Robust and Biocompatible Hybrid Matrix with Controllable Permeability for Microalgae Encapsulation.

Hybrid beads with entrapped microalgae Chlamydomonas reinhardtii were synthesized for the sustainable production of high value metabolites via photosynthesis. Encapsulating the microalgae requires an exquisite control of material properties, which has been achieved by modifying the composition (alginate, polycation, and silica). A coating of PDADMAC precluded cell leakage as indicated by the OD750 value of the culture medium, and the homogeneous distribution of silica prevented bead shrinkage from the strong electronic force of PDADMAC, resulting in a robust and biocompatible matrix for the cells. Besides fabricating suitable porous beads for the diffusion of expected metabolites, the permeability can be controlled to a certain degree by applying different molecular weights of PDADMAC. The hybrid alginate+silica/CaCl2+PDADMAC beads possessed sufficient mechanical rigidity to sheer force under constant stirring and good chemical stability to chelating agents such as sodium citrate. Moreover, the encapsulated cells exhibited excellent long-term viability and cellular functionality, which retained about 81.5% of the original value after a 120 day encapsulation as observed by microscopy and oximetry measurement. This study is not only significant for understanding the critical role of polycations and silica involved in the synthesis of hybrid beads but also important for real-scale bioengineering applications.

A comprehensive study of the reaction parameters involved in the synthesis of silica thin films with well-ordered uni-directional mesopores.

Ordered mesoporous thin films with well-orientated channels are an important feature in a series of applications including sensors, optics, photocatalysis, and solar cells. However, their preparation remains a great challenge. The structural optimization of highly organized mesoporous silica thin films, with channels perpendicularly orientated to the surface and prepared by a spin-coating technique, is reported. A large series of reaction parameters were revisited with a deep investigation such as the template, solvent, aging time, pH, rotation speed, and duration of spin-coating. The best conditions for each of these different parameters were subsequently used together to control the pore size and channel orientation of the well-organized films. Characterization of the films performed by X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that the films had homogeneous pores with a uni-directional orientation. Atomic force microscopy (AFM) and ellipsometric porosimetry analysis (EP) were employed to determine the orientation of the channels, pore size distribution, specific surface, thickness, and the accessible porosity. The present work constitutes an overall view of the different parameters which influence the formation of silica thin films, such as the thickness and the pore size distribution of a film which can be tailored to suit a potential application. The wettability properties of thin films have been studied by measuring the contact angle with different solvents such as water, isopropanol, and toluene.

Well-organized zeolite nanocrystal aggregates with interconnected hierarchically micro-meso-macropore systems showing enhanced catalytic performance.

Preparation and characterization of well-organized zeolitic nanocrystal aggregates with an interconnected hierarchically micro-meso-macro porous system are described. Amorphous nanoparticles in bimodal aluminosilicates were directly transformed into highly crystalline nanosized zeolites, as well as acting as scaffold template. All pores on three length scales incorporated in one solid body are interconnected with each other. These zeolitic nanocrystal aggregates with hierarchically micro-meso-macroporous structure were thoroughly characterized. TEM images and (29)Si NMR spectra showed that the amorphous phase of the initial material had been completely replaced by nanocrystals to give a micro-meso-macroporous crystalline zeolitic structure. Catalytic testing demonstrated their superiority due to the highly active sites and the presence of interconnected micro-meso-macroporosity in the cracking of bulky 1,3,5-triisopropylbenzene (TIPB) compared to traditional zeolite catalysts. This synthesis strategy was extended to prepare various zeolitic nanocrystal aggregates (ZSM-5, Beta, TS-1, etc.) with well-organized hierarchical micro-meso-macroporous structures.

Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compounds.

The use of porous materials to eliminate volatile organic compounds (VOCs) has proven very effective towards achieving sustainability and environmental protection goals. The activity of zeolites and macro-mesoporous metal-oxide supports in the total oxidation of VOCs has been investigated, with and without noble-metal deposition, to develop highly active catalyst systems where the formation of by-products was minimal. The first catalysts employed were zeolites, which offered a good activity in the oxidation of VOCs, but were rapidly deactivated by coke deposition. The effects of the acido-basicity and ionic exchange of these zeolites showed that a higher basicity was related to exchanged ions with lower electronegativities, resulting in better catalytic performances in the elimination of VOCs. Following on from this work, noble metals were deposited onto macro-mesoporous metal-oxide supports to form mono and bimetallic catalysts. These were then tested in the oxidation of toluene to study their catalytic performance and their deactivation process. PdAu/TiO(2) and PdAu/TiO(2) -ZrO(2) 80/20 catalysts demonstrated the best activity and life span in the oxidation of toluene and propene and offered the lowest temperatures for a 50 % conversion of VOCs and the lowest coke content after catalytic testing. Different characterization techniques were employed to explain the changes occurring in catalyst structure during the oxidation of toluene and propene.

Designing photobioreactors based on living cells immobilized in silica gel for carbon dioxide mitigation.

Atmospheric carbon dioxide levels have been rising since the industrial revolution, with the most dramatic increase occurring since the end of World War II. Carbon dioxide is widely regarded as one of the major factors contributing to the greenhouse effect, which is of major concern in today's society because it leads to global warming. Photosynthesis is Nature's tool for combating elevated carbon dioxide levels. In essence, photosynthesis allows a cell to harvest solar energy and convert it into chemical energy through the assimilation of carbon dioxide and water. Therefore photosynthesis is regarded as an ideal way to harness the abundance of solar energy that reaches Earth and convert anthropologically generated carbon dioxide into useful carbohydrates, providing a much more sustainable energy source. This Minireview aims to tackle the idea of immobilizing photosynthetic unicellular organisms within inert silica frameworks, providing protection both to the fragile cells and to the external ecosystem, and to use this resultant living hybrid material in a photobioreactor. The viability and activity of various unicellular organisms are summarized alongside design issues of a photobioreactor based on living hybrid materials.

Prolonging the lifetime and activity of silica immobilised Cyanidium caldarium.

Over the past few years the idea of living photosynthetic materials has advanced from concept to reality. This work outlines the improvements made in the immobilisation of the thermotolerant acidophile Cyanidium caldarium (Tilden) Geitler SAG 16.91 within porous and transparent silica gels with the view to targeting photochemical materials that can be used to mitigate rising CO(2) emissions. Our results suggest that the immobilised cells are autofluorescent for at least 75 days post encapsulation and can maintain a steady oxygen production rate over a similar timeframe corroborating the viability and physiological activity of silica immobilised C. caldarium.

Whole-cell based hybrid materials for green energy production, environmental remediation and smart cell-therapy.

This critical review highlights the advances that have been made over recent years in the domain of whole-cell immobilisation and encapsulation for applications relating to the environment and human health, particularly focusing on examples of photosynthetic plant cells, bacteria and algae as well as animal cells. Evidence that encapsulated photosynthetic cells remain active in terms of CO(2) sequestration and biotransformation (solar driven conversion of CO(2) into biofuels, drugs, fine chemicals etc.), coupled with the most recent advances made in the field of cell therapy, reveals the need to develop novel devices based on the preservation of living cells within abiotic porous frameworks. This review shall corroborate this statement by selecting precise examples that unambiguously demonstrate the necessity and the benefits of such smart materials. As will be described, the handling and exploitation of photosynthetic cells are enhanced by entrapment or encapsulation since the cells are physically separated from the liquid medium, thereby facilitating the recovery of the metabolites produced. In the case of animal cells, their encapsulation within a matrix is essential in order to create a physical barrier that can protect the cells auto-immune defenders upon implantation into a living body. For these two research axes, the key parameters that have to be kept in mind when designing hybrid materials will be identified, concentrating on essential aspects such as biocompatibility, mechanical strength and controlled porosity (264 references).

Living hybrid materials capable of energy conversion and CO2 assimilation.

This paper reviews our work on the fabrication of photobiochemical hybrid materials via immobilisation of photosynthetically active entities within silica materials, summarising the viability and productivity of these active entities post encapsulation and evaluating their efficiency as the principal component of a photobioreactor. Immobilisation of thylakoids extracted from spinach leaves as well as whole cells such as A. thaliana, Synechococcus and C. caldarium was carried out in situ using sol-gel methods. In particular, a comprehensive overview is given of the efforts to find the most biocompatible inorganic precursors that can extend the lifetime of the organisms upon encapsulation. The effect of matrix-cell interactions on cell lifetime and the photosynthetic efficiency of the resultant materials are discussed. Precursors based on alkoxides, commonly used in "Chimie Douce" to form porous silica gel, release by-products which are often cytotoxic. However by controlling the formation of gels from aqueous silica precursors and silica nanoparticles acting as "cements" one can significantly enhance the life span of the entrapped organelles and cells. Adapted characteristic techniques have shown survival times of up to 5 months with the photosynthetic production of oxygen recorded as much as 17 weeks post immobilisation. These results constitute a significant advance towards the final goal, long-lasting semi-artificial photobioreactors that can advantageously exploit solar radiation to convert polluting carbon dioxide into useful biofuels, sugars or medical metabolites.

Insight into cellular response of plant cells confined within silica-based matrices.

The encapsulation of living plant cells into materials could offer the possibility to develop new green biochemical technologies. With the view to designing new functional materials, the physiological activity and cellular response of entrapped cells within different silica-based matrices have been assessed. A fine-tuning of the surface chemistry of the matrix has been achieved by the in situ copolymerization of an aqueous silica precursor and a biocompatible trifunctional silane bearing covalently bound neutral sugars. This method allows a facile control of chemical and physical interactions between the entrapped plant cells and the scaffold. The results show that the cell-matrix interaction has to be carefully controlled in order to avoid the mineralization of the cell wall which typically reduces the bioavailability of nutrients. Under appropriate conditions, the introduction of a trifunctional silane (ca. 10%) during the preparation of hybrid gels has shown to prolong the biological activity as well as the cellular viability of plant cells. The relations of cell behavior with some other key factors such as the porosity and the contraction of the matrix are also discussed.