The Optimization of the One-Pot Synthesis of Au@SiO2Core-Shell Nanostructures: Modification with Dansyl Group and Their Fluorescent Properties.

This work describes the optimization of the one-pot synthesis of fine core-shell nanostructures based on nanogold (Au NPs) and silica (SiO2). The obtained core-shell nanomaterials were characterized by Transmission Electron Microscopy (TEM and by the method of spectroscopes such as UV-Vis Spectroscopy and Fourier Transform Infrared Spectroscopy (FT-IR). In addition, the measurement of the zeta potential and size of the obtained particles helped present a full characterization of Au@SiO2 nanostructures. The results show that the influence of reagents acting as reducers, stabilizers, or precursors of the silica shell affects the morphology of the obtained material. By controlling the effect of the added silica precursor, the thickness of the shell can be manipulated, the reducer has an effect on the shape and variety, and then the stabilizer affects their agglomeration. This work provides also a new approach for Au@SiO2core-shell nanostructure preparation by further modification with dansyl chloride (DNS-Cl). The results show that, by tuning the silica shell thickness, the intensity of the fluorescence spectrum of Au@SiO2-(CH2)3-NH-DNS nanocomposite is about 12 times higher than that of DNS-Cl.

Medical Applications of Silver and Gold Nanoparticles and Core-Shell Nanostructures Based on Silver or Gold Core: Recent Progress and Innovations.

Nanoparticles (NPs) of noble metals such as silver (Ag NPs) or gold (Au NPs) draw the attention of scientists looking for new compounds to use in medical applications. Scientists have used metal NPs because of their easy preparation, biocompatibility, ability to influence the shape and size or modification, and surface functionalization. However, to fully use their capabilities, both the benefits and their potential threats should be considered. One possibility to reduce the potential threat and thus prevent the extinction of their properties resulting from the agglomeration, they are covered with a neutral material, thus obtaining core-shell nanostructures that can be further modified and functionalized depending on the subsequent application. In this review, we focus on discussing the properties and applications of Ag NPs and Au NPs in the medical field such as the treatment of various diseases, drug carriers, diagnostics, and many others. In addition, the following review also discusses the use and potential applications of Ag@SiO2 and Au@SiO2 core-shell nanostructures, which can be used in cancer therapy and diagnosis, treatment of infections, or tissue engineering.

Novelty Cosmetic Filters Based on Nanomaterials Composed of Titanium Dioxide Nanoparticles.

The following work describes the synthesis of new physical filters based on TiO2/SiO2 and TiO2/Ag nanostructures. Titanium dioxide nanoparticles (TiO2 NPs) were applied as control material and a popular physical UV filter. The advantage of using materials on the nanometer scale is the elimination of the skin whitening effect that occurs when using photoprotective cosmetics containing titanium dioxide on a macro scale. In addition, the silica coating makes the material less harmful, and the silver coating enriches the material with antibacterial properties. Nanoparticles and nanostructures have been characterized by Energy Dispersive X-Ray Analysis (EDX), the Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), and Fourier-Transform Infrared Spectroscopy (FT-IR) methods. Due to the use of physical filters in anti-radiation protection cosmetics, water-in-oil (W/O) emulsion has been prepared. All cosmetic formulations have been tested for stability. The sun protection research with the Sun Protection Diagnostic SP37 was carried out. These studies made it possible to determine the natural sun protection time and to compare the synthesized materials. Furthermore, one of the most important parameters when describing this type of cosmetic is water resistance, which has also been measured. The results show that the new type of material of TiO2/Ag used as a new physical filter in emulsion W/O shows the best sun protection compared with other obtained nanomaterials. It is most likely due to the improved optical properties of the combination of noble metals, for example, silver with TiO2.

New Core-Shell Nanostructures for FRET Studies: Synthesis, Characterization, and Quantitative Analysis.

This work describes the synthesis and characterization of new core-shell material designed for Förster resonance energy transfer (FRET) studies. Synthesis, structural and optical properties of core-shell nanostructures with a large number of two kinds of fluorophores bound to the shell are presented. As fluorophores, strongly fluorescent rhodamine 101 and rhodamine 110 chloride were selected. The dyes exhibit significant spectral overlap between acceptor absorption and donor emission spectra, which enables effective FRET. Core-shell nanoparticles strongly differing in the ratio of donors to acceptor numbers were prepared. This leads to two different interesting cases: typical single-step FRET or multistep energy migration preceding FRET. The single-step FRET model that was designed and presented by some of us recently for core-shell nanoparticles is herein experimentally verified. Very good agreement between the analytical expression for donor fluorescence intensity decay and experimental data was obtained, which confirmed the correctness of the model. Multistep energy migration between donors preceding the final transfer to the acceptor can also be successfully described. In this case, however, experimental data are compared with the results of Monte Carlo simulations, as there is no respective analytical expression. Excellent agreement in this more general case evidences the usefulness of this numerical method in the design and prediction of the properties of the synthesized core-shell nanoparticles labelled with multiple and chemically different fluorophores.

Characterization and Cytotoxicity Comparison of Silver- and Silica-Based Nanostructures.

Core-shell structures are the most common type of composite material nanostructures due to their multifunctional properties. Silver nanoparticles show broad antimicrobial activity, but the safety of their utilization still remains an issue to tackle. In many applications, the silver core is coated with inorganic shell to reduce the metal toxicity. This article presents the synthesis of various materials based on silver and silica nanoparticles, including SiO2@Ag, Ag@SiO2, and sandwich nanostructures-Ag@SiO2@Ag-and the morphology of these nanomaterials based on transmission electron microscopy (TEM), UV-Vis spectroscopy, and FT-IR spectroscopy. Moreover, we conducted the angle measurements due to the strong relationship between the level of surface wettability and cell adhesion efficiency. The main aim of the study was to determine the cytotoxicity of the obtained materials against two types of human skin cells-keratinocytes (HaCaT) and fibroblasts (HDF). We found that among all the obtained structures, SiO2@Ag and Ag@SiO2 showed the lowest cell toxicity and very high half-maximal inhibitory concentration. Moreover, the measurements of the contact angle showed that Ag@SiO2 nanostructures were different from other materials due to their superhydrophilic nature. The novel approach presented here shows the promise of implementing core-shell type nanomaterials in skin-applied cosmetic or medical products.

Dansyl-Labelled Ag@SiO2 Core-Shell Nanostructures-Synthesis, Characterization, and Metal-Enhanced Fluorescence.

The present work describes synthesis, characterization, and use of a new dansyl-labelled Ag@SiO2 nanocomposite as an element of a new plasmonic platform to enhance the fluorescence intensity. Keeping in mind that typical surface plasmon resonance (SPR) characteristics of silver nanoparticles coincide well enough with the absorption of dansyl molecules, we used them to build the core of the nanocomposite. Moreover, we utilized 10 nm amino-functionalized silica shell as a separator between silver nanoparticles and the dansyl dye to prevent the dye-to-metal energy transfer. The dansyl group was incorporated into Ag@SiO2 core-shell nanostructures by the reaction of aminopropyltrimethoxysilane with dansyl chloride and we characterized the new dansyl-labelled Ag@SiO2 nanocomposite using transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR). Additionally, water wettability measurements (WWM) were carried out to assess the hydrophobicity and hydrophilicity of the studied surface. We found that the nanocomposite deposited on a semitransparent silver mirror strongly increased the fluorescence intensity of dansyl dye (about 87-fold) compared with the control sample on the glass, proving that the system is a perfect candidate for a sensitive plasmonic platform.

Efficient Method for the Concentration Determination of Fmoc Groups Incorporated in the Core-Shell Materials by Fmoc-Glycine.

In this paper, we described the synthesis procedure of TiO2@SiO2 core-shell modified with 3-(aminopropyl)trimethoxysilane (APTMS). The chemical attachment of Fmoc-glycine (Fmoc-Gly-OH) at the surface of the core-shell structure was performed to determine the amount of active amino groups on the basis of the amount of Fmoc group calculation. We characterized nanostructures using various methods: transmission electron microscope (TEM), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) to confirm the modification effectiveness. The ultraviolet-visible spectroscopy (UV-vis) measurement was adopted for the quantitative determination of amino groups present on the TiO2@SiO2 core-shell surface by determination of Fmoc substitution. The nanomaterials were functionalized by Fmoc-Gly-OH and then the fluorenylmethyloxycarbonyl (Fmoc) group was cleaved using 20% (v/v) solution of piperidine in DMF. This reaction led to the formation of a dibenzofulvene-piperidine adduct enabling the estimation of free Fmoc groups by measurement the maximum absorption at 289 and 301 nm using UV-vis spectroscopy. The calculations of Fmoc loading on core-shell materials was performed using different molar absorption coefficient: 5800 and 6089 dm3 × mol-1 × cm-1 for λ = 289 nm and both 7800 and 8021 dm3 × mol-1 × cm-1 for λ = 301 nm. The obtained results indicate that amount of Fmoc groups present on TiO2@SiO2-(CH2)3-NH2 was calculated at 6 to 9 µmol/g. Furthermore, all measurements were compared with Fmoc-Gly-OH used as the model sample.

Hydrogen bonding and protonation effects in amino acids' anthraquinone derivatives - Spectroscopic and electrochemical studies.

Six novel amino acid chromophores were synthesized and their spectroscopic, acid-base, and electrochemical properties are discussed in this work. In studied compounds, selected amino acid residues (l-Aspartic acid, l-Glutamic acid, l-Glutamine, l-Histidine, l-Lysine, l-Arginine) are attached to the 1-(piperazine) 9,10-anthraquinone skeleton via the amide bond between the carboxyl group of amino acid and nitrogen atom of the piperazine ring. All derivatives have been characterized using a variety of spectroscopic techniques (mass spectrometry, 1HNMR, UV-Vis, IR spectroscopy), acid-base (electrochemical and UV-Vis) titrations, and cyclic voltammetry methods. Basing on observed experimental effects, supported by quantum chemical simulations, the structure-properties links were established. They are indicative of the specific interactions within and/or in-between amino acid side groups, which are prone to form both, intra- and intermolecular hydrogen bonds as well as electrostatic interactions with the anthraquinone system.

Steady State and Time Resolved Fluorescence Studies of Azadioxatriangulenium (ADOTA) Fluorophore in Silica and PVA Thin Films.

A cationic azadioxatriangulenium (ADOTA) dye was entrapped in silica thin films obtained by the sol-gel process and in poly (vinyl) alcohol (PVA) thin films. Azadioxatriangulenium is a red emitting fluorophore with a long fluorescence lifetime of ~20 ns. The fluorescent properties of azadioxatriangulenium in silica thin films and PVA films were studied by means of steady-state and time resolved fluorescence techniques. We have found that the azadioxatriangulenium entrapped in silica thin film has a wider fluorescence lifetime distribution (Lorentzian distribution), lower fluorescence efficiencies, shorter lifetimes compared to Azadioxatriangulenium in a PVA film. The local environment of azadioxatriangulenium molecules in the silica thin film is rich with water and ethanol, which creates the possibility of forming excited state aggregates due to high concentration of dye within a small confined area. In contrast to the PVA matrices, the porous silica films allow restricted rotations of Azadioxatriangulenium molecules, which result in faster and complex fluorescence anisotropy decays suggesting energy migration among dye molecules.

Synthesis of α-collagen fragments and research of their influence on the degree of hydration of a model of epidermis.

INTRODUCTION: In recent years the interest into areas of science, such as cosmetology, dermatology, pharmacology or aesthetic medicine has increased significantly. Scientists are more frequently looking for ingredients that affect the skin's condition and slow down the aging process. Practically every year, the scientists discover a number of new chemical substances (both natural and synthetic) that can be potentially used to manufacture cosmetics. AIM: To evaluate the influence of selected peptides derived from α-collagen fragments on the degree of hydration of a model of epidermis isolated from a pig. MATERIAL AND METHODS: The synthesis of selected cosmetic oligopeptides were performed manually, on the solid medium, using procedure of SPPS (solid phase peptide synthesis). Following components: aqua, carbomer, glycerine, phenonip, D-panthenol, dimethicone and triethanolamine were used to prepare a reference hydrogel masks. Both the number of components and the composition of hydrogels have been developed individually for the purposes of this research. For this study the skin from a domestic pig was used. The degree of the skin hydration was measured with the SKINTEST plus camera, which uses the latest semiconductor technology. RESULTS: During the study the absorption of hydrogels with peptides was faster than that of the reference hydrogel mask. The combination of hydrophilic properties of the peptide with hydrophobic properties of Palm enabled receiving an amphiphilic structure. Such molecules are considered to be able to penetrate the corneum barrier with the greatest ease. CONCLUSIONS: The results showed that the modified compounds have contributed to water retention in the cells, thereby increasing the degree of hydration of the biological material.

Time-resolved emission spectra of 4-dimethylamino-4'-cyano-stilbene and resveratrol in high viscosity solvents and silica matrices.

Time-resolved emission spectra of 4-dimethylamino-4'-cyano-stilbene (DMACS) and 3,5,4'-trihydroxy-stilbene (resveratrol, RSV) in propylene glycol and in rigid silica xerogel matrix at 23°C were studied. For the polar molecule DMACS in propylene glycol, a 66nm shift of maximum wavelength of emission spectra was observed within 1ns after excitation, and most of the shift occurred during the first 200ps. For resveratrol in propylene glycol no such a shift was observed. The rigid silica environment eliminates some deactivation pathways and stabilizes spectroscopic properties of both molecules. Spectral properties of nonpolar and high dipole moment molecules in viscous liquids and rigid environments are compared. Results are explained on the basis of intramolecular processes and solute-solvent relaxation, as well.

Surface Plasmon-Coupled Emission of Rhodamine 110 Aggregates in a Silica Nanolayer.

First analysis of strong directional surface plasmon-coupled emission (SPCE) of ground-state formed intermolecular aggregates of Rhodamine 110 (R110) in silica nanofilms deposited on silver nanolayers is reported. Until now, the processes of energy transport and its trapping due to aggregate formation have not been studied in the presence of SPCE. A new approach to multicomponent systems with weakly and strongly fluorescent centers making use of fluorophore-surface plasmon interaction is presented. The analysis is based on comparison of experimental free-space emission spectra (F-SE), experimental SPCE with theoretical surface plasmon resonance spectra (SPR). It is shown that, due to the dispersion of SPCE, the detection of weak aggregate emission is straightforward if only the monomers and aggregates fluorescence spectra are somewhat spectrally shifted. SPCE studies confirmed the formation of weakly fluorescent higher order aggregates of R110 in silica films. The results indicate that the increase of energy transfer from monomers to aggregates is due to fluorophore-plasmon interaction.

Surface-plasmon-coupled emission of Rhodamine 110 in a silica nanolayer.

The first observation of strong directional surface-plasmon-coupled emission (SPCE) of Rhodamine 110 in silica nanofilms deposited on silver nanolayers is reported. The preparation of the material is described in detail. The intensity of SPCE exceeds 10 times that of free space fluorescence and total linear light polarization in the SPCE ring is observed. A new experimental setup and an original data collection method is presented. Our material completely preserves its fluorescence properties for at least eight months.