Sol-Gel Photonic Glasses: From Material to Application.

In this review, we present a short overview of the development of sol-gel glasses for application in the field of photonics, with a focus on some of the most interesting results obtained by our group and collaborators in that area. Our main attention is devoted to silicate glasses of different compositions, which are characterized by specific optical and spectroscopic properties for various applications, ranging from luminescent systems to light-confining structures and memristors. In particular, the roles of rare-earth doping, matrix composition, the densification process and the fabrication protocol on the structural, optical and spectroscopic properties of the developed photonic systems are discussed through appropriate examples. Some achievements in the fabrication of oxide sol-gel optical waveguides and of micro- and nanostructures for the confinement of light are also briefly discussed.

Cation-Exchange in Metal-Organic Framework as a Strategy to Obtain New Material for Ascorbic Acid Detection.

Ascorbic acid (AA) is an important biomolecule, the deficiency or maladjustment of which is associated with the symptoms of many diseases (e.g., cardiovascular disease or cancer). Therefore, there is a need to develop a fluorescent probe capable of detecting AA in aqueous media. Here, we report the synthesis, structural, and spectroscopic characterization (by means of, e.g., XRD, XPS, IR and Raman spectroscopy, TG, SEM, and EDS analyses), as well as the photoluminescent properties of a metal-organic framework (MOF) based on Cu2+ and Eu3+ ions. The ion-exchange process of the extraframework cation in anionic Cu-based MOF is proposed as an appropriate strategy to obtain a new material with a nondisturbed structure and a sensitivity to interaction with AA. Accordingly, a novel Eu[Cu3(µ3-OH)(µ3-4-carboxypyrazolato)3] compound for the selective optical detection of AA with a short detection time of 5 min is described.

Novel CaO-SiO2-P2O5 Nanobioglass Activated with Hafnium Phthalocyanine.

Bioactive glasses are materials which can be used in medicine for regeneration of hard and soft tissues. Their functionalization with active molecules or addition to composites broaden significantly the possible range of glass applications. Hereby, we describe photoactive nanoparticles of CaO-SiO2-P2O5 glass modified with dichlorohafnium (IV) phthalocyanine. The low-temperature, sol-gel based reverse micelle method was proposed for the synthesis, which allowed introduction of metal organic molecules into the glass composition. The morphology, structure, and composition of the material was described showing that spherical but agglomerated glass nanoparticles (size below 100 nm) were obtained in the ternary system. It was also shown that optical properties of the phthalocyanine complex were maintained after immobilization of the dye in the glass. The photoluminescence and generation of singlet oxygen molecules were observed under the light irradiation of the glass.

Eu3+ as a Powerful Structural and Spectroscopic Tool for Glass Photonics.

The unique properties of the Eu3+ ion make it a powerful spectroscopic tool to investigate structure or follow processes and mechanisms in several high-tech application areas such as biology and health, structural engineering, environment monitoring systems and quantum technology, mainly concerning photonics. The traditional method is to exploit the unique photoluminescent properties of Eu3+ ions to understand complex dynamical processes and obtain information useful to develop materials with specific characteristics. The objective of this review is to focus on the use of Eu3+ optical spectroscopy in some condensed matter issues. After a short presentation of the more significant properties of the Eu3+ ion, some examples regarding its use as a probe of the local structure in sol-gel systems are presented. Another section is devoted to dynamical processes such as the important technological role of nanocrystals as rare-earth sensitizers. The appealing effect of the site-selection memory, observed when exciting different sites into the 5D1 state, which the 5D0 → 7F0 emission band reflects following the sites' distribution, is also mentioned. Finally, a section is devoted to the use of Eu3+ in the development of a rare-earth-based platform for quantum technologies.

Solvothermally-derived nanoglass as a highly bioactive material.

A highly bioactive glass solvBG76 in a binary system 76SiO2-24CaO (wt%) was prepared following a solvothermal path of the synthesis. The facile synthesis, in terms of the steps and reagents needed, enabled the achievement of a mesoporous material. Many factors such as nano-size (<50 nm), different morphology (non-spherical), use of an unconventional network modifier (calcium hydroxide) during the synthesis, a structure free of crystalline impurities, and textural properties greatly enhanced the kinetic deposition process of hydroxyapatite (HA) when contacting with physiological fluids. The formation of a HA layer on the glass was analyzed by various techniques, namely XRD, IR-ATR, Raman, XPS, EDS analyses, SEM, and HR-TEM imaging. The results obtained were compared to the 45S5 glass tested as a reference biomaterial as well as 70S30C-a glass with similar size and composition to reported solvBG76 but obtained by the conventional sol-gel method. For the first time, superior apatite-mineralization ability in less than 1 h in a physiological-like buffer was achieved. This unique bioactivity is accompanied by biocompatibility and hemocompatibility, which was indicated by a set of various assays in human dermal fibroblasts and MC3T3 mouse osteoblast precursor cells, as well as hemolytic activity determination.

The Impact of Graphite Oxide Nanocomposites on the Antibacterial Activity of Serum.

Nanoparticles can interact with the complement system and modulate the inflammatory response. The effect of these interactions on the complement activity strongly depends on physicochemical properties of nanoparticles. The interactions of silver nanoparticles with serum proteins (particularly with the complement system components) have the potential to significantly affect the antibacterial activity of serum, with serious implications for human health. The aim of the study was to assess the influence of graphite oxide (GO) nanocomposites (GO, GO-PcZr(Lys)2-Ag, GO-Ag, GO-PcZr(Lys)2) on the antibacterial activity of normal human serum (NHS), serum activity against bacteria isolated from alveoli treated with nanocomposites, and nanocomposite sensitivity of bacteria exposed to serum in vitro (using normal human serum). Additionally, the in vivo cytotoxic effect of the GO compounds was determined with application of a Galleria mellonella larvae model. GO-PcZr(Lys)2, without IR irradiation enhance the antimicrobial efficacy of the human serum. IR irradiation enhances bactericidal activity of serum in the case of the GO-PcZr(Lys)2-Ag sample. Bacteria exposed to nanocomposites become more sensitive to the action of serum. Bacteria exposed to serum become more sensitive to the GO-Ag sample. None of the tested GO nanocomposites displayed a cytotoxicity towards larvae.

Patterns of Oral Microbiota in Patients with Apical Periodontitis.

In this study, microbial diversity of the root canal microbiota related to different endodontic infections was investigated. In total, 45 patients with endo-perio lesions (8 patients), chronic periapical periodontitis (29 patients) and pulp necrosis (8 patients) were recruited. In 19 (42.2%) patients there was secondary infection of root canals. Microbial specimens were collected from root canals of non-vital teeth with or without changes in periapical area visible in X-ray. Then, oral microbiota were detected and identified using the culture method and real-time PCR amplification primers and hydrolysis-probe detection with the 16S rRNA gene as the target. Overall, 1434 species/genes from 41 different genera of 90 various microbial species were retrieved. Of the major reported phyla, Firmicutes (62.9%), Actinobacteria (14.0%), Bacteroidetes (12.1%), Proteobacteria (9.1%) and Fusobacteria (4.2%) were detected. Of the bacterial species, 54.6% were strict anaerobes. Corynebacterium matruchotii (p = 0.039) was present significantly more frequently in chronic periapical periodontitis. Moreover, the higher values of Decayed, Missing and Filled Permanent Teeth index were positively correlated with relative abundance of Actinomyces spp. (p = 0.042), Lactobacillus spp. (p = 0.006), Propionibacterium spp. (p = 0.024) and Rothia spp. (p = 0.002). The multivariate analyses revealed differences in total root canal samples, where components that affected grouping of root samples into four main categories were identified. Anaerobic Gram-negative bacteria predominated in root canals of teeth with pulp necrosis and periapical lesions. Facultative anaerobic Gram-positive bacteria predominated in canals with secondary infections. All detected members of mixed population groups that might serve as keystone species contributed to the entire community in its clinical relevance.

Upconversion Luminescence of Silica-Calcia Nanoparticles Co-doped with Tm3+ and Yb3+ Ions.

Looking for upconverting biocompatible nanoparticles, we have prepared by the sol-gel method, silica-calcia glass nanopowders doped with different concentration of Tm3+ and Yb3+ ions (Tm3+ from 0.15 mol% up to 0.5 mol% and Yb3+ from 1 mol% up to 4 mol%) and characterized their structure, morphology, and optical properties. X-ray diffraction patterns indicated an amorphous phase of the silica-based glass with partial crystallization of samples with a higher content of lanthanides ions. Transmission electron microscopy images showed that the average size of particles decreased with increasing lanthanides content. The upconversion (UC) emission spectra and fluorescence lifetimes were registered under near infrared excitation (980 nm) at room temperature to study the energy transfer between Yb3+ and Tm3+ at various active ions concentrations. Characteristic emission bands of Tm3+ ions in the range of 350 nm to 850 nm were observed. To understand the mechanism of Yb3+-Tm3+ UC energy transfer in the SiO2-CaO powders, the kinetics of luminescence decays were studied.

Modification of insulin amyloid aggregation by Zr phthalocyanines functionalized with dehydroacetic acid derivatives.

Amyloid fibrils are widely studied both as target in conformational disorders and as basis for the development of protein-based functional materials. The three Zr phthalocyanines bearing dehydroacetic acid residue (PcZr(L1)2) and its condensed derivatives (PcZr(L2)2 and PcZr(L3)2) as out-of-plane ligands were synthesized and their influence on insulin fibril formation was studied by amyloid-sensitive fluorescent dye based assay, scanning electron microscopy, fluorescent and absorption spectroscopies. The presence of Zr phthalocyanines was shown to modify the fibril formation. The morphology of fibrils formed in the presence of the Zr phthalocyanines differs from that of free insulin and depends on the structure of out-of-plane ligands. It is shown that free insulin mostly forms fibril clusters with the length of about 0.3-2.1 µm. The presence of Zr phthalocyanines leads to the formation of individual 0.4-2.8 µm-long fibrils with a reduced tendency to lateral aggregation and cluster formation (PcZr(L1)2), shorter 0.2-1.5 µm-long fibrils with the tendency to lateral aggregation without clusters (PcZr(L2)2), and fibril-like 0.2-1.0 µm-long structures (PcZr(L3)2). The strongest influence on fibrils morphology made by PcZr(L3)2 could be explained by the additional stacking of phenyl moiety of the ligand with aromatic amino acids in protein. The evidences of binding of studied Zr phthalocyanines to mature fibrils were shown by absorption spectroscopy (for PcZr(L1)2 and PcZr(L2)2) and fluorescent spectroscopy (for PcZr(L3)2). These complexes could be potentially used as external tools allowing the development of functional materials on protein fibrils basis.

A Facile Synthesis and Characterization of Highly Crystalline Submicro-Sized BiFeO3.

In this study, a highly crystalline bismuth ferrite (BFO) powder was synthesized using a novel, very simple, and cost-effective synthetic approach. It was demonstrated that the optimal annealing temperature for the preparation of highly-pure BFO is 650 °C. At lower or higher temperatures, the formation of neighboring crystal phases was observed. The thermal behavior of BFO precursor gel was investigated by thermogravimetric and differential scanning calorimetry (TG-DSC) measurements. X-ray diffraction (XRD) analysis and Mössbauer spectroscopy were employed for the investigation of structural properties. Scanning electron microscopy (SEM) was used to evaluate morphological features of the synthesized materials. The obtained powders were also characterized by magnetization measurements, which showed antiferromagnetic behavior of BFO powders.

Photonic Crystal Stimuli-Responsive Chromatic Sensors: A Short Review.

Photonic crystals (PhC) are spatially ordered structures with lattice parameters comparable to the wavelength of propagating light. Their geometrical and refractive index features lead to an energy band structure for photons, which may allow or forbid the propagation of electromagnetic waves in a limited frequency range. These unique properties have attracted much attention for both theoretical and applied research. Devices such as high-reflection omnidirectional mirrors, low-loss waveguides, and high- and low-reflection coatings have been demonstrated, and several application areas have been explored, from optical communications and color displays to energy harvest and sensors. In this latter area, photonic crystal fibers (PCF) have proven to be very suitable for the development of highly performing sensors, but one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) PhCs have been successfully employed, too. The working principle of most PhC sensors is based on the fact that any physical phenomenon which affects the periodicity and the refractive index of the PhC structure induces changes in the intensity and spectral characteristics of the reflected, transmitted or diffracted light; thus, optical measurements allow one to sense, for instance, temperature, pressure, strain, chemical parameters, like pH and ionic strength, and the presence of chemical or biological elements. In the present article, after a brief general introduction, we present a review of the state of the art of PhC sensors, with particular reference to our own results in the field of mechanochromic sensors. We believe that PhC sensors based on changes of structural color and mechanochromic effect are able to provide a promising, technologically simple, low-cost platform for further developing devices and functionalities.

Consequences Of Long-Term Bacteria's Exposure To Silver Nanoformulations With Different PhysicoChemical Properties.

PURPOSE: Resistance to antibiotics is a major problem of public health. One of the alternative therapies is silver - more and more popular because of nanotechnology development and new possibilities of usage. As a component of colloid, powder, cream, bandages, etc., nanosilver is often recommended to treat the multidrug-resistant pathogens and we can observe its overuse also outside of the clinic where different physicochemical forms of silver nanoformulations (e.g. size, shape, compounds, surface area) are introduced. In this research, we described the consequences of long-term bacteria exposure to silver nanoformulations with different physicochemical properties, including changes in genome and changes of bacterial sensitivity to silver nanoformulations and/or antibiotics. Moreover, the prevalence of exogenous resistance to silver among multidrug-resistant bacteria was determined. MATERIALS AND METHODS: Gram-negative and Gram-positive bacteria strains are described as sensitive and multidrug-resistant strains. The sensitivity of the tested bacterial strains to antibiotics was carried out with disc diffusion methods. The sensitivity of bacteria to silver nanoformulations and development of bacterial resistance to silver nanoformulations has been verified via determination of the minimal inhibitory concentrations. The presence of sil genes was verified via PCR reaction and DNA electrophoresis. The genomic and phenotypic changes have been verified via genome sequencing and bioinformatics analysis. RESULTS: Bacteria after long-term exposure to silver nanoformulations may change their sensitivity to silver forms and/or antibiotics, depending on the physicochemical properties of silver nanoformulations, resulting from phenotypic or genetic changes in the bacterial cell. Finally, adaptants and mutants may become more sensitive or resistant to some antibiotics than wild types. CONCLUSION: Application of silver nanoformulations in the case of multiple resistance or multidrug-resistant bacterial infection can enhance or decrease their resistance to antibiotics. The usage of nanosilver in a clinic and outside of the clinic should be determined and should be under strong control. Moreover, each silver nanomaterial should be considered as a separate agent with a potential different mode of antibacterial action.

Ferromagnetic-like behavior of Bi0.9La0.1FeO3-KBr nanocomposites.

We studied magnetostatic response of the Bi0.9La0.1FeO3- KBr composites (BLFO-KBr) consisting of nanosized (≈100 nm) ferrite Bi0.9La0.1FeO3 (BLFO) conjugated with fine grinded ionic conducting KBr. When the fraction of KBr is rather small (less than 15 wt%) the magnetic response of the composite is very weak and similar to that observed for the BLFO (pure KBr matrix without Bi1-xLaxFeO3 has no magnetic response as anticipated). However, when the fraction of KBr increases above 15%, the magnetic response of the composite changes substantially and the field dependence of magnetization reveals ferromagnetic-like hysteresis loop with a remanent magnetization about 0.14 emu/g and coercive field about 1.8 Tesla (at room temperature). Nothing similar to the ferromagnetic-like hysteresis loop can be observed in Bi1-zLazFeO3 ceramics with z ≤ 0.15, which magnetization quasi-linearly increases with magnetic field. Different physical mechanisms were considered to explain the unusual experimental results for BLFO-KBr nanocomposites, but only those among them, which are highly sensitive to the interaction of antiferromagnetic Bi0.9La0.1FeO3 with ionic conductor KBr, can be relevant.

2D Optical Gratings Based on Hexagonal Voids on Transparent Elastomeric Substrate.

A chromatic vectorial strain sensor constituted by hexagonal voids on transparent elastomeric substrate has been successfully fabricated via soft colloidal lithography. Initially a highly ordered 1.6 microns polystyrene spheres monolayer colloidal crystal has been realized by wedge-shaped cell method and used as a suitable mold to replicate the periodic structure on a polydimethylsiloxane sheet. The replicated 2D array is characterized by high periodicity and regularity over a large area, as evidenced by morphological and optical properties obtained by means of SEM, absorption and reflectance spectroscopy. In particular, the optical features of the nanostructured elastomer have been investigated in respect to uniaxial deformation up to 10% of its initial length, demonstrating a linear, tunable and reversible response, with a sensitivity of 4.5 ± 0.1 nm/%. Finally, it has been demonstrated that the specific geometrical configuration allows determining simultaneously the vectorial strain-stress information in the x and y directions.

Similarities and Differences between Silver Ions and Silver in Nanoforms as Antibacterial Agents.

Silver is considered as antibacterial agent with well-known mode of action and bacterial resistance against it is well described. The development of nanotechnology provided different methods for the modification of the chemical and physical structure of silver, which may increase its antibacterial potential. The physico-chemical properties of silver nanoparticles and their interaction with living cells differs substantially from those of silver ions. Moreover, the variety of the forms and characteristics of various silver nanoparticles are also responsible for differences in their antibacterial mode of action and probably bacterial mechanism of resistance. The paper discusses in details the aforementioned aspects of silver activity.

Antimicrobial graphene family materials: Progress, advances, hopes and fears.

Graphene-based materials have become very popular bionanotechnological instruments in the last few years. Since 2010, the graphene family materials have been recognized as worthy of attention due to its antimicrobial properties. Functionalization of graphene (or rather graphene oxide) surface creates the possibilities to obtain efficient antimicrobial agents. In this review, progress and advances in this field in the last few years are described and discussed. Special attention is devoted to materials based on graphene oxide in which specifically selected components significantly modify biological activity of this carbon structure. Short introduction concerns the physicochemical properties of the graphene family materials. In the section on antimicrobial properties, proposed mechanisms of activity against microorganisms are given showing enhanced action of nanocomposites also under light irradiation (photoinduced activity). Another important feature, i.e. toxicity against eukaryotic cells, is presented with up-to-date data. Taking into account all the information on the properties of the described materials and usefulness of the graphene family as antimicrobial agents, hopes and fears concerning their application are discussed. Finally, some examples of promising usage in medicine and other fields, e.g. in phytobiology and water remediation, are shown.

Bioactive glass nanoparticles obtained through sol-gel chemistry.

Different sol-gel strategies based on the Stöber method are proposed enabling preparation of nanoparticles of SiO2-CaO bioactive glass with different size, narrow size distribution and good dispersion capability. Eu(3+)-doped glass nanoparticles with luminescent properties can also be obtained.

Hydroxyapatites and europium(III) doped hydroxyapatites as a carrier of silver nanoparticles and their antimicrobial activity.

Hydroxyapatites (Ca10(PO4)6(OH)2 and Eu3+:Ca10(PO4)6(OH)2) were synthesized by aqueous synthesis route. Hydroxyapatites were impregnated with silver ions that were subsequently reduced. XRD, TEM, and SAED measurements were used in order to determine the crystal structure and morphology of the final products. The results showed the well crystallized hydroxyapatite grains with diameter of about 35 nm and with silver nanoparticles on their surface. The antimicrobial activity of the nanoparticles against: Staphylococcus aureus ATCC 6538 as model of the Gram-positive bacteria, Escherichia coli ATCC 11229, and Klebsiella pneumoniae ATCC 4352 as model of Gram-negative bacteria, were shown with the best activity against K. pneumoniae. These nanocomposite powders can be a promising antimicrobial agent and a fluorescent material for biodetection due to their optical and bioactive properties.

The f-f emission of Pr3+ ion as an optical probe for the structural properties of YAG nanoceramics.

Transparent Pr-doped YAG nanoceramics composed of grains with an average size of about 42 nm, were fabricated with the Low Temperature High Pressure (LTHP) sintering technique using the corresponding nanopowders as the starting materials. The structure of the nanoceramics was analyzed by X-ray diffraction (XRD). The effect of the sintering conditions on the structural properties is discussed on the basis of the changes of the spectroscopic properties of Pr3+ ions. In particular, the intensities and decays of the emission transitions originating from the (3)P0 and (1)D2 levels are investigated and correlated with structural properties of the material, such as microstrains produced by the high-pressure process.