Synthesis and characterization of silver nanoparticles and titanium oxide nanofibers : toward multifibrous nanocomposites

A new method was investigated to produce new multiscale fibrous nanocomposites comprised of titanium oxide (TiO₂) nanofibers and silver (Ag) nanoparticles (NPs). The process involved electrospinning TiO₂ precursor solution containing colloidal solution of Ag NPs, and organic solvent (dimethyl-n′n-formamide) to fabricate a porous, nonwoven, free-standing nanofiber mesh. Postprocess heating of the electrospun nanofibers entailed calcination in air environment at 500°C for 3 h. Microemulsion processing was used to generate NPs of Ag in a monodispersed distribution throughout the colloidal solution. X-ray diffraction data were consistent with the anatase phase of TiO2, while transmission electron microscopy and hydrogen desorption measurements revealed a very porous microstructure. It was demonstrated that NP colloidal stability is solvent dependent. It is anticipated that incorporation of metal particles in nanofibers will lead to enhanced photocurrent generation, when used in functional devices.

Extraction of silver(i) from aqueous solutions in the absence and presence of copper(ii) with a methimazole-based ionic liquid

The ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf₂], facilitates the efficient extraction of silver(i) from aqueous media via interaction with both the cation and anion components of the IL. Studies with a conventional aqueous-IL two phase system as well as microextraction of silver(i) by a thick IL film adhered to an electrode monitored in situ by cyclic voltammetry, established that [mimSBu][NTf₂] can extract electroactive silver(i) ions from an aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu]⁺, which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of silver(i) further increase the acidity of the aqueous phase as a consequence of coordination with the IL cation component. Voltammetric and ¹H and ¹³C NMR techniques have been used to establish the nature of the silver(i) complexes extracted, and show that the form of interaction with the IL differs from that outlined previously for the extraction of copper(ii). Insights on the competition established when silver(i) is extracted in the presence of copper(ii) are provided. Finally, it is noted that metallic silver can be directly electrodeposited at the electrode surface after extraction of silver(i) into [mimSBu][NTf₂] and that back extraction of silver(i) into aqueous media is achieved by addition of an acidic aqueous solution.

Optical phase change at the interface between mica and thin silver film

We describe a simple experiment which allows unequivocal determination of optical phase change upon reflection of light at the mica-silver interface. While the physical origin of such a phase change at the dielectric-metal interface is well understood to lie in absorption of electromagnetic energy by the metal, inconsistency and ambiguity has persisted as to what its sign and magnitude should be in the field of thin film optics. Most commonly, it has been assigned to be negative for mathematical convenience or just arbitrarily. Our finding shows that with the convention exp(-iωt) for time dependence of the electromagnetic wave, the phase change at the interface between mica and the thin silver film is necessarily positive and its magnitude falls between π and 3π/2 for silver thicknesses down to nanometres. This gives a physically reasonable correspondence to an increased equivalent thickness of the dielectric material, and it clarifies the assignment of interference orders in the harmonic series in a spectrum.

Kinetic effects of halide ions on the morphological evolution of silver nanoplates

Time-resolved extinction spectroscopy is employed to study the reaction kinetics in the shape-conversion reaction involving halide ions (including Cl-, Br- and I-) etching (sculpturing) silver nanoplates. A series of time-resolved extinction spectra are obtained during the in situ etching process and the evolution of surface plasmon resonance (SPR) of the silver nanoparticles is analyzed. Spectral analysis indicates that the conversion of nanoprisms starts simultaneously with the emergence of nanodisks when the halide ions are added. The etching rate of different halide ions is evaluated through the in-plane dipole resonance peak intensity of silver nanoplates vs. the reaction time (dI/dt). The relationship between the etching rate and the halide ion concentration shows that the halide ion etching reaction can be considered as a pseudo-first-order reaction. The effect of different halide ions on the shape-conversion of silver nanoplates is compared in detail. The activation energy of the etching reaction is calculated, which indicates that the etching ability of different halide ions is on the order of Cl - < I- < Br-.

Photochemical formation of silver nanodecahedra : structural selection by the excitation wavelength

Silver decahedra have been successfully synthesized with high yield via a photochemical reaction using blue light-emitting diodes (LEDs) as the exciting light source. The decahedra display distinct properties with respect to the ability of light scattering. The photochemical growth process of silver decahedra was monitored by both extinction and scattering spectral evolution. A suggested formation mechanism of silver decahedron is discussed.

Photoinduced shape conversion and reconstruction of silver nanoprisms

A series of shapes of silver nanoplates were achieved by adjusting the concentration of citrate in the colloid in the photoinduced process. The local surface plasmon resonance (LSPR) of the silver nanoplates could be tuned gradually in a range from 740 to 440 nm. In contrast, the LSPR band can be photomediated again to the long wavelength region within 620-690 nm only by adding more citrate to the colloidal system. The initial silver nanoprisms converted to the discal shape under the light effect. In this conversion, the coupling effect of the plasmon resonance and the light source speeds up the photothermal reaction. Subsequently, the reconstruction of silver nanoprisms from the nanodisks took place in the presence of more citrate through the photoconversion.

The facet selectivity of inorganic ions on silver nanocrystals in etching reactions

The facet selectivity of the halide ions and chlorauric acid for several shaped silver nanocrystals is presented in this paper. Two inorganic ions show different representations when they are used for etching silver nanocrystals in the self-sacrificial template reaction. The morphological changes of the silver nanocrystals indicate that the halide ions prefer to etch the (110) facets of silver nanocrystals, while in the chlorauric acid etching reaction, gold first modifies the (110) facets and then lets chlorauric acid etch the (111) facets instead. The selective facet etching on individual nanoparticles in the solution phase has crucial significance in the control-synthesis of nanocrystals and the facet asymmetric reaction.

Real-time, in-situ, extinction spectroscopy studies on silver-nanoseed formation

In this paper, real-time extinction spectroscopy was employed to analyze in situ the fast formation process of silver seeds. The influencing factors for silver-seed formation, including the concentration of the reducer (NaBH 4), the amount of stabilizer (citrate), and the addition procedure of NaBH4, were evaluated. The configuration of the surface plasmon resonance (SPR) spectra of silver nanoparticles, which reflected the morphology of the produced silver seeds, was found to be distinctly affected by the NaBH4 concentration. Homogeneous silver nanoparticles were obtained when the added NaBH4 was lower in concentration than 2.00 mM. In contrast, higher concentrations of reducing agent (>3.00 mM NaBH4) resulted in uneven silver nanoparticles. Mie theory was applied to clarify the correlation of the SPR and the size of the silver seeds. Repeated additions of a small amount of the reducing agent could increase the monodispersity and isotropy of silver seeds. Real-time extinction spectroscopy is a convenient technique that achieves the in-situ and nondestructive measurement of intermediates in the formation process of silver nanoseeds.

Corneal staining and cell shedding during the development of solution-induced corneal staining

Purpose. This non-dispensing cross-over study was conducted to determine if lenses presoaked in Opti-Free RepleniSH (OFR) or ReNu MultiPlus (RMP) cause solution-induced corneal staining (SICS) and subsequent cell sloughing before the typical 2 h in vivo examination point.

Methods. Study lenses (PureVision) were worn bilaterally by 13 participants for periods of 15, 30, 60, and 120 min using two different contralateral care regimen pairings. The lens worn on the test eye was soaked overnight in either OFR or RMP and the control eye in Clear Care (CC). After lens removal, corneal staining was rated on a scale of 0 (negligible) to 100 (severe) for four peripheral quadrants and the central region, and the differential global staining score was calculated by subtracting baseline staining scores. Following the staining assessment, corneal cells were collected from the ocular surface using a non-contact irrigation system to determine ocular cell shedding rates.

Results. Differential global staining score with OFR was greater than CC with the differences being statistically significant at 30 and 60 min (p < 0.01). Maximum staining with RMP was significantly greater than OFR and peaked after 60 and 120 min of lens wear (p < 0.01). On average, 710 ± 470 ocular cells were collected after lens wear, with similar shedding seen independent of solution or lens wear duration (p > 0.05).

Conclusions. SICS occurred earlier but to a significantly lower degree when PureVision lenses were presoaked in OFR compared with RMP, while lenses presoaked in CC did not cause SICS. Ocular surface cell shedding after lens removal was not impacted by lens wear durations of <=2 h.

Corneal staining as a response to contact lens wear

Objective: To review the effects of contact lenses on the corneal surface.

Methods: A review of the literature and in-house research of corneal staining and its various forms of presentation.

Results: Corneal staining manifests in many different forms. The severity of staining or insult of the cornea is usually determined by the extent (area of coverage), density, and depth. The cause of staining is multifactorial, and its location is often linked to the type of lens that is being worn, the solution used to clean/disinfect the lens, the state of hydration of the soft lens, and the state of the cornea that has been affected by the lens.

Conclusions: Sodium fluorescein dye effectively highlights corneal integrity changes referred to as corneal staining. This review describes the manifestations, the cause, the mechanisms, and the methods of remediation of corneal staining.

Impact of a rub and rinse on solution-induced corneal staining

Purpose. To investigate whether the inclusion of a rub and rinse step before contact lens disinfection has an impact on solution-induced corneal staining.

Methods. This was a prospective, double-masked, single investigator study. Twenty participants were recruited for two visits, where balafilcon-A lenses were worn bilaterally for 2 h. Each pair of lenses was prepared using two different methodologies. The “control” lens was transferred from the blister pack directly into a storage case containing polyhexamethylene biguanide-based lens care solution. The contralateral “test” lens was rubbed and simultaneously rinsed using the same polyhexamethylene biguanide-based care solution, for either 60 s (visit 1) or 20 s (visit 2). Both lenses were then soaked in the solution overnight. After baseline corneal staining assessments, the lenses were inserted following a randomized contralateral model. After 2 h, lenses were removed, corneal staining was regraded, and comfort scores were obtained.

Results. Rubbed and rinsed test lenses induced significantly less corneal staining than control lenses for all participants during visit 1 (mean ± SD: 516 ± 843 vs. 2170 ± 902; p < 0.001) and visit 2 (522 ± 417 vs. 2091 ± 965; p < 0.001). There was no significant difference between the test lenses during visits 1 and 2 (p = 0.72) or controls (p = 0.50). Comfort scores did not differ between eyes (p > 0.05).

Conclusions. Corneal staining induced after 2 h of lens wear with the combination of balafilcon-A and polyhexamethylene biguanide-based lens care solution can be significantly reduced by including a rub and rinse step before overnight soaking. Further work is required to establish the longevity of this effect during the monthly wearing cycle.