RESUMO
Polystyrene (PS) is one of the main synthetic polymers produced around the world, and it is present in the composition of a wide variety of single-use objects. When released into the environment, these materials are degraded by environmental factors, resulting in microplastics. We investigated the ability of Chironomus sancticaroli (Diptera, Chironomidae) to promote the fragmentation of PS microspheres (24.5 ± 2.9 µm) and the toxic effects associated with exposure to this polymer. C. sancticaroli larvae were exposed to 3 different concentrations of PS (67.5, 135, and 270 particles g-1 of dry sediment) for 144 h. Significant lethality was observed only at the highest concentration. A significant reduction in PS particle size as well as evidence of deterioration on the surface of the spheres, such as grooves and cracks, was observed. In addition, changes in oxidative stress biomarkers (SOD, CAT, MDA, and GST) were also observed. This is the first study to report the ability of Chironomus sp. to promote the biofragmentation of microplastics. The information obtained demonstrates that the macroinvertebrate community can play a key role in the degradation of plastic particles present in the sediment of freshwater environments and can also be threatened by such particle pollution.
Assuntos
Chironomidae , Poluentes Químicos da Água , Animais , Microplásticos/toxicidade , Larva , Poliestirenos/toxicidade , Chironomidae/metabolismo , Plásticos/toxicidade , Poluentes Químicos da Água/análiseRESUMO
The resonant Raman (RR) and resonant SERS spectra of the thiadiazole-based dye dibromobenzo[c]-1,2,5-thiadiazole (DBTD) were studied through multiconfigurational XMS-CASPT2/CASSCF and experimental methods in solution. The results indicate that the S1 excited state of DBTD is described by π â π* with internal CT from the benzene ring to the thiadizole. In resonance conditions at 364 nm, the RR spectrum shows intensifications in modes that describe extensive geometrical changes at both the benzene ring and the thiadiazole region, indicating an internal CT character to the S1. The SERS spectra observed on gold and silver nanoparticles indicate different adsorption geometries, which leads to distinct enhancement patterns on the spectra with varying excitation energy. It evidences the major contribution of the chemical enhancement mechanism on the spectra from a metal â DBTD CT state, as confirmed by the simulated spectra. This theoretical approach proved strong in the prediction of the main features of the observed experimental resonant Raman and SERS spectra indicating a potential for adequate description of the chemical mechanism of SERS.
RESUMO
Time-Dependent Density-Functional Theory (TDDFT) and Extended Multi-State Complete Active Space Second-Order Perturbation Theory (XMS-CASPT2) methods, together with augmented correlation-consistent polarizable valence double-ζ (aug-cc-pVDZ) basis sets, were applied to simulate the vibronic and resonance Raman (RR) spectra of a push-pull model system, 4-nitroaniline (pNA) and its anion ([pNA]-), within the Independent Mode Displaced Harmonic Oscillator (IMDHO) model. Both methods predict adequately well the vertical absorption spectra for both species and the well-known charge-transfer (CT; S11(ππ*)) excited state of pNA. Nevertheless, pNA and [pNA]- absorption spectral band intensity and vibronic broadening are better reproduced at the XMS-CASPT2 level. RR spectra were also obtained using both methods, with a good agreement for both methods for pNA, for which the electronic wave functions are best described by a single state configuration. For the anion, for which the excited state presented a multiconfigurational nature, the TDDFT failed to predict the main intensification observed experimentally under resonance conditions. As to the resonance Raman excitation profile for the pNA species, the νS(NO2) vibrational mode carries most of the intensity of the vibronic spectrum, but for [pNA]- the contributions of main vibrational modes are more complex, being governed by different modes in different energies, with ring modes dominating at the maximum, as predicted by the XMS-CASPT2 method.
Assuntos
Modelos Biológicos , Vibração , Teoria da Densidade Funcional , Simulação por Computador , EletrônicaRESUMO
After more than 40 years, surface-enhanced Raman spectroscopy (SERS) stills attract much attention from chemists, not only because of the synthesis of plasmonic nanostructures but also due to the several simultaneous mechanisms which still remain unclear. One of the possibilities for a better understanding of the SERS mechanisms is the utilization of suitable inorganic complexes. The use of inorganic complexes makes it possible to observe the two main SERS mechanisms (electromagnetic and chemical) and to observe the intensification of Raman scattering due to the resonance Raman effect. In this publication, the observation of these mechanisms was possible utilizing an unpublished and very interesting complex with two oxo-triruthenium acetate clusters and an iron bis(terpyridine) in its structure (seven metals) and which interacted with bare gold nanoparticles and shell-isolated gold nanoparticles (SHIN), with a 1 nm silica shell. The utilization of SHIN allowed to quench the SERS chemical mechanism and led to a spectrum where iron-terpyridine peaks are absent and only the modes related to [Ru3O] center were observed (due to enhancement by resonance Raman, SERRS); it can be said that the the shell-isolated nanoparticles enhanced resonance Raman spectroscopy (SHINERRS) is observed. This approach led to a perfect selection of SERS mechanisms never seen before with any other molecule/complex. As can be seen in the UV-vis spectrum, this complex has a strong band around 700 nm, which suggests that silica shell enhances only surface-enhanced resonance Raman scattering, a long-distance phenomenon, different from chemical enhancement (a short-distance phenomenon). Additionally, along with the Raman spectroscopy results, cyclic voltammetry, UV-vis spectroelectrochemistry, resonance Raman (using 568 and 676 nm lasers), and density functional theory calculations of this new ruthenium cluster are presented.
RESUMO
In hybrid materials containing plasmonic nanoparticles such as Au and Ag, charge-transfer processes from and to Au or Ag can affect both activities and selectivity in plasmonic catalysis. Inspired by the widespread utilization of commercial Si wafers in surface-enhanced Raman spectroscopy (SERS) studies, we investigated herein the effect of the native SiO2 layer on Si wafers over the surface plasmon resonance (SPR)-mediated activities of the Au and Ag nanoparticles (NPs). We prepared SERS-active plasmonic comprised of Au and Ag NPs deposited onto a Si wafer. Here, two kinds of Si wafers were employed: Si with a native oxide surface layer (Si/SiO2 ) and Si without a native oxide surface layer (Si). This led to Si/SiO2 /Au, Si/SiO2 /Ag, Si/Au, and Si/Ag NPs. The SPR-mediated oxidation of p-aminothiophenol (PATP) to p,p'-dimercaptoazobenzene (DMAB) was employed as a model transformation. By comparing the performances and band structures for the Si/Au and Si/Ag relative to Si/SiO2 /Au and Si/SiO2 /Ag NPs, it was found that the presence of a SiO2 layer was crucial to enable higher SPR-mediated PATP to DMAB conversions. The SiO2 layer acts to prevent the charge transfer of SPR-excited hot electrons from Au or Ag nanoparticles to the Si substrate. This enabled SPR-excited hot electrons to be transferred to adsorbed O2 molecules, which then participate in the selective oxidation of PATP to DMAB. In the absence of a SiO2 layer, SPR-excited hot electrons are preferentially transferred to Si instead of adsorbed O2 molecules, leading to much lower PATP oxidation.
RESUMO
Ruthenium polypyridine complexes have shown promise as agents for photodynamic therapy (PDT) and tools for molecular biology (chromophore-assisted light inactivation). To accomplish these tasks, it is important to have at least target selectivity and great reactive oxygen species (ROS) photogeneration: two properties that are not easily found in the same molecule. To prepare such new agents, we synthesized two new ruthenium complexes that combine an efficient DNA binding moiety (dppz ligand) together with naphthyl-modified (1) and anthracenyl-modified (2) bipyridine as a strong ROS generator bound to a ruthenium complex. The compounds were fully characterized and their photophysical and photochemical properties investigated. Compound 2 showed one of the highest quantum yields for singlet oxygen production ever reported (ΦΔ= 0.96), along with very high DNA binding (log Kb = 6.78). Such photochemical behavior could be ascribed to the lower triplet state involving the anthracenyl-modified bipyridine, which is associated with easier oxygen quenching. In addition, the compounds exhibited moderate selectivity toward G-quadruplex DNA and binding to the minor groove of DNA, most likely driven by the pendant ligands. Interestingly, they also showed DNA photocleavage activity even upon exposure to a yellow light-emitting diode (LED). Regarding their biological activity, the compounds exhibited an exciting antibacterial action, particularly against Gram-positive bacteria, which was enhanced upon blue LED irradiation. Altogether, these results showed that our strategy succeeded in producing light-triggered DNA binding agents with pharmacological and biotechnological potential.
Assuntos
Complexos de Coordenação/farmacologia , DNA/química , Substâncias Intercalantes/farmacologia , Rutênio/química , 2,2'-Dipiridil/síntese química , 2,2'-Dipiridil/química , 2,2'-Dipiridil/farmacologia , 2,2'-Dipiridil/efeitos da radiação , Antracenos/síntese química , Antracenos/química , Antracenos/farmacologia , Antracenos/efeitos da radiação , Antibacterianos/síntese química , Antibacterianos/química , Antibacterianos/farmacologia , Antibacterianos/efeitos da radiação , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Complexos de Coordenação/efeitos da radiação , Dano ao DNA , Etídio/farmacologia , Bactérias Gram-Positivas/efeitos dos fármacos , Substâncias Intercalantes/síntese química , Substâncias Intercalantes/química , Substâncias Intercalantes/efeitos da radiação , Ligantes , Luz , Oxigênio/química , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/efeitos da radiação , Espécies Reativas de Oxigênio/síntese químicaRESUMO
In this work we demonstrate the use of the push-pull model system 4-(dimethylamino)benzonitrile (DMABN) as a convenient molecular probe to investigate the local solvation structure and dynamics by means of time-resolved infrared spectroscopy (TRIR). The photochemical features associated with this system provide several advantages due to the high charge separation between the ground and charge transfer states involving the characteristic nitrile bond, and an excited state lifetime that is long enough to observe the slow solvation dynamics in organic solvents and ionic liquids. The conversion from a locally excited state to an intramolecular charge transfer state (LE-ICT) in ionic liquids shows similar kinetic lifetimes in comparison to organic solvents. This similarity confirms that such conversion depends solely on the intramolecular reorganization of DMABN in the excited state, and not by the dynamics of solvation. In contrast, the relative shift of the ν(CN) vibration during the relaxation of the ICT state reveals two distinct lifetimes that are sensitive to the solvent environment. This study reveals a fast time component which is attributed to the dipolar relaxation of the solvent and a slower time component related to the rotation of the dimethylamino group of DMABN.
RESUMO
This investigation was undertaken to describe a natural process for the removal of silver and the simultaneous recovery of Ag/Ag2O nanoparticles by dead biomass of the yeast Rhodotorula mucilaginosa. The removal of silver ions from aqueous solution and the synthesis of Ag/Ag2O nanoparticles were analyzed based on physicochemical factors and equilibrium concentration, combined with transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy (FTIR). A successful process for the synthesis of Ag/Ag2O nanoparticles was obtained, following the Langmuir isotherm model, showing a high biosorption capacity of silver (49.0 mg g-1). The nanoparticles were spherical, had an average size of 11.0 nm, were synthesized intracellularly and capped by yeast proteins. This sustainable protocol is an attractive platform for the industrial-scale production of silver nanoparticles and of a silver nanobiosorbent.
Assuntos
Biomassa , Nanopartículas Metálicas/química , Óxidos/química , Rhodotorula/química , Compostos de Prata/química , Prata/química , Adsorção , Biodegradação Ambiental , Modelos Teóricos , Nanotecnologia , Rhodotorula/crescimento & desenvolvimento , Rhodotorula/ultraestrutura , Propriedades de SuperfícieRESUMO
An investigation comprising experimental techniques (absorption capacity of SO2 and vibrational spectroscopy) and molecular simulations (thermodynamics, structure, and dynamics) has been performed for the polymer poly(ethylene oxide) (PEO), the ionic liquid butyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([N4111][Tf2N]) and their mixtures as sulfur dioxide (SO2) absorbing materials. The polymer PEO has higher capacity to absorb SO2 than the neat ionic liquid, whereas the mixtures presented intermediary absorption capacities. The band assigned to the symmetric stretching band of SO2 at ca. 1140 cm-1, which is considered a spectroscopic probe for the strength of SO2 interactions with its neighborhood, shifts to lower wavenumbers as more negative total interaction energy values of SO2 were evaluated from the simulations. The solvation free energy of SO2, ΔGsol, correlates linearly with the absorption capacity of SO2. The negative values of ΔGsol are due to negative and positive values of enthalpy and entropy, respectively. In the ionic liquid, SO2 weakens the cation-anion interactions, whereas in the mixture with a high content of PEO these interactions are slightly increased. Such effects were correlated with the relative population of cisoid and transoid conformers of Tf2N anions as revealed by Raman spectroscopy. Moreover, the presence of SO2 in the systems provokes the increase of diffusion coefficients of the absorbing species in comparison with the systems without the gas. Proper to the slow dynamics of the polymer, the diffusion coefficient of ions and SO2 diminishes with the increase of the PEO content.
RESUMO
Nanorattles, comprised of a nanosphere inside a nanoshell, were employed as the next generation of plasmonic catalysts for oxidations promoted by activated O2 . After investigating how the presence of a nanosphere inside a nanoshell affected the electric-field enhancements in the nanorattle relative to a nanoshell and a nanosphere, the SPR-mediated oxidation of p-aminothiophenol (PATP) functionalized at their surface was investigated to benchmark how these different electric-field intensities affected the performances of Au@AgAu nanorattles, AgAu nanoshells and Au nanoparticles having similar sizes. The high performance of the nanorattles enabled the visible-light driven synthesis of azobenzene from aniline under ambient conditions. As the nanorattles allow the formation of electromagnetic hot spots without relying on the uncontrolled aggregation of nanostructures, it enables their application as catalysts in liquid phase under mild conditions using visible light as the main energy input.
RESUMO
Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO-Au NPs) were obtained by the in situ reduction of GO and AuCl4(-)(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O2 through the transfer of SPR-excited hot electrons to O2 molecules adsorbed from air. The SPR-mediated catalytic oxidation of p-aminothiophenol (PATP) to p,p'-dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR-mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge-transfer processes from rGO to Au took place and contributed to improved SPR-mediated activity. Since the transfer of electrons from Au to adsorbed O2 molecules is the crucial step for PATP oxidation, in addition to the SPR-excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au-to-O2 charge-transfer process.
RESUMO
The surface-plasmon-resonance (SPR)-mediated catalytic activities of Ag and Au nanoparticles have emerged a relatively new frontier in catalysis in which visible light can be employed as an eco-friendly energy input to drive chemical reactions. Although this phenomenon has been reported for a variety of transformations, the effect of the nanoparticle shape and crystalline structure on the activities remains unclear. In this paper, we investigated the SPR-mediated catalytic activity of Ag quasi-spheres, cubes, triangular prisms, and wires toward the oxidation of p-aminothiophenol to p,p'-dimercaptoazobenzene by activated O2. The activities at 632.8 nm excitation followed the order triangular prisms and quasi-spheres > wires â« cubes. These results indicated that the shape, optical properties, and crystal structure played an important role in the detected SPR-mediated activities.
RESUMO
Surface enhanced Raman spectroelectrochemistry (SERS) spectroelectrochemistry provides a very sensitive technique to investigate the vibrational characteristics of coordination compounds and their particular behavior under the influence of plasmonic surfaces, concomitant with the exploitation of their redox properties and electronic spectra. The results, however, depend upon the mechanisms involved in the intensification of Raman spectra associated with the electromagnetic, resonance Raman and charge-transfer excitation at the Fermi levels. By probing the model complex [(Ru3O)(CH3COO)6(4,4'-bipy)3](n) (n = 1, 0, -1) adsorbed onto rough gold electrode surfaces, contrasting SERS profiles were obtained at several successive redox potentials and oxidation states, which enables a critical discussion on the role of the complex interaction with the gold surface, and the influence of the specific electronic bands in the triruthenium acetate cluster. Density functional theory (DFT) and time-dependent DFT calculations were carried out for the complex bound to an Au20 cluster to show the participation of active lowest unoccupied molecular orbital levels centered on the gold atoms. The corresponding charge-transfer band was predicted around 1200 nm, which supports a charge-transfer interpretation for the SERS response observed at λexc = 1064 nm. The selective enhancement of the vibrational modes was discussed based on the Raman theoretical calculations.
RESUMO
Although catalytic processes mediated by surface plasmon resonance (SPR) excitation have emerged as a new frontier in catalysis, the selectivity of these processes remains poorly understood. Here, the selectivity of the SPR-mediated oxidation of p-aminothiophenol (PATP) employing Au NPs as catalysts was controlled by the choice of catalysts (Au or TiO2-Au NPs) and by the modulation of the charge transfer from UV-excited TiO2 to Au. When Au NPs were employed as catalyst, the SPR-mediated oxidation of PATP yielded p,p-dimercaptobenzene (DMAB). When TiO2-Au NPs were employed as catalysts under both UVâ illumination and SPRâ excitation, p-nitrophenol (PNTP) was formed from PATP in a single step. Interestingly, PNTP molecules were further reduced to DMAB after the UVâ illumination was removed. Our data show that control over charge-transfer processes may play an important role to tune activity, product formation, and selectivity in SPR-mediated catalytic processes.
RESUMO
By a combination of theoretical and experimental design, we probed the effect of a quasi-single electron on the surface plasmon resonance (SPR)-mediated catalytic activities of Ag nanoparticles. Specifically, we started by theoretically investigating how the E-field distribution around the surface of a Ag nanosphere was influenced by static electric field induced by one, two, or three extra fixed electrons embedded in graphene oxide (GO) next to the Ag nanosphere. We found that the presence of the extra electron(s) changed the E-field distributions and led to higher electric field intensities. Then, we experimentally observed that a quasi-single electron trapped at the interface between GO and Ag NPs in Ag NPs supported on graphene oxide (GO-Ag NPs) led to higher catalytic activities as compared to Ag and GO-Ag NPs without electrons trapped at the interface, representing the first observation of catalytic enhancement promoted by a quasi-single electron.
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This is the first study describing the rapid extracellular production of copper nanoparticles by dead biomass of Trichoderma koningiopsis. The production and uptake of copper nanoparticles by dead biomass of Trichoderma koningiopsis were characterized by investigating physicochemical factors, equilibrium concentrations and biosorption kinetics, combined with scanning electron microscopy (SEM), energy dispersive X-ray (EDS), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). A successful route for the metallic copper nanoparticles synthesis was achieved, and followed a Langmuir isotherm where a high biosorption capacity was observed, 21.1 mg g(-1). The kinetic analysis showed that copper biosorption followed a pseudo-second-order model. The nanoparticles mainly exhibited a spherical shape, with an average size of 87.5 nm, and were synthesized extracellularly. The presence of proteins as stabilizing agents of the nanoparticles was demonstrated. The extracellular biosynthesis and uptake of copper nanoparticles using dead fungal biomass is a low-cost green processes, and bioremediation of impacted local.
Assuntos
Cobre/metabolismo , Nanopartículas Metálicas/microbiologia , Trichoderma/metabolismo , Águas Residuárias/microbiologia , Biodegradação Ambiental , Biomassa , Biotransformação , Cinética , Nanopartículas Metálicas/química , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Trichoderma/crescimento & desenvolvimento , Trichoderma/ultraestrutura , Águas Residuárias/químicaRESUMO
The inherently high viscosity of ionic liquids (ILs) can limit their potential applications. One approach to address this drawback is to modify the cation side chain with ether groups. Herein, we assessed the structure-property relationship by focusing on acetate (OAc), a strongly coordinating anion, with 1,3-dialkylimidazolium cations with different side chains, including alkyl, ether, and hydroxyl functionalized, as well as their combinations. We evaluated their viscosity, thermal stabilities, and microstructure using Raman and infrared (IR) spectroscopies, allied to density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The viscosity data showed that the ether insertion significantly enhances the fluidity of the ILs, consistent with the coiling effect of the cation chain. Through a combined experimental and theoretical approach, we analyzed how the OAc anion interacts with ether ILs, revealing a characteristic bidentate coordination, particularly in hydroxyl functionalized ILs due to specific hydrogen bonding with the OH group. IR spectroscopy showed subtle shifts in the acidic hydrogens of imidazolium ring C(2)-H and C(4,5)-H, suggesting weaker interactions between OAc and the imidazolium ring in ether-functionalized ILs. Additionally, spatial distribution functions (SDF) and dihedral angle distribution obtained via AIMD confirmed the intramolecular hydrogen bonding due to the coiling effect of the ether side chain.
RESUMO
Microtubes obtained from the self-assembly of L-diphenylalanine (FF-MTs) were evaluated as potential vehicles for drug delivery. The biological marker Rhodamine B (RhB) was chosen as a model drug and conjugated to the peptide arrays during self-organization in the liquid phase. Microscopy and X-ray studies were performed to provide morphological and structural information. The data revealed that the cargo was distributed either in small aggregates at the hydrophobic surface of the FF-MTs or homogeneously embedded in the structure, presumably anchored at polar sites in the matrix. Raman spectroscopy revealed notable shifts of the characteristic RhB resonance peaks, demonstrating the successful conjugation of the fluorophore and peptide assemblies. In vitro assays were conducted in erythrocytes and fibroblast cells. Interestingly, FF-MTs were found to modulate the release of the load. The release of RhB from the FF-MTs followed first-order kinetics with a steady-state profile, demonstrating the potential of these carriers to deliver drugs at constant rates in the body. Cytotoxicity investigations revealed high cell viability up to concentrations of 5 mg mL(-1), demonstrating the low toxicity of the FF-MTs.
Assuntos
Sistemas de Liberação de Medicamentos , Eritrócitos/efeitos dos fármacos , Fibroblastos/efeitos dos fármacos , Fenilalanina/análogos & derivados , Células 3T3 , Animais , Sobrevivência Celular/efeitos dos fármacos , Dipeptídeos , Relação Dose-Resposta a Droga , Sistemas de Liberação de Medicamentos/efeitos adversos , Cinética , Masculino , Camundongos , Modelos Moleculares , Tamanho da Partícula , Fenilalanina/efeitos adversos , Fenilalanina/química , Fenilalanina/farmacocinética , Fenilalanina/farmacologia , Ratos Wistar , Estereoisomerismo , Relação Estrutura-Atividade , Propriedades de SuperfícieRESUMO
This paper describes a straightforward approach for the synthesis of hybrid materials composed of titanium dioxide (TiO(2)) colloidal spheres decorated with gold nanoparticles (Au NPs). In the reported method, monodisperse TiO(2) colloidal spheres (â¼220 nm in diameter) could be directly employed as templates for the nucleation and growth of Au NPs over their surface using AuCl(4)(-)(aq) as the Au precursor, ascorbic acid as the reducing agent, PVP as the stabilizer, and water as the solvent. The Au NPs presented a uniform distribution over the TiO(2) surface. Interestingly, the size of the Au NPs could be controlled by performing sequential reduction steps with AuCl(4)(-)(aq). This method could also be adapted for the production of TiO(2) colloidal spheres decorated with other metal NPs including silver (Ag), palladium (Pd), and platinum (Pt). The catalytic activities of the TiO(2)-Au materials as a function of composition and NPs size were investigated toward the reduction of 4-nitrophenol to 4-aminophenol under ambient conditions. An increase of up to 10.3-fold was observed for TiO(2)-Au relative to TiO(2). A surface-enhanced Raman scattering application for TiO(2)-Au was also demonstrated employing 4-mercaptopyridine as the probe molecule. The results presented herein indicate that our approach may serve as a platform for the synthesis of hybrid materials containing TiO(2) and metal NPs displaying well-defined morphologies, compositions, and sizes. This can have important implications for the design of TiO(2)-based materials with improved performances for photocatalysis and photovoltaic applications.
Assuntos
Ouro/química , Nanopartículas Metálicas/química , Titânio/química , Coloides/síntese química , Coloides/química , Tamanho da Partícula , Povidona/química , Propriedades de SuperfícieRESUMO
The polyol method has been widely employed for the synthesis of uniform silver nanowires (Ag NWs) in high yields. In this article, we describe the utilization of HCl oxidative etching as an effective strategy to control the width of Ag NWs produced by the polyol approach. More specifically, the width of the produced Ag NWs could be tuned from 65 to 765 nm by varying the HCl concentration in the polyol recipe. Our results indicate that the obtained widths displayed a linear and steady increase according to the HCl concentration employed in the reaction. Although the width was also dependent on other experimental parameters such as the AgNO(3) and polyvinylpirrolidone (PVP) concentrations and temperature, the HCl oxidative etching enabled the controlled synthesis of Ag NWs over the widest range of widths. The size-dependent optical property investigations revealed that the transverse mode surface plasmon resonance peak for the produced Ag NWs red-shifted from 378 to 467 nm as their width increased from 77 to 584 nm. The application of Ag NWs (77 nm) as SERS substrates for the detection of 4-mercaptopyridine was also demonstrated. As the properties of metal nanostructures are strongly dependent upon size, the results reported herein can have important implications for designing the synthesis of uniform Ag NWs in high yields displaying controlled and/or desired dimensions for applications in areas including plasmonics, electronics, and sensing.