Phase transition and electronic structure investigation of MoS2-reduced graphene oxide nanocomposite decorated with Au nanoparticles.

In this work a simple approach to transform MoS2 from its metallic (1T' to semiconductor 2H) character via gold nanoparticle surface decoration of a MoS2 reduced graphene oxide (rGO) nanocomposite is proposed. The possible mechanism to this phase transformation was investigated using different spectroscopy techniques, and supported by density functional theory theoretical calculations. A mixture of the 1T'- and 2H-MoS2 phases was observed from the Raman and Mo 3d high resolution x-ray photoelectron spectra analysis in the MoS2-rGO nanocomposite. After surface decoration with gold nanoparticles the concentration of the 1T' phase decreases making evident a phase transformation. According to Raman and valence band spectra analyzes, the Au nanoparticles (NPs) induce a p-type doping in MoS2-rGO nanocomposite. We proposed as a main mechanism to the MoS2 phase transformation the electron transfer from Mo 4d xy,xz,yz in 1T' phase to AuNPs conduction band. At the same time, the unoccupied electronic structure was investigated from S K-edge near edge x-ray absorption fine structure spectroscopy. Finally, the electronic coupling between unoccupied electronic states was investigated by the core hole clock approach using resonant Auger spectroscopy, showing that AuNPs affect mainly the MoS2 electronic states close to Fermi level.

Gold nanoparticles coupled with graphene quantum dots in organized medium to quantify aminoglycoside anti-biotics in yellow fever vaccine after solid phase extraction using a selective imprinted polymer.

The determination of kanamycin sulfate was made indirectly by measuring its effect on photoluminescent amino functionalized graphene quantum dots (GQDs-amino) associated with gold nanoparticles (AuNPs) that were produced by the reduction of AuCl4 with NaBH4 in an aqueous dispersion of GQDs-amino (obtained by the pyrolysis of citric acid and glutathione) also containing the cationic surfactant CTAB. The AuNPs-GQDs-amino-CTAB system presents a suppressed photoluminescence that is amplified in the presence of kanamycin. Under optimized experimental conditions, the photoluminescence amplification of the nanomaterial system showed a linear response as a function of kanamycin concentration, covering three orders of magnitude (10-7 to 10-5 mol L-1). The use of solid phase extraction with a cartridge packed with aminoglycoside selective molecularly imprinted polymer ensured selectivity in determinations made on yellow-fever vaccine and veterinary pharmaceutical formulations. The analytical results were statistically similar to those obtained with an HPLC-based fluorescence method (after chemical derivatization). The proposed method is a simple, sensitive and selective approach that does not involve the use of toxic reagents employed for chemical derivatization of aminoglycoside antibiotics.

Ultrafast charge transfer dynamics pathways in two-dimensional MoS2-graphene heterostructures: a core-hole clock approach.

Two-dimensional van der Waals heterostructures are attractive candidates for optoelectronic nanodevice applications. The charge transport process in these systems has been extensively investigated, however the effect of coupling between specific electronic states on the charge transfer process is not completely established yet. Here, interfacial charge transfer (CT) in the MoS2/graphene/SiO2 heterostructure is investigated from static and dynamic points of view. Static CT in the MoS2-graphene interface was elucidated by an intensity quenching, broadening and a blueshift of the photoluminescence peaks. Atomic and electronic state-specific CT dynamics on a femtosecond timescale are characterized using a core-hole clock approach and using the S1s core-hole lifetime as an internal clock. We demonstrate that the femtosecond electron transfer pathway in the MoS2/SiO2 heterostructure is mainly due to the electronic coupling between S3p-Mo4d states forming the Mo-S covalent bond in the MoS2 layer. For the MoS2/graphene/SiO2 heterostructure, we identify, with the support of density functional calculations, new pathways that arise due to the high density of empty electronic states of the graphene conduction band. The latter makes the transfer process time in the MoS2/graphene/SiO2/Si twice as fast as in the MoS2/SiO2/Si sample. Our results show that ultrafast electron delocalization pathways in van der Waals heterostructures are dependent on the electronic properties of each involved 2D material, creating opportunities to modulate their transport properties.

Spherical gold nanoparticles and gold nanorods for the determination of gentamicin.

Gentamicin is an antibiotic indicated to treat mastitis in dairy cattle and for the treatment of bacterial resistance in the context of hospital infections. The effect caused by gentamicin on the optical properties of gold nanoparticles aqueous dispersions were used to develop quantitative methods to determine this antibiotic. Two different aqueous dispersions, one containing spherical Au nanoparticles (AuNPs) and the other containing Au nanorods (AuNRs), had their conditions adjusted to enable a stable and sensitive response towards gentamicin. The use of AuNPs, with measurement at 681nm of the rising coupling plasmon band, enabled a limit of detection (LOD) of 0.4ngmL-1 (0.02ng absolute LOD), ten times lower than the one achieved by measuring the decreasing of the longitudinal surface plasmon resonance band (at 662nm). The linear analytical response of AuNPs measured at 681nm did not require rationing of signal values to correct for linearity. Stability of the analytical response resulted in intermediary precision below 2%. No significant interference was imposed by excipients traditionally present in injectable solutions for veterinary use. Percent recoveries obtained in such formulations were between 94.5 and 98.2% regardless the existence of any difference in the proportion of the compounds known as gentamicin (C1, C1a and C2) in standard and in the samples. The method requires no derivatization with toxic reagents as usually is required in other spectroscopic approaches.