Gold nanoparticles (AuNP) exhibit particular plasmonic properties when stimulated by visible light, which makes them a promising tool to many applications in sensor technology and biomedical applications, especially when associated to sulfur-based compounds. Sulfur species form a great variety of self-assembled structures that cap AuNP and this interaction rules the optical and plasmonic properties of the system. Here, we report the behavior of citrate-stabilized gold nanospheres in two distinct sulfur colloidal solutions, namely, thiocyanate and sulfide ionic solutions. Citrate-capped gold nanospheres were characterized using ultraviolet–visible (UV-Vis) absorption, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). In the presence of sulfur species, we have observed the formation of NP clusters and chain-like structures, giving rise to surface-enhanced effects. Surface-enhanced Raman spectroscopy (SERS) pointed to a modification in citrate vibrational modes, which suggests substitution of citrate by either thiocyanate or sulfide ions with distinct dynamics, as showed by in situ fluorescence. Moreover, we report the emergence of surface-enhanced infrared absorption (SEIRA) effect, which corroborates SERS conclusions. Further, SEIRA shows a great potential as a tool for specification of sulfur compounds in colloidal solutions, which is particularly useful when dealing with sensor technology.
WangG.LuY.YanC.LuY.“DNA-Functionalization Gold Nanoparticles Based Fluorescence Sensor for Sensitive Detection of Hg2+ in Aqueous Solution”. Sens. Actuators, B. 2015. 211: 1–6.
2.
ShaikhT.NafadyA.TalpurF.N.SirajuddinM.H.et al.“Tranexamic Acid Derived Gold Nanoparticles Modified Glassy Carbon Electrode as Sensitive Sensor for Determination of Nalbuphine”. Sens. Actuators, B. 2015. 211: 359–369.
3.
CompagnoneD.FusellaG.C.Del CarloM.PittiaP.et al.“Gold Nanoparticles-Peptide Based Gas Sensor Arrays for the Detection of Food Aromas”. Biosens. Bioelectron. 2012. 42: 618–625.
4.
WeiW.SunY.ZhuM.LiuX.et al.“Structural Insights and the Surprisingly Low Mechanical Stability of the Au-S Bond in the Gold-Specific Protein Go I B”. J. Am. Chem. Soc. 2015. 137(49): 15358–15361.
5.
YueG.SuS.LiN.ShuaiM.et al.“Gold Nanoparticles as Sensors in the Colorimetric and Fluorescence Detection of Chemical Warfare Agents”. Coord. Chem. Rev. 2016. 311: 75–84.
6.
ChenC.ZhaoD.LuL.YangF.et al.“A Simple and Rapid Colorimetric Sensor for Sulfide Anion Detection Based on Redox Reaction of ABTS with Au (III)”. Sens. Actuators, B. 2015. 220: 1247–1253.
7.
PienpinijthamP.HanX.X.EkgasitS.OzakiY.“Highly Sensitive and Selective Determination of Iodide and Thiocyanate Concentrations Using Surface-Enhanced Raman Scattering of Starch-Reduced Gold Nanoparticles”. Anal. Chem. 2011. 83(10): 3655–3662.
8.
PandeyS.K.KimK.-H.TangK.-T.“A Review of Sensor-Based Methods for Monitoring Hydrogen Sulfide”. TrAC, Trends Anal. Chem. 2012. 32(2): 87–99.
9.
ManoramaS.Sarala DeviG.RaoV.J.“Hydrogen Sulfide Sensor Based on Tin Oxide Deposited by Spray Pyrolysis and Microwave Plasma Chemical Vapor Deposition”. Appl. Phys. Lett. 1994. 64(23): 3163–3165.
10.
ManoramaS.V.Gopal ReddyC.V.RaoV.J.“Tin Dioxide Nanoparticles Prepared by Sol-Gel Method for an Improved Hydrogen Sulfide Sensor”. Nanostruct. Mater. 1999. 11(5): 643–649.
11.
SarfrazJ.IhalainenP.MäättänenA.PeltonenJ.et al.“Printed Hydrogen Sulfide Gas Sensor on Paper Substrate Based on Polyaniline Composite”. Thin Solid Films. 2013. 534: 621–628.
12.
ZhouT.WangN.LiC.YuanH.et al.“Sulfide Sensor Based on Room-Temperature Phosphorescence of PbO/SiO2 Nanocomposite”. Anal. Chem. 2010. 82(5): 1705–1711.
13.
HäkkinenH.“The Gold-Sulfur Interface at Nanoscale”. Nat. Chem. 2012. 4(6): 443–455.
14.
LoveJ.C.EstroffL.A.KriebelJ.K.NuzzoR.G.et al.“Self-Assembled Monolayers of Thiolates on Metals as a form of Nanotechnology”. Chem. Rev. 2015. 105(4): 1103–1169.
15.
XiC.MarinaP.F.XiaH.WangD.“Directed Self-Assembly of Gold Nanoparticles into Plasmonic Chains”. Soft Matter. 2015. 11(23): 4562–4571.
BellS.E.J.SirimuthuN.M.S.“Surface-Enhanced Raman Spectroscopy as a Probe of Competitive Binding by Anions to Citrate-Reduced Silver Colloids”. J. Phys. Chem. A. 2005. 109(33): 7405–7410.
18.
ZargarB.HatamieA.“A Simple and Fast Colorimetric Method for Detection of Hydrazine in Water Samples Based on Formation of Gold Nanoparticles as a Colorimetric Probe”. Sens. Actuators, B. 2013. 182: 706–710.
19.
SchumacherT.KratzerK.MolnarD.HentschelM.et al.“Nanoantenna-Enhanced Ultrafast Nonlinear Spectroscopy of a Single Gold Nanoparticle”. Nat. Commun. 2011. 2(1): 333.
20.
ZhangX.ZhengL.HeY.“Creatinine-Modified Gold Nanoparticles for Highly Sensitive Colorimetric Sensing of Nitroguanidine Explosive”. Plasmonics. 2016. 11(6): 1573–1578.
21.
ZhouY.DongH.LiuL.LiM.et al.“Selective and Sensitive Colorimetric Sensor of Mercury (II) Based on Gold Nanoparticles and 4- Mercaptophenylboronic Acid”. Sens. Actuators, B. 2014. 196: 106–111.
22.
TurkevichJ.StevensonP.C.HillierJ.“A Study of the Nucleation and Growth Processes in the Synthesis of Colloidal Gold”. Faraday Soc. 1951. 11: 55–75.
23.
ComptonO.C.OsterlohF.E.“Evolution of Size and Shape in the Colloidal Crystallization of Gold Nanoparticles”. J. Am. Chem. Soc. 2007. 129(25): 7793–7798.
24.
HaissW.ThanhN.T.K.AveyardJ.FernigD.G.“Determination of Size and Concentration of Gold Nanoparticles from UV−Vis Spectra”. Anal. Chem. 2007. 79(11): 4215–4221.
25.
D. Sarid. Scanning Force Microscopy. New York: Oxford University Press, 1994.
26.
WuithschickM.BirnbaumA.WitteS.SztuckiM.et al.“Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis”. ACS Nano. 2015. 9(7): 7052–7071.
27.
SrisombatL.JamisonA.C.LeeT.R.“Stability: A Key Issue for Self-Assembled Monolayers on Gold as Thin-Film Coatings and Nanoparticle Protectants”. Colloids Surf., A. 2011. 390(1–3): 1–19.
28.
ZhangD.-F.ZhangQ.NiuL.-Y.JiangL.et al.“Self-Assembly of Gold Nanoparticles into Chain-Like Structures and Their Optical Properties”. J. Nanopart. Res. 2011. 13(9): 3923–3928.
29.
MikhlinY.LikhatskiM.KaracharovA.ZaikovskiV.et al.“Formation of Gold and Gold Sulfide Nanoparticles and Mesoscale Intermediate Structures in the Reactions of Aqueous HAuCl4 with Sulfide and Citrate Ions”. Phys. Chem. Chem. Phys. 2009. 11(26): 5445–5454.
30.
FraireJ.C.PérezL.A.CoronadoE.A.“Cluster Size Effects in the Surface-Enhanced Raman Scattering Response of Ag and Au Nanoparticle Aggregates: Experimental and Theoretical Insight”. J. Phys. Chem. C. 2013. 117(44): 23090–23107.
31.
SchwartzbergA.M.GrantC.D.WolcottA.TalleyC.E.et al.“Unique Gold Nanoparticle Aggregates as a Highly Active Surface-Enhanced Raman Scattering Substrate”. J. Phys. Chem. B. 2004. 108(50): 19191–19197.
32.
GaoC.RozinaM.J.TaoA.R.“Plasmonic Nanocomposites: Polymer-Guided Strategies for Assembling Metal Nanoparticles”. Nanoscale. 2013. 5(13): 5677–5691.
33.
Olmos-AsarJ.A.LudueñaM.MariscalM.M.“Monolayer Protected Gold Nanoparticles: The Effect of the Headgroup-Au Interaction”. Phys. Chem. Chem. Phys. 2014. 16(30): 15979–15987.
34.
KudelskiA.PettingerB.“SERS on Carbon Chain Segments: Monitoring Locally Surface Chemistry”. Chem. Phys. Lett. 2000. 321(5–6): 356–362.
35.
RantitschG.BhattacharyyaA.SchenkJ.LünsdorfN.K.“Assessing the Quality of Metallurgical Coke by Raman Spectroscopy”. Int. J. Coal Geol. 2014. 130: 1–7.
36.
BjerneldE.J.SvedbergF.JohanssonP.KällM.“Direct Observation of Heterogeneous Photochemistry on Aggregated Ag Nanocrystals Using Raman Spectroscopy: The Case of Photoinduced Degradation of Aromatic Amino Acids”. J. Phys. Chem. A. 2004. 108(19): 4187–4193.
37.
EtchegoinP.G.LacharmoiseP.D.RuE.C. Le. “Influence of Photostability on Single-Molecule Surface Enhanced Raman Scattering Enhancement Factors”. Anal. Chem. 2009. 81(2): 682–688.
38.
N. Zeng, A.B. Murphy. “Heat Generation by Optically and Thermally Interacting Aggregates of Gold Nanoparticles Under Illumination”. Nanotechnology. 20(37): 375702.
39.
LittlefordR.E.CunninghamD.MatousekP.TowrieM.et al.“Surface-Enhanced Resonance Raman Scattering Using Pulsed and Continuous-Wave Laser Excitation”. J. Raman Spectrosc. 2005. 36(6–7): 600–605.
40.
XuJ.DuJ.JingC.ZhangY.et al.“Facile Detection of Polycyclic Aromatic Hydrocarbons by a Surface-Enhanced Raman Scattering Sensor Based on the Au Coffee Ring Effect”. ACS Appl. Mater. Interfaces. 2014. 6(9): 6891–6897.
41.
PinkhasovaP.YangL.ZhangY.SukhishviliS.et al.“Differential SERS Activity of Gold and Silver Nanostructures Enabled by Adsorbed Poly(vinylpyrrolidone)”. Langmuir. 2012. 28(5): 2529–2535.
42.
FarcauC.SangeethaN.M.DecordeN.AstileanS.et al.“Microarrays of Gold Nanoparticle Clusters Fabricated by Stop&Go Convective Self-Assembly for SERS-Based Sensor Chips”. Nanoscale. 2012. 4(24): 7870–7877.
43.
FrostM.S.DempseyM.J.WhiteheadD.E.“Highly Sensitive SERS Detection of Pb2+ Ions in Aqueous Media Using Citrate Functionalised Gold Nanoparticles”. Sens. Actuators, B. 2015. 221: 1003–1008.
44.
MabuchiM.TakenakaT.FujiyoshiY.UyedaN.“Surface Enhanced Raman Scattering of Citrate Ions Adsorbed on Gold Sol Particles”. Surf. Sci. 1982. 119(2–3): 150–158.
45.
GrasseschiD.AndoR.A.TomaH.E.ZamarionV.M.“Unraveling the Nature of Turkevich Gold Nanoparticles: The Unexpected Role of the Dicarboxyketone Species”. RSC Adv. 2015. 5(8): 5716–5724.
WulandariP.NagahiroT.FukadaN.KimuraY.et al.“Characterization of Citrates on Gold and Silver Nanoparticles”. J. Colloid Interface Sci. 2015. 438: 244–248.
48.
JensenP.S.BakJ.AndersenP.E.Andersson-EngelsS.“Fourier Transform Infrared Spectroscopy of Aqueous Solutions Using Optical Subtraction”. Proc. SPIE 4624, Optical Diagnostics and Sensing of Biological Fluids and Glucose and Cholesterol Monitoring II. 2002. 4624: 150–159.
49.
I. Bertini, A. Sabatini. “Infrared Spectra of Substituted Thiocyanate Complexes. The Effect of the Substituent on Bond Type. II”. 1966. 5(6): 1025–1028.
50.
SaarD.PetrucciS.“Infrared and Ultrasonic Spectra of Sodium Thiocyanate and Lithium Thiocyanate in Tetrahydrofuran”. J. Phys. Chem. 1986. 90(15): 3326–3330.
51.
MillerF.A.WilkinsC.H.“Infrared Spectra and Characteristic Frequencies of Inorganic Ions”. Anal. Chem. 1952. 24(8): 1253–1294.
52.
SmithD.H.SeshadriK.S.“Infrared Spectra of Mg2Ca(SO4)3, MgSO4, Hexagonal CaSO4, and Orthorhombic CaSO4”. Spectrochim. Acta, Part A. 1999. 55(4): 795–802.
53.
ForelM.-T.TranquilleM.“Spectres de Vibration du Diméthylsulfoxyde et du Diméthylsulfoxyde-d6”. Spectrochim. Acta, Part A. 1970. 26(5): 1023–1034.
54.
HorrocksW.D.Jr.CottonF.A.“Infrared and Raman Spectra and Normal Co-Ordinate Analysis of Dimethyl Sulfoxide and Dimethyl Sulfoxide-d6”. Spectrochim. Acta, Part A. 1961. 17(2): 134–147.
55.
LalS.LinkS.HalasN.J.“Nano-Optics from Sensing to Waveguiding”. Nat. Photonics. 2007. 1(11): 641–648.
56.
LeF.BrandlD.W.UrzhumovY.A.WangH.et al.“Metallic Nanoparticle Arrays: A Common Substrate for Both Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption”. ACS Nano. 2008. 2(4): 707–718.
57.
TakeiH.BesshoN.IshiiA.OkamotoT.et al.“Enhanced Infrared LSPR Sensitivity of Cap-Shaped Gold Nanoparticles Coupled to a Metallic Film”. Langmuir. 2014. 30(8): 2297–2305.
58.
TaylorR.W.EstebanR.MahajanS.AizpuruaJ.et al.“Optimizing SERS from Gold Nanoparticle Clusters: Addressing the Near Field by an Embedded Chain Plasmon Model”. J. Phys. Chem. C. 2016. 120(19): 10512–10522.
59.
SeelenbinderJ.A.BrownC.W.PivarnikP.RandA.G.“Colloidal Gold Filtrates as Metal Substrates for Surface-Enhanced Infrared Absorption Spectroscopy”. Anal. Chem. 1999. 71(10): 1963–1966.
60.
OsawaM.AtakaK.-I.YoshiiK.NishikawaY.“Surface-Enhanced Infrared Spectroscopy: The Origin of the Absorption Enhancement and Band Selection Rule in the Infrared Spectra of Molecules Adsorbed on Fine Metal Particles”. App. Spectrosc. 1993. 47(9): 1497–1502.
61.
ParkJ.-W.Shumaker-ParryJ.S.“Structural Study of Citrate Layers on Gold Nanoparticles: Role of Intermolecular Interactions in Stabilizing Nanoparticles”. J. Am. Chem. Soc. 2014. 136(5): 1907–1921.
62.
GoldysE.M.SobhanM.A.“Fluorescence of Colloidal Gold Nanoparticles is Controlled by the Surface Adsorbate”. Adv. Funct. Mater. 2012. 22(9): 1906–1913.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
