Hybrid Sol-gel Materials Research Articles

Synthesis of hybrid sol–gel materials and their biological evaluation with human mesenchymal stem cells

Surface engineering of biomaterials could promote the osseointegration of implants. In this work, two types of hybrid sol-gel materials were developed to stimulate cell attachment, proliferation and differentiation of osteogenic cells. One type was synthesised from vinyl triethoxysilane (VTES) and tetraethyl-orthosilicate (TEOS) at different molar ratios, while the other from VTES and hydroxyapatite particles (HAp). Hybrid materials were systematically investigated using nuclear magnetic resonance, Fourier transform infrared spectroscopy and contact angle metrology. The biocompatibility and osseoinduction of the coatings were evaluated by measuring mesenchymal stem cell proliferation using MTT assays and analysing the mineralised extracellular matrix production by quantifying calcium-rich deposits. The results highlighted the versatility of these coatings in obtaining different properties by changing the molar ratio of the VTES:TEOS precursors. Thus, mineralisation was stimulated by increasing TEOS content, while the addition of HAp improved cell proliferation but worsened mineralisation.

Single mode ridge waveguides based on vinyltriethoxysilane hybrid sol–gel material

In this work, fabrication and characterization of a single-mode vinyltriethoxysilane (VTES) based hybrid organic–inorganic sol–gel ridge waveguide is reported. VTES based hybrid sol–gel material has been deposited by multiple spin-coating process on quartz substrate. Channel waveguides have been fabricated by UV photopolymerization followed by wet etching process. Optical guided mode was observed to ensure the single mode condition while cut-back technique was performed for loss propagation measurement. Optical propagation losses were measured to be 1.6dB/cm at 1.31μm wavelength. This value shows that this material is a promising choice for the development of integrated optical circuits for telecommunication field.

Phenol Biodegradation by Fungal Cells Immobilized in Sol-Gel Hybrids

The capability of cells of the fungus Aspergillus awamori, either free or immobilized in hybrid sol-gel material cells, for phenol biodegradation was demonstrated. Phenol was present in the reaction mixture as the sole carbon and energy source, and its decomposition was followed in repeated batch degradation experiments. Atomic force microscopy provided information on the development of self-organizing structures in the materials synthesized by the sol-gel method. Phenol biodegradation was mediated only by the fungal cells, and no absorption by the hybrid matrix was observed. Ten cycles of phenol biodegradation using the immobilized cells system were conducted during which up to 2000 mg l(-1) phenol was completely decomposed. Immobilized cells degraded phenol at 8.33 mg h(-1), twice as fast as free cells. The good performance of the immobilized fungal cell system is promising for the development of an efficient technology for treating phenol-containing waste waters.

Preparation and Evaluation of a Molecularly Imprinted Sol-Gel Hybrid Material for Selective Solid-Phase Extraction of Sarafloxacin in Milk

Preparation and Evaluation of a Molecularly Imprinted Sol-Gel Hybrid Material for Selective Solid-Phase Extraction of Sarafloxacin in Milk

Development of a sol–gel photonic sensor platform for the detection of biofilm formation

This paper focuses on the development and characterization of a waveguide-based photonic sensing platform for the detection of biofilm. This integrated photonic platform is based upon the high sensitivity of an optical field distribution formed in optical waveguides and the resulting changes in the refractive index and absorption of this environment. The sensor platform and materials formulations were established from simulation studies conducted with the Olympios software. These simulations demonstrated the importance of correctly specifying the material refractive index to achieve single-mode waveguides. They also highlighted the necessity to deposit a high refractive index layer (HRIL) on top of the optical waveguides in order to increase the intensity of the evanescent field responsible for the sensing performance of the platform. Platform fabrication exploited a low-cost process using photocurable organic–inorganic hybrid sol–gel materials, which were microstructured by UV-photolithography to form channel optical waveguides. A tantalum-based material was synthesized using the sol–gel process with refractive index as high as 1.87. This material was developed, optically characterized and applied as an evanescent field enhancement layer, deposited at the surface of the waveguide to increase the sensitivity of the sensing platform. The sensor characterization was performed by monitoring the output intensity of the optical waveguide while contaminated water was monitored in a quasi-static flow-rate (0.5 ml/s) on the platform. It is shown that our biosensor platform was able to detect the biofilm formation after 10 min of reactions, demonstrating the early stage biofilm formation in quasi-static flow-rate. Furthermore, the sensing performances of our photonic platform were found to be strongly dependent on the thickness of the HRIL, confirming the simulations studies. This work proved the concept of employing a waveguide-based photonic platform for the early detection of biofilm formation, including the induction phase, and as such, we believe this system has immense potential for future applications as a label-free and real-time biosensor platform.

Phenyl-bridged polysilsesquioxane positive and negative resist for electron beam lithography

We present and characterize an organic–inorganic hybrid sol–gel material, phenyl-bridged polysilsesquioxane (ph-PSQ), for use as a new high resolution resist for electron beam lithography (EBL). The resist has a unique characteristic as the only positive tone silica-based resist available for EBL. Exploring the processing parameters has revealed that it is possible to switch the behaviour from negative to positive tone by application of a post-exposure bake (PEB). Based on the results from micro-FTIR spectroscopy, a description of the tone switching mechanisms is proposed. The negative tone behaviour is explained by the etch rate difference between silanol groups and cross-linked silica, present in unexposed and in exposed areas of the films, respectively. In the case of positive tone, after a PEB, the etch rate difference between a thermally densified cross-linked silica network and cage-like silica structures allows us to reveal the pattern. Contrast and sensitivity are estimated under different processing conditions, and the significant parameters for line edge roughness minimization are pointed out. Dense patterns down to 25 nm half-pitch and isolated structures down to 30 nm are demonstrated, exploiting the positive tone, and dense patterns down to 60 nm half-pitch are demonstrated in the negative tone. Etching selectivities in fluorinated gases for ph-PSQ nanostructures on silicon substrates are 1–9 for the positive tone and 1–12 for the negative tone.

Silica Hybrid Sol–Gel Materials with Unusually High Concentration of Pt–Organic Molecular Guests: Studies of Luminescence and Nonlinear Absorption of Light

The development of new photonic materials is a key step toward improvement of existing optical devices and for the preparation of a new generation of systems. Therefore synthesis of photonic hybrid materials with a thorough understanding and control of the microstructure-to-properties relationships is crucial. In this perspective, a new preparation method based on fast gelation reactions using simple dispersion of dyes without strong covalent bonding between dye and matrix has been developed. This new sol-gel method is demonstrated through synthesis of monolithic siloxane-based hybrid materials highly doped by various platinum(II) acetylide derivatives. Concentrations of the chromophores as high as 400 mM were obtained and resulted in unprecedented optical power limiting (OPL) performance at 532 nm of the surface-polished solids. Static and time-resolved photoluminescence of the prepared hybrid materials were consistent with both OPL data and previous studies of similar Pt(II) compounds in solution. The impacts of the microstructure and the chemical composition of the matrix on the spectroscopic properties, are discussed.

Laser fabrication of various polymer microoptical components

In this report we present micro/nanostructuring of novel metal isopropoxides-silica containing hybrid sol-gel materials by the femtosecond laser direct writing technique and apply it for the fabrication of various microoptical/nanophotonic components. This approach enables one to photostructure true three-dimensional objects with controlled sub-100 nm spatial definition. Due to self-smoothing effects, surface roughness can be formed below 30 nm making this technique widely applicable for microoptical/nanophotonics devices in visible and near-infra-red wavelengths. After photopolymerization, these materials inherit desired optical properties: high transmittance in the 400–1500 nm spectral range and nearly glass-matching optical refractive index. Doping with organic dyes or quantum dots offers additional functionalities. Fields of applications cover: light guiding, coupling/extraction, trapping, signal processing and transferring, microscopy, biology, etc. In brief, we investigated direct laser writing structurability of these materials and its optimization for manufacturing microoptical/nanophotonic components. We successfully produced microoptical components such as aspheric and Fresnel lenses. We demonstrate the flexibility and reproducibility of this approach to fabricate custom-shaped elements on the tip of the optical fiber, thus producing integrated microoptical devices. The micro/nanostructures were characterized by optical and scanning electron microscopies, and optical profilometry. Their optical functions were measured using a custom-built setup to serve the purpose. The obtained values were in close coincidence to the theoretical values. Further research in the direction of production integrated and multifunctional components to be applied in the fields of photonics, plasmonics and telecommunications as well as optofluidics is currently being carried out.

Use of a New Hybrid Sol–Gel Zirconia Matrix in the Removal of the Herbicide MCPA: A Sorption/Degradation Process

A class II hybrid sol-gel material was prepared starting from zirconium(IV) propoxide and 2,4-pentanedione and its catalytic activity in the removal of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) was revealed. The thermal and structural characterization, performed by thermogravimetry, differential thermal analysis, and diffuse reflectance Fourier transform infrared spectroscopy, demonstrated the hybrid nature of the material. The structure of the material can be described as a polymeric network of zirconium oxo clusters, on the surface of which large part of Zr(4+) ions are involved in strong complexation equilibria with acetylacetonate (acac) ligands. The incubation of MCPA in the presence of this material yielded an herbicide removal fraction up to 98%. A two-step mechanism was proposed for the MCPA removal, in which a reversible first-order adsorption of the herbicide is followed by its catalytic degradation. The nature of the products of the MCPA catalytic degradation as well as the reaction conditions adopted do not support typical oxidation pathways involving radicals, suggesting the existence of a different mechanism in which the Zr(4+):acac enol-type complex can act as Lewis acid catalyst.

Hybrid sol–gel double metal cyanide catalysts for the copolymerisation of styrene oxide and CO2

Hybrid sol–gel catalysts of zinc hexacyanocobaltate and SiO2 were prepared by co-precipitation of the double metal cyanide with silica. Hybrid catalysts prepared at moderately acidic conditions showed the best performance with respect to activity, selectivity and stability. The hybrid sol–gel materials displayed high catalytic activity for the copolymerisation of styrene oxide and carbon dioxide (up to 650 molSO (molZn h)−1) and high productivity (575 gPolymer gCatalyst−1). They also displayed good selectivity to the polymeric product (80–87%), while only little cyclic styrene carbonate was formed as side product. A detailed electron microscopy study of the hybrid sol–gel materials showed that the active phase consisted of thin platelets containing the metals in a molar ratio nZn/nCo = 2.1, whereby the double metal cyanide was closely associated with silica.

Graphene-doped photo-patternable ionogels: tuning of conductivity and mechanical stability of 3D microstructures

This work reports for the first time the development of enhanced-conductivity, graphene-doped photo-patternable hybrid organic-inorganic ionogels and the effect of the subsequent materials condensation on the conductivity and mechanical stability of three-dimensional microstructures fabricated by multi-photon polymerisation (MPP). Ionogels were based on photocurable silicon/zirconium hybrid sol–gel materials and phosphonium (trihexyltetradecylphosphonium dicyanamide) [P6,6,6,14][DCA] ionic liquid (IL). To optimise the dispersion of graphene within the ionogel matrices, aqueous solutions of graphene were prepared, as opposed to the conventional graphene powder approach, and employed as catalysts of hydrolysis and condensation reactions occurring in the sol–gel process. Ionogels were prepared via a two step process by varying the hydrolysis degree from 25 to 50%, IL content between 0–50 w/w%, and the inorganic modifier (zirconate complex) concentration from 30 to 60 mol.% against the photocurable ormosil and they were characterised via Raman, Electrochemical Impedance Spectroscopy and Transmission Electron Microscopy. MPP was performed on the hybrid ionogels, resulting in three-dimensional microstructures that were characterised using scanning electron microscopy. It is clearly demonstrated that the molecular formulation of the ionogels, including the concentration of graphene and the zirconate network modifier, plays a critical role in the conductivity of the ionogels and influences the resulting mechanical stability of the fabricated three-dimensional microstructures. This work aims to establish for the first time the relationship between the molecular design and condensation of materials in the physico-chemistry and dynamic of ionogels.

All-silica nanofluidic devices for DNA-analysis fabricated by imprint of sol–gel silica with silicon stamp

We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination of the imprinted hybrid sol-gel material produces purely inorganic silica, which has very low autofluorescence and can be fusion bonded to a glass lid. Compared to top-down processing of fused silica or silicon substrates, imprint of sol-gel silica enables fabrication of high-quality nanofluidic devices without expensive high-vacuum lithography and etching techniques. The applicability of the fabricated device for single-molecule studies is demonstrated by measuring the extension of DNA molecules of different lengths confined in the nanochannels.

The development and characterisation of novel hybrid sol–gel-derived films for optical pH sensing

This paper focuses on the development and detailed characterisation of a novel hybrid sol–gel material derived from 3-glycidoxypropyltrimethoxysilane (GPTMS) and ethyltriethoxysilane (ETEOS). The material has been doped with a fluorescent pH-sensitive dye, modified 8-hydroxy-1,3,6-pyrene trisulfonic acid (HPTS) and its application as a high-performance optical ratiometric pH sensor has been demonstrated. The optimum sol–gel-based material composition has been characterised using atomic force microscopy (AFM), scanning electron microscopy in combination with energy dispersive X-ray spectroscopy (SEM-EDX), thermal gravimetric-infrared (TGA-IR) analysis, Fourier transform infrared (FT-IR) and Raman spectroscopy, solid state 29Si and 13C nuclear magnetic resonance (NMR). AFM and SEM images demonstrated a high degree of homogeneity of the pH films. FT-IR, Raman and NMR results have shown that hydrolysis and condensation reactions were almost completed and extensive crosslinking occurred in the final material. They also revealed that an opening of the epoxy ring in GPTMS took place which was key to optimum pH response. The pH sensor produced using the hybrid material compares very well with the current state-of-the-art and exhibits very good reversibility, reproducibility, stability, short response time and no leaching. The dynamic range extends from pH 5.0 to 8.0 which is compatible with bioprocessing, environmental and clinical monitoring applications.

Sensing Performance of a Refractometric Optical Sensor Platform Based on Multimode Interference Couplers

This paper focuses on characterization of the sensing performance of a refractometric sensing platform based on multimode interference couplers (MMICs). Platform fabrication exploited a low-cost process using photocurable organic-inorganic hybrid sol-gel materials which were structured to form optical waveguides by direct UV laser writing. The sensing principle is based upon the high sensitivity of the optical field distribution formed in the MMIC toward changes in the refractive index of its environment. Simulations demonstrated the importance of correctly specifying the length of the MMIC section and illustrated that longer platforms are more sensitive due to a greater shift in self-image position. To characterize sensing performance, a porous sol-gel humidity sensing enrichment layer was coated on the MMIC. Relative humidity was detected by the system with a resolution of 0.097%. Refractive index resolution of the platform was determined to be ~ 2 × 10-6 RIU , which is an analyte-independent value and illustrates the generic nature of this platform. As such, this platform has immense potential for future applications as a label-free and real-time biosensor platform.

Improved negative bias illumination instability of sol-gel gallium zinc tin oxide thin film transistors

We investigated the Ga doping effect on the performance and negative bias illumination instability of sol-gel zinc tin oxide (ZTO) thin film transistors (TFTs). The performance of the Ga doped ZTO (GZTO) TFTs is controlled and optimized by the concentration of Ga ions, which suppress the formation of oxygen vacancies. The negative bias illumination instability of the devices with a sol-gel hybrid material passivation layer is compared through a time-evolution stress analysis and illumination wavelength dependence measurements. The GZTO TFT exhibits improved stability relative to the ZTO TFT, because Ga ions effectively decrease charge trapping sites originating from oxygen vacancies.

Preparation of sol–gel hybrid materials from γ-methacryloxypropyltrimethoxysilane and tetramethyl orthosilicate: study of the hydrolysis and condensation reactions

Organic–inorganic hybrid materials suitable for the development of sol–gel coatings for metallic surfaces were prepared by hydrolysis and condensation of γ-methacryloxypropyltrimethoxysilane (MAPTMS) and tetramethyl orthosilicate (TMOS). The hydrolysis of MAPTMS/TMOS was carried out in an ethanol/water solution. The prehydrolysis stage of MAPTMS/TMOS system was monitored by Fourier transform infrared spectroscopy (FTIR) and liquid-state 29Si and 13C nuclear magnetic resonance (29Si and 13C NMR). FTIR analysis indicated that the hydrolysis of MAPTMS/TMOS was accomplished as far as the (SiOMe) band corresponding to unhydrolyzed silane disappeared. The concentration of the alkoxy groups and the extent of self-condensation of mono-, di-, and trisubstituted siloxanes (T species) in the sol were estimated by using liquid-state 29Si NMR spectroscopy. The hydrolysis of the prepared sol was also evaluated by liquid-state 13C NMR spectroscopy. The results indicated that under the adopted synthesis strategy conditions, the hydrolysis process requires 4 h to be completed.

Two-photon excited luminescence of lanthanide complex in monolithic sol–gel hybrid material

A π-conjugated donor functionalized tris-dipicolinate complex, featuring promising two-photon excited luminescence properties in water was successfully embedded in a monolithic sol–gel material. A complete spectroscopic study unambiguously indicates that the europium complex conserves its integrity in this sol–gel matrix and the improvement of the luminescence lifetime clearly indicates a stabilisation of the complex in the matrix. Biphotonic confocal microscopy measurement shows that the Eu(III) luminescence can be sensitized in the sol–gel material using a two-photon antenna process, which is a first step towards the design of doped sol–gel nanoparticles for two-photon imaging applications.

Structure, dynamics and interactions of complex sol–gel hybrid materials through SSNMR and DSC: Part I, binary systems based on PE-PEG block copolymer, PHS and silica

This paper is the first part of a combined DSC and solid-state NMR study aimed at understanding the dynamic, morphological and interaction properties of three-component organic–inorganic hybrid coatings exhibiting interesting barrier properties against oxygen diffusion, obtained by sol–gel processes starting from triethoxysilane terminated polyethylene-b-poly(ethylene glycol) copolymer (PE-PEGSi), poly(4-hydroxystyrene) (PHS), and tetraethoxysilane (TEOS). This paper reports the results of the study of the corresponding simpler two-component hybrids, which, beside the interest of these systems by themselves, was necessary for unravelling the characterization of the complex three-component systems. The phase, dynamic and interaction properties of binary systems PE-PEG/SiO2, PHS/SiO2, and PE-PEG/PHS have been here investigated and compared with those of the single components. Evidences of the occurrence of hydrogen bonds between PHS and both silica and PEG have been obtained. The interaction with silica and PHS seems to strongly inhibit the crystallization of PEG segments but to not prevent PE from segregating into crystalline domains. Moreover a noticeable mobility of amorphous PEG segments and the presence of mobile isolated or loosely packed PE segments in all-trans conformations have been highlighted in PE-PEG/SiO2 hybrids. The structural and phase behaviour of PHS results to be strongly affected by the presence of either silica or PEG. In PHS/SiO2 hybrids a two-state model with PHS chains either tightly- or loosely bound to silica domains has been proposed, while in PE-PEG/PHS blends the presence of a PEG-PHS miscible amorphous phase has been observed.

Structure, dynamics and interactions of complex sol–gel hybrid materials through SSNMR and DSC: Part II, ternary systems based on PE–PEG block copolymer, PHS and silica

This work is the second part of a study aimed at understanding in more depth structure, dynamics, interactions and correlations between morphology and barrier properties against oxygen diffusion of complex PE–PEG/PHS/SiO2 hybrids prepared through a sol–gel process. Using a combined DSC and solid-state NMR approach, including 13C and 29Si experiments and 1H ultra-fast MAS spectra, the structural, phase and interaction properties of three PE–PEG/PHS/SiO2 samples with different compositions, exhibiting different barrier performances, have been investigated, also taking into account the results obtained for the simpler one- and two-component systems (Part I). While the structure of the silica domains has been found to be not affected by composition, many differences have been observed concerning the phase and dynamic properties of the organic components (PE and PEG crystallinity and mobility of their amorphous domains) and the inter-component interactions (strength of the hydrogen bonds between PHS and both silica and PEG and PHS/PEG miscibility). In particular peculiar phase and interaction properties of the sample exhibiting the best barrier properties have been identified and characterized.

Tailor-made three-dimensional hybrid scaffolds for cell cultures

The construction of the ideal three-dimensional scaffold for cell culture is one of the most intriguing topics in tissue engineering. It has been shown that cells can be cultured on most organic biomimetic materials, which now are losing popularity in favour of novel, hybrid systems. In this study, a series of photosensitive sol–gel hybrid materials, based on silicon–zirconium and silicon–titanium oxides, have been investigated for their suitability in three-dimensional scaffold fabrication. These materials can be structured by two-photon polymerization, a laser-based technique allowing the fabrication of micrometre-size structures with submicron resolution. The work presented here examined the effect of the organic/inorganic composition of the materials on cell behaviour and the establishment of a ‘cell-culture friendly’ environment. This is vital for cell adhesion, growth and differentiation, as the organic part of the material provides the soft matrix for cell growth, whereas the inorganic component gives the mechanical stability and rigidity of the three-dimensional structures. In addition, the use of femtosecond laser structuring permits the fabrication of a wide range of mechanically stable scaffolds of different sizes and shapes to be tested in terms of cell viability, proliferation and orientation.