Trimercaptotriazine-modified gold nanoparticles exhibit strong SERS effects, yielding vibrational profiles very sensitive to the presence of heavy metal ions. Because of the contrasting response observed for selected vibrational bands in the SERS profiles, they provide useful nanoprobes for Hg2+ and Cd2+ ions, allowing direct quantitative assays by employing relative peak intensity ratios instead of using internal standards.

Nas nanopartículas de ouro, as propriedades químicas e físicas são ditadas principalmente pelos átomos da superfície, os quais podem interagir com espécies doadoras-aceitadoras, ou ligantes, da mesma forma que os complexos metálicos correspondentes. Além disso, os elétrons podem entrar em ressonância com a luz incidente dando origem aos plasmons de superfície, que levam à intensificação do campo elétrico local e ao efeito SERS, proporcionando uma ampla variedade de aplicações na química, biologia e nanotecnologia. Ligantes de ponte, multifuncionais, podem ser usados para intermediar a ligação de íons metálicos aos átomos de ouro da superfície. Essa estratégia permite controlar a estabilização em solução através das cargas dos complexos metálicos, acrescentando, ao mesmo tempo, novas características químicas e maior funcionalidade às nanopartículas modificadas. Dessa forma, uma nova química de coordenação pode ser vislumbrada, combinando nanopartículas metálicas, como as de ouro, e complexos, à luz da química supramolecular e dos efeitos de ressonância plasmônica de superfície.In gold nanoparticles the surface metal atoms play a major role, determining their chemical and physical properties by interacting with donor-acceptor species or ligands in a similar way as the related metal complexes. In addition, coherent oscillations of the metal electrons in resonance with the frequency of the exciting light give rise to localized surface plasmons responsible for an enhancement of the local electric field and SERS effect, allowing a wide range of applications in chemistry, biology and nanotechnology. Multifunctional bridging ligands can be employed for simultaneously binding metal ions and surface atoms. The attractive point of this approach is the possibility of exploiting the charge controlled stabilization by the metal complexes, while imparting new characteristics and properties to the modified nanoparticles. As a matter of fact, a new, exciting field of coordination chemistry can be envisaged, combining metal nanoparticles and metal complexes, in the light of supramolecular and surface plasmon resonance effects.

Traditional Feigl's spot tests can be greatly improved with the aid of gold nanoparticles and Raman probes, by monitoring the changes in the surface enhanced Raman scattering (SERS) of the analytes directly applied on a filter paper previously impregnated with the selective organic reagent. As a proof of concept, diphenylthiocarbazone (dithizone) was treated with citrate stabilized gold nanoparticles and employed in paper spot tests for a variety of transition and heavy metal ions. Below 10(-5) mol L(-1), only mercury(II) ions were able to displace the dithizone molecules from the "coordination shell" of the gold nanoparticles, leading to a systematic decay of the Raman signals. Because of the huge enhancement of the dithizone vibrational peaks, the SERS spot tests allowed the detection of picograms of Hg(2+) ions.

Chemisorption of muonium onto the surface of gold nanoparticles has been observed. Muonium (μ+e−), a light hydrogen-like atom, reacts chemically with uncapped 7 nm gold nanoparticles embedded in mesoporous silica (SBA-15) with a strong temperature-dependent rate. The addition rate is fast enough to allow coherent spin transfer into a diamagnetic muon state on the nanoparticle surface. The muon is well established as a sensitive probe of static or slowly fluctuating magnetic fields in bulk matter. These results represent the first muon spin rotation signal on a nanoparticle surface or any metallic surface. Only weak magnetic effects are seen on the surface of these Au nanoparticles consistent with Pauli paramagnetism.

In this paper we show how surface coordination chemistry can elucidate one of the reproducibility issues related to the classical synthesis of gold nanoparticles by the Turkevich method.

Gold nanoparticles (AuNPs) have been a subject of considerable interest in recent years due to both their magnetic and catalytic properties. This paper reports a two-fold study of the reactivity at 300 K of the isotopic hydrogen atom, muonium (Mu = μ + e − ), (i) with bare uncapped AuNPs of different sizes encapsulated in mesoporous (SBA-15) silica hosts, forming a diamagnetic final state in the Mu + AuNP → MuAuNP reaction, and (ii) with surface-adsorbed benzene on these NPs forming the muoniated cyclohexadienyl radical in the Mu + C 6 H 6 → MuC ̇6H 6 addition reaction. The measured muon-spin relaxation rates, λ C , for the chemisorption reaction of Mu with the bare AuNPs show some variation with AuNP size. The Mu + C 6 H 6 addition reaction has been studied over a range of benzene loadings both on bare silica and in the AuNP/silica samples. The measured muon-spin relaxation rates, λ Tot , exhibit a linear dependence on benzene concentration over the full range of loadings in both cases, in accord with an Eley−Rideal model of surface reactivity. Rate constants, k Bz , were determined from this dependence which exhibit a 2−3-fold faster reaction rate on the AuNPs than on the bare silica, suggesting a catalytic effect due to benzene adsorbed on these NP surfaces.

A systematic study on the surface-enhanced Raman scattering (SERS) for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) adsorbed onto citrate-modified gold nanoparticles (cit-AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit-AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge-transfer (CT) effects. The most strongly enhanced vibrations belong to a 1 and b 2 representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system.

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