Abstract
Stable solutions of gold nanoparticles with an average diameter of 13 nm and CAu = 5×10–4 M were obtained by the reduction of HAuCl4 with an equivalent amount of sodium sulfite at 80–100 °C in the presence of 2% PEG 6000 as a stabilizer: AuCl4– + 3/2 SO32– + 3/2 H2O → Au0 + 3/2 SO42– + 3 H+ + 4 Cl–. The resulting solutions of nanoparticles do not contain additional components capable of complexation, redox, and acid-based interactions. The effect of additives of thiourea, cysteine, thiomalate, and glutathione at various pH on the stability of such solutions to the aggregation has been studied. It was shown that the values of the protonation constants and charges of species of a thiol-containing component are not the only factors determining stability. Using thiomalate (HTM2–) as an example, it was shown also that at pH 7–8, the chemisorption is not followed by the release of H+ ions into the solution.
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References
Dykman LA, Bogatyrev VA (2007) Gold nanoparticles: preparation, functionalization and applications in biochemistry and immunochemistry. Russ Chem Rev 76:181–194. https://doi.org/10.1070/RC2007v076n02ABEH003673
Hashmi ASK, Hutchings GJ (2006) Gold catalysis. Angew Chem Int Ed Eng 45:7896–7936. https://doi.org/10.1002/anie.200602454
Haruta M (2004) Gold as a novel catalyst in the 21st century: preparation, working mechanism and applications. Gold Bull 37:27–36. https://doi.org/10.1007/BF03215514
Hutchings GJ (2004) New directions in gold catalysis. Gold Bull 37:3–11
Brown CL, Bushell G, Whitehouse MW, Agrawal DS, Tupe SG, Paknikar KM, Tiekink ERT (2007) Nanogoldpharmaceutics. Gold Bull 40:245–250. https://doi.org/10.1007/BF03215588
Torrisi L (2017) Evaluation of the radiotherapy and proton therapy improvements using gold nanoparticles. Gold Bull 50:299–311. https://doi.org/10.1007/s13404-017-0216-x
Hendrich CM, Sekine K, Koshikawa T, Tanaka K, Hashmi ASK (2020) Homogeneous and heterogeneous gold catalysis for materials science. Chem Rev. https://doi.org/10.1021/acs.chemrev.0c00824
Hendel T, Wuithschick M, Kettemann F (2014) In situ determination of colloidal gold concentrations with UV−Vis spectroscopy: limitations and perspectives. Anal Chem 86:11115–11124. https://doi.org/10.1021/ac502053s
Brust M, Walker M, Bethell D et al (1994) Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system. J Chem Soc, Chem Commun 801–802. https://doi.org/10.1039/C39940000801
Sergievskaya AP, Tatarchuk VV, Makotchenko EV, Mironov IV (2015) Formation of gold nanoparticles during the reduction of HAuBr4 in reverse micelles of oxyethylated surfactant: Influence of gold precursor on the growth kinetics and properties of the particles. J Mater Res 30:1925–1933. https://doi.org/10.1557/jmr.2015.121
Stiufiuc R, Iacovita C, Nicoara R et al (2013) One-step synthesis of PEGylated gold nanoparticles with tunable surface charge. J. Nanomater 1–7. https://doi.org/10.1155/2013/146031
Sengania M, Grumezescub AM, Rajeswari VD (2017) Recent trends and methodologies in gold nanoparticle synthesis – a prospective review on drug delivery aspect. OpenNano 2:37–46. https://doi.org/10.1016/j.onano.2017.07.00
Azcárate JC, Addato MAF, Rubert A et al (2014) Surface chemistry of thiomalic acid adsorption on planar gold and gold nanoparticles. Langmuir 30:1820–1826. https://doi.org/10.1021/la404674m
Pensa E, Cortes E, Corthey G et al (2012) The chemistry of the sulfur–gold interface: in search of a unified model. Acc Chem Res 45:1183–1192. https://doi.org/10.1021/ar200260p
Vericat C, Vela ME, Benítez G et al (2010) Self-assembled monolayers of thiols and dithiols on gold: new challenges for a well-known system. Chem Soc Rev 39:1805–1834. https://doi.org/10.1039/B907301A
Vasilev K, Zhu T, Glasser G, Knoll W, Kreiter M (2008) Preparation of gold nanoparticles in an aqueous medium using 2-mercaptosuccinic acid as both reduction and capping agent. J Nanosci Nanotechnol 8:2062–2068. https://doi.org/10.1166/jnn.2008.057
Corthey G, Giovanetti LJ, Ramallo-Lopez JM et al (2010) Synthesis and characterization of gold@gold(I)–thiomalate core@shell nanoparticles. ACS Nano 4:3413–3421. https://doi.org/10.1021/nn100272q
Söptei B, Mihály J, Szigyártó ICS (2015) The supramolecular chemistry of gold and l-cysteine: formation of photoluminescent, orange-emitting assemblies with multilayer structure. Colloids Surf A Physicochem Eng Asp 470:8–14. https://doi.org/10.1016/j.colsurfa.2015.01.048
Finley JW, Wheeler EL, Witt SC (1981) Oxidation of glutathione by hydrogen peroxide and other oxidizing agents. J Agric Food Chem 29:404–407. https://doi.org/10.1021/jf00104a045
Shaw CF III, Cancro MP, Witkiewicz PL, Eldridge JE (1980) Gold(III) oxidation of disulfides in aqueous solution. Inorg Chem 19:3198–3201. https://doi.org/10.1021/ic50212a080
Hu Y, Feng J, Li Y, Sun YY, Xu L, Zhao YM, Gao QY (2012) Kinetic study on hydrolysis and oxidation of formamidine disulfide in acidic solutions. Sci China Chem 55:235–241. https://doi.org/10.1007/s11426-011-4378-8
Gao Q, Wang G, Sun Y, Epstein IR (2008) Simultaneous tracking of sulfur species in the oxidation of thiourea by hydrogen peroxide. J Phys Chem A 112:5771–5773. https://doi.org/10.1021/jp8003932
Đurović MD, Bugarčić ŽD, Heinemann FW, Eldik R (2014) Substitution versus redox reactions of gold(III) complexes with L-cysteine, L-methionine and glutathione. Dalton Trans 43:3911–3921. https://doi.org/10.1039/c3dt53140f
Mironov IV, Kharlamova VY (2018) Additional aspects of complexation of gold(I) with thiomalate. J Solut Chem 47:511–527. https://doi.org/10.1007/s10953-018-0735-y
Huergo MA, Giovanetti LJ, Rubert AA, Grillo CA, Moreno MS, Requejo FG, Salvarezza RC, Vericat C (2019) The surface chemistry of near-infrared resonant gold nanotriangles obtained via thiosulfate synthesis. Appl Surf Sci 464:131–139. https://doi.org/10.1016/j.apsusc.2018.09.009
Berglund J, Elding LI (1995) Kinetics and mechanism for reduction of tetrachloroaurate(III), trans-dicyanodichloraurate(III), and trans-dicyanodibromoaurate(III) by sulfite and hydrogen sulfite. Inorg Chem 34:513–519. https://doi.org/10.1021/ic00106a013
Peschevitskii BI, Erenburg AM (1970) The stability of some sulfur containing compounds of gold(I) in the aqueous solutions. Izv Sib Otd An Khim+ 9:83–87
Hydes PC, Middleton H (1979) The sulphito complexes of gold. Their chemistry and applications in gold electrodeposition. Gold Bull 12:90–95. https://doi.org/10.1007/BF03215106
Dobos D (1975) Electrochemical data. Akademiai Kiado, Budapest, pp 86–87
Mironov IV, Kharlamova VY (2020) Gold(III) chlorohydroxo complexes in aqueous solutions at increased temperatures. Russ J Inorg Chem 65:420–425. https://doi.org/10.1134/S0036023620030092
Kettemann F, Birnbaum A, Witte S et al (2016) Missing piece of the mechanism of the turkevich method: the critical role of citrate protonation. Chem Mater 28:4072–4081. https://doi.org/10.1021/acs.chemmater.6b01796
Ji X, Song X, Li J, Bai Y, Yang W, Peng X (2007) Size control of gold nanocrystals in citrate reduction: the third role of citrate. J Am Chem Soc 129:13939–13948. https://doi.org/10.1021/ja074447k
Tyagi H, Kushwaha A, Kumar A, Aslam M (2016) A facile pH controlled citrate-based reduction method for gold nanoparticle synthesis at room temperature. Nanoscale Res Lett 11:362. https://doi.org/10.1186/s11671-016-1576-5
Polyakova NY, Polyakov AY, Sukhorukova IV, Shtansky DV, Grigorieva AV (2017) The defining role of pH in the green synthesis of plasmonic gold nanoparticles using Citrus limon extract. Gold Bull 50:131–136. https://doi.org/10.1007/s13404-017-0203-2
Nie WY, Li L, Li DL, Liu X (2014) A new preparation method of gold nanoparticles by intra-reduction of sodium gold(I) sulfite. Chin Chem Lett 25:380–382. https://doi.org/10.1016/j.cclet.2013.11.030
Olenic L, Mihailescu G, Pruneanu S et al (2005) Nanoparticles from a gold complex with sulfite ion as ligand: preparation and characterization. Part Sci Technol 23(1):79–83. https://doi.org/10.1080/02726350590886144
Mironov IV, Kharlamova VY (2017) Gold(I) cysteinate complexes in aqueous solutions. Russ J Inorg Chem 62:1014–1020. https://doi.org/10.1134/S0036023617070154
Oram PD, Fang X, Fernando Q (1996) The formation constants of mercury(II) – glutathione complexes. Chem Res Toxicol 9:709–712. https://doi.org/10.1021/tx9501896
Groenewald T (1975) Electrochemical studies on gold electrodes in acidic solutions of thiourea containing gold(I) thiourea complex ions. J Appl Electrochem 5:71–78. https://doi.org/10.1007/BF00625961
Acres RG, Feyer V, Tsud N et al (2014) Mechanisms of aggregation of cysteine functionalized gold nanoparticles. J Phys Chem C 118:10481–10487. https://doi.org/10.1021/jp502401w
Mocanu A, Cernica I, Tomoaia G, Bobos LD, Horovitz O, Tomoaia-Cotisel M (2009) Self-assembly characteristics of gold nanoparticles in the presence of cysteine. Colloids Surf A: Physicochem Eng Aspects 338:93–101. https://doi.org/10.1016/j.colsurfa.2008.12.041
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Mironov, I.V., Kharlamova, V.Y. Synthesis of gold nanoparticles in aqueous solutions not containing additional interfering components using sulfite method: the effect of thiol-containing acid additives. Gold Bull 54, 37–44 (2021). https://doi.org/10.1007/s13404-021-00291-8
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DOI: https://doi.org/10.1007/s13404-021-00291-8