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Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li 6 PS 5 X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10 -2  S cm -1 ) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250 °C. Moreover, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa., (© 2024 Wiley-VCH GmbH.)

Nanostructured solid-state batteries (SSBs) are poised to meet the demands of next-generation energy storage technologies by realizing performance competitive to their liquid-based counterparts while simultaneously offering improved safety and expanded form factors. Atomic layer deposition (ALD) is among the tools essential to fabricate nanostructured devices with challenging aspect ratios. Here, we report the fabrication and electrochemical testing of the first nanoscale sodium all-solid-state battery (SSB) using ALD to deposit both the V 2 O 5 cathode and NaPON solid electrolyte followed by evaporation of a thin-film Na metal anode. NaPON exhibits remarkable stability against evaporated Na metal, showing no electrolyte breakdown or significant interphase formation in the voltage range of 0.05-6.0 V vs Na/Na + . Electrochemical analysis of the SSB suggests intermixing of the NaPON/V 2 O 5 layers during fabrication, which we investigate in three ways: in situ spectroscopic ellipsometry, time-resolved X-ray photoelectron spectroscopy (XPS) depth profiling, and cross-sectional cryo-scanning transmission electron microscopy (cryo-STEM) coupled with electron energy loss spectroscopy (EELS). We characterize the interfacial reaction during the ALD NaPON deposition on V 2 O 5 to be twofold: (1) reduction of V 2 O 5 to VO 2 and (2) Na + insertion into VO 2 to form Na x VO 2 . Despite the intermixing of NaPON-V 2 O 5 , we demonstrate that NaPON-coated V 2 O 5 electrodes display enhanced electrochemical cycling stability in liquid-electrolyte coin cells through the formation of a stable electrolyte interphase. In all-SSBs, the Na metal evaporation process is found to intensify the intermixing reaction, resulting in the irreversible formation of mixed interphases between discrete battery layers. Despite this graded composition, the SSB can operate for over 100 charge-discharge cycles at room temperature and represents the first demonstration of a functional thin-film solid-state sodium-ion battery.

Chemotaxis is a fundamental bacterial response mechanism to changes in chemical gradients of specific molecules known as chemoattractant or chemorepellent. The advancement of biological platforms for bacterial chemotaxis research is of significant interest for a wide range of biological and environmental studies. Many microfluidic devices have been developed for its study, but challenges still remain that can obscure analysis. For example, cell migration can be compromised by flow-induced shear stress, and bacterial motility can be impaired by nonspecific cell adhesion to microchannels. Also, devices can be complicated, expensive, and hard to assemble. We address these issues with a three-channel microfluidic platform integrated with natural biopolymer membranes that are assembled in situ . This provides several unique attributes. First, a static, steady and robust chemoattractant gradient was generated and maintained. Second, because the assembly incorporates assembly pillars, the assembled membrane arrays connecting nearby pillars can be created longer than the viewing window, enabling a wide 2D area for study. Third, the in situ assembled biopolymer membranes minimize pressure and/or chemiosmotic gradients that could induce flow and obscure chemotaxis study. Finally, nonspecific cell adhesion is avoided by priming the polydimethylsiloxane (PDMS) microchannel surfaces with Pluronic F-127. We demonstrated chemotactic migration of Escherichia coli as well as Pseudomonas aeruginosa under well-controlled easy-to-assemble glucose gradients. We characterized motility using the chemotaxis partition coefficient (CPC) and chemotaxis migration coefficient (CMC) and found our results consistent with other reports. Further, random walk trajectories of individual cells in simple bright field images were conveniently tracked and presented in rose plots. Velocities were calculated, again in agreement with previous literature. We believe the biopolymer membrane-integrated platform represents a facile and convenient system for robust quantitative assessment of cellular motility in response to various chemical cues.

A key trailblazer in the development of thin-film solid-state electrolytes has been lithium phosphorous oxynitride (LiPON), the success of which has led to recent progress in thin-film ion conductors. Here we compare the structural, electrochemical, and processing parameters between previously published LiPON and NaPON ALD processes with a novel ALD process for the K analogue potassium phosphorous oxynitride (KPON). In each ALD process, alkali tert -butoxides and diethylphosphoramidate are used as precursors. To understand the ALD surface reactions, this work proposes a reaction mechanism determined by in-operando mass spectrometry for the LiPON process as key to understanding the characteristics of the APON (A = Li, Na, K) family. As expected, NaPON and LiPON share similar reaction mechanisms as their structures are strikingly similar. KPON, however, exhibits similar ALD process parameters but the resulting film composition is quite different, showing little nitrogen incorporation and more closely resembling a phosphate glass. Due to the profound difference in structure, KPON likely undergoes an entirely different reaction mechanism. This paper presents a comprehensive summary of ALD ion conducting APON films as well as a perspective that highlights the versatility of ALD chemistries as a tool for the development of novel thin film ion-conductors.

The development of novel materials that are compatible with nanostructured architectures is required to meet the demands of next-generation energy-storage technologies. Atomic layer deposition (ALD) allows for the precise synthesis of new materials that can conformally coat complex 3D structures. In this work, we demonstrate a thermal ALD process for sodium phosphorus oxynitride (NaPON), a thin-film solid-state electrolyte (SSE), for sodium-ion batteries (SIBs). NaPON is analogous to the commonly used lithium phosphorus oxynitride SSE in lithium-ion batteries. The ALD process produces a conformal film with a stoichiometry of Na 4 PO 3 N, corresponding to a sodium polyphosphazene structure. The electrochemical properties of NaPON are characterized to evaluate its potential in SIBs. The NaPON film exhibited a high ionic conductivity of 1.0 × 10 -7 S/cm at 25 °C and up to 2.5 × 10 -6 S/cm at 80 °C, with an activation energy of 0.53 eV. In addition, the ionic conductivity is comparable and even higher than the ionic conductivities of ALD-fabricated Li + conductors. This promising result makes NaPON a viable SSE or passivation layer in solid-state SIBs.

The rapidly growing demand for portable electronics, electric vehicles, and grid storage drives the pursuit of high-performance electrical energy storage (EES). A key strategy for improving EES performance is exploiting nanostructured electrodes that present nanoconfined environments of adjacent electrolytes, with the goal to decrease ion diffusion paths and increase active surface areas. However, fundamental gaps persist in understanding the interface-governed electrochemistry in such nanoconfined geometries, in part because of the imprecise and variable dimension control. Here, we report quantification of lithium insertion under nanoconfinement of the electrolyte in a precise lithography-patterned nanofluidic cell. We show a mechanism that enhances ion insertion under nanoconfinement, namely, selective ion accumulation when the confinement length is comparable to the electrical double layer thickness. The nanofabrication approach with uniform and accurate dimensional control provides a versatile model system to explore fundamental mechanisms of nanoscale electrochemistry, which could have an impact on practical energy storage systems.

Detailed understanding of solid-solid interface structure-function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and Li x CoO 2 cathode, have been reported to generate solid-electrolyte interphase (SEI)-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy Li x CoO 2 (104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Three-dimensional thin-film solid-state batteries (3D TSSB) were proposed by Long et al. in 2004 as a structure-based approach to simultaneously increase energy and power densities. Here, we report experimental realization of fully conformal 3D TSSBs, demonstrating the simultaneous power-and-energy benefits of 3D structuring. All active battery components-electrodes, solid electrolyte, and current collectors-were deposited by atomic layer deposition (ALD) onto standard CMOS processable silicon wafers microfabricated to form arrays of deep pores with aspect ratios up to approximately 10. The cells utilize an electrochemically prelithiated LiV 2 O 5 cathode, a very thin (40-100 nm) Li 2 PO 2 N solid electrolyte, and a SnN x anode. The fabrication process occurs entirely at or below 250 °C, promising compatibility with a variety of substrates as well as integrated circuits. The multilayer battery structure enabled all-ALD solid-state cells to deliver 37 μAh/cm 2 ·μm (normalized to cathode thickness) with only 0.02% per-cycle capacity loss. Conformal fabrication of full cells over 3D substrates increased the areal discharge capacity by an order of magnitude while simulteneously improving power performance, a trend consistent with a finite element model. This work shows that the exceptional conformality of ALD, combined with conventional semiconductor fabrication methods, provides an avenue for the successful realization of long-sought 3D TSSBs which provide power performance scaling in regimes inaccessible to planar form factor cells.

In the pursuit of energy storage devices with higher energy and power, new ion storage materials and high-voltage battery chemistries are of paramount importance. However, they invite-and often enhance-degradation mechanisms, which are reflected in capacity loss with charge/discharge cycling and sometimes in safety problems. Degradation mechanisms are often driven by fundamentals such as chemical and electrochemical reactions at electrode-electrolyte interfaces, volume expansion and stress associated with ion insertion and extraction, and profound inhomogeneity of electrochemical behavior. While it is important to identify and understand these mechanisms at some reasonable level, it is even more critical to design strategies to mitigate these degradation pathways and to develop means to implement and validate the strategies. A growing set of research highlights the mitigation benefits achievable by forming thin protection layers (PLs) intentionally created as artificial interphase regions at the electrode-electrolyte interface. These advances illustrate a promising-perhaps even generic-pathway for enabling higher-energy and higher-voltage battery configurations. In this Account, we summarize examples of such PLs that serve as mitigation strategies to avoid degradation in lithium metal anodes, conversion-type electrode materials, and alloy-type electrodes. Examples are chosen from a larger body of electrochemical degradation research carried out in Nanostructures for Electrical Energy Storage (NEES), our DOE Energy Frontier Research Center. Overall, we argue on the basis of experimental and theoretical evidence that PLs effectively stabilize the electrochemical interfaces to prevent parasitic chemical and electrochemical reactions and mitigate the structural, mechanical, and compositional degradation of the electrode materials at the electrode-electrolyte interfaces. The evidenced improvement in performance metrics is accomplished by (1) establishing a homogeneous interface for ion insertion and extraction, (2) providing mechanical constraints to maintain structural integrity and robust electronic and ionic conduction pathways, and (3) introducing spatial confinements on the electrode material matrix to alter the phase transformation (delaying the occurrence of the conversion reaction) upon Li insertion, which results in superior electrode performance, excellent capacity retention, and improved reversibility. Taken together, these examples portray a valuable role for thin protection layers synthesized over electrode surfaces, both for their benefit to cycle stability and for revealing insights into degradation and mitigation mechanisms. Furthermore, they underscore the impact of complex electrochemical behavior at nanoscale materials and nanostructure interfaces in modulating the behavior of energy storage devices at the mesoscale and macroscale.

Here we report the high performance and cyclability of an asymmetric full cell nanopore battery, comprised of V 2 O 5 as the cathode and prelithiated SnO 2 as the anode, with integrated nanotubular Pt current collectors underneath each nanotubular storage electrode, confined within an anodized aluminium oxide (AAO) nanopore. Enabled by atomic layer deposition (ALD), this coaxial nanotube full cell is fully confined within a high aspect ratio nanopore (150 nm in diameter, 50 μm in length), with an ultra-small volume of about 1 fL. By controlling the amount of lithium ion prelithiated into the SnO 2 anode, we can tune the full cell output voltage in the range of 0.3 V to 3 V. When tested as a massively parallel device (∼2 billion cm -2 ), this asymmetric nanopore battery array displays exceptional rate performance and cyclability: when cycled between 1 V and 3 V, capacity retention at the 200C rate is ∼73% of that at 1C, and at 25C rate only 2% capacity loss occurs after more than 500 charge/discharge cycles. With the increased full cell output potential, the asymmetric V 2 O 5 -SnO 2 nanopore battery shows significantly improved energy and power density over the previously reported symmetric cell, 4.6 times higher volumetric energy and 5.2 times higher power density - an even more promising indication that controlled nanostructure designs employing nanoconfined environments with large electrode surface areas present promising directions for future battery technology.

Chemotaxis is a phenomenon which enables cells to sense concentrations of certain chemical species in their microenvironment and move towards chemically favorable regions. Recent advances in microbiology have engineered the chemotactic properties of bacteria to perform novel functions, but traditional methods of characterizing chemotaxis do not fully capture the associated cell motion, making it difficult to infer mechanisms that link the motion to the microbiology which induces it. Microfluidics offers a potential solution in the form of gradient generators. Many of the gradient generators studied to date for this application are flow-based, where a chemical species diffuses across the laminar flow interface between two solutions moving through a microchannel. Despite significant research efforts, flow-based gradient generators have achieved mixed success at accurately capturing the highly subtle chemotactic responses exhibited by bacteria. Here we present an analysis encompassing previously published versions of flow-based gradient generators, the theories that govern their gradient-generating properties, and new, more practical considerations that result from experimental factors. We conclude that flow-based gradient generators present a challenge inherent to their design in that the residence time and gradient decay must be finely balanced, and that this significantly narrows the window for reliable observation and quantification of chemotactic motion. This challenge is compounded by the effects of shear on an ellipsoidal bacterium that causes it to preferentially align with the direction of flow and subsequently suppresses the cross-flow chemotactic response. These problems suggest that a static, non-flowing gradient generator may be a more suitable platform for chemotaxis studies in the long run, despite posing greater difficulties in design and fabrication.

Here we introduce a strategy for creating nanotube array electrodes which feature periodic regions of porous interconnections providing open pathways between adjacent nanotubes within the array, utilizing a combination of anodized aluminum oxide growth modification (AAO) and atomic layer deposition. These porous interconnected structures can then be used as testbed electrodes to explore the influence of mesoscale structure on the electrochemical properties of the interconnected mesoporous electrodes. Critically, these unique structures allow the solid state lithium diffusion pathways to be held essentially constant, while the larger structure is modified. While it was anticipated that this strategy would simply provide increased mass loading, the kinetics of the Li + ion insertion reaction in the porous interconnected electrodes are dramatically improved, demonstrating significantly better capacity retention at high rates than their aligned counterparts. We utilize a charge deconvolution method to explore the kinetics of the charge storage reactions. We are able to trace the origin of the structural influence on rate performance to electronic effects within the electrodes.

Conventional electrical energy storage (EES) electrodes, such as rechargeable batteries, are mostly based on composites of monolithic micrometer sized particles bound together with polymeric and conductive carbon additives and binders. The kinetic limitations of these monolithic chunks of material are inherently linked to their electrical properties, the kinetics of ion insertion through their interface and ion migration in and through the composite phase. Redox chemistry of nanostructured materials in EES systems offer vast gains in power and energy. Furthermore, due to their thin nature, ion and electron transport is dramatically increased, especially when thin heterogeneous conducting layers are employed synergistically. However, since the stability of the electrode material is dictated by the nature of the electrochemical reaction and the accompanying volumetric and interfacial changes from the perspective of overall system lifetime, research with nanostructured materials has shown often indefinite conclusions: in some cases, an increase in unwanted side-reactions due to the high surface area (bad). In other cases, results have shown significantly better handling of mechanical stress that results from lithiation/delithiation (good). Despite these mixed results, scientifically informed design of thin electrode materials, with carefully chosen architectures, is considered a promising route to address many limitations witnessed in EES systems by reducing and protecting electrodes from parasitic reactions, accommodating mechanical stress due to volumetric changes from electrochemical reactions, and optimizing charge carrier mobilities from both the "ionic" and "electronic" points of view. Furthermore, precise nanoscale control over the electrode structure can enable accurate measurement through advanced spectroscopy and microscopy techniques. This Account summarizes recent findings related to thin electrode materials synthesized by atomic layer deposition (ALD) and electrochemical deposition (ECD), including nanowires, nanotubes, and thin films. Throughout the Account, we will show how these techniques enabled us to synthesize electrodes of interest with precise control over the structure and composition of the material. We will illustrate and discuss how the electrochemical response of thin electrodes made by these techniques can facilitate new mechanisms for ion storage, mediate the interfacial electrochemical response of the electrode, and address issues related to electrode degradation over time. The effects of nanosizing materials and their electrochemical response will be mechanistically reviewed through two categories of ion storage: (1) pseudocapacitance and (2) ion insertion. Additionally, we will show how electrochemical processes that are more complicated because of accompanying volumetric changes and electrode degradation pathways can be mediated and controlled by application of thin functional materials on the electrochemically active interface; examples include conversion electrodes, reactive lithium metal anodes, and complex reactions in a Li/O 2 cathode system. The goal of this Account is to illustrate how careful design of thin materials either as active electrodes or as mediating layers can facilitate desirable interfacial electrochemical activity and resolve or shed light on mechanistic limitations of electrochemical processes related to micrometer size particles currently used in energy storage electrodes.

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite-free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg(-1) ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx . Herein, we demonstrate the first reversible Al/S battery in ionic-liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid-state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid-state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Morphologically complex electrochemical systems such as composite or nanostructured lithium ion battery electrodes exhibit spatially inhomogeneous internal current distributions, particularly when driven at high total currents, due to resistances in the electrodes and electrolyte, distributions of diffusion path lengths, and nonlinear current-voltage characteristics. Measuring and controlling these distributions is interesting from both an engineering standpoint, as nonhomogenous currents lead to lower utilization of electrode material, as well as from a fundamental standpoint, as comparisons between theory and experiment are relatively scarce. Here we describe a new approach using a deliberately simple model battery electrode to examine the current distribution in a electrode material limited by poor electronic conductivity. We utilize quantitative spatially resolved X-ray photoelectron spectroscopy to measure the spatial distribution of the state-of-charge of a V2O5 model electrode as a proxy measure for the current distribution on electrodes discharged at varying current densities. We show that the current at the electrode-electrolyte interface falls off with distance from the current collector, and that the current distribution is a strong function of total current. We compare the observed distributions with a simple analytical model which reproduces the dependence of the distribution on total current, but fails to predict the correct length scale. A more complete numerical simulation suggests that dynamic changes in the electronic conductivity of the V2O5 concurrent with lithium insertion may contribute to the differences between theory and experiment. Our observations should help inform design criteria for future electrode architectures.

Materials that undergo conversion reactions to form different materials upon lithiation typically offer high specific capacity for energy storage applications such as Li ion batteries. However, since the reaction products often involve complex mixtures of electrically insulating and conducting particles and significant changes in volume and phase, the reversibility of conversion reactions is poor, preventing their use in rechargeable (secondary) batteries. In this paper, we fabricate and protect 3D conversion electrodes by first coating multiwalled carbon nanotubes (MWCNT) with a model conversion material, RuO2, and subsequently protecting them with conformal thin-film lithium phosphous oxynitride (LiPON), a well-known solid-state electrolyte. Atomic layer deposition is used to deposit the RuO2 and the LiPON, thus forming core double-shell MWCNT@RuO2@LiPON electrodes as a model system. We find that the LiPON protection layer enhances cyclability of the conversion electrode, which we attribute to two factors. (1) The LiPON layer provides high Li ion conductivity at the interface between the electrolyte and the electrode. (2) By constraining the electrode materials mechanically, the LiPON protection layer ensures electronic connectivity and thus conductivity during lithiation/delithiation cycles. These two mechanisms are striking in their ability to preserve capacity despite the profound changes in structure and composition intrinsic to conversion electrode materials. This LiPON-protected structure exhibits superior cycling stability and reversibility as well as decreased overpotentials compared to the unprotected core-shell structure. Furthermore, even at very low lithiation potential (0.05 V), the LiPON-protected electrode largely reduces the formation of a solid electrolyte interphase.

Mg metal is a promising anode material for next generation rechargeable battery due to its dendrite-free deposition and high capacity. However, the best cathode for rechargeable Mg battery was based on high molecular weight MgxMo3S4, thus rendering full cell energetically uncompetitive. To increase energy density, high capacity cathode material like sulfur is proposed. However, to date, only limited work has been reported on Mg/S system, all plagued by poor reversibility attributed to the formation of electrochemically inactive MgSx species. Here, we report a new strategy, based on the effect of Li(+) in activating MgSx species, to conjugate a dendrite-free Mg anode with a reversible polysulfide cathode and present a truly reversible Mg/S battery with capacity up to 1000 mAh/gs for more than 30 cycles. Mechanistic insights supported by spectroscopic and microscopic characterization strongly suggest that the reversibility arises from chemical reactivation of MgSx by Li(+).

Lithium metal is considered to be the most promising anode for next-generation batteries due to its high energy density of 3840 mAh g(-1). However, the extreme reactivity of the Li surface can induce parasitic reactions with solvents, contamination, and shuttled active species in the electrolyte, reducing the performance of batteries employing Li metal anodes. One promising solution to this issue is application of thin chemical protection layers to the Li metal surface. Using a custom-made ultrahigh vacuum integrated deposition and characterization system, we demonstrate atomic layer deposition (ALD) of protection layers directly on Li metal with exquisite thickness control. We demonstrate as a proof-of-concept that a 14 nm thick ALD Al2O3 layer can protect the Li surface from corrosion due to atmosphere, sulfur, and electrolyte exposure. Using Li-S battery cells as a test system, we demonstrate an improved capacity retention using ALD-protected anodes over cells assembled with bare Li metal anodes for up to 100 cycles.

One of the greatest obstacles for the realization of the nonaqueous Li-O2 battery is finding a solvent that is chemically and electrochemically stable under cell operating conditions. Dimethyl sulfoxide (DMSO) is an attractive candidate for rechargeable Li-O2 battery studies; however, there is still significant controversy regarding its stability on the Li-O2 cathode surface. We performed multiple experiments (in situ XPS, FTIR, Raman, and XRD) which assess the stability of the DMSO-Li2O2 interface and report perspectives on previously published studies. Our electrochemical experiments show long-term stable cycling of a DMSO-based operating Li-O2 cell with a platinum@carbon nanotube core-shell cathode fabricated via atomic layer deposition, specifically with >45 cycles of 40 h of discharge per cycle. This work is complemented by density functional theory calculations of DMSO degradation pathways on Li2O2. Both experimental and theoretical evidence strongly suggests that DMSO is chemically and electrochemically stable on the surface of Li2O2 under the reported operating conditions.

The human gut is over a meter in length, liquid residence times span several hours. Recapitulating the human gut microbiome "on chip" holds promise to revolutionize therapeutic strategies for a variety of diseases, as well as for maintaining homeostasis in healthy individuals. A more refined understanding of bacterial-bacterial and bacterial-epithelial cell signalling is envisioned and such a device is a key enabler. Indeed, significant advances in the study of bacterial cell-cell signalling have been reported, including at length and time scales of the cells and their responses. Few reports exist, however, where signalling events that span physiologically relevant time scales are monitored and coordinated. Here, we employ principles of biofabrication to assemble, in situ, cell communities that are (i) spatially adjacent within partitioned microchannels for studying near communication and (ii) distally connected within longitudinal microfluidic networks so as to mimic long distance signalling among intestinal flora. We observed native signalling processes of the bacterial quorum sensing autoinducer-2 (AI-2) system among and between these communities. Cells in an upstream device successfully self-reported their activities and also secreted autoinducers that were carried downstream to the assembled networks of bacteria that reported on their presence. Furthermore, active signal modulation of among distal populations was demonstrated in a "programmed" manner where "enhancer" and "reducer" communities were assembled adjacent to the test population or "reporter" cells. The modulator cells either amplified or attenuated the cell-cell signalling between the distal, already communicating cell populations. Modulation was quantified with a bioassay, and the reaction rates of signal production and consumption were further characterized using a first principles mathematical model. Simulated distribution profiles of signalling molecules in the cell-gel composites agreed well with the observed cellular responses. We believe this simple platform and the ease by which it is assembled can be applied to other cell-cell interaction studies among various species or kingdoms of cells within well-regulated microenvironments.

Pushing lithium-ion battery (LIB) technology forward to its fundamental scaling limits requires the ability to create designer heterostructured materials and architectures. Atomic layer deposition (ALD) has recently been applied to advanced nanostructured energy storage devices due to the wide range of available materials, angstrom thickness control, and extreme conformality over high aspect ratio nanostructures. A class of materials referred to as conversion electrodes has recently been proposed as high capacity electrodes. RuO2 is considered an ideal conversion material due to its high combined electronic and ionic conductivity and high gravimetric capacity, and as such is an excellent material to explore the behavior of conversion electrodes at nanoscale thicknesses. We report here a fully characterized atomic layer deposition process for RuO2, electrochemical cycling data for ALD RuO2, and the application of the RuO2 to a composite carbon nanotube electrode scaffold with nucleation-controlled RuO2 growth. A growth rate of 0.4 Å/cycle is found between ∼ 210-240 °C. In a planar configuration, the resulting RuO2 films show high first cycle electrochemical capacities of ∼ 1400 mAh/g, but the capacity rapidly degrades with charge/discharge cycling. We also fabricated core/shell MWCNT/RuO2 heterostructured 3D electrodes, which show a 50× increase in the areal capacity over their planar counterparts, with an areal lithium capacity of 1.6 mAh/cm(2).

A single nanopore structure that embeds all components of an electrochemical storage device could bring about the ultimate miniaturization in energy storage. Self-alignment of electrodes within each nanopore may enable closer and more controlled spacing between electrodes than in state-of-art batteries. Such an 'all-in-one' nanopore battery array would also present an alternative to interdigitated electrode structures that employ complex three-dimensional geometries with greater spatial heterogeneity. Here, we report a battery composed of an array of nanobatteries connected in parallel, each composed of an anode, a cathode and a liquid electrolyte confined within the nanopores of anodic aluminium oxide, as an all-in-one nanosize device. Each nanoelectrode includes an outer Ru nanotube current collector and an inner nanotube of V₂O₅ storage material, forming a symmetric full nanopore storage cell with anode and cathode separated by an electrolyte region. The V₂O₅ is prelithiated at one end to serve as the anode, with pristine V₂O₅ at the other end serving as the cathode, forming a battery that is asymmetrically cycled between 0.2 V and 1.8 V. The capacity retention of this full cell (relative to 1 C values) is 95% at 5 C and 46% at 150 C, with a 1,000-cycle life. From a fundamental point of view, our all-in-one nanopore battery array unveils an electrochemical regime in which ion insertion and surface charge mechanisms for energy storage become indistinguishable, and offers a testbed for studying ion transport limits in dense nanostructured electrode arrays.

Surface enhanced Raman spectroscopy (SERS) is a powerful spectroscopic technique capable of detecting trace amounts of chemicals and identifying them based on their unique vibrational characteristics. While there are many complex methods for fabricating SERS substrates, there has been a recent shift towards the development of simple, low cost fabrication methods that can be performed in most labs or even in the field. The potential of SERS for widespread use will likely be realized only with development of cheaper, simpler methods. In this Perspective article we briefly review several of the more popular methods for SERS substrate fabrication, discuss the characteristics of simple SERS substrates, and examine several methods for producing simple SERS substrates. We highlight potential applications and future directions for simple SERS substrates, focusing on highly SERS active three-dimensional nanostructures fabricated by inkjet and screen printing and galvanic displacement for portable SERS analysis - an area that we believe has exciting potential for future research and commercialization.

Cellulose fibers with porous structure and electrolyte absorption properties are considered to be a good potential substrate for the deposition of energy material for energy storage devices. Unlike traditional substrates, such as gold or stainless steel, paper prepared from cellulose fibers in this study not only functions as a substrate with large surface area but also acts as an interior electrolyte reservoir, where electrolyte can be absorbed much in the cellulose fibers and is ready to diffuse into an energy storage material. We demonstrated the value of this internal electrolyte reservoir by comparing a series of hierarchical hybrid supercapacitor electrodes based on homemade cellulose paper or polyester textile integrated with carbon nanotubes (CNTs) by simple solution dip and electrodeposited with MnO2. Atomic layer deposition of Al2O3 onto the fiber surface was used to limit electrolyte absorption into the fibers for comparison. Configurations designed with different numbers of ion diffusion pathways were compared to show that cellulose fibers in paper can act as a good interior electrolyte reservoir and provide an effective pathway for ion transport facilitation. Further optimization using an additional CNT coating resulted in an electrode of paper/CNTs/MnO2/CNTs, which has dual ion diffusion and electron transfer pathways and demonstrated superior supercapacitive performance. This paper highlights the merits of the mesoporous cellulose fibers as substrates for supercapacitor electrodes, in which the water-swelling effect of the cellulose fibers can absorb electrolyte, and the mesoporous internal structure of the fibers can provide channels for ions to diffuse to the electrochemical energy storage materials.

Conversion-type electrodes represent a broad class of materials with a new Li(+) reactivity concept. Of these materials, RuO2 can be considered a model material due to its metallic-like conductivity and its high theoretical capacity of 806 mAh/g. In this paper, we use in situ transmission electron microscopy to study the reaction between single-crystal RuO2 nanowires and Li(+). We show that a large volume expansion of 95% occurs after lithiation, 26% of which is irreversible after delithiation. Significant surface roughening and lithium embrittlement are also present. Furthermore, we show that the initial reaction from crystalline RuO2 to the fully lithiated mixed phase of Ru/Li2O is not fully reversible, passing through an intermediate phase of LixRuO2. In subsequent cycles, the phase transitions are between amorphous RuO2 in the delithiated state and a nanostructured network of Ru/Li2O in the fully lithiated phase.

We describe an innovation in the immobilization, culture, and imaging of cells in calcium alginate within microfluidic devices. This technique allows unprecedented optical access to the entirety of the calcium alginate hydrogel, enabling observation of growth and behavior in a chemical and mechanical environment favored by many kinds of cells.

Interfacial instability is a fundamental issue in heterostructures ranging from biomaterials to joint replacement and electronic packaging. This challenge is particularly intriguing for lithium ion battery anodes comprising silicon as the ion storage material, where ultrahigh capacity is accompanied by vast mechanical stress that threatens delamination of silicon from the current collectors at the other side of the interface. Here, we describe Si-beaded carbon nanotube (CNT) strings whose interface is controlled by chemical functionalization, producing separated amorphous Si beads threaded along mechanically robust and electrically conductive CNT. In situ transmission electron microscopy combined with atomic and continuum modeling reveal that the chemically tailored Si-C interface plays important roles in constraining the Si beads, such that they exhibit a symmetric "radial breathing" around the CNT string, remaining crack-free and electrically connected throughout lithiation-delithiation cycling. These findings provide fundamental insights in controlling nanostructured interfaces to effectively respond to demanding environments such as lithium batteries.

Escherichia coli were genetically modified to enable programmed motility, sensing, and actuation based on the density of features on nearby surfaces. Then, based on calculated feature density, these cells expressed marker proteins to indicate phenotypic response. Specifically, site-specific synthesis of bacterial quorum sensing autoinducer-2 (AI-2) is used to initiate and recruit motile cells. In our model system, we rewired E. coli's AI-2 signaling pathway to direct bacteria to a squamous cancer cell line of head and neck (SCCHN), where they initiate synthesis of a reporter (drug surrogate) based on a threshold density of epidermal growth factor receptor (EGFR). This represents a new type of controller for targeted drug delivery as actuation (synthesis and delivery) depends on a receptor density marking the diseased cell. The ability to survey local surfaces and initiate gene expression based on feature density represents a new area-based switch in synthetic biology that will find use beyond the proposed cancer model here.

A multiwall carbon nanotube (MWCNT) sponge network, coated by ALD V(2)O(5), presents the key characteristics needed to serve as a high-performance cathode in Li-ion batteries, exploiting (1) the highly electron-conductive nature of MWCNT, (2) unprecedented uniformity of ALD thin film coatings, and (3) high surface area and porosity of the MWCNT sponge material for ion transport. The core/shell MWCNT/V(2)O(5) sponge delivers a stable high areal capacity of 816 μAh/cm(2) for 2 Li/V(2)O(5) (voltage range 4.0-2.1 V) at 1C rate (1.1 mA/cm(2)), 450 times that of a planar V(2)O(5) thin film cathode. At much higher current (50×), the areal capacity of 155 μAh/cm(2) provides a high power density of 21.7 mW/cm(2). The compressed sponge nanoarchitecture thus demonstrates exceptional robustness and energy-power characteristics for thin film cathode structures for electrochemical energy storage.

Signaling between cells guides biological phenotype. Communications between individual cells, clusters of cells and populations exist in complex networks that, in sum, guide behavior. There are few experimental approaches that enable high content interrogation of individual and multicellular behaviors at length and time scales commensurate with the signal molecules and cells themselves. Here we present "biofabrication" in microfluidics as one approach that enables in-situ organization of living cells in microenvironments with spatiotemporal control and programmability. We construct bacterial biofilm mimics that offer detailed understanding and subsequent control of population-based quorum sensing (QS) behaviors in a manner decoupled from cell number. Our approach reveals signaling patterns among bacterial cells within a single biofilm as well as behaviors that are coordinated between two communicating biofilms. We envision versatile use of this biofabrication strategy for cell-cell interaction studies and small molecule drug discovery., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Nanostructures can improve the performance of electrical energy storage devices. Recently, metal-insulator-metal (MIM) electrostatic capacitors fabricated in a three-dimensional cylindrical nanotemplate of anodized aluminum oxide (AAO) porous film have shown profound increase in device capacitance (100× or more) over planar structures. However, inherent asperities at the top of the nanostructure template cause locally high field strengths and lead to low breakdown voltage. This severely limits the usable voltage, the associated energy density (1/2 CV(2)), and thus the operational charge-discharge window of the device. We describe an electrochemical technique, complementary to the self-assembled template pore formation process in the AAO film, that provides nanoengineered topographies with significantly reduced local electric field concentrations, enabling breakdown fields up to 2.5× higher (to >10 MV/cm) while reducing leakage current densities by 1 order of magnitude (to ∼10(-10) A/cm(2)). In addition, we consider and optimize the AAO template and nanopore dimensions, increasing the capacitance per planar unit area by another 20%. As a result, the MIM nanocapacitor devices achieve an energy density of ∼1.5 Wh/kg--the highest reported.

The electrodeposition of hydrogels provides a programmable means to assemble soft matter for various technological applications. We report an anodic method to deposit hydrogel films of the aminopolysaccharide chitosan. Evidence suggests the deposition mechanism involves the electrolysis of chloride to generate reactive chlorine species (e.g., HOCl) that partially oxidize chitosan to generate aldehydes that can couple covalently with amines (presumably through Schiff base linkages). Chitosan's anodic deposition is controllable spatially and temporally. Consistent with a covalent cross-linking mechanism, the deposited chitosan undergoes repeated swelling/deswelling in response to pH changes. Consistent with a covalent conjugation mechanism, proteins could be codeposited and retained within the chitosan film even after detergent washing. As a proof-of-concept, we electroaddressed glucose oxidase to a side-wall electrode of a microfabricated fluidic channel and demonstrated this enzyme could perform electrochemical biosensing functions. Thus, anodic chitosan deposition provides a reagentless, single-step method to electroaddress a stimuli-responsive and biofunctionalized hydrogel film.

Many recent advances in bioprocessing have been enabled by developments in miniaturization and microfluidics. A continuing challenge, however, is integrating multiple unit operations that require distinct spatial boundaries, especially with included labile biological components. We have suggested "biofabrication" as a means for organizing cells and biomolecules in complex configurations while preserving function of individual components. Polysaccharide films of chitosan and alginate that are assembled on-chip by electrodeposition are "smart" configurable interfaces that mediate communication between the biological systems and microfabricated devices. Here, we demonstrate the scalable performance of a production address, where incubated cells secrete antibodies, and a capture address, where secreted antibody is retained with specificity and subsequently assayed. The antibody exchange from one electro-address to another exemplifies integrated in-film bioprocessing, facilitated by the integrated biofabrication techniques used. This in-film approach enables complex processes without need for microfluidics and valving. Finally, we have shown scalability by reducing electrode sizes to a 1 mm scale without compromising film biofabrication or bioprocessing performance. The in situ reversible deposition of viable cells, productivity characterization, and capture of secreted antibodies could find use in bioprocessing applications such as clonal selection, run-to-run monitoring, initial scale-up, and areas including drug screening and biopsy analysis., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Melamine can be detected in infant formula without the need for additional sample preparation or purification using a simple galvanic displacement reaction to fabricate portable silver SERS substrates. The reaction is rapid, inexpensive, and robust enough to perform well on highly heterogeneous common metal objects such as tape and coins.

Two thin-film assembly methods are coupled to address proteins. Electrodeposition confers programmability and generates a template for layer-by-layer (LbL) assembly. LbL enables precise control of film thickness and the incorporation of labile biological components. The capabilities are demonstrated using glucose oxidase (GOx) based electrochemical biosensing within a microfabricated fluidic device., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

High power electrical energy storage systems are becoming critical devices for advanced energy storage technology. This is true in part due to their high rate capabilities and moderate energy densities which allow them to capture power efficiently from evanescent, renewable energy sources. High power systems include both electrochemical capacitors and electrostatic capacitors. These devices have fast charging and discharging rates, supplying energy within seconds or less. Recent research has focused on increasing power and energy density of the devices using advanced materials and novel architectural design. An increase in understanding of structure-property relationships in nanomaterials and interfaces and the ability to control nanostructures precisely has led to an immense improvement in the performance characteristics of these devices. In this review, we discuss the recent advances for both electrochemical and electrostatic capacitors as high power electrical energy storage systems, and propose directions and challenges for the future. We asses the opportunities in nanostructure-based high power electrical energy storage devices and include electrochemical and electrostatic capacitors for their potential to open the door to a new regime of power energy.

MnO(2)/TiN nanotubes are fabricated using facile deposition techniques to maximize the surface area of the electroactive material for use in electrochemical capacitors. Atomic layer deposition is used to deposit conformal nanotubes within an anodic aluminium oxide template. After template removal, the inner and outer surfaces of the TiN nanotubes are exposed for electrochemical deposition of manganese oxide. Electron microscopy shows that the MnO(2) is deposited on both the inside and outside of TiN nanotubes, forming the MnO(2)/TiN nanotubes. Cyclic voltammetry and galvanostatic charge-discharge curves are used to characterize the electrochemical properties of the MnO(2)/TiN nanotubes. Due to the close proximity of MnO(2) with the highly conductive TiN as well as the overall high surface area, the nanotubes show very high specific capacitance (662 F g(-1) reported at 45 A g(-1)) as a supercapacitor electrode material. The highly conductive and mechanically stable TiN greatly enhances the flow of electrons to the MnO(2) material, while the high aspect ratio nanostructure of TiN creates a large surface area for short diffusion paths for cations thus improving high power. Combining the favourable structural, electrical and energy properties of MnO(2) and TiN into one system allows for a promising electrode material for supercapacitors., (This journal is © the Owner Societies 2011)

Surface-enhanced Raman scattering (SERS) has grown dramatically as an analytical tool for the sensitive and selective detection of molecules adsorbed on nano-roughened noble metal structures. Quantification with SERS based on signal intensity remains challenging due to the complicated fabrication process to obtain well-dispersed nanoparticles and well-ordered substrates. We report a new biofabrication strategy of SERS substrates that enable quantification through a newly discovered spectroscopic shift resulting from the chitosan-analyte interactions in solution. We demonstrate this phenomenon by the quantification of adenine, which is an essential part of the nucleic acid structure and a key component in pathways which generate signal molecules for bacterial communications. The SERS substrates were fabricated simply by sequential electrodeposition of chitosan on patterned gold electrodes and electroplating of a silver nitrate solution through the chitosan scaffold to form a chitosan-silver nanoparticle composite. Active SERS signals of adenine solutions were obtained in real time from the chitosan-silver composite substrates with a significant concentration-dependent spectroscopic shift. The Lorentzian curve fitting of the dominant peaks suggests the presence of two separate peaks with a concentration-dependent area percentage of the separated peaks. The chitosan-mediated composite SERS substrates can be easily biofabricated on predefined electrodes within microfluidic channels for real-time detection in microsystems.

Programmable 3D cell assembly under physiological pH conditions is achieved using electrodeposited stimuli-responsive alginate gels in a microfluidic device, with parallel sidewall electrodes enabling direct observation of the cell assembly. Electrically triggered assembly and subsequent viability of mammalian cells is demonstrated, along with spatially programmable, multi-address assembly of different strains of E. coli cells. Our approach enables in vitro study of dynamic cellular and inter-cellular processes, from cell growth and stimulus/response to inter-colony and inter-species signaling.

Covalent chemistry typically occurs randomly on the graphene lattice of a carbon nanotube because electrons are delocalized over thousands of atomic sites, and rapidly destroys the electrical and optical properties of the nanotube. Here we show that the Billups-Birch reductive alkylation, a variant of the nearly century-old Birch reduction, occurs on single-walled carbon nanotubes by defect activation and propagates exclusively from sp(3) defect sites, with an estimated probability more than 1,300 times higher than otherwise random bonding to the 'π-electron sea'. This mechanism quickly leads to confinement of the reaction fronts in the tubular direction. The confinement gives rise to a series of interesting phenomena, including clustered distributions of the functional groups and a constant propagation rate of 18 ± 6  nm per reaction cycle that allows straightforward control of the spatial pattern of functional groups on the nanometre length scale.

Electroaddressing, the use of imposed electrical stimuli to guide assembly, is attractive because electrical stimuli can be conveniently applied with high spatial and temporal resolution. Several electroaddressing mechanisms have been reported in which electrode-induced pH gradients trigger stimuli-responsive materials to undergo localized sol-gel transitions to form hydrogel matrices. A common feature of existing hydrogel electrodeposition mechanisms is that the deposited matrix retains residual charged, acidic, or basic (macro)molecules. Here, we report that pH-responsive fluorenyl-9-methoxycarbonyl-phenylalanine (Fmoc-Phe) can be used to codeposit the neutral and thermally responsive polysaccharide agarose. Upon cooling, an agarose network is generated and Fmoc-Phe can be removed. The Fmoc-Phe-mediated codeposition of agarose is simple, rapid, spatially selective, and allows for the electroaddressing of a bioactive matrix., (© 2011 American Chemical Society)

Chitosan is a naturally derived polymer with applications in a variety of industrial and biomedical fields. Recently, it has emerged as a promising material for biological functionalization of microelectromechanical systems (bioMEMS). Due to its unique chemical properties and film forming ability, chitosan serves as a matrix for the assembly of biomolecules, cells, nanoparticles, and other substances. The addition of these components to bioMEMS devices enables them to perform functions such as specific biorecognition, enzymatic catalysis, and controlled drug release. The chitosan film can be integrated in the device by several methods compatible with standard microfabrication technology, including solution casting, spin casting, electrodeposition, and nanoimprinting. This article surveys the usage of chitosan in bioMEMS to date. We discuss the common methods for fabrication, modification, and characterization of chitosan films, and we review a number of demonstrated chitosan-based microdevices. We also highlight the advantages of chitosan over some other functionalization materials for micro-scale devices.

The self-limiting reactions which distinguish atomic layer deposition (ALD) provide ultrathin film deposition with superb conformality over the most challenging topography. This work addresses how the shapes (i.e., surface profiles) of nanostructures are modified by the conformality of ALD. As a nanostructure template, we employ a highly scalloped surface formed during the first anodization of the porous anodic alumina (PAA) process, followed by removal of the alumina to expose a scalloped Al surface. SEM and AFM reveal evolution of surface profiles that change with ALD layer thickness, influenced by the way ALD conformality decorates the underlying topography. The evolution of surface profiles is modeled using a simple geometric 3D extrusion model, which replicates the measured complex surface topography. Excellent agreement is obtained between experimental data and the results from this model, suggesting that for this ALD system conformality is very high even on highly structured, sharp features of the initial template surface. Through modeling and experimentation, the benefits of ALD to manipulate complex surface topographies are recognized and will play an important role in the design and nanofabrication of next generation devices with increasingly high aspect ratios as well as nanoscale features.

The last century witnessed spectacular advances in both microelectronics and biotechnology yet there was little synergy between the two. A challenge to their integration is that biological and electronic systems are constructed using divergent fabrication paradigms. Biology fabricates bottom-up with labile components, while microelectronic devices are fabricated top-down using methods that are 'bio-incompatible'. Biofabrication--the use of biological materials and mechanisms for construction--offers the opportunity to span these fabrication paradigms by providing convergent approaches for building the bio-device interface. Integral to biofabrication are stimuli-responsive materials (e.g. film-forming polysaccharides) that allow directed assembly under near physiological conditions in response to device-imposed signals. Biomolecular engineering, through recombinant technology, allows biological components to be endowed with information for assembly (e.g. encoded in a protein's amino acid sequence). Finally, self-assembly and enzymatic assembly provide the mechanisms for construction over a hierarchy of length scales. Here, we review recent advances in the use of biofabrication to build the bio-device interface. We anticipate that the biofabrication toolbox will expand over the next decade as more researchers enlist the unique construction capabilities of biology. Further, we look forward to observing the application of this toolbox to create devices that can better diagnose disease, detect pathogens and discover drugs. Finally, we expect that biofabrication will enable the effective interfacing of biology with electronics to create implantable devices for personalized and regenerative medicine.

The emergence of bacteria that evade antibiotics has accelerated research on alternative approaches that do not target cell viability. One such approach targets cell-cell communication networks mediated by small molecule signaling. In this report, we assemble biological nanofactories within a bioMEMS device to capture and manipulate the behavior of quorum sensing (QS) bacteria as a step toward modifying small molecule signaling. Biological nanofactories are bio-inspired nanoscale constructs which can include modules with different functionalities, such as cell targeting, molecular sensing, product synthesis, and ultimately self-destruction. The biological nanofactories reported here consist of targeting, sensing, synthesis and, importantly, assembly modules. A bacteria-specific antibody constitutes the targeting module while a genetically engineered fusion protein contains the sensing, synthesis and assembly modules. The nanofactories are assembled on chitosan electrodeposited within a microchannel of the bioMEMS device; they capture QS bacteria in a spatially selective manner and locally synthesize and deliver the "universal" small signaling molecule autoinducer-2 (AI-2) at the captured cell surface. The nanofactory based AI-2 delivery is demonstrated to alter the progression of the native AI-2 based QS response of the captured bacteria. Prospects are envisioned for utilizing our technique as a test-bed for understanding the AI-2 based QS response of bacteria as a means for developing the next generation of antimicrobials.

We report the in situ generation of pH gradients in microfluidic devices for biofabrication of freestanding, semi-permeable chitosan membranes. The pH-stimuli-responsive polysaccharide chitosan was enlisted to form a freestanding hydrophilic membrane structure in microfluidic networks where pH gradients are generated at the converging interface between a slightly acidic chitosan solution and a slightly basic buffer solution. A simple and effective pumping strategy was devised to realize a stable flow interface thereby generating a stable, well-controlled and localized pH gradient. Chitosan molecules were deprotonated at the flow interface, causing gelation and solidification of a freestanding chitosan membrane from a nucleation point at the junction of two converging flow streams to an anchoring point where the two flow streams diverge to two output channels. The fabricated chitosan membranes were about 30-60 microm thick and uniform throughout the flow interface inside the microchannels. A T-shaped membrane formed by sequentially fabricating orthogonal membranes demonstrates flexibility of the assembly process. The membranes are permeable to aqueous solutions and are removed by mildly acidic solutions. Permeability tests suggested that the membrane pore size was a few nanometres, i.e., the size range of antibodies. Building on the widely reported use of chitosan as a soft interconnect for biological components and microfabricated devices and the broad applications of membrane functionalities in microsystems, we believe that the facile, rapid biofabrication of freestanding chitosan membranes can be applied to many biochemical, bioanalytical, biosensing applications and cellular studies.

Nanostructured devices have the potential to serve as the basis for next-generation energy systems that make use of densely packed interfaces and thin films. One approach to making such devices is to build multilayer structures of large area inside the open volume of a nanostructured template. Here, we report the use of atomic layer deposition to fabricate arrays of metal-insulator-metal nanocapacitors in anodic aluminium oxide nanopores. These highly regular arrays have a capacitance per unit planar area of approximately 10 microF cm-2 for 1-microm-thick anodic aluminium oxide and approximately 100 microF cm-2 for 10-microm-thick anodic aluminium oxide, significantly exceeding previously reported values for metal-insulator-metal capacitors in porous templates. It should be possible to scale devices fabricated with this approach to make viable energy storage systems that provide both high energy density and high power density.

Biological microelectromechanical systems (bioMEMS) provide an attractive approach to understanding and modifying enzymatic pathways by separating and interrogating individual reaction steps at localized sites in a microfluidic network. We have previously shown that electrodeposited chitosan enables immobilization of an enzyme at a specific site while maintaining its catalytic activity. While promising as a methodology to replicate metabolic pathways and search for inhibitors as drug candidates, these investigations also revealed unintended (or parasitic) effects, including products generated by the enzyme either (1) in the homogeneous phase (in the liquid), or (2) nonspecifically bound to microchannel surfaces. Here we report on bioMEMS designs which significantly suppress these parasitic effects. To reduce homogeneous reactions we have developed a new packaging and assembly strategy which eliminates fluid reservoirs that are commonly used for fluidic interconnects with external tubing. To suppress reactions by nonspecifically bound enzyme on microchannel walls we have implemented a cross-flow microfluidic network design so that enzyme flow for assembly and substrate/product for reaction share only the region where the enzyme is immobilized at the intended reaction site. Our results show that the signal-to-background ratio of sequential enzymatic reactions increases from 0.72 to 1.28 by eliminating the packaging reservoirs, and increases to 2.43 by separating the flow direction of enzymatic reaction from that of enzyme assembly step. These techniques can be easily applied to versatile microfluidic devices to minimize parasitic reactions in sequential biochemical reactions.

We report an approach for spatially selective assembly of an enzyme onto selected patterns of microfabricated chips. Our approach is based on electrodeposition of the aminopolysaccharide chitosan onto selected electrode patterns and covalent conjugation of a target enzyme to chitosan upon biochemical activation of a genetically fused "pro-tag." We report assembly of S-adenosylhomocysteine nucleosidase (Pfs) fused with a C-terminal pentatyrosine pro-tag. Pfs is a member of the bacterial autoinducer-2 biosynthesis pathway, catalyzing the irreversible cleavage of S-adenosylhomocysteine. The assembled Pfs retains its catalytic activity and structure, as demonstrated by retained antibody recognition. Assembly is controlled by the electrode area, resulting in reproducible rates of catalytic conversion for a given area, and thus allowing for area-based manipulation of catalysis and small molecule biosynthesis. Our approach enables optimization of small molecule biosynthesis in 1-step as well as multistep enzymatic reactions, including entire metabolic pathways, and we envision a wide variety of potential applications.