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At least 199 records · Page 11

Eudicot Nutshells: Cell-Wall Composition and Biofuel Feedstock Potential

Nutshells are the recalcitrant and membranous layers that encompass and provide protection to the seed of a fruit. Rich in lignin, these are often waste products of the food industry and are a potential energy-dense feedstock for biorefineries to convert to biofuels. Here, assessing their potential requires an understanding of the relative amounts of cellulose, hemicelluloses, and lignin, the composition and structure of the lignin, and a saccharifiability assessment, all provided here. In the context of understanding the general character of phylogenetically diverse eudicot species, we provide a chemical analysis of the lignin in the shells of commonly eaten nuts and detail the chemical composition of their lignins. Particularly striking observations include the >40% levels of Klason lignins in the nutshells from macadamia, pecan, and Brazil nut and lignin compositions ranging from <1% syringyl (S) in macadamia to 77% S in pistachio and essentially 0% p-hydroxyphenyl (H) in mango to as high as 7.5% H in walnut. Novel units in the lignin polymer (such as the hydroxystilbenes recently discovered in macaúba and coconut shell lignins) were not evident in any of the samples, but the series provided such a range of compositions that it aided more detailed assignment.

NMR↗

Electric fields near undulating dielectric membranes

Dielectric interfaces are crucial to the behavior of charged membranes, from graphene to synthetic and biological lipid bilayers. Understanding electrolyte behavior near these interfaces remains a challenge, especially in the case of rough dielectric surfaces. A lack of analytical solutions consigns this problem to numerical treatments. Here, we report an analytic method for determining electrostatic potentials near curved dielectric membranes in a two-dimensional periodic “slab” geometry using a periodic summation of Green’s functions. This method is amenable to simulating arbitrary groups of charges near surfaces with two-dimensional deformations. We concentrate on one-dimensional undulations. We show that increasing membrane undulation increases the asymmetry of interfacial charge distributions due to preferential ionic repulsion from troughs. In the limit of thick membranes, we recover results mimicking those for electrolytes near a single interface. Our work demonstrates that rough surfaces generate charge patterns in electrolytes of charged molecules or mixed-valence ions.

Chemistry↗

In situ oxidation of reduced graphene oxide membranes by peracetic acid for dye desalination

Graphene oxide (GO) membranes with tunable interlayer spacings are of interest for dye removal from salty textile wastewater, and the membranes are often reduced to improve their stability, which inevitably lowers water permeance. Herein, we demonstrate that reduced GO (rGO) membranes can be facilely modified using peracetic acid (PAA) in situ to dramatically enhance water permeance while retaining dye rejection. Specifically, PAA-modified membranes (PrGO) are synthesized by vacuum-filtering hydrazine-reduced rGO nanosheets onto Nylon substrate and then exposing them to PAA solutions. The effects of the rGO layer thickness, PAA content, and PAA exposure time on the membrane chemistry, nanostructures, and salt/dye separation properties are thoroughly examined. For example, the PAA oxidation of a 100 nm-thick rGO membrane for 10 min increases water permeance by 180 %, from 35 to 93 Liter m −2 h −1 bar −1 , and decreases Na 2 SO 4 rejection from 10 % to 3.3 % while retaining the rejection of Congo red at ≈99.7 %. The PrGO membranes exhibit stable water permeance and >99 % dye rejection in multi-cycle tests in a crossflow system, surpassing state-of-the-art GO membranes and showcasing their potential for practical applications.

Dye desalination↗

Study of Cathode Gas Diffusion Architecture for Improved Oxygen Transport in Hydroxide Exchange Membrane Fuel Cells

The high pH environment in hydroxide exchange membrane fuel cells (HEMFCs) has the potential to reach lower costs than the current proton exchange membrane fuel cells (PEMFCs), the incumbent technology. A significant difference between HEMFCs and PEMFCs is the location of water production within the cell. In PEMFCs, the water is produced on the cathode, limiting oxygen transport. In HEMFCs, the water is produced on the anode where the fuel is pure hydrogen. This allows the cathode to be optimized for oxygen transport without the presence of excess liquid water. Limiting current analysis, a technique previously used in PEMFCs, is adopted in HEMFCs to evaluate the oxygen mass transport resistances for different sections of the cathode. Through elimination of the microporous layer (MPL), gas diffusion layer (GDL), and traditional flow field and using porous nickel foam for gas distribution, the transport resistance at an operating condition of 150 kPa(g) and with the cell temperature at 80 °C was decreased from 112 s m −1 to 48 s m −1 , effectively halved. The optimal configuration for performance was found with Ni foam and a GDL, eliminating the MPL and traditional flow field, which vastly improved oxygen transport while maintaining adequate electrical contact with the cathode catalyst layer.

25 ENERGY STORAGE↗

Pressure-stable supported ionic liquid membranes using isoporous supports for evaluating pure- and mixed-gas light paraffin fractionation

Advances in horizontal drilling and hydraulic fracturing have spurred the growth of domestic U.S. energy production. Membranes, typically silicone rubbers, have found utility in shale gas treatment as fuel gas conditioning units to selectively remove C 2 + hydrocarbons at pressures up to 30 bar, producing clean CH 4 for gas engines. However, more selective materials could be beneficial for broader shale gas treatment applications, such as dew point control units. Supported ionic liquid membranes (SILMs) offer a potential opportunity for improving C 3 H 8 /CH 4 selectivity, but they lack pressure-stability. Here, we report C 3 H 8 /CH 4 selective and pressure-stable SILMs using isoporous supports. SILMs with supports that had minimal defects remained stable up to 15 bar of transmembrane pressure. This stability allowed for pure- and mixed-gas testing of the resulting membranes at elevated pressures. Furthermore, these tests revealed that low viscosity ILs (<100 cp) may display mixed-gas permeances and permselectivity nearly identical to pure-gas results. On the other hand, higher viscosity ILs may display increasing permeances and permselectivity with increasing C 3 H 8 fugacity, similar to rubbery polymers. Ultimately, the SILMs demonstrated relatively high pressure-stability due to the isoporous supports and competitive mixed-gas C 3 H 8 /CH 4 permselectivity compared to silicone rubber.

Rosenthal, Justin J. [University of Texas at Austi↗

Gratings Fabricated on Flat Surfaces and Reproduced on Non-Flat Substrates

A method has been developed for fabricating gratings on flat substrates, and then reproducing the groove pattern on a curved (concave or convex) substrate and a corresponding grating device. First, surface relief diffraction grating grooves are formed on flat substrates. For example, they may be fabricated using photolithography and reactive ion etching, maskless lithography, holography, or mechanical ruling. Then, an imprint of the grating is made on a deformable substrate, such as plastic, polymer, or other materials using thermoforming, hot or cold embossing, or other methods. Interim stamps using electroforming, or other methods, may be produced for the imprinting process or if the same polarity of the grating image is required. The imprinted, deformable substrate is then attached to a curved, rigid substrate using epoxy or other suitable adhesives. The imprinted surface is facing away from the curved rigid substrate. As an alternative fabrication method, after grating is imprinted on the deformable substrate as described above, the grating may be coated with thin conformal conductive layer (for example, using vacuum deposition of gold). Then the membrane may be mounted over an opening in a pressured vessel in a manner of a membrane on a drum, grating side out. The pressure inside of the vessel may be changed with respect to the ambient pressure to produce concave or convex membrane surface. The shape of the opening may control the type of the surface curvature (for example, a circular opening would create spherical surface, oval opening would create toroidal surface, etc.). After that, well-known electroforming methods may be used to create a replica of the grating on the concave or convex membrane. For example, the pressure vessel assembly may be submerged into an electro-forming solution and negative electric potential applied to the metal coated membrane using an insulated wire. Positive electric potential may be then applied to a nickel or other metal plate submerged into the same solution. Metal ions would transfer from the plate through the solution into the membrane, producing high fidelity metal replica of the grating on the membrane. In one variation, an adhesive may be deposited on the deformable substrate, and then cured without touching the rigid, curved substrate. Edges of the deformable substrate may be attached to the rigid substrate to ensure uniform deformation of the deformable substrate. The assembly may be performed in vacuum, and then taken out to atmospheric pressure conditions to ensure that no air is trapped between the deformable and rigid substrates. Alternatively, a rigid surface with complementary curvature to the rigid substrate may be used to ensure uniform adhesion of the deformable substrate to the rigid substrate. Liquid may be applied to the surface of the deformable substrate to uniformly distribute pressure across its surface during the curing or hardening of the adhesive, or the film may be pressed into the surface using a deformable object or surface. After the attachment is complete, the grooves may be coated with reflective or dielectric layers to improve diffraction efficiency.

Content, David↗

Non-Contact Eddy Current Method for Assessing Proton Conductivity in Nafion Membranes

Accurate measurement of proton conductivity in Proton Exchange Membranes (PEMs) is vital for fuel cell performance and durability. This study explores eddy current testing as a non-destructive, non-contact and high-rate quality control (QC) method for measuring Nafion membrane proton conductivity, with potential for high-volume manufacturing applications.

33 ADVANCED PROPULSION SYSTEMS↗

Potent Antiviral Activity against HSV-1 and SARS-CoV-2 by Antimicrobial Peptoids

Viral infections, such as those caused by Herpes Simplex Virus-1 (HSV-1) and SARS-CoV-2, affect millions of people each year. However, there are few antiviral drugs that can effectively treat these infections. The standard approach in the development of antiviral drugs involves the identification of a unique viral target, followed by the design of an agent that addresses that target. Antimicrobial peptides (AMPs) represent a novel source of potential antiviral drugs. AMPs have been shown to inactivate numerous different enveloped viruses through the disruption of their viral envelopes. However, the clinical development of AMPs as antimicrobial therapeutics has been hampered by a number of factors, especially their enzymatically labile structure as peptides. We have examined the antiviral potential of peptoid mimics of AMPs (sequence-specific N-substituted glycine oligomers). These peptoids have the distinct advantage of being insensitive to proteases, and also exhibit increased bioavailability and stability. Our results demonstrate that several peptoids exhibit potent in vitro antiviral activity against both HSV-1 and SARS-CoV-2 when incubated prior to infection. In other words, they have a direct effect on the viral structure, which appears to render the viral particles non-infective. Visualization by cryo-EM shows viral envelope disruption similar to what has been observed with AMP activity against other viruses. Furthermore, we observed no cytotoxicity against primary cultures of oral epithelial cells. These results suggest a common or biomimetic mechanism, possibly due to the differences between the phospholipid head group makeup of viral envelopes and host cell membranes, thus underscoring the potential of this class of molecules as safe and effective broad-spectrum antiviral agents. We discuss how and why differing molecular features between 10 peptoid candidates may affect both antiviral activity and selectivity.

60 APPLIED LIFE SCIENCES↗

Field Validation of a Pilot-Scale Black Liquor Membrane for Water Removal

Pulp and paper processing is considered one of the most energy-intensive industries in the manufacturing sector. Concentrating black liquor is a particularly energy-intensive process in this industry, used to recover pulping chemicals and generate high-pressure steam from dissolved wood solids. About 7% of pulp and paper energy usage, or nearly 164 trillion British thermal units (Btu) per year, is used to remove water from black liquor in U.S. kraft mills. The U.S. Department of Energy’s Industrial Efficiency and Decarbonization Office is interested in this black liquor membrane technology because it offers the potential for a more energy-efficient and less carbon-intensive kraft pulping process. The membrane is intended to pretreat black liquor to reduce natural gas usage in evaporators that remove water from black liquor. This technology has the potential to be replicated across 99 kraft pulp mills in 24 states. This membrane technology is considered precommercial, and the demonstration was a small-scale side-stream field validation. To make an assessment on performance with a higher level of certainty, additional studies at larger scales are recommended.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Optimal design of multi-stage vacuum membrane distillation and integration with supercritical water desalination for improved zero liquid discharge desalination

Herein this paper proposes a novel concept for the optimal design of multi-stage vacuum membrane distillation (VMD). Generally, a multi-stage VMD is designed with an equal temperature difference between each stage. However, such a design is energy inefficient and increases VMD area. An analytical methodology for calculating the optimal stage temperature is proposed. By selecting the optimal stage temperature, the energy efficiency and required membrane area can be potentially improved by 16% and 30%, respectively. The proposed concept applies to all heat sources, including latent, sensible, and waste heat. To illustrate the method, multi-stage VMD is integrated with the waste heat from a supercritical water desalination (SCWD) system to achieve zero liquid discharge. SCWD is an energy-intensive process, requires high-quality thermal heat (>450 °C), and exhibits high waste heat rejection. The integrated VMD-SCWD approach is approximately 50% more energy-efficient and 35% more cost-efficient than the standalone SCWD system. Compared to the commercially used brine concentrator and crystallizer, the multi-stage VMD-SCWD system is more energy efficient for feed concentrations >5%. VMD-SCWD system is 30% cheaper, due to less expensive membrane distillation modules compared to a brine concentrator. The proposed design concept can replace the brine concentrator and crystallizer as an improved alternative for a zero-liquid discharge desalination system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unlocking bulk and surface oxygen transport properties of mixed oxide-ion and electron conducting membranes with combined oxygen permeation cell and oxygen probe method

Surface exchange kinetics and bulk diffusion of oxygen are of paramount importance to the activity of oxygen electrocatalysis and performance of electrochemical devices such as fuel cell, metal-air batteries, and oxygen separation membranes. Conventional approaches to obtaining these transport properties are often limited to single property under a specific non-operation related condition. Here we use a combined oxygen permeation cell and oxygen probe methodology to simultaneously attain rates of oxygen surface exchange and bulk conductivity/chemical diffusivity of three representative mixed oxide-ion and electron conductors, namely SrCo 0.9 Ta 0.1 O 3-δ (SCT), La 0.6 Sr 0.4 CoO 3-δ (LSC) and La 0.6 Sr 0.4 FeO 3-δ (LSF), operated under a steady-state oxygen flux. The results explicitly show that SCT exhibit the highest oxide-ion conductivity/chemical diffusivity, fastest rates of surface oxygen exchange kinetics, thus promising to be the best oxygen electrocatalyst. Here, we have also mapped out the distribution of oxygen chemical potential gradient across the membranes and applied B-transport number concept to illustrate the rate-limiting steps in the overall oxygen permeation process.

42 ENGINEERING↗

Synergistically combining peracetic acid and reduced graphene oxide membranes to degrade trace organic contaminants

The removal of trace organic contaminants is a critical step for the reuse of municipal and industrial wastewater. Herein, we demonstrate a catalytic membrane platform synergistically integrating reduced graphene oxide (rGO) membranes and peracetic acid (PAA) oxidation, using a dye of methylene blue (MB) and a pesticide of 2,4-dichlorophenoxyacetic acid (2,4-D) as model contaminants. In a crossflow system with rGO membrane and 25 ppm PAA, the degradation rates of MB and 2,4-D were 22 and 0.12 g h −1 per g rGO, with an initial concentration of 10 and 1.1 ppm, respectively. The degradation time profile of MB and 2,4-D follows a pseudo-first-order model, and the degradation rate constant increases with increasing initial PAA doses. Here, the rGO membranes also exhibited good stability over a 1-month test for 2,4-D degradation. In addition to the nanofiltration performance of the rGO membrane, the integrated PAA-rGO membrane process shows great potential to degrade various organic contaminants without the need to separate and recover the metal-free catalyst in downstream treatment.

2,4-D↗

Optimization-based modeling and economic comparison of membrane distillation configurations for application in shale gas produced water treatment

Membrane distillation (MD) is an emerging membrane technology with great potential for treatment of hypersaline wastewater generated by unconventional (shale) oil and gas reservoirs. However, the low energy efficiency of this technology makes the operating cost of MD systems relatively high, especially in the absence of waste heat. There are several MD configurations with inherent advantages and disadvantages and varying performance. As such, there is a need for thermo-economic optimization of MD systems in a systematic manner to assess their economic performance. Here we present an optimization framework to model and compare the performance of six MD configurations (DCMD, AGMD, PGMD, CGMD, SGMD, and VMD) in continuous recirculation mode for treatment of hypersaline wastewater. The optimization results show that AGMD with small gap size operated at low stream Reynolds number outperforms all other configurations with treatment cost of 4.57 US $/m 3 of feed. However, restricting the system design to more practically relevant operating conditions, such as higher Reynolds number and larger gap size, diminishes the cost superiority of AGMD over other configurations. We also observed that treatment cost using PGMD configuration approaches those of CGMD and DCMD, particularly when modules with small gaps are used.

42 ENGINEERING↗

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Lastly, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultra-Sharp Nanowire Arrays Natively Permeate, Record, and Stimulate Intracellular Activity in Neuronal and Cardiac Networks

Intracellular access with high spatiotemporal resolution can enhance the understanding of how neurons or cardiomyocytes regulate and orchestrate network activity and how this activity can be affected with pharmacology or other interventional modalities. Nanoscale devices often employ electroporation to transiently permeate the cell membrane and record intracellular potentials, which tend to decrease rapidly with time. Here, one reports innovative scalable, vertical, ultrasharp nanowire arrays that are individually addressable to enable long-term, native recordings of intracellular potentials. One reports electrophysiological recordings that are indicative of intracellular access from 3D tissue-like networks of neurons and cardiomyocytes across recording days and that do not decrease to extracellular amplitudes for the duration of the recording of several minutes. The findings are validated with cross-sectional microscopy, pharmacology, and electrical interventions. The experiments and simulations demonstrate that the individual electrical addressability of nanowires is necessary for high-fidelity intracellular electrophysiological recordings. This work advances the understanding of and control over high-quality multichannel intracellular recordings and paves the way toward predictive, high-throughput, and low-cost electrophysiological drug screening platforms.

36 MATERIALS SCIENCE↗

Imaginary admittance and charge transfer resistance correlate to the physiological status of Shewanella oneidensis cultures in real time

Monitoring microbial activity is essential for industrial and environmental applications to proceed efficiently. To minimize time and labor-intensive monitoring, a new paradigm is required for in-situ, real time analysis. Since bioconversion of organics is accomplished by microorganisms through the oxidation of feedstocks linked to the reduction of electron acceptors, microorganisms can be viewed as electrochemical catalysts. In this respect, cell membranes have an electrical potential, which is analogous to a conventional capacitor and linked dynamically to cellular activity. Here, in this study, we demonstrate the use of electrochemical impedance spectrometry (EIS) and cyclic voltammetry (CV) for monitoring microbial metabolic activity in real time, in-situ. The effect of organic electron donors as a function of concentration to the physiological status of strains of Shewanella oneidensis was determined. In this study, the pyomelanin overproducer (S. oneidensis ΔhmgA) and the pyomelanin deficient mutant (S. oneidensis ΔmelA) were chosen due to different surface electrochemical characteristics along with differences in oxygen utilization efficiency. CV, relative admittance, phase shift and permittivity changed with growth status and correlated with electron flow from organic carbon sources and terminal electron acceptor availability. This work offers a novel and inexpensive approach to real time monitoring with the advantage of abundant data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

3D-Printed Membranes with a Zwitterionic Hydrogel Coating for More Robust Oil–Water Separation

Three-dimensional (3D)-printed membranes via stereolithography (SLA) are promising in oil–water separation, which is the key in the purification of industrial oily wastewater. To achieve gravity-driven oil–water separation, the membrane material needs to be simultaneously hydrophilic/oleophobic. However, most of the state-of-the-art materials for SLA do not meet the requirement. While water-adsorbing hydrogel is simultaneously hydrophilic/oleophobic and there have been reports on 3D printing of hydrogels in biomedical applications, the hydrogel is too soft for membrane application. Here, we report a simple approach to tackle the issue: a hydrogel coating on SLA-based plastic membranes. The coating is fabricated, using [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide as the zwitterionic monomer and acrylamide as the comonomer, via in situ polymerization on SLA-based plastic membranes. The contact angle tests and Fourier transform infrared spectrum show that such a membrane readily adsorbs water and becomes simultaneously hydrophilic/oleophobic. The oil–water separation tests indicate that the water-adsorbed membrane is highly efficient in gravity-driven oil–water separation in 31 repeating cycles. Our results indicate the great potential of 3D-printed membranes in oil–water separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the Nature of Field-Enhanced Water Dissociation in Bipolar Membranes

Bipolar membranes (BPMs) possess the potential to optimize pH environments for electrochemical synthesis applications when employed in reverse bias. Unfortunately, the performance of BPMs in reverse bias has long been limited by the rate of water dissociation (WD) occurring at the interface of the BPM. Herein, we develop a continuum model of the BPM that agrees with experiment to understand and enhance WD catalyst performance by considering multiple kinetic pathways for WD in the BPM junction catalyst layer. Here, the model reveals that WD catalysts with a more highly alkaline or acidic pH at the point of zero charge (pH PZC ) exhibit accelerated WD kinetics because the more acidic or alkaline pH PZC catalysts possess greater surface charge, enhancing the local electric field and rate of WD. The model is then employed to explore the sensitivity of the BPM performance to various BPM physical parameters. Finally, the model is used to simulate the operation of bimetallic WD catalysts, demonstrating that an optimal bimetallic catalyst has an acidic pH PZC catalyst matched with the cation-exchange layer and an alkaline pH PZC catalyst matched with the anion-exchange layer. The study provides insight into the operation of BPM WD catalysts and gives direction toward the development of next-generation WD catalysts for optimal BPM performance under water-splitting and related conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗