Activation of crosslinked lipases in mesoporous silica via lid opening for recyclable biodiesel production.

Lipases catalyze a wide range of industrially important reactions, including the transesterification of triglycerides with alcohols for biodiesel production, and the stabilization of lipases are critical to achieve their recycled uses. Here, nanoscale enzyme reactor (NER) of lipase from Rhizopus oryzae (LP) was prepared via a simple two-step process, comprising of enzyme adsorption into magnetically-separable mesoporous silica and follow-up crosslinking of adsorbed enzymes. In aqueous phase, the specific hydrolysis activity of NER-LP was 4.7 times lower than that of free LP. On the other hand, however, the specific transesterification activity of NER-LP (130.4 µmol/min/mg LP) in organic phase for biodiesel production was 50 times higher than that of free LP (2.6 µmol/min/mg LP). These results reveal that the enzyme crosslinking for the preparation of NER does not interfere with the interfacial activation of LP molecules, opening the lid of LP active site under an optimal hydrophobic environment provided by the combination of organic solvent and mesoporous silica. Magnetic separation and optimized washing protocol facilitated the recycled uses of NER-LP. Highly stable and active NER-LP in magnetically-separable mesoporous silica has demonstrated its great potentials as an environmentally-friendly nanobiocatalyst for various lipase applications, including plasticizers, biosurfactants, functional fatty acids, as well as recyclable biodiesel production.

A class of diatomic 2-D soft granular crystals undergoing pattern transformations.

We propose a class of diatomic 2-D soft granular crystals, which features pattern transformation under compression with lateral confinement. The proposed granular crystals are composed of two different types of cylinders: large soft cylinders and small hard cylinders. The pattern-transformable granular crystals are obtained by exploring perturbed packing patterns as potential configurations, and compression with lateral confinement as the driving force of the transition. As a demonstration of the proof-of-concept, we first show the results of desktop-scaled experiments and finite element simulations for a representative case. Then, we present the procedure to obtain these new pattern transformations in soft granular crystals based on the compact packing theory of diatomic circles. The scale-independent compact packing theory serves as an important part of the veiled underlying mechanism of the observed pattern transformations, so the proposed granular crystals can open new avenues in the microstructural design of functional materials towards practical applications.

Highly Sensitive, Flexible, and Wearable Pressure Sensor Based on a Giant Piezocapacitive Effect of Three-Dimensional Microporous Elastomeric Dielectric Layer.

We report a flexible and wearable pressure sensor based on the giant piezocapacitive effect of a three-dimensional (3-D) microporous dielectric elastomer, which is capable of highly sensitive and stable pressure sensing over a large tactile pressure range. Due to the presence of micropores within the elastomeric dielectric layer, our piezocapacitive pressure sensor is highly deformable by even very small amounts of pressure, leading to a dramatic increase in its sensitivity. Moreover, the gradual closure of micropores under compression increases the effective dielectric constant, thereby further enhancing the sensitivity of the sensor. The 3-D microporous dielectric layer with serially stacked springs of elastomer bridges can cover a much wider pressure range than those of previously reported micro-/nanostructured sensing materials. We also investigate the applicability of our sensor to wearable pressure-sensing devices as an electronic pressure-sensing skin in robotic fingers as well as a bandage-type pressure-sensing device for pulse monitoring at the human wrist. Finally, we demonstrate a pressure sensor array pad for the recognition of spatially distributed pressure information on a plane. Our sensor, with its excellent pressure-sensing performance, marks the realization of a true tactile pressure sensor presenting highly sensitive responses to the entire tactile pressure range, from ultralow-force detection to high weights generated by human activity.

Effective antifouling using quorum-quenching acylase stabilized in magnetically-separable mesoporous silica.

Highly effective antifouling was achieved by immobilizing and stabilizing an acylase, disrupting bacterial cell-to-cell communication, in the form of cross-linked enzymes in magnetically separable mesoporous silica. This so-called "quorum-quenching" acylase (AC) was adsorbed into spherical mesoporous silica (S-MPS) with magnetic nanoparticles (Mag-S-MPS), and further cross-linked for the preparation of nanoscale enzyme reactors of AC in Mag-S-MPS (NER-AC/Mag-S-MPS). NER-AC effectively stabilized the AC activity under rigorous shaking at 200 rpm for 1 month, while free and adsorbed AC lost more than 90% of their initial activities in the same condition within 1 and 10 days, respectively. When applied to the membrane filtration for advanced water treatment, NER-AC efficiently alleviated the biofilm maturation of Pseudomonas aeruginosa PAO1 on the membrane surface, thereby enhancing the filtration performance by preventing membrane fouling. Highly stable and magnetically separable NER-AC, as an effective and sustainable antifouling material, has a great potential to be used in the membrane filtration for water reclamation.

3D soft metamaterials with negative Poisson's ratio.

Buckling is exploited to design a new class of three-dimensional metamaterials with negative Poisson's ratio. A library of auxetic building blocks is identified and procedures are defined to guide their selection and assembly. The auxetic properties of these materials are demonstrated both through experiments and finite element simulations and exhibit excellent qualitative and quantitative agreement.

One-pot synthesis of tin-embedded carbon/silica nanocomposites for anode materials in lithium-ion batteries.

We report a facile "one-pot" method for the synthesis of Sn-embedded carbon-silica (CS) mesostructured (nanostructured) composites through the selective interaction of resol (carbon precursor), tetraethylorthosilicate (TEOS), and tributylphenyltin (Sn precursor) with an amphiphilic diblock copolymer, poly(ethylene oxide-b-styrene), PEO-b-PS. A unique morphology transition from Sn nanowires to spherical Sn nanoparticles embedded in CS framework has been obtained. Metallic Sn species are homogeneously embedded in a rigid CS framework and are effectively confined within the nanostructures. The resulting composites are used as anode materials for lithium-ion batteries and exhibit high specific capacities (600 mA h g⁻¹ at a current density of 45 mA g⁻¹, and 440 mA h g⁻¹ at a current density of 300 mA g⁻¹) and an excellent cyclability of over 100 cycles with high Coulombic efficiency. Most of all, the novel method developed in this work for synthesizing functional hybrid materials can be extended to the preparation of various functional nanocomposites owing to its versatility and facileness.

A convenient alcohol sensor using one-pot nanocomposite entrapping alcohol oxidase and magnetic nanoparticles as peroxidase mimetics.

A colorimetric biosensor for convenient quantification of ethanol and methanol is described. The biosensor utilizes a 'one-pot' nanocomposite consisting of Fe3O4 magnetic nanoparticles (MNPs) and alcohol oxidase (Al Ox) simultaneously entrapped in large pore sized mesocellular silica. Al Ox immobilized in the silica generates H2O2 in the presence of alcohol in a sample, which subsequently activates MNPs in the mesopores of the silica to convert a colorimetric substrate into a colored product. Using this strategy, a target alcohol was specifically detected through a very convenient colorimetric signal resulting from the combined reactions. This strategy enabled successful sensing of ethanol and methanol in a linear concentration range from 100 to 500 microM with a detection limit as low as 25 microM by employing 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) diammonium salt (ABTS) as a peroxidase substrate. Along with excellent reusability via simple magnetic capturing, enhanced operational stability was achieved by the nanocomposite system. The present nanocomposite would serve as a novel platform for rapid and convenient analysis of alcohol.

One-pot synthesis of intermetallic electrocatalysts in ordered, large-pore mesoporous carbon/silica toward formic acid oxidation.

This study describes the one-pot synthesis and single-cell characterization of ordered, large-pore (>30 nm) mesoporous carbon/silica (OMCS) composites with well-dispersed intermetallic PtPb nanoparticles on pore wall surfaces as anode catalysts for direct formic acid fuel cells (DFAFCs). Lab-synthesized amphiphilic diblock copolymers coassemble hydrophobic metal precursors as well as hydrophilic carbon and silica precursors. The final materials have a two-dimensional hexagonal-type structure. Uniform and large pores, in which intermetallic PtPb nanocrystals are significantly smaller than the pore size and highly dispersed, enable pore backfilling with ionomers and formation of the desired triple-phase boundary in single cells. The materials show more than 10 times higher mass activity and significantly lower onset potential for formic acid oxidation as compared with commercial Pt/C, as well as high stability due to better resistivity toward CO poisoning. In single cells, the maximum power density was higher than that of commercial Pt/C, and the stability highly improved, compared with commercial Pd/C. The results suggest that PtPb-based catalysts on large-pore OMCSs may be practically applied as real fuel cell catalysts for DFAFC.

Buckling-induced encapsulation of structured elastic shells under pressure.

We introduce a class of continuum shell structures, the Buckliball, which undergoes a structural transformation induced by buckling under pressure loading. The geometry of the Buckliball comprises a spherical shell patterned with a regular array of circular voids. In order for the pattern transformation to be induced by buckling, the possible number and arrangement of these voids are found to be restricted to five specific configurations. Below a critical internal pressure, the narrow ligaments between the voids buckle, leading to a cooperative buckling cascade of the skeleton of the ball. This ligament buckling leads to closure of the voids and a reduction of the total volume of the shell by up to 54%, while remaining spherical, thereby opening the possibility of encapsulation. We use a combination of precision desktop-scale experiments, finite element simulations, and scaling analyses to explore the underlying mechanics of these foldable structures, finding excellent qualitative and quantitative agreement. Given that this folding mechanism is induced by a mechanical instability, our Buckliball opens the possibility for reversible encapsulation, over a wide range of length scales.

Nano-graphite functionalized mesocellular carbon foam with enhanced intra-penetrating electrical percolation networks for high performance electrochemical energy storage electrode materials.

Mesocellular carbon foam (MSU-F-C) is functionalized with hollow nanographite by a simple solution-phase method to enhance the intrapenetrating electrical percolation network. The electrical conductivity of the resulting material, denoted as MSU-F-C-G, is increased by a factor of 20.5 compared with the pristine MSU-F-C. Hollow graphite nanoparticles are well-dispersed in mesocellular carbon foam, as confirmed by transmission electron microscopy (TEM), and the d spacing of the (002) planes is 0.343 nm, which is only slightly larger than that of pure graphite (0.335 nm), suggesting a random combination of graphitic and turbostratic stacking. After nanographitic functionalization, the BET surface area and total pore volume decreased from 928 m(2) g(-1) and 1.5 cm(3) g(-1) to 394 m(2) g(-1) and 0.7 cm(3) g(-1), respectively. Thermogravimetric analysis in air shows that the thermal stability of MSU-F-C-G is improved relative to that of MSU-F-C, and the one-step weight loss indicates that the nanographite is homogeneously functionalized on the MSU-F-C particles. When the resulting mesocellular carbon materials are used as electrode materials for an electric double layer capacitor (EDLC), the specific capacitances (C(sp)) of the MSU-F-C and MSU-F-C-G electrodes at 4 mV s(-1) are 109 F g(-1) and 93 F g(-1), respectively. The MSU-F-C-G electrode exhibited a very high area capacitance (C(area), 23.5 µF cm(-2)) compared with that of the MSU-F-C electrode (11.7 µF cm(-2)), which is attributed to the enhanced intraparticle conductivity by the nanographitic functionalization. MSU-F-C-G exhibited high capacity retention (52%) at a very high scan rate of 512 mV s(-1), while only a 23% capacity retention at 512 mV s(-1) was observed in the case of the MSU-F-C electrode. When applied as an anode in a lithium ion battery, a significant increase in the initial efficiency (44%), high reversible discharge capacity (580 mA h g(-1)) in the lower voltage region, and a higher rate capability were observed. The high rate capability of the MSU-F-C-G electrode as charge storage was due to the low resistance derived from the nanographitic functionalization.

Colorimetric quantification of galactose using a nanostructured multi-catalyst system entrapping galactose oxidase and magnetic nanoparticles as peroxidase mimetics.

A colorimetric method for quantification of galactose, which utilizes a nanostructured multi-catalyst system consisting of Fe(3)O(4) magnetic nanoparticles (MNPs) and galactose oxidase (Gal Ox) simultaneously entrapped in large pore sized mesocellular silica, is described. Gal Ox, immobilized in a silica matrix, promotes reaction of galactose to generate H(2)O(2) that subsequently activates MNPs in silica mesopores to convert a colorimetric substrate into a colored product. By using this colorimetric method, galactose can be specifically detected. Along with excellent reusability via application of simple magnetic capturing, enhanced operational stability was achieved by employing a cross-linked enzyme aggregate (CLEA) method for Gal Ox immobilization. This protocol leads to effective prevention of enzyme leaching from the pores of mesocellular silica. The analytical utility of the new colorimetric biosensor was demonstrated by its use in diagnosing galactosemia, a genetic metabolic disorder characterized by the inability to utilize galactose, through analysis of clinical dried blood spot specimens. A microscale well-plate format was employed that possesses a multiplexing capability. The multi-catalyst system entrapping Gal Ox and MNPs represents a new approach for rapid, convenient, and cost-effective quantification of galactose in human blood and it holds promise as an alternative method for galactosemia diagnosis, replacing the laborious procedures that are currently in use.

Modeling of cardiac muscle thin films: pre-stretch, passive and active behavior.

Recent progress in tissue engineering has made it possible to build contractile bio-hybrid materials that undergo conformational changes by growing a layer of cardiac muscle on elastic polymeric membranes. Further development of such muscular thin films for building actuators and powering devices requires exploring several design parameters, which include the alignment of the cardiac myocytes and the thickness/Young's modulus of elastomeric film. To more efficiently explore these design parameters, we propose a 3-D phenomenological constitutive model, which accounts for both the passive deformation including pre-stretch and the active behavior of the cardiomyocytes. The proposed 3-D constitutive model is implemented within a finite element framework, and can be used to improve the current design of bio-hybrid thin films and help developing bio-hybrid constructs capable of complex conformational changes.

Fabrication of nanoporous nanocomposites entrapping Fe3O4 magnetic nanoparticles and oxidases for colorimetric biosensing.

A nanostructured multicatalyst system consisting of Fe(3)O(4) magnetic nanoparticles (MNPs) as peroxidase mimetics and an oxidative enzyme entrapped in large-pore-sized mesoporous silica has been developed for convenient colorimetric detection of biologically important target molecules. The construction of the nanocomposites begins with the incorporation of MNPs on the walls of mesocellular silica pores by impregnating Fe(NO(3))(3)·9H(2)O, followed by the immobilization of oxidative enzymes. Glutaraldehyde crosslinking was employed to prevent enzymes leaching from the pores and led to over 20 wt% loading of the enzyme. The oxidase in the nanocomposite generates H(2)O(2) through its catalytic action for target molecules and subsequently activates MNPs to convert selected substrates into colored products. Using this strategy, two different biosensing systems were constructed employing glucose oxidase and cholesterol oxidase and their analytical capabilities were successfully verified by colorimetrically detecting the corresponding target molecules with excellent selectivity, sensitivity, reusability, and stability. Future potential applications of this technology range from biosensors to multicatalyst reactors.

Block copolymer directed one-pot simple synthesis of L10-phase FePt nanoparticles inside ordered mesoporous aluminosilicate/carbon composites.

A "one-pot" synthetic method was developed to produce L1(0)-phase FePt nanoparticles in ordered mesostructured aluminosilicate/carbon composites using polyisoprene-block-poly(ethylene oxide) (PI-b-PEO) as a structure-directing agent. PI-b-PEO block copolymers with aluminosilicate sols are self-assembled with a hydrophobic iron precursor (dimethylaminomethyl-ferrocene) and a hydrophobic platinum precursor (dimethyl(1,5-cyclooctadiene)platinum(II)) to obtain mesostructured composites. The as-synthesized material was heat-treated to 800 °C under an Ar/H(2) mixture (5% v/v), resulting in the formation of fct FePt nanocrystals encapsulated in ordered mesopores. By changing the quantities of the Fe and Pt precursors in the composite materials, the average particle size of the resulting fct FePt, estimated using the Debye-Scherer equation with X-ray diffraction patterns, can be easily controlled to be 2.6-10.4 nm. Using this simple synthetic method, we can extend the size of directly synthesized fct FePt up to ∼10 nm, which cannot be achieved directly in the colloidal synthetic method. All fct FePt nanoparticles show hysteresis behavior at room temperature, which indicates that ferromagnetic particles are obtained inside mesostructued channels. Well-isolated, ∼10 nm fct FePt have a coercivity of 1100 Oe at 300 K. This coercivity value is higher than values of fct FePt nanoparticles synthesized through the tedious hard template method by employing SBA-15 as a host material. The coercivity value for FePt-1 (2.6 nm) at 5 K is as high as 11 900 Oe, which is one of the largest values reported for FePt nanoparticles, or any other magnetic nanoparticles. The fct FePt nanoparticles also showed exchange-bias behavior.

Enhanced photocatalytic activity of highly crystallized and ordered mesoporous titanium oxide measured by silicon resonators.

Ordered mesoporous TiO(2) was synthesized using the combined assembly of soft and hard chemistries method and deposited as a film coating on a microcantilever sensor array along with two other types of TiO(2) film: one from nanoparticles and one prepared via a sol-gel reaction. After loading methylene blue molecules on the TiO(2) films, the films were exposed to ultraviolet radiation. The photocatalytic decomposition of methylene blue was monitored by measuring changes in the resonance frequency of each cantilever. The mesoporous TiO(2) film showed higher photocatalytic activity than conventional TiO(2) films fabricated from nanoparticles or via a sol-gel reaction; this difference is attributed to the purely anatase crystalline morphology of the mesoporous TiO(2) film as well as its well-organized pore structure. The three-dimensionally interconnected pore network facilitates the diffusion of methylene blue molecules to the photocatalytically active sites of the mesoporous TiO(2).