Neutron Reflectivity Experiments Research Articles

Impact of surface hydrophilicity on the ordering and transport properties of bicontinuous microemulsions.

Microemulsions (MEs) have many industrial applications, where recent developments have shown that MEs can be utilized for electrochemical applications, including potentially in redox flow batteries. However, understanding the structure and dynamics of these systems, including at a surface, is needed to direct and rationally control their electrochemical behavior. While bulk solution measurements have provided insight into their structure, their assembly at an interface also impacts the electron (to the electrode) and ion (across the surfactant) charge transfer processes in the system. To address this shortcoming, neutron reflectivity experiments and molecular simulations have been completed that document the near surface structure of a series of deuterated water (D2O)/polysorbate-20/toluene MEs on hydrophilic and amphiphilic surfaces. These results show that the microemulsions form complex layered structures near a hard electrode surface, where most layers are not purely one component. Decreasing the D2O concentration in the ME increases the number of and purity of the layers established on the solid surface. These lamellar-type layers transition from the surface to the bulk microemulsion as a series of mixed layers (i.e., containing oil, water, and surfactant) that are consistent with perforated lamellae. Additionally, these mixed lamellae appear to become more perforated with oil and water pathways on an amphiphilic surface. The purity and thickness of these layers will influence the accessibility of an electrode by redox active species, as well as ion transport required to satisfy the electroneutrality condition.

Characterizing Hygroscopic Films of Polyzwitterions in Electric Fields Using Neutron and X-ray Reflectometries: Electrostriction or Mass Loss?

We study responses of thermally annealed ultrathin films deposited on silicon substrates and containing polyzwitterions to applied electric fields by using specular neutron reflectometry (NR). In particular, we applied 7 kV under vacuum at 150 °C on the films containing poly(1-(3-sulfonatopropyl)-2-vinylpyridinium) (P2VPPS) and its blends with either a deuterated ionic liquid (EMIMBF4-d11), potassium bromide (KBr), or deuterated sodium polystyrenesulfonate (NaPSS-d7). The voltage was applied over an air gap, and the in situ neutron reflectivity measurements allowed us to measure changes in the films. In all the cases, we measured decreases in thicknesses of the films, which varied up to ∼8% depending on the added salt. Posteriori X-ray reflectivity (XRR) measurements on the same films at room temperature reveal that these films were highly hygroscopic, which led to the presence of water in these films. Analysis of the NR and the XRR revealed that the decrease in the thickness of the films in the neutron reflectivity experiments on heating resulted from the loss of water and the ionic liquid but not from electrostrictive effects. The in situ NR and posteriori XRR experiments revealed not only the hygroscopic nature of these films but also depth-resolved structural rearrangements due to the applied electric fields in the films containing electrolytes and polyelectrolytes. This work shows that a combination of NR and XRR can be used to distinguish between mass loss and electrostriction in films containing charged polymers such as polyzwitterions.

Adsorption of monoclonal antibody fragments at the water-oil interface: A coarse-grained molecular dynamics study.

Monoclonal antibodies (mAbs) can undergo structural changes due to interaction with oil-water interfaces during storage. Such changes can lead to aggregation, resulting in a loss of therapeutic efficacy. Therefore, understanding the microscopic mechanism controlling mAb adsorption is crucial to developing strategies that can minimize the impact of interfaces on the therapeutic properties of mAbs. In this study, we used MARTINI coarse-grained molecular dynamics simulations to investigate the adsorption of the Fab and Fc domains of the monoclonal antibody COE3 at the oil-water interface. Our aim was to determine the regions on the protein surface that drive mAb adsorption. We also investigate the role of protein concentration on protein orientation and protrusion to the oil phase. While our structural analyses compare favorably with recent neutron reflectivity measurements, we observe some differences. Unlike the monolayer at the interface predicted by neutron reflectivity experiments, our simulations indicate the presence of a secondary diffused layer near the interface. We also find that under certain conditions, protein-oil interaction can lead to a considerable distortion in the protein structure, resulting in enhanced adsorption behavior.

Insights into Chemical Interactions and Related Toxicities of Deep Eutectic Solvents with Mammalian Cells Observed Using Synchrotron Macro–ATR–FTIR Microspectroscopy

Deep eutectic solvents (DESs) and ionic liquids (ILs) are highly tailorable solvents that have shown a lot of promise for a variety of applications including cryopreservation, drug delivery, and protein stabilisation. However, to date, there is very limited information on the detailed interactions of these solvents with mammalian cells. In this work, we studied six DESs and one IL that show promise as cryoprotective agents, applying synchrotron macro–ATR–FTIR to examine their effects on key biochemical components of HaCat mammalian cells. These data were paired with resazurin metabolic assays and neutron reflectivity experiments to correlate cellular interactions with cellular toxicity. Stark differences were observed even between solvents that shared similar components. In particular, it was found that solvents that are effective cryoprotective agents consistently showed interactions with cellular membranes, while high toxicity correlated with strong interactions of the DES/IL with nucleic acids and proteins. This work sheds new light on the interactions between novel solvents and cells that may underpin future biomedical applications.

Structural insights on ionizable Dlin-MC3-DMA lipids in DOPC layers by combining accurate atomistic force fields, molecular dynamics simulations and neutron reflectivity.

Ionizable lipids such as the promising Dlin-MC3-DMA (MC3) are essential for the successful design of lipid nanoparticles (LNPs) as drug delivery agents. Combining molecular dynamics simulations with experimental data, such as neutron reflectivity experiments and other scattering techniques, is essential to provide insights into the internal structure of LNPs, which is not fully understood to date. However, the accuracy of the simulations relies on the choice of force field parameters and high-quality experimental data is indispensable to verify the parametrization. For MC3, different parameterizations in combination with the CHARMM and the Slipids force fields have recently emerged. Here, we complement the existing efforts by providing parameters for cationic and neutral MC3 compatible with the AMBER Lipid17 force field. Subsequently, we carefully assess the accuracy of the different force fields by providing a direct comparison to neutron reflectivity experiments of mixed lipid bilayers consisting of MC3 and DOPC at different pHs. At low pH (cationic MC3) and at high pH (neutral MC3) the newly developed MC3 parameters in combination with AMBER Lipid17 for DOPC give good agreement with the experiments. Overall, the agreement is similar compared to the Park-Im parameters for MC3 in combination with the CHARMM36 force field for DOPC. The Ermilova-Swenson MC3 parameters in combination with the Slipids force field underestimate the bilayer thickness. While the distribution of cationic MC3 is very similar, the different force fields for neutral MC3 reveal distinct differences ranging from strong accumulation in the membrane center (current MC3/AMBER Lipid17 DOPC), over mild accumulation (Park-Im MC3/CHARMM36 DOPC) to surface accumulation (Ermilova-Swenson MC3/Slipids DOPC). These pronounced differences highlight the importance of accurate force field parameters and their experimental validation.

The development of a [formula omitted]Li-based pixelated neutron detector for neutron reflectometry at the Spallation Neutron Source

We present a high-rate 6Li-based pixelated neutron detector developed for neutron reflectometry instruments at the Spallation Neutron Source (SNS). The neutron detector has a pixelated design: each 6Li scintillator element has its own photosensor and independent channel readout. This paper focuses on the general overview of the detector design and construction, the characterization of the pixelated detector, and the results of the first neutron reflectivity experiments conducted using the pixelated neutron detector at the SNS Liquid Reflectometer (BL-4B). The pixelated neutron detector demonstrated a global time-average count rate of ≥1.8×106cps, at least 3 orders of magnitude higher than that of the existing neutron detector (3He-based Multi-Wire Proportional Counter), and a local instantaneous count rate of ≥1.73×106cps/cm2. The maximum counting rate of the detector has not yet been determined as the detector is capable of handling the maximum flux available at the beamline. The outcome of the neutron reflectivity experiments showed that the pixelated neutron detector is a promising candidate for next-generation neutron reflectometry instruments at the SNS.

Insights into Extended Structures and Their Driving Force: Influence of Salt on Polyelectrolyte/Surfactant Mixtures at the Air/Water Interface.

This paper addresses the effect of polyelectrolyte stiffness on the surface structure of polyelectrolyte (P)/surfactant (S) mixtures. Therefore, two different anionic Ps with different intrinsic persistence length lP are studied while varying the salt concentration (0-10-2 M). Either monosulfonated polyphenylene sulfone (sPSO2-220, lP ∼20 nm) or sodium poly(styrenesulfonate) (PSS, lP ∼1 nm) is mixed with the cationic surfactant tetradecyltrimethylammonium bromide (C14TAB) well below its critical micelle concentration and studied with tensiometry and neutron reflectivity experiments. We kept the S concentration (10-4 M) constant, while we varied the P concentration (10-5-10-3 M of the monomer, denoted as monoM). P and S adsorb at the air/water interface for all studied mixtures. Around the bulk stoichiometric mixing point (BSMP), PSS/C14TAB mixtures lose their surface activity, whereas sPSO2-220/C14TAB mixtures form extended structures perpendicular to the surface (meaning a layer of S with attached P and additional layers of P and S underneath instead of only a monolayer of S with P). Considering the different P monomer structures as well as the impact of salt, we identified the driving force for the formation of these extended structures: compensation of all interfacial charges (P/S ratio ∼1) to maximize the gain of entropy. By increasing the flexibility of P, we can tune the interfacial structures from extended structures to monolayers. These findings may help improve applications based on the adsorption of P/S mixtures in the fields of cosmetic or oil recovery.

Molecular Dynamics Simulation and Cryo-Electron Microscopy Investigation of AOT Surfactant Structure at the Hydrated Mica Surface

Structural properties of the anionic surfactant dioctyl sodium sulfosuccinate (AOT or Aerosol-OT) adsorbed on the mica surface were investigated by molecular dynamics simulation, including the effect of surface loading in the presence of monovalent and divalent cations. The simulations confirmed recent neutron reflectivity experiments that revealed the binding of anionic surfactant to the negatively charged surface via adsorbed cations. At low loading, cylindrical micelles formed on the surface, with sulfate head groups bound to the surface by water molecules or adsorbed cations. Cation bridging was observed in the presence of weakly hydrating monovalent cations, while sulfate groups interacted with strongly hydrating divalent cations through water bridges. The adsorbed micelle structure was confirmed experimentally with cryogenic electronic microscopy, which revealed micelles approximately 2 nm in diameter at the basal surface. At higher AOT loading, the simulations reveal adsorbed bilayers with similar surface binding mechanisms. Adsorbed micelles were slightly thicker (2.2–3.0 nm) than the corresponding bilayers (2.0–2.4 nm). Upon heating the low loading systems from 300 K to 350 K, the adsorbed micelles transformed to a more planar configuration resembling bilayers. The driving force for this transition is an increase in the number of sulfate head groups interacting directly with adsorbed cations.

Correlation of Magnetic and Superconducting Properties with the Strength of the Magnetic Proximity Effect in La0.67Sr0.33MnO3/SrTiO3/YBa2Cu3O7-δ Heterostructures.

The effect of the stacking sequence on magnetic and superconducting properties in La0.67Sr0.33MnO3 (LSMO)/YBa2Cu3O7-δ (YBCO) and LSMO/SrTiO3/YBCO heterostructures, which consequently affected the magnetic proximity effect (MPE), was investigated using spin-polarized neutron reflectivity experiments. The results established the intrinsic nature of MPE and its correlation with stacking sequence-dependent magnetic and superconducting properties in these oxide heterostructure systems. We found an increase in the superconducting transition temperature (Tsc) and magnetization for both of the heterostructures as compared to heterostructures with a reversed stacking order. The evolution of the magnetization of the interfacial ferromagnetic (FM) layer, studied as a function of temperature for both heterostructures, showed a decrease in the MPE-induced magnetic depleted layer thickness for heterostructures at a higher Tsc. A comparison of the results of different studies with the present results suggested that the average magnetization and transition temperatures of a FM and a superconductor (SC) were important parameters that dictate the strength of the proximity effect due to the complex interaction of SC and FM in these systems. Tuning the strength of MPE in FM/SC and FM/I/SC oxide heterostructures may provide a promising platform for the effective realization of devices.

Cononsolvency of Poly[2-(methacryloyloxy)ethyl phosphorylcholine] in Ethanol-Water Mixtures: A Neutron Reflectivity Study.

Molecular mechanisms underlying the cononsolvency, a re-entrant coil-to-globule-to-coil conformational transition of polymer chains in mixtures of two good solvents, of poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC) in ethanol-water binary mixtures were complementarily investigated. This was accomplished by following a statistical mechanical model for competitive hydrogen bonding combined with the cooperative solvation concept as well as neutron reflectivity (NR) experiments employing contrast variation in the cononsolvents. The experimental re-entrant aggregation of the PMPC chains in ethanol-water mixed solvents, obtained on the basis of turbidity was accurately reproduced by theoretical calculations. The calculation proved the relatively strong cooperativity of ethanol and the preferential interaction of water, while the total coverage of solvents was the lowest at an ethanol volume fraction (fethanol) of 0.90. At this level, the cononsolvency was the most significant, and the collapsed PMPC chains were solvated with more water than the bulk mixed solvent. The ethanol-water cononsolvency for the PMPC brushes on a planar silicon wafer was investigated by NR experiments, and the solvent composition involved in the collapsed PMPC brush was addressed according to the contrast variation study with mixed solvents of water, deuterium oxide, ethanol-d5, and ethanol-d6. The collapsed PMPC brushes at fethanol = 0.90 contained more water than the bulk solvent. The preferential distribution of water in the collapsed PMPC brush was consistent with the simulation results. Therefore, the molecular mechanism for the cononsolvency of PMPC in ethanol-water mixed solvents based on competitive hydrogen bonding coupled with cooperative solvation was experimentally rationalized.

Suppression of the superconducting proximity effect in ferromagnetic-superconducting oxide heterostructures with ion-irradiation

The effect of ion irradiation on the proximity effect in YBa2Cu3O7−δ/La0.67Sr0.33MnO3 and YBa2Cu3O7−δ/SrTiO3/La0.67Sr0.33MnO3 heterostructures has been investigated using spin-polarized neutron reflectivity experiments. We demonstrate that the magnetization in the ferromagnetic (La0.67Sr0.33MnO3) layer at the interface is correlated with the suppression of the superconductivity in the YBa2Cu3O7−δ layer after irradiation, while the layer structure of the heterostructures remains intact. The evolution of the magnetization of the interfacial ferromagnetic layer studied as a function of temperature for both the irradiated heterostructures shows the absence of the proximity effect observed in the un-irradiated samples. The absence of a proximity effect is attributed to the suppression of the superconductivity, as seen in macroscopic magnetization measurements of the heterostructures after ion irradiation.

Effects of interfacial roughness on the GMR of Ta/Co/Ta multilayers studied by neutron reflectometer

To study the effects of the roughness of magnetic nano-multilayer films on the giant magnetoresistance (GMR) performance, we used magnetron sputtering to prepare Ta/Co/Ta films with different Co thicknesses on a silicon substrate. The surface and interfacial roughness of the multilayer films were investigated using atomic force microscopy (AFM) and neutron reflectometry. The AFM results with a range of 10 μm indicated that the surface undulation increased with the increment of the Co thickness and the root-mean-square (RMS) roughness increased from 0.48 to 2.26 nm. The neutron reflectometry results proved that the thicker the Co layer, the rougher the interface in the multilayer film, with an increase from 1 to 2.7 nm. The four probe method was used to study the GMR properties of the films. It indicated that the GMR effect was enhanced and the GMR value shifted from − 0.04% to − 1.13% with increasing Co thickness from 6.5 to 20 nm. The enhancement in the GMR effect originated from the thicker Co layer, which led to increasing interfacial roughness, thereby enhancing the spin-dependent scattering of the interface and increasing the absolute value of the GMR. Nevertheless, when the Co thickness increased to 42 nm, the GMR absolute value decreased from 1.13 to 0.8% and the GMR effect was destroyed. This behavior originated from the increased shunt of the ferromagnetic layer and the rougher Ta capping layer increasing the spin-independent scattering center, thereby eventually undermining the GMR effect. Diffusion between the multilayer films was observed using a polarized neutron reflection experiment, further illustrating that the GMR effect could be adjusted by the interfacial roughness.

Investigation of the adsorption of a mixture of two anionic surfactants, AOT and SDBS, on silica at ambient temperature

Chemical flooding, one of the Enhanced Oil Recovery (EOR) techniques used to increase oil production, consists in the injection in the well of an aqueous formulation containing various chemical additives such as surfactants. However, its performance can be significantly altered by the loss of surfactants in reservoir rocks. More precisely, surfactant loss due to adsorption on the reservoir rock may have a non-negligible impact on the efficiency of the injected formulation. In this article, we considered the adsorption of a mixture of two anionic surfactants having an important industrial relevance for EOR applications. Adsorption was studied on silica, representative of reservoir rocks such as sandstone, by combining Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) and neutron reflectivity experiments. A preliminary characterization of the surfactant mixture solution demonstrated the formation of unilamellar vesicles in the bulk. Whereas an adsorbed layer was measured with the single AOT vesicles, but not with the SDBS micelles, we observed that mixing both anionic surfactants change the adsorption phenomenon. Indeed, non-negligible adsorption was measured for the mixture even at concentrations where only slight adsorption had been observed with the individual surfactants. This suggests that the structure of the aggregates formed in the bulk has a non-negligible impact on the adsorption. We note that the addition of salt tends to enhance the adsorption by screening the repulsive interactions between both negatively charged surfactants and silica at neutral pH. The present work provides new insights into the description of the adsorption of a mixture of surfactants of same nature in unfavorable conditions.

Exchange bias adjust resonance frequency in FeNi/FeMn nanofilm based on polarized neutron reflectometer

To study the relationship between the exchange bias effect and the resonance frequency of magnetic nanofilms, FeNi and FeNi/FeMn exchange-coupled films were fabricated on a silicon substrate by magnetron sputtering deposition. The static and dynamic magnetic properties of the multilayer films were investigated using a vibrating sample magnetometer (VSM) and a vector network analyzer (VNA). The VSM results indicate that after introducing the FeMn layer, the exchange bias field increased to 62 Oe and the magnetic anisotropy field shifted from 6 to 107 Oe. The VNA results show that the resonance frequency increased from 0.72 to 2.8 GHz, originating from the interface exchange coupling strength. In addition, as a probe for the surface and interface structure, a time-of-flight polarized neutron reflectometer was used to observe the microstructure of the multilayer films. The diffusion with a 2.5 nm thickness between the multilayer films was observed by the polarized neutron reflection experiment, further illustrating that the exchange bias effect is derived from the interaction between the FeNi/FeMn layers. It is concluded that the magnetic induction of a FeNi layer is 0.98 T through fitting the data obtained from the polarized neutron reflection experiment.

Insight into Kinetics and Mechanisms of AOT Vesicle Adsorption on Silica in Unfavorable Conditions.

The structure of adsorbed surfactant layers at the equilibrium state has already been investigated using various experimental techniques. However, the comprehension of the formation of structural intermediates in nonequilibrium states and the resulting adsorption kinetics still remain a challenging task. The temporal characterization of these intermediate structures provides further understanding of the layer structure at equilibrium and of the main interactions involved in the adsorption process. In this article, we studied the adsorption kinetics of AOT vesicles on silica at different pHs at ambient temperature. The AOT vesicles were formed in a brine solution. Quartz crystal microbalance with dissipation monitoring (QCM-D) was used to obtain information on the kinetics of surfactant adsorption and on the structure of the adsorbed layer at the equilibrium state. Additionally, neutron reflectivity experiments were performed to provide a detailed description of the mean surfactant concentration profile normal to the surface at equilibrium. Results suggest that vesicles in the bulk influence the adsorption mechanisms. In acidic conditions, after a time-dependent structural rearrangement step, followed by the rupture of initially adsorbed vesicles, the formation of a bilayer was observed. At an intermediate and basic pH, in spite of the electrostatic repulsion between the negatively charged surfactants and silica, results demonstrated the existence of an adsorbed layer composed of AOT vesicles. Vesicles are more or less closely packed depending on the pH of the solution. Results show a non-negligible influence of NaCl addition at pH values where adsorption is initially inhibited. Vesicle adsorption at the intermediate and basic pH is probably due to the combination of attractive van der Waals interactions promoted in high ionic strength systems and the formation of hydrogen bonds. Interpretation of adsorption kinetics gave insight into adsorption mechanisms in an electrostatic repulsion environment.

Effect of Trapped Solvent on the Interface between PS-b-PMMA Thin Films and P(S-r-MMA) Brush Layers

The orientation of block copolymer (BCP) features in thin films can be obtained by spin-coating a BCP solution on a substrate surface functionalized by a polymer brush layer of the appropriate random copolymer (RCP). Although this approach is well established, little work reporting the amount and distribution of residual solvent in the polymer film after the spin-coating process is available. Moreover, no information can be found on the effect of trapped solvent on the interface between the BCP film and RCP brush. In this work, systems consisting of poly(styrene)-b-poly(methyl methacrylate) thin films deposited on poly(styrene-r-methyl methacrylate) brush layers are investigated by combining neutron reflectivity (NR) experiments with simulation techniques. An increase in the amount of trapped solvent is observed by NR as the BCP film thickness increases accompanied by a significant decrease of the interpenetration length between the BCP and RCP, thus suggesting that the interpenetration between grafted chains and block copolymer chains is hampered by the solvent. Hybrid particle-field molecular dynamics simulations of the analyzed system confirm the experimental observations and demonstrate a clear correlation between the interpenetration length and the amount of trapped solvent.

Superconductivity-driven negative interfacial magnetization in YBa2Cu3O7−δ/SrTiO3/La0.67Sr0.33MnO3 heterostructures

Using spin-polarized neutron reflectivity experiments, we demonstrate an unusual proximity behavior when a superconductor (SC) and a ferromagnet (FM) are coupled through an insulator (I) in YBa2Cu3O7−δ (SC)/SrTiO3 (I)/La0.67Sr0.33MnO3 (FM) heterostructures. We have observed an unexpected magnetic reversal confined to the interface region of the FM below the superconducting transition temperature. The magnetization of the interfacial FM layer at the I/FM interface was found to be aligned opposite to the magnetization of the rest of the FM layer. This result indicates that the Cooper pairs tunnel across the insulator, interact with the local magnetization in the interfacial region (extending ∼30 Å) of the FM, and then modify the magnetization at the interface. This unexpected magnetic behavior cannot be explained on the basis of the existing theoretical models. However, the length scale associated here clearly suggests the long-range proximity effect as a result of tunneling of Cooper pairs. The magnetic exchange field-effect across SC/I/FM interfaces driven by tunneling may serve as the basis for application in superconducting spintronic devices.

Comment on “Surface properties of ethanol/water mixture: Thickness and composition”

A controversial discussion regarding the estimation of surface thickness in aqueous ethanol as calculated by Phan and co-workers (2019) from neutron reflectivity experiments and by Bagheri et al. (2016) and Santos and Reis (2018) from surface tension data and equality of chemical potentials is addressed. The theoretical link among equilibrium mole fractions, Gibbs excess concentration, surface molar volume and interfacial thickness developed by Phan and co-workers is rearranged into an explicit expression for the calculation of thickness, which is shown to be inconsistent with their Gibbs excess concentration estimating equation from neutron reflectivity experiments. A correction is proposed, and the recalculated equivalent thickness values present an increase, with increasing ethanol contents, in fair agreement with the values reported by Santos and Reis (2018).

Attractive Interaction between Fully Charged Lipid Bilayers in a Strongly Confined Geometry.

We investigate the interaction between highly charged lipid bilayers in the presence of monovalent counterions. Neutron and X-ray reflectivity experiments show that the water layer between like-charged bilayers is thinner than for zwitterionic lipids, demonstrating the existence of counterintuitive electrostatic attractive interaction between them. Such attraction can be explained by taking into account the correlations between counterions within the Strong Coupling limit, which falls beyond the classical Poisson-Boltzmann theory of electrostatics. Our results show the limit of the Strong Coupling continuous theory in a highly confined geometry and are in agreement with a decrease in the water dielectric constant due to a surface charge-induced orientation of water molecules.

Continuous Mesoporous Aluminum Oxide Film with Perpendicularly Oriented Mesopore Channels.

Mesoporous aluminum oxide (MAO) films with perpendicularly oriented cylindrical mesopores (pore diameter: ca. 10 nm) were successfully deposited on a glass substrate by a surfactant-templating approach using aluminum nitrate as an aluminum source. The perpendicular orientation of mesopores was confirmed by grazing-incidence small-angle X-ray scattering and neutron reflection experiments. The thickness of the MAO film was around 100 nm, with a surface roughness of less than 6 nm. Since the inner surface of MAO pores was positively charged, negatively charged glucose oxidase molecules could be densely loaded into the cylindrical mesopores without significant loss of enzymatic activity. The present MAO film is potentially useful as an inorganic host material for an enzyme toward the development of a biocatalytic system.