Hybrid Membranes of the Ureasil-Polyether Containing Glucose for Future Application in Bone Regeneration.

The application of mesenchymal stem cells (MSC) in bone tissue regeneration can have unpredictable results due to the low survival of cells in the process since the lack of oxygen and nutrients promotes metabolic stress. Therefore, in this work, polymeric membranes formed by organic-inorganic hybrid materials called ureasil-polyether for modified glucose release were developed in order to overcome the problems posed by a of lack of this nutrient. Thus, membranes formed by polymeric blend of polypropylene oxide (PPO4000) and polyethylene oxide (PEO500) with 6% glucose incorporation were developed. Physical-chemical characterization techniques were performed, as well as tests that evaluated thermal properties, bioactivity, swelling, and release in SBF solution. The results of the swelling test showed an increase in membrane mass correlated with an increase in the concentration of ureasil-PEO500 in the polymeric blends. The membranes showed adequate resistance when subjected to the application of a high compression force (15 N). X-ray diffraction (XRD) evidenced peaks corresponding to orthorhombic crystalline organization, but the absence of glucose-related peaks showed characteristics of the amorphous regions of hybrid materials, likely due to solubilization. Thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses showed that the thermal events attributed to glucose and hybrid materials were similar to that seen in the literature, however when glucose was incorporated into the PEO500, an increase in rigidity occurs. In PPO400, and in the blends of both materials, there was a slight decrease in Tg values. The smaller contact angle for the ureasil-PEO500 membrane revealed the more hydrophilic character of the material compared to other membranes. The membranes showed bioactivity and hemocompatibility in vitro. The in vitro release test revealed that it is possible to control the release rate of glucose and the kinetic analysis revealed a release mechanism characteristic of anomalous transport kinetics. Thus, we can conclude that ureasil-polyether membranes have great potential to be used as a glucose release system, and their future application has the potential to optimize the bone regeneration process.

Organic-Inorganic Hybrid Pigments Based on Bentonite: Strategies to Stabilize the Quinoidal Base Form of Anthocyanin.

Anthocyanins are one of the natural pigments that humanity has employed the most and can substitute synthetic food dyes, which are considered toxic. They are responsible for most purple, blue, and red pigment nuances in tubers, fruits, and flowers. However, they have some limitations in light, pH, oxygen, and temperature conditions. Combining biomolecules and inorganic materials such as clay minerals can help to reverse these limitations. The present work aims to produce materials obtained using cetyltrimethylammonium bromide in bentonite clay for incorporation and photostabilization of anthocyanin dye. Characterizations showed that the organic molecules were intercalated between the clay mineral layers, and the dye was successfully incorporated at a different pH. Visible light-driven photostability tests were performed with 200 h of irradiation, confirming that the organic-inorganic matrices were efficient enough to stabilize the quinoidal base form of anthocyanin. The pigment prepared at pH 10 was three-fold more stable than pH 4, showing that the increase in the synthesis pH promotes more stable colors, probably due to the stronger intermolecular interaction obtained under these conditions. Therefore, organobentonite hybrids allow to stabilize the fragile color coming from the quinoidal base form of anthocyanin dyes.

Practical and Rapid Membrane-Based Biosensor for Phenol Using Copper/Calcium-Enzyme Hybrid Nanoflowers.

Phenol, a pollutant frequently found in chemical industries effluents, is highly toxic even in low concentrations. This study reports a green, simple, and rapid method for qualitative phenol biosensing using horseradish peroxidase (HRP) hybrid nanoflowers made with copper (Cu2+-hNF) or calcium (Ca2+-hNF) ions. The enzyme was immobilized through protein-inorganic self-assembly into hybrid structures and subsequently supported onto a polyvinylidene fluoride (PVDF) membrane. SEM, EDS, FTIR, and XRD techniques sustained the effective enzyme encapsulation into hybrid structures. The protein concentration in the structures was 0.25 mg.mL-1 for both ions. The best temperature and pH were 60 °C and 7.4, respectively, for both hybrids and the free enzyme, suggesting that the immobilization did not affect the optimal conditions of the free HRP. Thermal stability from 25 to 70 °C and pH stability from 4.0 to 9.0 of the hybrids were also determined. Finally, using copper and calcium hybrids, both biosensors produced onto a PVDF membrane could detect phenol in concentrations ranging from 0.72 to 24.00 µmol.mL-1 in 1 min. In contrast, control biosensors produced with free enzyme have not presented a visible color change in the same conditions. The findings suggest a promising application of the developed biosensors in functional phenol detection.

Structural Properties of Epoxy-Silica Barrier Coatings for Corrosion Protection of Reinforcing Steel.

Reinforcement steel extensively applied in civil construction is susceptible to corrosion due to the carbonation process in reinforced concrete and chloride ions diffusion. Epoxy-silica-based coatings are a promising option to guarantee the long-term stability of reinforced concrete structures. In this study, the influence of the proportion between the poly (bisphenol-A-co-epichlorhydrin) resin (DGEBA) and the curing agent diethylenetriamine (DETA) on the structural, morphological, and barrier properties of epoxy-silica nanocomposites were evaluated. To simulate different stages of concrete aging, electrochemical impedance spectroscopy (EIS) assays were performed for coated samples in a 3.5 wt.% NaCl solution (pH 7) and in simulated concrete pore solutions (SCPS), which represent the hydration environment in fresh concrete (SCPS2, pH 14) and after carbonation (SCPS1, pH 8). The results showed that coatings with an intermediate DETA to DGEBA ratio of 0.4, presented the best long-term corrosion protection with a low-frequency impedance modulus of up to 3.8 GΩ cm2 in NaCl and SCPS1 solutions. Small-angle X-ray scattering and atomic force microscopy analysis revealed that the best performance observed for the intermediate DETA proportion is associated with the presence of larger silica nanodomains, which act as a filler in the cross-linked epoxy matrix, thus favoring the formation of an efficient diffusion barrier.

Dexamethasone-Loaded Ureasil Hydrophobic Membrane for Bone Guided Regeneration.

Physical barrier membranes have been used to release active substances to treat critical bone defects; however, hydrophilic membranes do not present a prolonged release capacity. In this sense, hydrophobic membranes have been tested. Thus, this study aimed to develop hydrophobic membranes based on mixtures of ureasil-polyether-type materials containing incorporated dexamethasone (DMA) for the application in guided bone regeneration. The physicochemical characterization and biological assays were carried out using small-angle X-ray scattering (SAXS), an in vitro DMA release study, atomic force microscopy (AFM), a hemolysis test, and in vivo bone formation. The swelling degree, SAXS, and release results revealed that the u-PPO400/2000 membrane in the proportion of 70:30 showed swelling (4.69% ± 0.22) similar to the proportions 90:10 and 80:20, and lower than the proportion 60:40 (6.38% ± 0.49); however, an equal release percentage after 134 h was observed between the proportions 70:30 and 60:40. All u-PPO materials presented hemocompatibility (hemolysis ≤2.8%). AFM results showed that the treatments with or without DMA did not present significant differences, revealing a flat/smooth surface, with no pores and/or crystalline precipitates. Finally, in vivo results revealed that for both the commercial hydrophilic membrane and u-PPO400/2000 (70:30) after 60 days, the bone formation volume was 21%. In conclusion, hybrid membranes present unique characteristics for treating critical bone defects, considering the delayed and prolonged release results associated with the physical barrier capacity.

Hybrid Organic-Inorganic Materials and Interfaces With Mixed Ionic-Electronic Transport Properties: Advances in Experimental and Theoretical Approaches.

The main goal of this mini-review is to provide an updated state-of-the-art of the hybrid organic-inorganic materials focusing mainly on interface phenomena involving ionic and electronic transport properties. First, we review the most relevant preparation techniques and the structural features of hybrid organic-inorganic materials prepared by solution-phase reaction of inorganic/organic precursor into organic/inorganic hosts and vapor-phase infiltration of the inorganic precursor into organic hosts and molecular layer deposition of organic precursor onto the inorganic surface. Particular emphasis is given to the advances in joint experimental and theoretical studies discussing diverse types of computational simulations for hybrid-organic materials and interfaces. We make a specific revision on the separately ionic, and electronic transport properties of these hybrid organic-inorganic materials focusing mostly on interface phenomena. Finally, we deepen into mixed ionic-electronic transport properties and provide our concluding remarks and give some perspectives about this growing field of research.

Nitric Oxide-Releasing Supramolecular Cellulose Nanocrystal/Silsesquioxane Foams.

Cellulose nanocrystals (CNC)-based foams are promising tissue engineering materials that may facilitate implant-tissue integration and allow localized and controlled drug delivery. Herein, hybrid CNC-based foams, which are ultralightweight (30-100 mg cm-3 ), highly porous (>95%), ominiphilic and superabsorbent (1500-3000 wt% of water and/or toluene uptake) are obtained by the in situ condensation of poly(ethylene glycol) ditriethoxysilyl (TES-PEG-TES) into a 3D network, where silsesquioxane nanoparticles (SS-NP) are the crosslinking nodes, and CNC are entrapped forming ionic interactions, in a supramolecular structure. In a new approach, using 3-mercaptopropyltrimethoxysilane, sulfhydryl groups are inserted on the SS-NP periphery and S-nitrosated to enable the functionalization of SS-NP with S-nitrosothiol groups, which can nitric oxide (NO), in a process triggered by the hydration of the foams and modulated by their supramolecular structure. CNC-SS-PEG foams exhibit elevated thermal and structural stability, compressive strength compatible with various soft human tissues, and NO release rates (1-18 pmol mg-1 min-1 ) within the range of the beneficial NO actions. Thus, the CNC-SS-PEG foams herein described represent a new platform of supramolecular hybrid materials for localized delivery of NO, with potential uses in tissue engineering and other biomedical applications.

High performance biocatalyst based on ß-d-galactosidase immobilized on mesoporous silica/titania/chitosan material.

A new support for the immobilization of ß-d-galactosidase from Kluyveromyces lactis was developed, consisting of mesoporous silica/titania with a chitosan coating. This support presents a high available surface area and adequate pore size for optimizing the immobilization efficiency of the enzyme and, furthermore, maintaining its activity. The obtained supported biocatalyst was applied in enzyme hydrolytic activity tests with o-NPG, showing high activity 1223 Ug-1, excellent efficiency (74%), and activity recovery (54%). Tests of lactose hydrolysis in a continuous flow reactor showed that during 14 days operation, the biocatalyst maintained full enzymatic activity. In a batch system, after 15 cycles, it retained approximately 90% of its initial catalytic activity and attained full conversion of the lactose 100% (±12%). Additionally, with the use of the mesoporous silica/titania support, the biocatalyst presented no deformation and fragmentation, in both systems, demonstrating high operational stability and appropriate properties for applications in food manufacturing.

Synthesis of ureasil-polyether film forming materials by using environmentally friendly solvent

Organic inorganic hybrids present several advantages as drug release systems, such as: high flexibility, high mechanical and thermal resistance, transparency, and low water solubility. These hybrids are synthesized through a chemical route named sol-gel that usually uses as solvente tetrahydrofuran (THF). Objetives: To develop film formers from hybrid materials replacing THF with ethanol, a less toxic solvent for skin application and for the environment. Methods: Four polymers were used: two based on polyethylene oxide (PEO) with molecular weight of 500 and 1900 g mol-1 and two based on polypropylene oxide (PPO), with molecular weight of 400 and 2000 g mol-1. The structural analysis was performed by FTIR, 1H-NMR and 29Si-NMR, and the thermal-mechanical analysis by DSC and TG-DTA. Results: The results of the thermo-mechanical analysis revealed that the solvent replacement did not affect the thermal stability and flexibility of the di-ureasil hybrid. Conclusions: Structural characterization confirmed the formation of hybrids both in THF and in ethanol. Therefore, ethanol is an excellent solvent for the synthesis of these hybrid matrices, since it allows obtaining the same material without changing its characteristics, with some advantages, however, over THF. Furthermore, this paper describes the efficiency of ethanol as a solvent, which is environmentally friendly, to replace THF in the physical-chemical characteristics of these filming former materials.

Hydroxyapatite and ß-TCP modified PMMA-TiO2 and PMMA-ZrO2 coatings for bioactive corrosion protection of Ti6Al4V implants.

Organic-inorganic hybrid coatings deposited on different types of metallic alloys have shown outstanding anticorrosive performance. The incorporation of osteoconductive additives such as hydroxyapatite (HA) and ß-tricalcium phosphate (ß-TCP) into organic-inorganic hybrid coatings is promising to improve the osseointegration and corrosion resistance of Ti6Al4V alloys, which are the most widely used metallic orthopedic and dental implant materials today. Therefore, this study evaluated the capability of poly(methyl methacrylate) (PMMA)-TiO2 and PMMA-ZrO2 hybrid coatings modified with HA and ß-TCP to act as bioactive and corrosion protection coatings for Ti6Al4V alloys. In terms of cell growth and mineralization, osteoblast viability, Ca+2 deposition and alkaline phosphatase assays revealed a significant improvement for the HA and ß-TCP modified coatings, compared to the bare alloy. This can be explained by an increase in nanoscale roughness and associated higher surface free energy, which lead to enhanced protein adsorption to promote osteoblast attachment and functions on the coatings. The effect of HA and ß-TCP additives on the anticorrosive efficiency was studied by electrochemical impedance spectroscopy (EIS) in a simulated body fluid (SBF) solution. The coatings presented a low-frequency impedance modulus of up to 430 GΩ cm2, 5 decades higher than the bare Ti6Al4V alloy. These findings provide clear evidence of the beneficial role of HA and ß-TCP modified hybrid coatings, improving both the biocompatibility and corrosion resistance of the Ti6Al4V alloy.

Mini-Review: Mixed Ionic-Electronic Charge Carrier Localization and Transport in Hybrid Organic-Inorganic Nanomaterials.

In this mini-review, a comprehensive discussion on the state of the art of hybrid organic-inorganic mixed ionic-electronic conductors (hOI-MIECs) is given, focusing on conducting polymer nanocomposites comprising inorganic nanoparticles ranging from ceramic-in-polymer to polymer-in-ceramic concentration regimes. First, a brief discussion on fundamental aspects of mixed ionic-electronic transport phenomena considering the charge carrier transport at bulk regions together with the effect of the organic-inorganic interphase of hybrid nanocomposites is presented. We also make a recount of updated instrumentation techniques to characterize structure, microstructure, chemical composition, and mixed ionic-electronic transport with special focus on those relevant for hOI-MIECs. Raman imaging and impedance spectroscopy instrumentation techniques are particularly discussed as relatively simple and versatile tools to study the charge carrier localization and transport at different regions of hOI-MIECs including both bulk and interphase regions to shed some light on the mixed ionic-electronic transport mechanism. In addition, we will also refer to different device assembly configurations and in situ/operando measurements experiments to analyze mixed ionic-electronic conduction phenomena for different specific applications. Finally, we will also review the broad range of promising applications of hOI-MIECs, mainly in the field of energy storage and conversion, but also in the emerging field of electronics and bioelectronics.

Partial replacement of inorganic phosphorus (P) by organic manure reshapes phosphate mobilizing bacterial community and promotes P bioavailability in a paddy soil.

The optimization of more sustainable fertilization practice to relieve phosphorus (P) resource scarcity and increase P fertilizer utilization, a better understanding of the regulatory roles of microbes in P mobilization is urgently required to reduce P input. The genes phoD and pqqC are responsible for regulating organic and inorganic P mobilization, respectively. Using high-throughput sequencing, the corresponding bacterial communities harbored by these genes were determined. We conducted a 4-year rice-rice-crop rotation to investigate the responses of phoD- and pqqC-harboring bacterial communities to the partial replacement of inorganic P fertilizer by organic manure with reduced P input. The results showed that a combination of organic and inorganic fertilization maintained high rice yield, and also produced a more complex and stable phosphate mobilizing bacterial community, which contributed to phosphatase activities more than their gene abundances in the model analysis. Compared with the conventional mineral fertilization, organic-inorganic fertilization with the reduced P input slightly increased pqqC gene abundance while significantly enhanced the abundance of phoD-harboring bacteria, especially the genera Bradyrhizobium and Methylobacterium known as potential organic P mineralizers which can maintain high rice production. Moreover, the increased pH was the most impactful factor for the phoD- and pqqC-harboring bacterial communities, by promoting microbial P turnover and greatly increasing bioavailable P pools (H2O-Pi and NaHCO3-Pi, NaOH-Pi) in this P-deficient paddy soil. Hence, our study demonstrated that the partial replacement of mineral P with organic manure could reshape the inorganic phosphate solubilizing and alkaline-phosphomonoesterase encoding bacterial communities towards more resilient and effective to the high P utilization and productivity over intense cultivation, providing insights into the potential of soil microbes in the efficient management of agricultural P fertilization.

Ultrafast fabrication of thermally stable protein-coated silver iodide nanoparticles for solid-state superionic conductors.

Solid-state ionic conductor is an essential and critical part of electrochemical devices such as batteries and sensors. Nano-sized silver iodide (AgI) is the most promising ionic conductor due to its superionic conductivity at room temperature. In recent years, proteins have been used as organic templates to obtain high-performance solid-state ionic conductors as well as to extend their applications in a biosensor. Here, we report the unprecedented ultrafast synthesis of thermally stable protein-coated AgI nanoparticles (NPs) through the photo-irradiation method for solid-state electrolyte. The synthesis was performed using a hyperthermostable bacterial ß-glucosidase. The protein-coated AgI NPs with an approximate diameter of 13 nm showed that the controllable transition from the α- to ß-/γ-phase was drastically suppressed down to 41 °C in the cooling process. After drying, the product represents a thermally stable organic-inorganic hybrid system with superionic conductivity. It is noteworthy that the superionic conductivity (σ ˜ 0.14 S/cm at 170 °C) of thermally stable protein-coated AgI NPs is maintained during several thermal cycles (25-170 °C). To our knowledge, this is the first report showing the diffusion of mobile Ag+ ions on the surface of the AgI NPs through a protein matrix. The facile synthesis method and high performance of the protein-coated AgI NPs may provide a latent application in the mass production of nanobatteries and other technological applications.

Recent Advances in Synthesis and Properties of Hybrid Halide Perovskites for Photovoltaics.

The progress made by the scientific community in emerging photovoltaic technologies over the past two decades has been outstanding. Numerous methods have been developed for the preparation of hybrid organic-inorganic perovskite solar cells. The power conversion efficiency has been up to 14% by a one-step vacuum deposition technique. A serious concern is the toxicity of the materials. In this review, several methods aimed at resolving these problems to some extent have been compiled, including eco-friendly synthesis. Further efficiency enhancements are expected following optimization, and a better fundamental understanding of the internal electron charge transfer, electron-hole diffusion to the corresponding layers, flexibility, and stability-dependent bandgaps is reported. This paper explores the green synthesis of organic-inorganic perovskites for industrialization. Concerning the above facts, a simple low-cost model called "dispersed photovoltaic cells" is presented.

Removal of the emerging contaminant bisphenol A by an ureasil-PEO hybrid membrane: experimental study and molecular dynamic simulation.

This work reports the use of a cross-linked ureasil-PEO hybrid matrix (designated PEO800) as an efficient adsorbent to retain the emerging contaminant bisphenol A (BPA) from an aqueous medium. The in-deep experimental and theoretical results provide information about the interactions between PEO800 and BPA. The in situ UV-vis spectroscopy data and the pseudo-first order, pseudo-second order, Elovich, and Morris-Webber intraparticle diffusion models allowed us to propose a three-step mechanism for the adsorption of BPA onto PEO800. The results indicate that the pseudo-first-order kinetic model effectively describes the adsorption of BPA onto PEO800. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy confirmed the interaction of PEO800 with BPA, showing an alteration in the chemical environment of the polymer ether oxygen atoms present in the hybrid matrix. The molecular dynamic simulation provides further evidence that the BPA molecules interact preferentially with PEO. The amount of desorbed BPA depended on the pH and solvent used in the assays. This work provides new opportunities for using the hydrophilic ureasil-PEO matrix which has demonstrated its abilities in being a fast and easy alternative to successfully removing organic contaminants from aqueous mediums and therefore having potential applications in water remediation. Graphical abstract.

Drug Delivery Systems Obtained from Silica Based Organic-Inorganic Hybrids.

This is a review of hybrid materials based on silica as an inorganic phase used as drug delivery systems (DDS). Silica based DDS have shown effectivity when compared with traditional delivery systems. They present advantages such as: (a) ability to maintain the therapeutic range with minor variations; (b) prevention of local and systemic toxic effects; (c) plasma concentrations increase of substances with a short half-life; and (d) reduction of the number of daily doses, which may increase patient adherence to the treatment. These advantages occur due to the physical, chemical and optical properties of these materials. Therefore, we discuss the properties and characteristics of them and we present some applications, using different approaches of DDS to ensure therapeutic effectiveness and side effects reduction such as implantable biomaterial, film-forming materials, stimuli-responsive systems and others.

Analysis of drugs in plasma samples from schizophrenic patients by column-switching liquid chromatography-tandem mass spectrometry with organic-inorganic hybrid cyanopropyl monolithic column.

This study reports on the development of a rapid, selective, and sensitive column-switching liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to analyze sixteen drugs (antidepressants, anticonvulsants, anxiolytics, and antipsychotics) in plasma samples from schizophrenic patients. The developed organic-inorganic hybrid monolithic column with cyanopropyl groups was used for the first dimension of the column-switching arrangement. This arrangement enabled online pre-concentration of the drugs (monolithic column) and their subsequent analytical separation on an XSelect SCH C18 column. The drugs were detected on a triple quadrupole tandem mass spectrometer (multiple reactions monitoring mode) with an electrospray ionization source in the positive ion mode. The developed method afforded adequate linearity for the sixteen target drugs; the coefficients of determination (R(2)) lay above 0.9932, the interassay precision had coefficients of variation lower than 6.5%, and the relative standard error values of the accuracy ranged from -14.0 to 11.8%. The lower limits of quantification in plasma samples ranged from 63 to 1250pgmL(-1). The developed method successfully analyzed the target drugs in plasma samples from schizophrenic patients for therapeutic drug monitoring (TDM).

Two novel organic-inorganic hybrid materials from tetrachloridometallate(II) salts and 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium.

Two organic-inorganic hybrid compounds have been prepared by the combination of the 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium cation with perhalometallate anions to give 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium tetrachloridocobaltate(II), (C12H12N2)[CoCl4], (I), and 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium tetrachloridozincate(II), (C12H12N2)[ZnCl4], (II). The compounds have been structurally characterized by single-crystal X-ray diffraction analysis, showing the formation of a three-dimensional network through X-H...ClnM(-) (X = C, N(+); n = 1, 2; M = Co(II), Zn(II)) hydrogen-bonding interactions and π-π stacking interactions. The title compounds were also characterized by FT-IR spectroscopy and thermogravimetric analysis (TGA).

Improved selective cholesterol adsorption by molecularly imprinted poly(methacrylic acid)/silica (PMAA-SiO2) hybrid material synthesized with different molar ratios.

The present paper describes the synthesis of molecularly imprinted polymer - poly(methacrylic acid)/silica and reports its performance feasibility with desired adsorption capacity and selectivity for cholesterol extraction. Two imprinted hybrid materials were synthesized at different methacrylic acid (MAA)/tetraethoxysilane (TEOS) molar ratios (6:1 and 1:5) and characterized by FT-IR, TGA, SEM and textural data. Cholesterol adsorption on hybrid materials took place preferably in apolar solvent medium, especially in chloroform. From the kinetic data, the equilibrium time was reached quickly, being 12 and 20 min for the polymers synthesized at MAA/TEOS molar ratio of 6:1 and 1:5, respectively. The pseudo-second-order model provided the best fit for cholesterol adsorption on polymers, confirming the chemical nature of the adsorption process, while the dual-site Langmuir-Freundlich equation presented the best fit to the experimental data, suggesting the existence of two kinds of adsorption sites on both polymers. The maximum adsorption capacities obtained for the polymers synthesized at MAA/TEOS molar ratios of 6:1 and 1:5 were found to be 214.8 and 166.4 mg g(-1), respectively. The results from isotherm data also indicated higher adsorption capacity for both imprinted polymers regarding to corresponding non-imprinted polymers. Nevertheless, taking into account the retention parameters and selectivity of cholesterol in the presence of structurally analogue compounds (5-α-cholestane and 7-dehydrocholesterol), it was observed that the polymer synthesized at the MAA/TEOS molar ratio of 6:1 was much more selective for cholesterol than the one prepared at the ratio of 1:5, thus suggesting that selective binding sites ascribed to the carboxyl group from MAA play a central role in the imprinting effect created on MIP.