene; c) AlMe\u003csub\u003e3\u003c/sub\u003e, ratio 1:10:5,\u003csub\u003e \u003c/sub\u003ereaction in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e; d) AlEt\u003csub\u003e3\u003c/sub\u003e, ratio 1:10:5,\u003csub\u003e \u003c/sub\u003ereaction\u003csub\u003e \u003c/sub\u003ein CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e; e) AlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e3\u003c/sub\u003e, ratio 1:10:5,\u003csub\u003e \u003c/sub\u003ereaction\u003csub\u003e \u003c/sub\u003ein CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5608886/v1/b55456c4938d01e742b372db.png"},{"id":71161380,"identity":"acd834ea-240a-42c0-9a79-70240d0e317d","added_by":"auto","created_at":"2024-12-11 16:35:29","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":105423,"visible":true,"origin":"","legend":"\u003cp\u003eXPS of AuNP obtained in the system HAuCl\u003csub\u003e4\u003c/sub\u003e·nH\u003csub\u003e2\u003c/sub\u003eO-HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e-\u003cstrong\u003e1\u003c/strong\u003e: a) experimental spectrum; b),c) – deconvolution results; d) sum of deconvolution results.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5608886/v1/eca149bde6280fed56dd0fbb.png"},{"id":71164142,"identity":"c6edc4b4-196e-4585-89ff-029e26850bfa","added_by":"auto","created_at":"2024-12-11 17:07:33","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1004262,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5608886/v1/77f63304-54ce-43c4-984a-aae808b7cee3.pdf"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eSynthesis of Au nanoparticles by the reaction of HAuCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e·nH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO with organoaluminum compounds\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eIn recent decades, gold nanoparticles (AuNPs) have become the subject of an exponentially growing number of research. The unique combination of physical and chemical properties of AuNPs has facilitated their successful application in biomedicine for disease visualization and diagnosis, selective delivery of therapeutic agents, enhancement of cellular and tissue sensitivity to treatment regimens, monitoring and guidance of surgical procedures, as well as preferential introduction of electromagnetic radiation into disease sites, among other applications [\u003cspan additionalcitationids=\"CR2 CR3 CR4\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. Promising and significant areas of AuNP utilization include analytics [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e], electronics [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e], and nonlinear optical processes [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Considerable attention is being paid to the study of the catalytic properties of AuNPs [\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], particularly their use as catalysts for the liquid-phase oxidation of polyols, alcohols, and carbohydrates [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e], the formation of C-C bonds [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e], and a wide range of reactions involving alkenes, alkynes, and enamines [\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAmong the methods for synthesizing metal nanoparticles, the \"bottom-up\" approach is considered the most promising. By varying the precursor, reducing agent, conditions, and the nature of the stabilizing ligand, it becomes possible to control the size, shape, stability, and functionality of the resulting nanoparticles. Most methods for producing gold nanoparticles (AuNPs) are based on the chemical reduction of Au(III) salts in solution in the presence of surface stabilizers, which prevent the aggregation of the formed Au particles [\u003cspan additionalcitationids=\"CR18 CR19 CR20\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. In particular, Turkevich et al. developed a synthetic method for gold nanoparticles (AuNPs) synthesis in 1951 by treating HAuCl\u003csub\u003e4\u003c/sub\u003e with citric acid in boiling water, where citrate acts as both a reducing and stabilizing agent [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. The strength of the bond between the Au surface and citrate anions used in the Turkevich-Frens method is comparable to that of hydrogen bonds, making it easily replaceable with thiols or amines [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. In 1994, Brust and Schiffrin synthesized AuNPs with a size range of 1.5\u0026ndash;5 nm. According to their method, the synthesis of organic-soluble, thiol-stabilized AuNPs is carried out in a mixture of toluene and water in the presence of thiol, tetrabutylammonium bromide (TBAB) as a phase transfer reagent, and sodium borohydride (NaBH\u003csub\u003e4\u003c/sub\u003e) as a reducing agent [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. This methodology allows for the production of AuNPs with low polydispersity by varying the reaction conditions (the ratio of [Au] to thiol, reduction rate, reaction temperature) [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Thiolated AuNPs exhibit greater stability compared to most other AuNPs, can be thoroughly dried, and re-dispersed in solution without any aggregation, making them excellent precursors for further functionalization [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTypically, thiolate ligands on the surface of nanoparticles form self-assembled monolayers that dictate the structure, stability, electrochemical properties, and functionality of the synthesized nanoparticles. Changes in the structure of the surface ligand can lead to the formation of entirely different structures with varying properties. However, the fundamental aspects of the dependence of nanoparticle structure on ligand nature remain a pertinent issue in the field of nanotechnology and materials science [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eEarlier, we developed methods for the synthesis of thiols and thioesters, which included the thermal hydroalumination of terminal alkene dimers, oxidation of organoaluminum compounds, and thiolation of the oxidation product with thiourea, as well as the reaction of the hydroalumination product with dimethyl disulfide. Direct functionalization of dimers using P\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e5\u003c/sub\u003e in the presence of catalytic amounts of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) resulted in the selective formation of tertiary alkane thiol\u0026mdash;a Markovnikov product [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. The obtained product, featuring a thiol group and a branched alkyl substituent, is of interest as a new stabilizer for metal nanoparticles.\u003c/p\u003e \u003cp\u003eThus, the aim of the present study was to develop a new method for the synthesis of AuNP via reduction of HAuCl\u003csub\u003e4\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO by organoaluminum reagents (HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e or AlR\u003csub\u003e3\u003c/sub\u003e, where R\u0026thinsp;=\u0026thinsp;Me, Et, Bui) and to investigate the potential use of S-functionalized 1-hexene dimer as a stabilizer for metal nanoparticles. The obtained AuNP were characterized using electron microscopy, X-ray photoelectron spectroscopy, photon cross-correlation spectroscopy, and UV-vis spectroscopy.\u003c/p\u003e"},{"header":"2 Materials and methods","content":"\u003cp\u003eAll operations for organometallic compounds were performed under argon, according to Schlenk technique. Commercially available HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e (99%, Aldrich), AlMe\u003csub\u003e3\u003c/sub\u003e (97%, Aldrich), AlEt\u003csub\u003e3\u003c/sub\u003e (98%, Merck), AlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e3\u003c/sub\u003e (95%, Strem), НAuCl\u003csub\u003e4\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO, n\u0026thinsp;=\u0026thinsp;3\u0026ndash;4 (49% Au), and deionized ultra-filtered water (Merck) were used. Toluene were distilled from triisobutylaluminium immediately prior to use. CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e were distilled from P\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e immediately prior to use. The synthesis of tertiary thiol \u003cb\u003e1\u003c/b\u003e (5-methylundecane-5-thiol) was carried out according to the methodology described in Ref. [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe microstructure of the samples was studied using field emission scanning electron microscopy (FE-SEM) on a Hitachi Regulus 8230 electron microscope (Japan, 2020). Target-oriented approach was utilized for the optimization of the analytic measurements [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. Samples were pre-treated using ultrasound (UZDN-2T, F\u0026thinsp;=\u0026thinsp;44 kHz, W\u0026thinsp;=\u0026thinsp;25 W, T\u0026thinsp;=\u0026thinsp;295 K) in isopropanol. Before measurements the samples were deposited on the 3 mm carbon-coated copper grids from isopropanol suspension. Images were acquired in transmitted electron mode at 30kV or 20 kV accelerating voltage.). The image analysis was conducted using ImageJ Analysis.\u003c/p\u003e \u003cp\u003eThe particle size distribution was studied by the means of Photon Cross-correlation Spectroscopy (PCCS) implemented in the NanoPhox (Sympatec, Germany). Particle size analysis was performed using the PAQXOS 4.2 program. Each sample was measured three times at 25\u0026deg;C. Nanosphere\u0026trade; Size Standards (ThermoFisher Scientific) with particle sizes 23\u0026thinsp;\u0026plusmn;\u0026thinsp;2, 100 and 510\u0026thinsp;\u0026plusmn;\u0026thinsp;7 nm were examined prior to analysis to verify the accuracy.\u003c/p\u003e \u003cp\u003eXPS spectra were obtained using a JEOL JPS 9010MX spectrometer (Japan) equipped with an X-ray source (Mg Kα). The pressure in the analytical chamber during spectrum acquisition was less than 7\u0026middot;10\u003csup\u003e\u0026minus;\u0026thinsp;8\u003c/sup\u003e Pa. The samples of AuNP solutions were deposited on a titanium plated (Grade 4) in an argon atmosphere, and then dried from the solvent under an argon flow. Spectra were collected from 0 to 1100 eV with a pass energy of 50 eV and a step size of 0.5 eV. Binding energies (BE) were corrected by adjusting the position of the C1s peak to 284.7 eV. The JEOL SpecSurf software was used to determine peak areas, calculate elemental composition from peaks, and fit peaks to high-resolution spectra. Deconvolution of the spectra was performed using the Voigt function with the JEOL SpecSurf v. 1.9.0 software.\u003cdiv class=\"BlockQuote\"\u003e\u003cp\u003e \u003cb\u003eReaction of HAuCl\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e.\u003cb\u003enH\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO with HAlBu\u003c/b\u003e\u003csup\u003e\u003cb\u003ei\u003c/b\u003e\u003c/sup\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e\u003cp\u003eUnder argon, HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e (0.47\u0026ndash;1.26 mmol) was added to the reactor containing 4 mL of toluene or dichloromethane and 0.13\u0026ndash;0.18 mmol of HAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO (molar ratio [Au]:[Al]\u0026thinsp;=\u0026thinsp;1:(2.6\u0026ndash;10)). The mixture was stirred for 16 hours. The solution turned black with a purple tint. Then, upon cooling to 0\u0026deg;C, 4 mL of deionized ultra-filtered water was added, and stirring continued for an additional 16 hours. Subsequently, 0.52\u0026ndash;0.90 mmol of thiol \u003cb\u003e1\u003c/b\u003e was introduced into the reactor, and the reaction mixture was stirred for 8 hours.\u003c/p\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003e \u003cb\u003eReaction of HAuCl\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e.\u003cb\u003enH\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO with AlR\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e \u003cb\u003e(R\u0026thinsp;=\u0026thinsp;Me, Et, Bu\u003c/b\u003e\u003csup\u003e\u003cb\u003ei\u003c/b\u003e\u003c/sup\u003e\u003cb\u003e)\u003c/b\u003e\u003c/p\u003e \u003cp\u003eUnder argon, AlR\u003csub\u003e3\u003c/sub\u003e (1.80 mmol) was added to the reactor containing 4 mL of toluene or dichloromethane and 0.18 mmol of HAuCl\u003csub\u003e4\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO to achieve a molar ratio of [Au]:[Al]\u0026thinsp;=\u0026thinsp;1:10, and the mixture was stirred for 16 hours. Subsequently, the mixture was cooled to 0\u0026deg;C, and 4 mL of deionized ultra-filtered water was added, followed by stirring for an additional 16 hours at room temperature. Then, 0.9 mmol of thiol \u003cb\u003e1\u003c/b\u003e was introduced into the biphasic system, and the reaction mixture was stirred for another 8 hours.\u003c/p\u003e"},{"header":"3 Results and Discussion","content":"\u003cp\u003eIn this study, we propose an approach in which HAuCl\u003csub\u003e4\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO (with w\u003csub\u003eAu\u003c/sub\u003e = 49%) reacts with organoaluminum compounds (OACs) ‒ HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e or AlR\u003csub\u003e3\u003c/sub\u003e (R\u0026thinsp;=\u0026thinsp;Me, Et, Bu\u003csup\u003ei\u003c/sup\u003e), in a toluene or dichloromethane solution, followed by hydrolysis in the presence of alkanethiol \u003cb\u003e1\u003c/b\u003e. Alkanethiol \u003cb\u003e1\u003c/b\u003e was obtained through the reaction of vinylidene dimer, synthesized in the Cp\u003csub\u003e2\u003c/sub\u003eZrCl\u003csub\u003e2\u003c/sub\u003e-HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e-MAO-1-hexene system [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e], with P\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e5\u003c/sub\u003e in the presence of catalytic amounts of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe addition of OACs to HAuCl\u003csub\u003e4\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO in a toluene or dichloromethane solution was carried out while cooling to 0\u0026deg;C, followed by stirring at room temperature for 16 hours. The OAC residues were decomposed with water while cooling and were stirred at room temperature for 16 hours Finally, thiol \u003cb\u003e1\u003c/b\u003e was introduced into the two-phasic system under vigorous stirring. The results of the synthesis are presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThe synthesis of AuNP by reducing HAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO with organoaluminum compounds (AlMe\u003csub\u003e3\u003c/sub\u003e, AlEt\u003csub\u003e3\u003c/sub\u003e, AlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e3\u003c/sub\u003e, HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e) in the presence of thiol \u003cb\u003e1\u003c/b\u003e.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eEntry\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMolar ratio\u003c/p\u003e \u003cp\u003eHAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO/ OAC/1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eОАС\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSolvent\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eParticle size (PCCS), nm\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eUV-vis (SPR), nm\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:2.6:4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etoluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e13; 138\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:2.6:4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e38; 47; 477\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e537\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etoluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e14; 20\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e533\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e9; 103\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e525\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAlMe\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etoluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e24; 265\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e535\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAlMe\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e24; 45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e546\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAlEt\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etoluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e17; 192\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAlEt\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e517\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etoluene\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e72; 852\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1:10:5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e22; 45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e525\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003csup\u003eа\u003c/sup\u003e particle sizes evaluated by STEM ‒ 2\u0026ndash;20 nm; \u003csup\u003eb\u003c/sup\u003e particle sizes evaluated by STEM ‒ 2\u0026ndash;14 nm.\u003cdiv class=\"BlockQuote\"\u003e\u003cp\u003eThe reduction of HAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO by HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e occurred exothermically, with the color of the solutions changing from black at the beginning of the reaction to purple at the end, which was maintained during subsequent treatments with water and thiol. The reaction of HAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO with HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e in toluene with following processing with water and thiol, at a mole ratio [Au]:[Al]:[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] 1:2.6:4, proceeded to yield nanoparticles with bimodal distribution at values of 13 nm and 138 nm, as evidenced by PCCS method (entry 1, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The reaction carried out in methylene chloride was accompanied by the formation of larger particles exhibiting a trimodal distribution (entry 2). The increase in the amounts of OAC and thiol to a ratio of 1:10:5, along with conducting the reaction in toluene, resulted in a more homogeneous distribution and a reduction in the quantity of the fraction with larger sizes (entry 3). Particle size analysis using STEM in this case provided values ranging from 2 to 20 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). A bimodal distribution was observed by the PCCS method, specifically at sizes of 14 and 20 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). UV-vis analysis showed peaks in the range of 533\u0026ndash;543 nm for the aqueous phase (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003c/p\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe use of alternative AOCs as reducing agents yielded larger particle sizes (enties 5\u0026ndash;10). In these experiments, the reaction in methylene chloride did not afford the particles exceeding 100 nm (enties 6, 8, 10). Thus, the reaction with AlMe\u003csub\u003e3\u003c/sub\u003e produced particles with sizes of 24 and 265 nm in toluene (entry 5), 24 and 45 nm in dichloromethane (entry 6), which were found in the analysis of the aqueous phase by the PCCS method. In the reaction of HAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO with AlEt\u003csub\u003e3\u003c/sub\u003e a bimodal distribution of particles was observed at 17 and 192 nm in toluene (entry 7) and 96 nm in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e (entry 8). In the system HAuCl\u003csub\u003e4\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO-AlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e3\u003c/sub\u003e in toluene, the formation of the largest particles with a bimodal distribution of 72 and 852 nm was found (entry 9). When the reaction was carried out in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, the particle sizes decreased to 22 and 45 nm (entry 10\u003c/p\u003e \u003cp\u003eUV-vis analysis showed surface plasmon resonance (SPR) peaks in the range of 517\u0026ndash;546 nm for the aqueous phase (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e), which confirms the formation of nanoparticles with a varied size distribution [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe XPS spectrum of AuNP samples, obtained in the system HAuCl\u003csub\u003e4\u003c/sub\u003e.nH\u003csub\u003e2\u003c/sub\u003eO-HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e-\u003cb\u003e1\u003c/b\u003e with a ratio of 1:2.6:4, exhibited two doublet signals corresponding to Au4f\u003csub\u003e7/2\u003c/sub\u003e and Au4f\u003csub\u003e5/2\u003c/sub\u003e. Peaks at 83.5 eV and 87.3 eV were assigned to Au\u003csup\u003e0\u003c/sup\u003e [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], whereas the peaks at 84.8 eV and 88.5 eV probably belong to Au\u003csup\u003e+\u0026thinsp;1\u003c/sup\u003e [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e] (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e), which may be a component of a nanoparticle in the form of [AuX\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e and/or Au\u003csub\u003en\u003c/sub\u003e(SR)\u003csub\u003em\u003c/sub\u003e clusters [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eResearch aimed at optimizing the nanoparticle synthesis process through the variation of reagent ratios, the structure of sulfur containing ligands, and synthesis conditions, as well as comprehensive characterization of the resulting NPs, is currently being conducted by our group.\u003c/p\u003e"},{"header":"4 Conclusion","content":"\u003cp\u003eA novel method for the synthesis of gold nanoparticles (AuNP) has been developed. The method implies the reduction of HAuCl\u003csub\u003e4\u003c/sub\u003e by organoaluminum compounds (HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e or AlR\u003csub\u003e3\u003c/sub\u003e, where R\u0026thinsp;=\u0026thinsp;Me, Et, Bu\u003csup\u003ei\u003c/sup\u003e), followed by hydrolysis in the presence of a tertiary thiol - S-functionalized dimer of 1-hexene. This method allows for the production of AuNP with particle sizes ranging from 2 to 20 nm. The particle size distribution depends on the structure of organoaluminum compound and reaction conditions. This method can be further utilized for the deposition of metal nanoparticles onto solid supports for applications in catalysis and other fields.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was financially supported by the Russian Science Foundation, grant number 23-73-00024, https://rscf.ru/project/23-73-00024.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest\u003c/strong\u003e The authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eHossain, A.; Rayhan, T.; Mobarak, H.; Rimon I.H.; Hossain, N.; Islam, S.; Al Kafi, A. 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B\u003c/em\u003e \u003cstrong\u003e1997\u003c/strong\u003e, \u003cem\u003e101\u003c/em\u003e, 7885-7891. https://doi.org/10.1021/jp971438x\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[{"identity":"6d60ae6a-bc0a-44f2-969a-99f26bfc5318","identifier":"10.13039/501100006769","name":"Russian Science Foundation","awardNumber":"23-73-00024","order_by":0}],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Au nanoparticles, Organoaluminum compounds, Alkanethiols, Scanning transmission electron microscopy, Photon cross-correlation spectroscopy, X-ray photoelectron spectroscopy","lastPublishedDoi":"10.21203/rs.3.rs-5608886/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5608886/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe reaction of\u0026nbsp;HAuCl\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e.\u003c/sup\u003enH\u003csub\u003e2\u003c/sub\u003eO with organoaluminum compounds (HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2 \u003c/sub\u003eor\u003csub\u003e \u003c/sub\u003eAlR\u003csub\u003e3, \u003c/sub\u003eR=Me, Et, Bu\u003csup\u003ei\u003c/sup\u003e) in organic solvents, followed by hydrolysis in the presence of a tertiary thiol (5-methylundecane-5-thiol), afforded gold nanoparticles (AuNPs). The proposed method enables the production of AuNPs with particle sizes ranging from 2 to 20 nm. The smallest particle sizes were observed when reducing\u0026nbsp;HAuCl\u003csub\u003e4 \u003c/sub\u003ewith HAlBu\u003csup\u003ei\u003c/sup\u003e\u003csub\u003e2\u003c/sub\u003e. Nanoparticles have been characterized by the means of STEM, PCCS, XPS, and UV-Vis spectroscopy. The proposed method may be further utilized for the deposition of metal nanoparticles onto solid supports for applications in catalysis and other fields.\u003c/p\u003e","manuscriptTitle":"Synthesis of Au nanoparticles by the reaction of HAuCl4·nH2O with organoaluminum compounds","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-12-11 16:35:24","doi":"10.21203/rs.3.rs-5608886/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"1fab6955-6ce7-4b1c-b639-a8b16f922b75","owner":[],"postedDate":"December 11th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":41349385,"name":"Materials Chemistry"}],"tags":[],"updatedAt":"2024-12-11T16:35:24+00:00","versionOfRecord":[],"versionCreatedAt":"2024-12-11 16:35:24","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5608886","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5608886","identity":"rs-5608886","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}