Nanoconfinement of Carbon Dioxide within Interfacial Aqueous/Ionic Liquid Systems.

Nanoporous, gas-selective membranes have shown encouraging results for the removal of CO2 from flue gas, yet the optimal design for such membranes is often unknown. Therefore, we used molecular dynamics simulations to elucidate the behavior of CO2 within aqueous and ionic liquid (IL) systems ([EMIM][TFSI] and [OMIM][TFSI]), both confined individually and as an interfacial aqueous/IL system. We found that within aqueous systems the mobility of CO2 is reduced due to interactions between the CO2 oxygens and hydroxyl groups on the pore surface. Within the IL systems, we found that confinement has a greater effect on the [EMIM][TFSI] system as opposed to the [OMIM][TFSI] system. Paradoxically, the larger and more asymmetrical [OMIM]+ molecule undergoes less efficient packing, resulting in fewer confinement effects. Free energy surfaces of the nanoconfined aqueous/IL interface demonstrate that CO2 will transfer spontaneously from the aqueous to the IL phase.

Bio-inspired incorporation of phenylalanine enhances ionic selectivity in layer-by-layer deposited polyelectrolyte films.

The addition of a common amino acid, phenylalanine, to a Layer-by-Layer (LbL) deposited polyelectrolyte (PE) film on a nanoporous membrane can increase its ionic selectivity over a PE film without the added amino acid. The addition of phenylalanine is inspired by detailed knowledge of the structure of the channelrhodopsins family of protein ion channels, where phenylalanine plays an instrumental role in facilitating sodium ion transport. The normally deposited and crosslinked PE films increase the cationic selectivity of a support membrane in a controllable manner where higher selectivity is achieved with thicker PE coatings, which in turn also increases the ionic resistance of the membrane. The increased ionic selectivity is desired while the increased resistance is not. We show that through incorporation of phenylalanine during the LbL deposition process, in solutions of NaCl with concentrations ranging from 0.1 to 100 mM, the ionic selectivity can be increased independently of the membrane resistance. Specifically, the addition is shown to increase the cationic transference of the PE films from 81.4% to 86.4%, an increase on par with PE films that are nearly triple the thickness while exhibiting much lower resistance compared to the thicker coatings, where the phenylalanine incorporated PE films display an area specific resistance of 1.81 Ω cm2 in 100 mM NaCl while much thicker PE membranes show a higher resistance of 2.75 Ω cm2 in the same 100 mM NaCl solution.

Microtubule-based nanomaterials: Exploiting nature's dynamic biopolymers.

For more than a decade now, biomolecular systems have served as an inspiration for the development of synthetic nanomaterials and systems that are capable of reproducing many of unique and emergent behaviors of living systems. One intriguing element of such systems may be found in a specialized class of proteins known as biomolecular motors that are capable of performing useful work across multiple length scales through the efficient conversion of chemical energy. Microtubule (MT) filaments may be considered within this context as their dynamic assembly and disassembly dissipate energy, and perform work within the cell. MTs are one of three cytoskeletal filaments in eukaryotic cells, and play critical roles in a range of cellular processes including mitosis and vesicular trafficking. Based on their function, physical attributes, and unique dynamics, MTs also serve as a powerful archetype of a supramolecular filament that underlies and drives multiscale emergent behaviors. In this review, we briefly summarize recent efforts to generate hybrid and composite nanomaterials using MTs as biomolecular scaffolds, as well as computational and synthetic approaches to develop synthetic one-dimensional nanostructures that display the enviable attributes of the natural filaments.

Surfactant-induced assembly of enzymatically-stable peptide hydrogels.

The secondary structure of peptides in the presence of interacting additives is an important topic of study, having implications in the application of peptide science to a broad range of modern technologies. Surfactants constitute a class of biologically relevant compounds that are known to influence both peptide conformation and aggregation or assembly. We have characterized the secondary structure of a linear nonapeptide composed of a hydrophobic alanine/phenylalanine core flanked by hydrophilic acid/amine units. We show that the anionic surfactant sodium dodecyl sulfate (SDS) induces the formation of ß-sheets and macroscopic gelation in this otherwise unstructured peptide. Through comparison to related additives, we propose that SDS-induced secondary structure formation is the result of amphiphilicity created by electrostatic binding of SDS to the peptide. In addition, we demonstrate a novel utility of surfactants in manipulating and stabilizing peptide nanostructures. SDS is used to simultaneously induce secondary structure in a peptide and to inhibit the activity of a model enzyme, resulting in a peptide hydrogel that is impervious to enzymatic degradation. These results complement our understanding of the behavior of peptides in the presence of interacting secondary molecules and provide new potential pathways for programmable organization of peptides by the addition of such components.

Amphiphilic triblocks to control assembly of mixed or segregated bilayers and monolayers.

Triblock amphiphilic molecules composed of three distinct segments provide a large parameter space to obtain self-assembled structures beyond what is achievable with conventional amphiphiles. To obtain a molecular understanding of the thermodynamics of self-assembly, we develop a coarse-grained triblock polymer model and apply self-consistent field theory to investigate the packing mechanism into layer structures. By tuning the structural and interaction asymmetry, we are able to obtain bilayers and monolayers, where the latter may additionally be mixed (symmetric) or segregated (asymmetric). Of particular interest for a variety of applications are the asymmetric monolayers, where segregation of end blocks to opposite surfaces is expected to have important implications for the development of functional nanotubes and vesicles with distinct surface chemistries.

Supramolecular assembly of asymmetric self-neutralizing amphiphilic peptide wedges.

Mimicking the remarkable dynamic and multifunctional utility of biological nanofibers, such as microtubules, is a challenging and technologically attractive objective in synthetic supramolecular chemistry. Understanding the complex molecular interactions that govern the assembly of synthetic materials, such as peptides, is key to meeting this challenge. Using molecular dynamics simulations to guide molecular design, we explore here the self-assembly of structurally and functionally asymmetric wedge-shaped peptides. Supramolecular assembly into nanofiber gels or multilayered lamellar structures was determined by cooperative influences of hydrogen bonding, amphiphilicity (hydrophilic asymmetry), and the distribution of electrostatic charges on the aqueous self-assembly of asymmetric peptides. Molecular amphiphilicity and ß-sheet forming capacity were both identified as necessary, but not independently sufficient, to form supramolecular nanofibers. Imbalances in positive and negative charges prevented nanofiber assembly, while the asymmetric distribution of balanced charges within a peptide is believed to affect peptide conformation and subsequent self-assembly into either nanofibers or lamellar structures. Insights into cooperative molecular interactions and the effects of molecular asymmetry on assembly may aid the development of next-generation supramolecular nanomaterial assemblies.

Synergizing Fe2O3 Nanoparticles on Single Atom Fe-N-C for Nitrate Reduction to Ammonia at Industrial Current Densities.

The electrochemical reduction of nitrates (NO3 -) enables a pathway for the carbon neutral synthesis of ammonia (NH3), via the nitrate reduction reaction (NO3RR), which has been demonstrated at high selectivity. However, to make NH3 synthesis cost-competitive with current technologies, high NH3 partial current densities (jNH3) must be achieved to reduce the levelized cost of NH3. Here, the high NO3RR activity of Fe-based materials is leveraged to synthesize a novel active particle-active support system with Fe2O3 nanoparticles supported on atomically dispersed Fe-N-C. The optimized 3×Fe2O3/Fe-N-C catalyst demonstrates an ultrahigh NO3RR activity, reaching a maximum jNH3 of 1.95 A cm-2 at a Faradaic efficiency (FE) for NH3 of 100% and an NH3 yield rate over 9 mmol hr-1 cm-2. Operando XANES and post-mortem XPS reveal the importance of a pre-reduction activation step, reducing the surface Fe2O3 (Fe3+) to highly active Fe0 sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe2O3 particles and Fe-Nx sites at highly cathodic potentials, maintaining a current of -1.3 A cm-2 over 24 hours. This work exhibits an effective and durable active particle-active support system enhancing the performance of the NO3RR, enabling industrially relevant current densities and near 100% selectivity.

Development of AMOEBA Polarizable Force Field for Rare-Earth La3+ Interaction with Bioinspired Ligands.

Rare-earth metals (REMs) are crucial for many important industries, such as power generation and storage, in addition to cancer treatment and medical imaging. One promising new REM refinement approach involves mimicking the highly selective and efficient binding of REMs observed in relatively recently discovered proteins. However, realizing any such bioinspired approach requires an understanding of the biological recognition mechanisms. Here, we developed a new classical polarizable force field based on the AMOEBA framework for modeling a lanthanum ion (La3+) interacting with water, acetate, and acetamide, which have been found to coordinate the ion in proteins. The parameters were derived by comparing to high-level ab initio quantum mechanical (QM) calculations that include relativistic effects. The AMOEBA model, with advanced atomic multipoles and electronic polarization, is successful in capturing both the QM distance-dependent La3+-ligand interaction energies and experimental hydration free energy. A new scheme for pairwise polarization damping (POLPAIR) was developed to describe the polarization energy in La3+ interactions with both charged and neutral ligands. Simulations of La3+ in water showed water coordination numbers and ion-water distances consistent with previous experimental and theoretical findings. Water residence time analysis revealed both fast and slow kinetics in water exchange around the ion. This new model will allow investigation of fully solvated lanthanum ion-protein systems using GPU-accelerated dynamics simulations to gain insights on binding selectivity, which may be applied to the design of synthetic analogues.

Transport and Energetics of Carbon Dioxide in Ionic Liquids at Aqueous Interfaces.

A major hurdle in utilizing carbon dioxide (CO2) lies in separating it from industrial flue gas mixtures and finding suitable storage methods that enable its application in various industries. To address this issue, we utilized a combination of molecular dynamics simulations and experiments to investigate the behavior of CO2 in common room-temperature ionic liquids (RTIL) when in contact with aqueous interfaces. Our investigation of RTILs, [EMIM][TFSI] and [OMIM][TFSI], and their interaction with a pure water layer mimics the environment of a previously developed ultrathin enzymatic liquid membrane for CO2 separation. We analyzed diffusion constants and viscosity, which reveals that CO2 molecules exhibit faster mobility within the selected ILs compared to what would be predicted solely based on the viscosity of the liquids using the standard Einstein-Stokes relation. Moreover, we calculated the free energy of translocation for various species across the aqueous-IL interface, including CO2 and HCO3-. Free energy profiles demonstrate that CO2 exhibits a more favorable partitioning behavior in the RTILs compared to that in pure water, while a significant barrier hinders the movement of HCO3- from the aqueous layer. Experimental measurement of the CO2 transport in the RTILs corroborates the model. These findings strongly suggest that hydrophobic RTILs could serve as a promising option for selectively transporting CO2 from aqueous media and concentrating it as a preliminary step toward storage.

Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites.

Electrocatalytic reduction of waste nitrates (NO3-) enables the synthesis of ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3d-, 4d-, 5d- and f-block M-N-C catalysts. The selectivity and activity of NO3- reduction to NH3 in neutral media, with a specific focus on deciphering the role of the NO2- intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO2- reduction activity and NO3- reduction selectivity for NH3. Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO2- evolution, over the normal M-N4 sites and their oxo-form (O-M-N4) for oxyphilic metals. This work provides a platform for designing multi-element NO3RR cascades with single-atom sites or their hybridization with extended catalytic surfaces.

Evaluation of Electrodialysis Desalination Performance of Novel Bioinspired and Conventional Ion Exchange Membranes with Sodium Chloride Feed Solutions.

Electrodialysis (ED) desalination performance of different conventional and laboratory-scale ion exchange membranes (IEMs) has been evaluated by many researchers, but most of these studies used their own sets of experimental parameters such as feed solution compositions and concentrations, superficial velocities of the process streams (diluate, concentrate, and electrode rinse), applied electrical voltages, and types of IEMs. Thus, direct comparison of ED desalination performance of different IEMs is virtually impossible. While the use of different conventional IEMs in ED has been reported, the use of bioinspired ion exchange membrane has not been reported yet. The goal of this study was to evaluate the ED desalination performance differences between novel laboratory­scale bioinspired IEM and conventional IEMs by determining (i) limiting current density, (ii) current density, (iii) current efficiency, (iv) salinity reduction in diluate stream, (v) normalized specific energy consumption, and (vi) water flux by osmosis as a function of (a) initial concentration of NaCl feed solution (diluate and concentrate streams), (b) superficial velocity of feed solution, and (c) applied stack voltage per cell-pair of membranes. A laboratory­scale single stage batch-recycle electrodialysis experimental apparatus was assembled with five cell­pairs of IEMs with an active cross-sectional area of 7.84 cm2. In this study, seven combinations of IEMs (commercial and laboratory-made) were compared: (i) Neosepta AMX/CMX, (ii) PCA PCSA/PCSK, (iii) Fujifilm Type 1 AEM/CEM, (iv) SUEZ AR204SZRA/CR67HMR, (v) Ralex AMH-PES/CMH-PES, (vi) Neosepta AMX/Bare Polycarbonate membrane (Polycarb), and (vii) Neosepta AMX/Sandia novel bioinspired cation exchange membrane (SandiaCEM). ED desalination performance with the Sandia novel bioinspired cation exchange membrane (SandiaCEM) was found to be competitive with commercial Neosepta CMX cation exchange membrane.

Buckyballs meet viral nanoparticles: candidates for biomedicine.

Fullerenes such as C(60) show promise as functional components in several emerging technologies. For biomedical applications, C(60) has been used in gene- and drug-delivery vectors, as imaging agents, and as photosensitizers in cancer therapy. A major drawback of C(60) for bioapplications is its insolubility in water. To overcome this limitation, we covalently attached C(60) derivatives to Cowpea mosaic virus and bacteriophage Qbeta virus-like particles, which are examples of naturally occurring viral nanoparticle (VNP) structures that have been shown to be promising candidates for biomedicine. Two different labeling strategies were employed, giving rise to water-soluble, stable VNP-C(60) and VNP-PEG-C(60) conjugates. Samples were characterized using a combination of transmission electron microscopy, scanning transmission electron microscopy (STEM), gel electrophoresis, size-exclusion chromatography, dynamic light scattering, and Western blotting. "Click" chemistry bioconjugation using a poly(ethylene glycol) (PEG)-modified propargyl-O-PEG-C(60) derivative gave rise to high loadings of fullerene on the VNP surface, as indicated by the imaging of individual C(60) units using STEM. The cellular uptake of dye-labeled VNP-PEG-C(60) complexes in a human cancer cell line was found by confocal microscopy to be robust, showing that cell internalization was not inhibited by the attached C(60) units. These results open the door for the development of novel therapeutic devices with potential applications in photoactivated tumor therapy.

How non-bonding domains affect the active assembly of microtubule spools.

Structural defects can determine and influence various properties of materials, and many technologies rely on the manipulation of defects (e.g., semiconductor industries). In biological systems, management of defects/errors (e.g. DNA repair) is critical to an organism's survival, which has inspired the design of artificial nanomachines that mimic nature's ability to detect defects and repair damage. Biological motors have captured considerable attention in developing such capabilities due to their ability to convert energy into directed motion in response to environmental stimuli, which maximizes their ability for detection and repair. The objective of the present study was to develop an understanding of how the presence of non-bonding domains, here considered as a "defect", in microtubule (MT) building blocks affect the kinesin-driven, active assembly of MT spools. The assembly/joining of micron-scale bonding (i.e., biotin-containing) and non-bonding (i.e., no biotin) MTs resulted in segmented MT building blocks consisting of alternating bonding and non-bonding domains. Here, the introduction of these MT building blocks into a kinesin gliding motility assay along with streptavidin-coated quantum dots resulted in the active assembly of spools with altered morphology but retained functionality. Moreover, it was noted that non-bonding domains were autonomously and preferentially released from the spools over time, representing a mechanism by which defects may be removed from these structures. Overall, our findings demonstrate that this active assembly system has an intrinsic ability for quality control, which can be potentially expanded to a wide range of applications such as self-regulation and healing of active materials.

Titanium with aligned, elongated pores for orthopedic tissue engineering applications.

Porous titanium with elongated and aligned pores, mimicking the anisotropic structure of bone, was created by solid-state expansion of argon trapped in elongated pores between titanium wires. Both elastic moduli and yield strengths are larger in the longitudinal direction (E = 51 GPa, sigma y = 338 MPa) than in the transverse direction (E = 41 GPa, sigma y = 267 MPa). Finite-element analysis of simplified anisotropic structures provides insight into the local micromechanical behavior of these porous materials, evaluating elastic modulus, resistance to plastic deformation, and localized stress concentrations which may be experienced under biological loading. Preliminary in vitro cell culture studies further demonstrate the influence of the elongated porous microstructure on osteoblast colonization behavior. These studies suggest that as an optimized material, titanium with aligned, elongated pores is promising for applications in orthopedic tissue engineering, as it combines high strength, toughness, and biocompatibility of titanium with the reduced stiffness and open porosity suitable for mechanical integration with bone tissue produced by aligned pores.

Polyelectrolyte layer-by-layer deposition on nanoporous supports for ion selective membranes.

This work demonstrates that the ionic selectivity and ionic conductivity of nanoporous membranes can be controlled independently via layer-by-layer (LbL) deposition of polyelectrolytes and subsequent selective cross-linking of these polymer layers. LbL deposition offers a scalable, inexpensive method to tune the ion transport properties of nanoporous membranes by sequentially dip coating layers of cationic polyethyleneimine and anionic poly(acrylic acid) onto polycarbonate membranes. The cationic and anionic polymers are self-assembled through electrostatic and hydrogen bonding interactions and are chemically crosslinked to both change the charge distribution and improve the intermolecular integrity of the deposited films. Both the thickness of the deposited coating and the use of chemical cross-linking agents influence charge transport properties significantly. Increased polyelectrolyte thickness increases the selectivity for cationic transport through the membranes while adding polyelectrolyte films decreases the ionic conductivity compared to an uncoated membrane. Once the nanopores are filled, no additional decrease in conductivity is observed with increasing film thickness and, upon cross-linking, a portion of the lost conductivity is recovered. The cross-linking agent also influences the ionic selectivity of the resulting polyelectrolyte membranes. Increased selectivity for cationic transport occurs when using glutaraldehyde as the cross-linking agent, as expected due to the selective cross-linking of primary amines that decreases the net positive charge. Together, these results inform deposition of chemically robust, highly conductive, ion-selective membranes onto inexpensive porous supports for applications ranging from energy storage to water purification.

Extraordinary Corrosion Protection from Polymer-Clay Nanobrick Wall Thin Films.

Metals across all industries demand anticorrosion surface treatments and drive a continual need for high-performing and low-cost coatings. Here we demonstrate polymer-clay nanocomposite thin films as a new class of transparent conformal barrier coatings for protection in corrosive atmospheres. Films assembled via layer-by-layer deposition, as thin as 90 nm, are shown to reduce copper corrosion rates by >1000× in an aggressive H2S atmosphere. These multilayer nanobrick wall coatings hold promise as high-performing anticorrosion treatment alternatives to costlier, more toxic, and less scalable thin films, such as graphene, hexavalent chromium, or atomic-layer-deposited metal oxides.

Secondary nucleation and growth of ZnO.

Recently we discovered that under certain conditions new crystal growth (branch) can be induced on specific crystalline planes of the same material. This is a new phenomenon and is in sharp contrast to typical nucleation and growth in which a crystal will simply grow larger in preferred directions depending on the surface energy of the specific crystalline planes. Based on our observation, we developed a sequential nucleation and growth technique offering the power to assemble complex hierarchical crystals step-by-step. However, the key questions of when and how the secondary nucleation takes place have not been answered. Here we systematically study secondary ZnO crystal growth using organic diamine additives with a range of chain lengths and concentration. We found that ZnO branches form for a narrow diamine concentration range with a critical lower and upper critical nucleation concentration limit, which increases by about a factor of 5 for each additional carbon in the diaminoalkane chain. Our results suggest that the narrow window for secondary growth is dictated by the solubility of the ZnO crystals, where the low critical nucleation concentration is determined by slight etching of the surface to produce new nucleation sites, and the upper critical concentration is determined by the supersaturation concentration. Kinetic measurements show that the induction time and growth rate increase with increasing diamine concentration and follow classical nucleation and growth theory. Observations of branch morphological evolution reveal the mechanisms guiding the tunable crystal size and morphology.

Synthesis of a poly(L-lysine)-calcium phosphate hybrid on titanium surfaces for enhanced bioactivity.

Titanium has been a successful implant material owing to its excellent strength to weight ratio, toughness, and bioinert oxide surface. Significant progress has been made on the improvement of titanium's bioactivity by coating its oxide surface with calcium phosphates and bioactive molecules. Here, we report on the coating of titanium with a poly(L-lysine)-calcium phosphate hybrid material with a nanoscale texture. This hybrid coating was grown by first nucleating seed crystals of calcium phosphate, directly on the Ti surface and then exposing this surface to solutions containing Ca(2+), PO(4)(3-), and poly(L-lysine). The resultant hybrid coating was characterized by electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and elemental analysis. This material contained 14% by weight poly(L-lysine), and this organic component decreased greatly the dimensions of the surface features, thus enhancing surface area relative to the inorganic control. The highly textured hybrid material was more susceptible than the control to acidic and enzymatic degradation. The amino acid cysteine was covalently linked to the hybrid material, demonstrating the potential of this coating for further functionalization. These hybrid coatings may prove useful in enhancing the bioactivity of titanium.

A bioactive titanium foam scaffold for bone repair.

While titanium has been clinically successful as an orthopedic or dental implant material, performance problems still persist related to implant-bone interfacial strength and mechanical modulus mismatch between titanium and tissue. We describe here the preparation of a titanium foam as a better mechanical match to tissue with surfaces attractive to bone cells through deposition of an organically-modified apatite layer (organoapatite). In a rotating bioreactor, these organoapatite-coated foams are successfully colonized by preosteoblastic cells. Finite element analyses suggest that ingrown tissue in these systems may improve both implant performance and tissue formation through load-sharing and stress distribution. The novel metal-ceramic-polymer hybrid materials described here hold great promise for bone tissue engineering.