Spectroscopies and Electron Microscopies Unravel the Origin of the First Colour Photographs

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIX^th century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV-visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours.     

Green synthesis of silver nanoparticles using Macrotyloma uniflorum

Green synthesis of noble metal nanoparticles is a vast developing area of research. In this paper we report the green synthesis of silver nanoparticles using aqueous seed extract of Macrotyloma uniflorum. The effect of experimental parameters such as amount of extract, temperature and pH on the formation of silver nanoparticles was studied. The as prepared samples are characterized using XRD, TEM, UV-Visible and FTIR techniques. The formation of silver nanoparticles is evidenced by the appearance of signatory brown colour of the solution and UV-vis spectra. The XRD analysis shows that the silver nanoparticles are of face centered cubic structure. Well-dispersed silver nanoparticles with anisotropic morphology having size ～12 nm are seen in TEM images. FTIR spectrum indicates the presence of different functional groups in capping the nanoparticles. The possible mechanism leading to the formation of silver nanoparticles is suggested.     

Size characterization and quantification of silver nanoparticles by asymmetric flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry

A method for determining the size of silver nanoparticles and their quantification by asymmetric flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry (ICP-MS) is proposed and was tested in consumer products. Experimental conditions were studied in detail to avoid aggregation processes or alteration of the original size distributions. Additionally, losses from sorption processes onto the channel membrane were minimized for correct quantification of the nanoparticles. Mobile phase composition, injection/focusing, and fractionation conditions were evaluated in terms of their influence on both separation resolution and recovery. The ionic strength, pH, and the presence of ionic and nonionic surfactants had a strong influence on both separation and recovery of the nanoparticles. In general, better results were obtained under those conditions that favored charge repulsions with the membrane. Recovery values of 83 ± 8% and 93 ± 4% with respect to the content of silver nanoparticles were achieved for the consumer products studied. Silver nanoparticle standards were used for size calibration of the channel. The results were compared with those obtained by photon correlation spectroscopy and images taken by transmission electron microscopy. The quantification of silver nanoparticles was performed by direct injection of ionic silver standard solutions into the ICP-MS system, integration of the corresponding peaks, and interpolation of the fractogram area. A limit of detection of 5.6 μg L^-1 silver, which corresponds to a number concentration of 1×10¹² L^-1 for nanoparticles of 10 nm, was achieved for an injection volume of 20 μL.     

Silica–silver core–shell particles for antibacterial textile application

The silica–silver core–shell particles were synthesized by simple one pot chemical method and were employed on the cotton fabric as an antibacterial agent. Extremely small (1–2 nm) silver nanoparticles were attached on silica core particles of average 270 nm size. The optimum density of the nano silver particles was found which was sufficient to show good antibacterial activity as well as the suppression in their surface plasmon resonance responsible for the colour of the core–shell particle for antibacterial textile application. The change in the density and size of the particles in the shell were monitored and confirmed by direct evidence of their transmission electron micrographs and by studying surface plasmon resonance characteristics. The colony counting method of antibacterial activity testing showed excellent results and even the least silver containing core–shell particles showed 100% activity against bacterial concentration of 10⁴ colony counting units (cfu). The bonding between core–shell particles and cotton fabric was examined by X-ray photoelectron spectroscopy. The antibacterial activity test confirmed the firm attachment of core–shell particles to the cotton fabric as a result 10 times washed sample was as good antibacterial as that of unwashed sample. The bacterial growth was inhibited on and beneath the coated fabric, at the same time no zone of inhibition which occurs due to the migration of silver ions into the medium was observed indicating immobilization of silver nanoparticles on silica and core–shell particles on fabric by strong bonding.     

Plasmonic-based colorimetric and spectroscopic discrimination of acetic and butyric acids produced by different types of Escherichia coli through the different assembly structures formation of gold nanoparticles

We present a plasmonic-based strategy for the colourimetric and spectroscopic differentiation of various organic acids produced by bacteria. The strategy is based on our discovery that particular concentrations of dl-lactic, acetic, and butyric acids induce different assembly structures, colours, and optical spectra of gold nanoparticles. We selected wild-type (K-12 W3110) and genetically-engineered (JHL61) Escherichia coli (E. coli) that are known to primarily produce acetic and butyric acid, respectively. Different assembly structures and optical properties of gold nanoparticles were observed when different organic acids, obtained after the removal of acid-producing bacteria, were mixed with gold nanoparticles. Moreover, at moderate cell concentrations of K-12 W3110 E. coli, which produce sufficient amounts of acetic acid to induce the assembly of gold nanoparticles, a direct estimate of the number of bacteria was possible based on time-course colour change observations of gold nanoparticle aqueous suspensions. The plasmonic-based colourimetric and spectroscopic methods described here may enable onsite testing for the identification of organic acids produced by bacteria and the estimation of bacterial numbers, which have applications in health and environmental sciences.     

Thermal and structural analysis of germanate glass and thin films co-doped with silver nanoparticles and rare earth ions with insights from visible and Raman spectroscopy

This paper reports on the thermal and optical properties of germanate glasses GeO₂–PbO co-doped with silver nanoparticles and rare earth ions (Tm³⁺, Er³⁺ and Yb³⁺) with a focus on the thermal diffusivity (D). The presence of rare earth ions and nanoparticles is evidenced by absorption spectra and TEM images, respectively. Additionally, a structural comparison between thin films and bulk glass with the same nominal composition is given. It is found that D increases up to 20% in samples where nanoparticles are present, although their quantity corresponds only to a volume fraction of 1.7%. Therefore, such enhancement could be associated with the nanoparticles. Nevertheless, a Raman analysis revealed a structural change after the thermal treatment used for the nucleation of the nanoparticles. A decrease in the intensity of the band at 534 cm⁻¹ in the Raman spectra is interpreted as the disruption of the 3-membered rings of the GeO₄ tetrahedra. The Raman analysis also revealed the formation of small crystals of α-GeO₂ type quartz and the adsorption of carbon dioxide on the surface of the silver nanoparticles inserted in the germanate thin film.     

In situ formation of silver nanoparticles within an amphiphilic graft copolymer film

Silver nanoparticles were prepared by UV irradiation from silver salts, such as AgBF₄ or AgNO₃, when dissolved in an amphiphilic film of poly((oxyethylene)₉ methacrylate)‐graft‐poly((dimethyl siloxane)_n methacrylate), POEM‐g‐mPDMS. The in situ formation of silver nanoparticles in the graft copolymer film was confirmed by transmission electron microscopy (TEM), UV‐visible spectroscopy, and wide angle X‐ray scattering (WAXS). The results demonstrated that the use of AgBF₄ yielded silver nanoparticles with a smaller size (～5 nm) and narrower particle distribution when compared with AgNO₃. The formation of silver nanoparticles was explained in terms of the interaction strength of the silver ions with the ether oxygens of POEM, as revealed by differential scanning calorimetry (DSC) and X‐ray photoelectron spectroscopy (XPS). It was thus concluded that a stronger interaction of silver ions with the ether oxygens results in a more stable formation of silver nanoparticles, which produces uniform and small‐sized nanoparticles. DSC and small angle X‐ray scattering (SAXS) data also showed the selective incorporation and in situ reduction of the silver ions within the hydrophilic POEM domains. Excellent mechanical properties of the nanocomposite films (3–5 × 10⁵ dyn/cm²) were observed, mostly because of the confinement of silver nanoparticles in the POEM chains as well as interfaces created by the microphase separation of the graft copolymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1283–1290, 2007     

Efficient Excitation‐Energy Transfer in Ion‐Based Organic Nanoparticles with Versatile Tunability of the Fluorescence Colours

Organic nanoparticles consisting of 3,3′‐diethylthiacyanine (TC) and ethidium (ETD) dyes are synthesized by ion‐association between the cationic dye mixture (10 % ETD doping) and the tetrakis(4‐fluorophenyl)borate (TFPB) anion, in the presence of a neutral stabilizing polymer, in aqueous solution. Doping with ETD makes the particle size smaller than without doping. Size tuning can also be conducted by varying the molar ratio (ρ) of the loaded anion to the cationic dyes. The fluorescence spectrum of TC shows good overlap with the absorption of ETD in the 450–600 nm wavelength region, so efficient excitation‐energy transfer from TC (donor) to ETD (acceptor) is observed, yielding organic nanoparticles whose fluorescence colours are tunable. Upon ETD doping, the emission colour changes significantly from greenish‐blue to reddish or whitish. This change is mainly dependent on ρ. For the doped nanoparticle sample with ρ=1, the intensity of fluorescence ascribed to ETD is ～150‐fold higher than that from pure ETD nanoparticles (efficient antenna effect). Non‐radiative Förster resonance‐energy transfer (FRET) is the dominant mechanism for the ETD fluorescence enhancement. The organic nanoparticles of a binary dye system fabricated by the ion‐association method act as efficient light‐harvesting antennae, which are capable of transferring light energy to the dopant acceptors in very close proximity to the donors, and can have multi‐wavelength emission colours with high fluorescence quantum yields.     

Effect of cationization on adsorption of silver nanoparticles on cotton surfaces and its antibacterial activity

Cotton was cationized by exhaustion method using 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC) as a cation-generating agent. Adsorption of silver nanoparticles on normal and cationized cotton was studied by exhaustion method at temperatures of 80°C and 100°C. Two exhaustion baths were used, containing nanosilver colloidal solutions stabilized by two different stabilizers and various concentrations of silver nanoparticles. Fourier-transform infrared (FT-IR) spectra of normal and cationized samples confirmed the existence of quaternary ammonium groups on cationized cellulose fibers. X-ray diffraction (XRD) patterns showed that crystallinity of the modified cellulose fibers was decreased. Scanning electron microscope (SEM) images revealed that the surface of the modified cotton was rougher than that of normal cotton. In addition, SEM images showed the presence of silver nanoparticles on the surface of treated fabric samples. The amount of silver particles adsorbed on the fabric samples was determined using inductively coupled plasma-optical emission spectrometer. Antibacterial tests were performed against Escherichia coli bacteria as an indication of antibacterial effect of samples. Cationized cotton samples adsorbed more silver nanoparticles and then had greater ability to inhibit bacteria.     

Rapid Synthesis of Silver Nanoparticles by Microwave-Polyol Method with the Assistance of Latex Copolymer

Highly stable and monodispersed silver nanoparticles with uniform morphology have been successfully prepared by microwave (MW) irradiation within a few seconds from the mixture of silver nitrate, ethanol and latex copolymer. The aqueous emulsion of latex copolymer acts as both reducing and stabilizing agent. To the best of our knowledge, it was the first time that the effect of MW irradiation time and latex concentration on the silver nanoparticle preparation and properties was analyzed. The formation of silver nanoparticles was confirmed by Ultraviolet–visible spectroscopy and transmission electron microscopy (TEM). The UV–Vis spectra are marked by the characteristic surface plasmon absorption band in the range 410–420 nm. From TEM images, silver nanoparticles were observed to be spherical with sizes ranging from 4 to 10 nm. Electron diffraction patterns on selected area, indicated that the silver nanoparticles are crystalline with face centered cubic structure.     

Fabrication of highly porous poly (ɛ-caprolactone) fibers for novel tissue scaffold via water-bath electrospinning

A non-toxic route was used for the preparation of silver nanoparticles using tryptophan (Trp) as reducing/stabilizing agent in the presence of cetyltrimethyl ammonium bromide (CTAB). Role of water soluble neutral polymer poly(vinylpyrrolidone) (PVP) has been studied on the growth of yellow colour silver nanoparticle formation. The synthesized nanostructures were characterized by UV–Visible absorption spectroscopy, transmission electron microscopy (TEM) by observing the size and distribution of silver nanoparticles. As the reaction proceeded, particles grew up to about 10 and 20 nm in the presence and absence of PVP, respectively, as determined by TEM. The formed nanoparticles showed the highest absorption plasmon band at 425 nm. Rate of silver sol formation increases with the [Trp], [CTAB] and [PVP], reaching a limiting value and then decreases with the increase in concentrations of these reagents. It was observed that nanoparticles are spherical, aggregated and poly dispersed in the absence and presence of PVP, respectively. On the basis of kinetic data, a suitable mechanism is proposed and discussed for the silver sol formation.     

Enhancement of the Surface Activity for Some Monomeric and Polymeric Thiol Surfactants Using Silver Nanoparticles

In the present work, the self-assembling of some synthesized thiol surfactants namely (6-(3-amino phenoxy) hexane-1-thiol, 8-(3-amino phenoxy) octane-1-thiol, 10-(3-amino phenoxy) decane-1-thiol, 12-(3-amino phenoxy) dodecane-1-thiol, and their polymers on silver nanoparticles was investigated. The self-assembling of these surfactants on silver nanoparticles was characterized using different techniques such as ultraviolet (UV) spectroscopy, powder x-ray diffraction (XRD), electrone diffraction (ED), and transmission electron microscopy (TEM). The effect of the self-assembling of these surfactants on the stabilization of the silver nanoparticles (AgNPs) was studied using TEM images. The growth of the silver nanoparticles was investigated with respect to the increase of alkyl chain in the synthesized thiol surfactants. The effect of silver nanoparticles on the surface, interfacial tension, and the emulsion stability of these surfactants with paraffin oil was studied. The results show that the silver nanoparticles have the ability to effect on the behavior of these surfactants in solution and improve their surface activity.     

Influence of dose on particle size of colloidal silver nanoparticles synthesized by gamma radiation

Colloidal silver nanoparticles were synthesized by γ-irradiation-induced reduction method of an aqueous solution containing silver nitrate as a precursor in various concentrations between 7.40×10^?4 and 1.84×10^?3 M, polyvinyl pyrrolidone for capping colloidal nanoparticles, isopropanol as radical scavenger of hydroxyl radicals and deionised water as a solvent. The irradiations were carried out in a ⁶⁰Co γ source chamber at doses up to 70 kGy. The optical absorption spectra were measured using UV–vis spectrophotometer and used to study the particle distribution and electronic structure of silver nanoparticles. As the radiation dose increases from 10 to 70 kGy, the absorption intensity increases with increasing dose. The absorption peak λ_max blue shifted from 410 to 403 nm correspond to the increase of absorption conduction electron energy from 3.02 to 3.08 eV, indicating the particle size decreases with increasing dose. The particle size was determined by photon cross correlation spectroscopy and the results showed that the particle diameter decreases exponentially with the increase of dose. The transmission electron microscopy images were taken at doses of 20 and 60 kGy and the results confirmed that as the dose increases the diameter of colloidal silver nanoparticle decreases and the particle distribution increases.     

Surface-enhanced Raman scattering of 4-aminobenzenethiol on silver nanoparticles substrate

Active surface-enhanced Raman scattering (SERS) silver nanoparticles substrate was prepared by multiple depositions of Ag nanoparticles on glass slides. The substrate is based on five depositions of Ag nanoparticles on 3-aminopropyl-trimetoxisilane (APTMS) modified glass slides, using APTMS sol–gel as linker molecules between silver layers. The SERS performance of the substrate was investigated using 4-aminobenzenethiol (4-ABT) as Raman probe molecule. The spectral analyses reveal a 4-ABT Raman signal enhancement of band intensities, which allow the detection of this compound in different solutions. The average SERS intensity decreases significantly in 4-ABT diluted solutions (from 10⁻⁴ to 10⁻⁶ mol L⁻¹), but the compound may still be detected with high signal/noise ratio. The obtained results demonstrate that the Ag nanoparticles sensor has a great potential as SERS substrate.     

Smart synthesis of silver nanoparticles supported in porous polybenzoxazine nanocomposites via a main-chain type benzoxazine resin

Novel silver nanoparticles immobilized on macroporous polybenzoxazine nanocomposites were prepared as catalysts for catalytic reduction reaction.     

Synthesis and Catalytic Evaluation of Silver Nanoparticles Synthesized with <Emphasis Type="Italic">Aloysia triphylla</Emphasis> Leaf Extract

In this investigation, we report the biosynthesis of the silver nanoparticles using Aloysia triphylla leaves extract. The as-prepared silver nanoparticles were characterized by ultraviolet–visible (Uv–vis) spectroscopy, X-ray diffractometry, scanning electron microscopy and transmission electron microscopy The infrared spectroscopy (FTIR) and Raman spectroscopy techniques were also used to evaluate the chemical groups of the plant extract involved in the silver ions bioreduction. The results indicate that as the plant extract/precursor salt ratio increases, the size of the nanoparticles decreases. Also, as the reaction temperature increases, the reduction rate increased too, resulting in the formation of smaller nanoparticles-size ranges. Uv–vis spectroscopy illustrates absorption peaks in the range of wavelengths of 430–445 nm corresponding to surface plasmon resonance band of silver nanoparticles. The X-ray diffraction (XRD) confirmed the presence of silver solids with fcc structure type. The FTIR analysis showed that the bands corresponding to phenolic compounds and the amide group were involved in the synthesis and stabilization of silver nanoparticles, respectively. The Raman studies showed bands at 1380 and 1610 cm^?1, which correspond to the aromatic and amide compounds, confirming the FTIR results. The Uv–vis results indicate the capacity of silver nanoparticles to reduce the methylene blue.     

Detection and Determination of Released Ions in the Presence of Nanoparticles: Selectivity or Strategy?

Metallic nanoparticles can release ionic species, but also both species can occur in the same samples. Therefore, there is a need of efficient and cost‐effective methods to determine these ionic species in the presence of the corresponding nanoparticles. Electroanalytical techniques open the door to this selective detection of NPs and their ions. In this work, a methodology that allows the direct determination of ionic silver (Ag⁺) in the presence of silver nanoparticles based on anodic stripping voltammetry was implemented. Silver nanoparticles were determined, after acidic digestion of the sample, by difference with respect to the total content of silver. The method was validated in terms of specific identification of silver ions, linearity, working range, limit of detection, limit of quantification, recovery, repeatability and ruggedness. All parameters are adequate for an analytical method following Eurachem recommendations. The validated method was used to determine the concentration of Ag⁺ and total silver in two commercial products of colloidal silver. The results were compared with those obtained by atomic absorption spectrometry in combination with an ultrafiltration step for isolation of ionic silver. There were no significant differences in the results. The proposed methodology benefits from the intrinsic selectivity of the electroanalysis methods, allowing to eliminate the steps of pretreatments of the samples, which are necessary in other techniques. The novelty of the article lies in the direct determination of Ag (I) ions in the presence of AgNPs, without the use of previous separation steps.     

Alga-mediated facile green synthesis of silver nanoparticles: Photophysical,catalytic and antibacterial activity

A facile, convenient and green method has been employed for the synthesis of silver nanoparticles (AgNPs) using dried biomass of a green alga, Chlorella ellipsoidea. The phytochemicals from the alga, as a mild and non-toxic source, are believed to serve as both reducing and stabilizing agents. The formation of silver nanoparticles was confirmed from the appearance of a surface plasmon resonance band at 436 nm and energy dispersive X-ray spectroscopy. The transmission electron microscopy images showed the nanoparticles to be nearly spherical in shape with different sizes. A dynamic light scattering study revealed the average particle size to be 220.8 ± 31.3 nm. Fourier transform infrared spectroscopy revealed the occurrence of alga-derived phytochemicals attached to the outer surface of biogenically accessed silver nanoparticles. The powder X-ray diffraction study revealed the face-centred cubic crystalline structure of the nanoparticles. The as-synthesized biomatrix-loaded AgNPs exhibited a high photocatalytic activity for the degradation of the hazardous pollutant dyes methylene blue and methyl orange. The catalytic efficiency was sustained even after three reduction cycles. A kinetic study indicated the degradation rates to be pseudo-first order with the degradation rate being 4.72 × 10⁻² min⁻¹ for methylene blue and 3.24 × 10⁻² min⁻¹ for methyl orange. The AgNPs also exhibited significant antibacterial activity against four selected pathogenic bacterial strains.     

Synthesis and adsorption and luminescence properties of hydrophobic silver nanoparticles in the presence of pyrene

A procedure was developed for the synthesis of hydrophobic silver nanoparticles with an average size of 4 nm in two-phase water-organic emulsions. The physical properties of the obtained silver organosol were studied by molecular spectroscopy and electron microscopy. It was found that the synthesized silver nanoparticles had a specific surface of 60–110 m²/g. It was shown that chemically modified silver nanoparticles can be used as an adsorbent for preconcentrating polycyclic aromatic hydrocarbons (using pyrene as an example) from dilute n-hexane solutions followed by luminescence determination at room temperature.     

Green Synthesis of Silver Nanoparticles Using an Aqueous Extract of <Emphasis Type="Italic">Monotheca buxifolia</Emphasis> (Flac.) Dcne

This study deals with the synthesis and physicochemical investigation of silver nanoparticles using an aqueous extract of Monotheca buxifolia (Flac.). On the treatment of aqueous solution of silver nitrate with the plant extract, silver nanoparticles were rapidly fabricated. The synthesized particles were characterized by using UV–visible spectrophotometry (UV), Fourier transform infrared spectroscopy (FTIR), Energy dispersive X-ray (EDX) and Scanning electron microscopy (SEM). The formation of AgNPs was confirmed by noting the change in colour through visual observations as well as via UV–Vis spectroscopy. UV–Vis spectrum of the aqueous medium containing silver nanoparticles showed an absorption peak at around 440 nm. FTIR was used to identify the chemical composition of silver nanoparticles and Ag-capped plant extract. The presence of elemental silver was also confirmed through EDX analysis. The SEM analysis of the silver nanoparticles showed that they have a uniform spherical shape with an average size in the range of 40–78 nm. This green system showed better capping and stabilizing agent for the fine particles. Further, in vitro the antioxidant activity of Monotheca buxifolia (Flac.) and Ag-capped with the plant was also evaluated using FeCl₃/K₃Fe (CN)₆ essay.