Development of Photonic Multi-Sensing Systems Based on Molecular Gates Biorecognition and Plasmonic Sensors: The PHOTONGATE Project.

This paper presents the concept of a novel adaptable sensing solution currently being developed under the EU Commission-founded PHOTONGATE project. This concept will allow for the quantification of multiple analytes of the same or different nature (chemicals, metals, bacteria, etc.) in a single test with levels of sensitivity and selectivity at/or over those offered by current solutions. PHOTONGATE relies on two core technologies: a biochemical technology (molecular gates), which will confer the specificity and, therefore, the capability to be adaptable to the analyte of interest, and which, combined with porous substrates, will increase the sensitivity, and a photonic technology based on localized surface plasmonic resonance (LSPR) structures that serve as transducers for light interaction. Both technologies are in the micron range, facilitating the integration of multiple sensors within a small area (mm2). The concept will be developed for its application in health diagnosis and food safety sectors. It is thought of as an easy-to-use modular concept, which will consist of the sensing module, mainly of a microfluidics cartridge that will house the photonic sensor, and a platform for fluidic handling, optical interrogation, and signal processing. The platform will include a new optical concept, which is fully European Union Made, avoiding optical fibers and expensive optical components.

What Is Driving the Growth of Inorganic Glass in Smart Materials and Opto-Electronic Devices?

Inorganic glass is a transparent functional material and one of the few materials that keeps leading innovation. In the last decades, inorganic glass was integrated into opto-electronic devices such as optical fibers, semiconductors, solar cells, transparent photovoltaic devices, or photonic crystals and in smart materials applications such as environmental, pharmaceutical, and medical sensors, reinforcing its influence as an essential material and providing potential growth opportunities for the market. Moreover, inorganic glass is the only material that is 100% recyclable and can incorporate other industrial offscourings and/or residues to be used as raw materials. Over time, inorganic glass experienced an extensive range of fabrication techniques, from traditional melting-quenching (with an immense diversity of protocols) to chemical vapor deposition (CVD), physical vapor deposition (PVD), and wet chemistry routes as sol-gel and solvothermal processes. Additive manufacturing (AM) was recently added to the list. Bulks (3D), thin/thick films (2D), flexible glass (2D), powders (2D), fibers (1D), and nanoparticles (NPs) (0D) are examples of possible inorganic glass architectures able to integrate smart materials and opto-electronic devices, leading to added-value products in a wide range of markets. In this review, selected examples of inorganic glasses in areas such as: (i) magnetic glass materials, (ii) solar cells and transparent photovoltaic devices, (iii) photonic crystal, and (iv) smart materials are presented and discussed.

Improving hydraulic permeability, mechanical properties, and chemical functionality of cellulose acetate-based membranes by co-polymerization with tetraethyl orthosilicate and 3-(aminopropyl)triethoxysilane.

Composite cellulose acetate (CA) membranes are widely used but their multiphase nature results in additive losses, poor mechanical strength, low chemical resistance and thermal stability, limiting their separation/purification yields. To overcome this, we fabricated monophasic hybrid membranes using a modified phase inversion technique, where tetraethylorthosilicate and 3-(aminopropyl)triethoxysilane were added to the CA casting solution. The resulting co-polymerization between CA, silanols and amine-functionalized silica groups, through sol-gel chemistry, was proved by ATR-FTIR (1118 cm-1, ν(SiOC)). The presence of propyl-amine groups increases the hydraulic permeability (3×), the rupture elongation (×1.5), and decreases the Young modulus (×1/2), due to the disruption of the CA-silica 3D network. For high propyl-amine contents this behaviour is reversed due to intensive cross-linking between CA-silica chains (decrease in 903 cm-1, ν(CH3COOC-)). The addition of silica- and amine-based structures to the CA framework increases the system degrees of freedom, opening the door to the design of new CA membranes.

Synthesis and Characterization of Novel Integral Asymmetric Monophasic Cellulose-Acetate/Silica/Titania and Cellulose-Acetate/Titania Membranes.

Two series of novel integral asymmetric monophasic hybrid membranes, cellulose acetate/silica/titania (CA/SiO2/TiO2-series 1) and cellulose acetate/titania (CA/TiO2-series 2), were developed by the coupling of sol-gel technology and a modified version of the phase inversion technique. SEM micrographs confirmed the integral asymmetric structure of all membranes. ATR-FTIR and ICP-OES results showed that, for the membranes in series 1, TiO2 is covalently bound to SiO2, which, in turn, is covalently bound to CA, while for the membranes in series 2, TiO2 is directly and covalently bound to the CA matrix. Permeation experiments revealed that the permeation performance of the membranes in series 1 is unaffected by the introduction of TiO2. In contrast, the introduction of TiO2 in the series 2 membranes increased the hydraulic permeability by a factor of at least 2 when compared to the pristine CA membrane and that incremental additions of TiO2 further increased the Lp.

SPIONs Prepared in Air through Improved Synthesis Methodology: The Influence of γ-Fe2O3/Fe3O4 Ratio and Coating Composition on Magnetic Properties.

Superparamagnetic iron oxide nanoparticles (SPIONs) have shown great potential in biomedicine due to their high intrinsic magnetization behaviour. These are small particles of magnetite or maghemite, and when coated, their surface oxidation is prevented, their aggregation tendency is reduced, their dispersity is improved, and the stability and blood circulation time are increased, which are mandatory requirements in biomedical applications. In this work, SPIONs were synthesized in air through a reduction-precipitation method and coated with four different polymers (Polyethylene glycol(PEG) 1000/6000 and dextran T10/T70). All the synthesized samples were structurally and magnetically characterized by transmission electron microscopy, Fourier transform infra-red spectroscopy, X-ray powder diffraction, Mössbauer spectroscopy, and Superconducting Quantum Interference Device (SQUID) magnetometry. SPIONs centrifuged and dried in vacuum with an average diameter of at least 7.5 nm and a composition ≤60% of maghemite and ≥40% of magnetite showed the best magnetization results, namely a saturation magnetization of ~64 emu/g at 300 K, similar to the best reported values for SPIONs prepared in controlled atmosphere. As far as SPIONs' coatings are concerned, during their preparation procedure, surface polymers must be introduced after the SPIONs' precipitation. Furthermore, polymers with shorter chains do not affect the SPIONs' magnetization performance, although longer chain polymers significantly decrease the coated particle magnetization values, which is undesirable.

Daylight Bactericidal Titania Textiles: A Contribution to Nosocomial Infections Control.

: Daylight bactericidal cotton (100% cotton) textiles are presented and proposed for future hospital use. Amorphous titania (a-TiO2) and amorphous titania/chitosan complexes (a-TiO2//CS) were the selected bactericidal agents. Nanoparticles (NPs) and films were the two paths designed. Cotton textiles were impregnated with a-TiO2-based NPs or coated with a-TiO2 films. Industrial impregnation/coating will be implemented during the textile finishing treatments. A novel (room temperature and base-catalyzed), green (hydrothermal water as a catalyst), time-saving, and easy scale-up sol-gel process was established to produce the a-TiO2-based NPs. Amorphous-TiO2 films were produced by a dip-in (acid catalyzed) sol-gel solution. The daylight bactericidal performance (without the need of an external ultraviolet light source) of a-TiO2 NPs, films, and impregnated/coated textiles was proven according to AATCC 100 and ASTM E2149, using Staphylococcus aureus (ATCC®6538TM) as the bacterial indicator strain. A bacterial reduction of 99.97% was achieved for the a-TiO2 films and of 99.97% for the a-TiO2/CS NPs. Regarding the impregnated textiles, a bacterial reduction of 91.66% was achieved with a-TiO2/CS NPs, and 99.97% for cotton textiles coated with an a-TiO2 film.

Sol-gel Silica Nanoparticles in Medicine: A Natural Choice. Design, Synthesis and Products.

Silica is one of the most abundant minerals in the Earth's crust, and over time it has been introduced first into human life and later into engineering. Silica is present in the food chain and in the human body. As a biomaterial, silica is widely used in dentistry, orthopedics, and dermatology. Recently amorphous sol-gel SiO2 nanoparticles (NPs) have appeared as nanocarriers in a wide range of medical applications, namely in drug/gene target delivery and imaging diagnosis, where they stand out for their high biocompatibility, hydrophilicity, enormous flexibility for surface modification with a high payload capacity, and prolonged blood circulation time. The sol-gel process is an extremely versatile bottom-up methodology used in the synthesis of silica NPs, offering a great variety of chemical possibilities, such as high homogeneity and purity, along with full scale pH processing. By introducing organic functional groups or surfactants during the sol-gel process, ORMOSIL NPs or mesoporous NPs are produced. Colloidal route, biomimetic synthesis, solution route and template synthesis (the main sol-gel methods to produce monosized silica nanoparticles) are compared and discussed. This short review goes over some of the emerging approaches in the field of non-porous sol-gel silica NPs aiming at medical applications, centered on the syntheses processes used.

Photonic Band Gap and Bactericide Performance of Amorphous Sol-Gel Titania: An Alternative to Crystalline TiO2.

In addition to its traditional application in white pigments, nanocrystalline titania (TiO2) has optoelectronic and photocatalytic properties (strongly dependent on crystallinity, particle size, and surface structure) that grant this naturally occurring oxide new technological applications. Sol-gel is one of the most widely used methods to synthesize TiO2 films and NPs, but the products obtained (mostly oxy-hydrated amorphous phases) require severe heat-treatments to promote crystallization, in which control over size and shape is difficult to achieve. In this work, we obtained new photocatalytic materials based on amorphous titania and measured their electronic band gap. Two case studies are reported that show the enormous potential of amorphous titania as bactericide or photocatalyst. In the first, amorphous sol-gel TiO2 thin films doped with N (TiO2−xNx, x = 0.75) were designed to exhibit a photonic band gap in the visible region. The identification of Ti-O-N and N-Ti-O bindings was achieved by XPS. The photonic band gaps were found to be 3.18 eV for a-TiO2 and 2.99 eV for N-doped a-TiO2. In the second study, amorphous titania and amine-functionalized amorphous titania nanoparticles were synthetized using a novel base-catalysed sol-gel methodology. All the synthesized amorphous TiO2 nanoparticles exhibit bactericide performance (E. coli, ASTME 2149-13).

Structure of water in hybrid cellulose acetate-silica ultrafiltration membranes and permeation properties.

Hybrid cellulose acetate (CA) silica (SiO2) (CA/SiO2) membranes were synthesized by promoting the in situ condensation between silanols from the SiO2 precursor and the COH or acetate groups from the CA polymer. For all the CA/SiO2 membranes, the ATR-FTIR peak assigned to (SiOC) proves the hybrid condensation reaction and confirms the synthesis of monophasic hybrid membranes. ATR-FTIR shows the presence of uncondensed highly reactive SiOH species, in membranes with silica contents higher than 20 mol%. Together with RMN studies, results show molecular water strongly hydrogen-bonded with SiOH groups, yielding a drastic decrease in the membrane hydraulic permeability, from 57 to 10 kg/h/m2/bar. The incorporation of 5 and 10 mol% of silica increased the hydraulic permeability from 32 to 82 kg/h/m2/bar when compared to the CA membrane.

Development of New Contrast Agents for Imaging Function and Metabolism by Magnetic Resonance Imaging.

Liposomes are interesting nanosystems with a wide range of medical application. One particular application is their ability to enhance contrast in magnetic resonance images; when properly loaded with magnetic/superparamagnetic nanoparticles, this means to act as contrast agents. The design of liposomes loaded with magnetic particles, magnetoliposomes, presents a large number of possibilities depending on the application from image function to metabolism. More interesting is its double function application as theranostics (diagnostics and therapy). The synthesis, characterization, and possible medical applications of two types of magnetoliposomes are reviewed. Their performance will be compared, in particular, their efficiency as contrast agents for magnetic resonance imaging, measured by their relaxivities r1 and r2 relating to their particular composition. One of the magnetoliposomes had 1,2-diacyl-sn-glycero-3-phosphocholine (soy) as the main phospholipid component, with and without cholesterol, varying its phospholipid to cholesterol molar ratios. The other formulation is a long-circulating liposome composed of 1,2-diacyl-sn-glycero-3-phosphocholine (egg), cholesterol, and 1,2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000]. Both nanosystems were loaded with superparamagnetic iron oxide nanoparticles with different sizes and coatings.

Greensilica® vectors for smart textiles.

The present work aims developing a versatile Greensilica® vector/carrier, able to bind to a wide range of textile matrices of carbohydrate polymers and susceptible of being loaded with chemicals/drugs/therapeutic molecules, to create a green tailor-made (multi)functional high-tech textile. A green, eco-friendly, ammonia-free, easily scalable, time-saving sol-gel process was established for the production of those silica-based colloidal particles (SiO2, amine-SiO2, diamine-SiO2, and epoxy-SiO2). Two different textile matrices (cotton, polyester) were functionalized, through the impregnation of Greensilica® particles. The impregnation was performed with and without cure. Diamine-SiO2 colloidal particles exhibited the higher bonding efficiency in cured textile matrices (both cotton and polyester), while with no cure the best adherence to cotton and polyester textile matrices was achieved with diamine-SiO2 and amine-SiO2, respectively. Use once and throw away and continued use applications were envisaged and screened through washing tests. The efficiency of the textiles impregnation was confirmed by SEM, and quantified by ICP.

Relaxivities of magnetoliposomes: the effect of cholesterol.

We present relaxivities measurements for both the longitudinal and transverse relaxations of two types of liposomes loaded with ultra small superparamagnetic iron oxide nanoparticles. The magnetoliposome systems presented are soybean phosphatidylcholine liposomes, with and without cholesterol, in the phospholipid bilayer with different molar ratios lipid:cholesterol. In fact, cholesterol is needed to obtain stable liposomes for intravenous administration. The longitudinal and transverse relaxivities were measured with a NMR spectrometer in a 7T magnetic field. For the studied concentrations, the liposomes show a negligible effect on the longitudinal relaxation time T1 of the medium, but they are very efficient on decreasing the transverse relaxation time T2, the behaviour one expects for a negative CA. We observed a lower transverse relaxivity for the magnetoliposome nanosystem with cholesterol, which strongly decreases with the cholesterol content in the liposome bilayer.