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1.
ACS Appl Mater Interfaces ; 12(44): 50152-50160, 2020 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-33084299

RESUMEN

Viral capsid-like particles tiled with mosaic patches have attracted great attention as they imitate nature's design to achieve advanced material properties and functions. Here, we develop a facile one-pot soft-template method to synthesize biomimetic gold capsid-like colloids with tunable particle size and surface roughness. Uniform submicron-to-micron-sized hollow gold colloidal particles are successfully achieved by using tannic acids as soft templates and reducing agents, which first self-assemble into spherical complex templates before the reduction of Au3+ ions via their surface hydroxyl groups. The surface roughness, the size, and the total number of the patches of the prepared gold particles are further tuned, utilizing a mechanism that offers morphology control by varying the number of surface hydroxyl groups participating in the reduction reactions. Among different capsid-like gold colloids, those possessing a rough surface display superior catalytic properties and show promising results as surface-enhanced Raman spectroscopy (SERS) solid substrates for detecting small organic molecules and biomimetic enzymes in a liquid phase for sensing biomolecules in real samples. These capsid-like gold colloids are also expected to find practical applications in delivery systems, electronics, and optics. We believe that our strategy of imitating nature's design of capsid-like structures should also be used in the design and fabrication of other functional colloidal particles.


Asunto(s)
Materiales Biomiméticos/síntesis química , Oro/química , Materiales Biomiméticos/química , Catálisis , Coloides/síntesis química , Coloides/química , Estructura Molecular , Tamaño de la Partícula , Espectrometría Raman , Propiedades de Superficie
2.
Int J Mol Sci ; 20(21)2019 Oct 28.
Artículo en Inglés | MEDLINE | ID: mdl-31661810

RESUMEN

The adsorption of amyloidogenic peptides, amyloid beta 1-40 (Aß1-40), alpha-synuclein (α-syn), and beta 2 microglobulin (ß2m), was attempted over the surface of nano-gold colloidal particles, ranging from d = 10 to 100 nm in diameter (d). The spectroscopic inspection between pH 2 and pH 12 successfully extracted the critical pH point (pHo) at which the color change of the amyloidogenic peptide-coated nano-gold colloids occurred due to aggregation of the nano-gold colloids. The change in surface property caused by the degree of peptide coverage was hypothesized to reflect the ΔpHo, which is the difference in pHo between bare gold colloids and peptide coated gold colloids. The coverage ratio (Θ) for all amyloidogenic peptides over gold colloid of different sizes was extracted by assuming Θ = 0 at ΔpHo = 0. Remarkably, Θ was found to have a nano-gold colloidal size dependence, however, this nano-size dependence was not simply correlated with d. The geometric analysis and simulation of reproducing Θ was conducted by assuming a prolate shape of all amyloidogenic peptides. The simulation concluded that a spiking-out orientation of a prolate was required in order to reproduce the extracted Θ. The involvement of a secondary layer was suggested; this secondary layer was considered to be due to the networking of the peptides. An extracted average distance of networking between adjacent gold colloids supports the binding of peptides as if they are "entangled" and enclosed in an interfacial distance that was found to be approximately 2 nm. The complex nano-size dependence of Θ was explained by available spacing between adjacent prolates. When the secondary layer was formed, Aß1-40 and α-syn possessed a higher affinity to a partially negative nano-gold colloidal surface. However, ß2m peptides tend to interact with each other. This difference was explained by the difference in partial charge distribution over a monomer. Both Aß1-40 and α-syn are considered to have a partial charge (especially δ+) distribution centering around the prolate axis. The ß2m, however, possesses a distorted charge distribution. For a lower Θ (i.e., Θ <0.5), a prolate was assumed to conduct a gyration motion, maintaining the spiking-out orientation to fill in the unoccupied space with a tilting angle ranging between 5° and 58° depending on the nano-scale and peptide coated to the gold colloid.


Asunto(s)
Péptidos beta-Amiloides/química , Péptidos beta-Amiloides/ultraestructura , Proteínas Amiloidogénicas/química , Proteínas Amiloidogénicas/ultraestructura , Oro Coloide/química , Adsorción , Coloides/química , Oro/química , Concentración de Iones de Hidrógeno , Nanopartículas del Metal/química , Nanopartículas del Metal/ultraestructura , Microscopía Electrónica de Transmisión , Simulación de Dinámica Molecular , Nanogeles/química , Nanogeles/ultraestructura , Tamaño de la Partícula , Análisis Espectral , Propiedades de Superficie , alfa-Sinucleína/química , alfa-Sinucleína/ultraestructura , Microglobulina beta-2/química , Microglobulina beta-2/ultraestructura
3.
Front Chem ; 7: 548, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31475132

RESUMEN

This work is a detailed study on how to optimize gold colloids preparation and their deposition to very different in nature carbon materials. The change of the continuous phase and its dielectric constant is used to assure the good dispersion of the hydrophilic/hydrophobic carbons and the successful transfer of the preformed small size colloids to their surface. The sintering behavior of the particles during the calcination step is also studied and the optimal conditions to reduce to a minimum the particle size increase during the protecting agent removal phase are found. The as prepared catalysts have been tested in a relevant reaction in the field of environmental catalysis such as the reduction of 4-nitrophenol leading to promising results. Overall, this work proposes an important methodology to follow when a carbonaceous material are selected as catalyst supports for green chemistry reactions.

4.
Bioenergy Res ; 12: 409-418, 2019 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-31984113

RESUMEN

Insufficient light supply is a major limitation in cultivation of cyanobacteria for scaled up biofuel production and other biotechnological applications, which has driven interest in nanoparticle-mediated enhancement of cellular light capture. In the present study, Fremyella diplosiphon wild type (Fd33) and halotolerant (HSF33-2) strains were grown in solution with 20, 100, and 200 nm-diameter gold nanoparticles (AuNPs) to determine their impact on biomass accumulation, pigmentation, and fatty acid methyl ester (FAME) production. Results revealed a significant increase in growth of Fd33 (0.244 ± 0.006) and HSF33-2 (0.112 ± 0.003) when treated with 200 nm AuNPs. In addition, we observed a significant increase in chlorophyll a accumulation in 200 nm AuNP-treated Fd33 (25.7%) and HSF33-2 (36.3%) indicating that NPs enhanced photosynthetic pigmentation. We did not observe any alteration in FAME composition and biodiesel properties of transesterified F. diplosiphon lipids among all AuNP treatments. Interactions between F. diplosiphon and AuNPs were visualized using scanning electron microscopy. Energy dispersive X-ray spectroscopy confirmed the presence of AuNPs outside cells with aggregation in high cell density locales. Our findings indicate that nanotechnological approaches could significantly enhance growth of the organism with no negative effect on FAME-derived biodiesel properties, thus augmenting F. diplosiphon as a potential biofuel agent.

5.
J Chromatogr A ; 1579: 115-120, 2018 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-30366691

RESUMEN

A fast and facile method was developed for on-site detection of aflatoxins (AFs) in moldy agricultural products using thin layer chromatography combined with surface-enhanced Raman spectroscopy (TLC-SERS). Four different AFs were successfully separated by TLC and then a small portable Raman spectrometer, with gold colloids as the SERS-active substrate, was applied to identify the separated spots. TLC-SERS application to on-site detection of AFs was systematically investigated. Qualitative and quantitative AF detection was found to be easily accomplished and limits of detection were estimated to be 1.5 × 10-6, 1.1 × 10-5, 1.2 × 10-6, and 6.0 × 10-7 M for AFB1, AFB2, AFG1, and AFG2, respectively. The proposed method was also highly selective, enabling successful AF identifications in complex extracts from moldy peanuts. The study showed that TLC-SERS could be effectively used for separation and detection of these four AFs, demonstrating good prospects for on-site qualitative screening of agricultural products.


Asunto(s)
Aflatoxinas/análisis , Arachis/química , Arachis/microbiología , Cromatografía en Capa Delgada , Análisis de los Alimentos/métodos , Espectrometría Raman
6.
J Colloid Interface Sci ; 437: 17-23, 2015 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-25310578

RESUMEN

The multifunctional nanoobjects that can be controlled, manipulated and triggered using external stimuli represent very promising candidates for nanoscale therapeutic and diagnostic applications. In this study we report the successful synthesis and characterization of a new class of very stable multifunctional nanoobjects, containing cationic liposomes decorated with PEGylated gold nanoparticles (PEGAuNPs). The multifunctional hybrid nanoobjects (mHyNp) were prepared by taking advantage of the electrostatic interactions between small unilamelar cationic liposomes and negatively charged gold nanoparticles. The mHyNps have been investigated by UV-VIS absorption spectroscopy, Dynamic Light Scattering (DLS), Zeta Potential Measurements and Transmission Electron Microscopy (TEM). The TEM images clearly revealed the attachment of individual gold nanoparticles onto the spherical outer surface of the cationic liposomes which was also confirmed by DLS and UV-VIS data. Furthermore, the plasmonic properties of the hybrid complexes have been evaluated by using the Surface Enhanced Raman Spectroscopy (SERS) technique. It is shown that PEG mediated interaction between the liposomes and the gold nanoparticles enabled the recording of the SER spectra of the liposomes in aqueous environment, thus demonstrating the plasmonic properties of the hybrids.


Asunto(s)
Liposomas , Polietilenglicoles/química , Microscopía Electrónica de Transmisión , Dispersión de Radiación , Espectrofotometría Ultravioleta
7.
Nanotoxicology ; 8 Suppl 1: 118-27, 2014 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-24289310

RESUMEN

Abstract To examine gold nanoparticle reprotoxicity, bovine spermatozoa were challenged with ligand-free or oligonucleotide-conjugated gold nanoparticles synthesized purely without any surfactants by laser ablation. Sperm motility declined at nanoparticle mass dose of 10 µg/ml (corresponding to ∼14 000 nanoparticles per sperm cell) regardless of surface modification. Sperm morphology and viability remained unimpaired at all concentrations. Transmission electron microscopy showed an modification dependant attachment of nanoparticles to the cell membrane of spermatozoa, but provided no evidence for nanoparticle entrance into sperm cells. A molecular examination revealed a reduction of free thiol residues on the cell membrane after nanoparticle exposure, which could explain the decrease in sperm motility. Sperm fertilising ability decreased after exposure to 10 µg/ml of ligand-free nanoparticles indicating that agglomerated ligand-free nanoparticles interfere with membrane properties necessary for fertilisation. In conclusion, nanoparticles may impair key sperm functions solely by interacting with the sperm surface membrane.


Asunto(s)
Oro/química , Nanopartículas del Metal/toxicidad , Espermatozoides/efectos de los fármacos , Adsorción , Animales , Bovinos , Membrana Celular/efectos de los fármacos , Membrana Celular/metabolismo , Masculino
8.
Artículo en Inglés | MEDLINE | ID: mdl-24295778

RESUMEN

In this paper, surface-enhanced Raman scattering (SERS) spectra of maleic hydrazide (MH, 6-hydroxy-3(2H)-pyridazinone) were studied by using citrate-reduced gold colloidal nanoparticles. Comparisons between the prominent SERS bands and the precise mode descriptions predicted through density functional theory (DFT) simulations at the B3LYP/6-311++g(d,p) level allowed an in-depth orientation analysis of the adsorbed species on gold surfaces. And main forms of hydrogen bonds in the solid state of MH were also determined to be O-H⋯O. Furthermore, the effects of concentration and pH on the SERS spectra of the molecule were discussed. It is found that with the different adsorbate concentration, the SERS spectra of MH show significant changes in their features, indicating different orientations and adsorption sites of the molecule on the gold colloidal surface. The SERS and absorption spectra under different pH conditions show that a basic environment leads to the deprotonation of N2 and the nearly parallel orientation of the MH molecule on the gold surface. Moreover, the enhanced characteristic bands were observed at MH concentrations down to about 1 ppm with the gold colloids, demonstrating a potential of the technique in the analysis of MH residues.


Asunto(s)
Oro/química , Hidrazida Maleica/química , Espectrometría Raman , Absorción Fisicoquímica , Adsorción , Coloides/química , Concentración de Iones de Hidrógeno , Conformación Molecular , Nanopartículas/química , Cebollas/química , Espectrofotometría Ultravioleta , Estereoisomerismo , Propiedades de Superficie , Temperatura
9.
Anal Chim Acta ; 517(1-2): 139-144, 2004 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-31896834

RESUMEN

We describe a new approach for glucose determination with tunable glucose dynamic sensing ranges, dependent on the properties of new nanosensors, which are comprised of Con A-aggregated dextran-coated gold colloids. Dextran-coated 10 or 20 nm gold colloids can be aggregated with Con A in a controlled fashion, the change in absorbance at an arbitrary wavelength used to monitor the extent of aggregation, which can be optimized for sensing. The presence of any glucose competitively binds with Con A, dissociating the dextran-coated colloids, affording for the reverse gold plasmon change and hence the determination of glucose concentrations. For one of our sensor systems, a 500K dextran-20 nm gold sensor, crosslinked with 8.70 µM Con A, a change in absorbance at 650 nm of 0.03 was observed, in response to as little as 3 mM glucose. In contrast, a 500K dextran-10 nm gold 18.7 µM Con A aggregate sensor, produced a 0.05 and 0.1 change in absorbance, respectively, by the addition of 50 and 100 mM glucose. We have found that the glucose sensing ranges can be somewhat tuned by altering the properties, and therefore the extent of aggregation of the gold aggregate sensors. Reducing the gold colloid size and dextran molecular weight typically reduces the glucose sensing range (lower [glucose]) but also reduces the long-term stability of the gold aggregate sensor. Similarly the concentration of Con A used to aggregate the system also has an effect on long term sensor stability and glucose response. In this paper, we present our findings, which offer unique opportunities and perspectives for building tunable plasmonic type glucose sensors.

10.
Forensic Sci Rev ; 13(1): 29-64, 2001 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-26256143

RESUMEN

Silver physical developers consist of silver ions and a reducing (developing) agent. They were formulated for developing latent images on photosensitive materials such as photographic emulsions. The mechanism of how the latent image nuclei catalyze the reduction of silver ions by a reducing agent to form black colloidal silver particles has been extensively studied. These developers also happen to visualize latent prints on porous surfaces such as paper. Several hypotheses exist that identify the components in latent print residue that trigger physical development; also several hypotheses exist that explain why such developers work better on porous rather than non-porous surfaces. The more common of these developers use ferrous ions (from a ferrous/ferric redox couple) to reduce silver ions on the surface of latent print residue. Five such silver physical developers are compared through their cell potential ΔE (and the corresponding reaction quotient Q). Each developer is represented by a point on a line given by R = QC where R = [Fe3+]/[Fe2+] and C = [Ag+] and has a point on the line given by Req = QeqCeq where Qeq = K = 1.22 corresponds ΔE = 0. The quantity C - Ceq is the maximum amount of silver it can deposit. The development rate of a silver physical developer is directly related to its cell potential ΔE, the temperature, the maximum amount of silver that it can deposit, and the magnitude of [Fe2+]/[Ag+]. The contrast of a physically developed latent print (on light or dark surfaces) can be enhanced by optical, image enhancement, scanning electron, x-ray, and chemical methods. The latter includes bleaching or intensifying methods, fluorescent dye toning, and radioactive sulfur toning.

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