Nanometers In Diameter Research Articles

Effect of nano-encapsulated food flavorings on streptozotocin-induced diabetic rats.

Flavors and aromas are widely used in food and pharmaceutical industries to enhance food palatability. However, it is worth noting that they may also have bioactivity. This study aims to examine the potential impact of key flavors and their nanocapsules on health and diseases, such as type 2 diabetes mellitus (T2DM). The 36 nanocapsules of key flavorings were prepared by high shear homogenization (HSH). Seventy-two male Sprague-Dawley rats received a single dosage of streptozotocin (35 mg kg-1 body weight) intraperitoneally. All of the nutritional and biochemical parameters were statistically analyzed. A virtual docking study was conducted. Linalool nanoemulsion results showed the highest encapsulation efficiency (86.76%), while isoamyl acetate nanoparticles showed the lowest (69.99%). According to GC-MS analysis, encapsulation did not affect the flavoring structure with particle size distributions ranging from 277.3 to 628.8 nm. Using TEM, nanoemulsion particles appeared spherical with a desired nanometric diameter size. In the oral glucose tolerance test, flavorings in oil and nanoforms had no discernible hypoglycemia effects in normal rats. The nutritional and biochemical parameters confirmed that both normal and nanoencapsulation forms demonstrated a potential anti-hyperglycemic effect, and enhanced the rat health compared to the raw flavorings. The studied flavorings and their nanocapsules seem to have the potential double effect of a flavor compound as a food palatability enhancer with a potential beneficial effect on type 2 diabetes mellitus without any health drawbacks.

Forced Gradient Copolymer for Rational Design of Mussel-Inspired Adhesives and Dispersants.

In recent years, there has been considerable research into functional materials inspired by living things. Much attention has been paid to the development of adhesive materials that mimic the adhesive proteins secreted by a mussel's foot. These mussel-inspired materials have superior adhesiveness to various adherents owing to the non-covalent interactions of their polyphenolic moieties, e.g., hydrogen bonding, electrostatic interactions, and even hydrophobic interactions. Various factors significantly affect the adhesiveness of mussel-inspired polymers, such as the molecular weight, cross-linking density, and composition ratio of the components, as well as the chemical structure of the polyphenolic adhesive moieties, such as l-3,4-dihydroxyphenylalanine (l-Dopa). However, the contributions of the position and distribution of the adhesive moiety in mussel-inspired polymers are often underestimated. In the present study, we prepared a series of mussel-inspired alkyl methacrylate copolymers by controlling the position and distribution of the adhesive moiety, which are known as "forced gradient copolymers". We used a newly designed gallic-acid-bearing methacrylate (GMA) as the polyphenolic adhesive moiety and copolymerized it with 2-ethylhexyl methacrylate (EHMA). The resulting forced gradient adhesive copolymer of GMA and EHMA (poly(GMA-co-EHMA), Poly1) was subjected to adhesion and dispersion tests with an aluminum substrate and a BaTiO3 nanoparticle in organic solvents, respectively. In particular, this study aims to clarify how the monomer position and distribution of the adhesive moiety in the mussel-inspired polymer affect its adhesion and dispersion behavior on a flat metal oxide surface and spherical inorganic oxide surfaces of several tens of nanometers in diameter, respectively. Here, forced gradient copolymer Poly1 consisted of a homopolymer moiety of EHMA (Poly3) and a random copolymer moiety of EHMA and GMA (Poly4). The composition ratio of GMA and the molecular weight were kept constant among the Poly1 series. Simultaneous control of the molecular lengths of Poly3 and Poly4 allowed us to discuss the effects on the distribution of GMA in Poly1. Poly1 exhibited apparent distribution dependency with regard to the adhesiveness and the dispersibility of BaTiO3. Poly1 showed the highest adhesion strength when the composition ratio of GMA was approximately 9 mol% in the portion of the Poly4 segment. In contrast, the block copolymer consisting of the Poly3 segment and Poly4 segment with only adhesive moiety 1 showed the lowest viscosity for dispersion of BaTiO3 nanoparticles. These results indicate that copolymers with mussel-inspired adhesive motifs require the proper design of the monomer position and distribution in Poly1 according to the shape and characteristics of the adherend to maximize their functionality. This research will facilitate the rational design of bio-inspired adhesive materials derived from plants that outperform natural materials, and it will eventually contribute to a sustainable circular economy.

Preparation and characterization of carex meyeriana Kunthcellulose nanofibers by electrospinning

The cellulose of carex meyeriana kunth (CMKC) was used as raw material, and the spinning solution was prepared by combining with polyacrylonitrile (PAN). The nano-cellulose fiber of carex meyeriana kunth (CMKN) was prepared by electrospinning. Used to remove methylene blue dye (MB) in aqueous solution. In the electrospinning experiment, the addition of CMKC was in the range of 5% ~ 25%, the feed rate of spinning parameters was set in the range of 0.2 ~ 1.0 mL/h, the distance from the needle tip to the collecting plate was in the range of 10 ~ 25 cm, and the voltage was changed in the range of 15 ~ 25 kV. The obtained CMKN was characterized by scanning electron microscope, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy. The MB removal rate was evaluated in the dye removal experiment, and the effects of CMKN on MB removal rate under the factors of CMKC dosage, temperature, shock time and MB initial concentration were discussed. The optimum process conditions were determined by response surface methodology. The results show that the prepared fibers are superfine fibers with nanometer diameter, and the spun nanofibers have smooth surface, high overall orientation and strong uniformity. The adsorption kinetics of prepared CMKN accords with quasi-second order model, and the adsorption isotherm accords with Langmuir model. The maximum dye removal rate of CMKN is 63.24%.

Electron heating and radiation in high aspect ratio sub-micron plasma generated by an ultrafast Bessel pulse within a solid dielectric

When propagating inside dielectrics, an ultrafast Bessel beam creates a high aspect-ratio cylinder of plasma with nanometric diameter that extends over several tens of micrometers to centimeters. We analyze the interaction between the intense ultrafast laser pulse and the plasma rod using particle-in-cell simulations. We show that electrons are heated and accelerated up to keV energies via transit acceleration inside the resonance lobes in the vicinity of the critical surface and compute their radiation pattern.

Antimicrobial Properties of a Copper/Silicone Composite Membrane Prepared Using a Two-Step Immersion Process in Iodine and Copper Sulfate Solutions.

Silicone (polydimethylsiloxane) materials are widely used in various applications. Due to microbe adherence and biofilm formation at the surface of silicone materials, silicone materials must possess antibacterial properties. To achieve this, we prepared copper (Cu)-silicone composite membranes using a simple two-step process of immersion in iodine and copper sulfate solutions. Subsequent scanning electron microscopy revealed Cu nanoparticles (CuNPs) of 10 to 200 nanometers in diameter on the silicone membrane surface, which were identified as copper iodide using energy-dispersive X-ray spectroscopy. The mechanical strength of the material did not change significantly as a result of the two-step immersion treatment and the Cu/silicone membrane showed excellent antibacterial efficacy against Escherichia coli and Staphylococcus aureus, maintaining R > 2 even after a physical impact such as stomacher treatment. Additionally, the Cu ions eluted from the Cu/silicone membrane remained at very low concentrations, suggesting firm immobilization of CuNPs on the silicone membrane. This proposed antimicrobial treatment method does not require special equipment, can be performed at room temperature, and has the potential for use on silicone materials other than membranes.

Design, Formulation, and Characterization of Valsartan Nanoethosomes for Improving Their Bioavailability.

The objective of this study was to formulate and evaluate valsartan (VLT) ethosomes to prepare an optimized formula of VLT-entrapped ethosomes that could be incorporated into a sustained release transdermal gel dosage form. The formulation of the prepared ethosomal gel was investigated and subjected to in vitro drug release studies, ex vivo test, and in vivo studies to assess the effectiveness of ethosomal formulation in enhancing the bioavailability of VLT as a poorly soluble drug and in controlling its release from the transdermal gel dosage form. The acquired results are as follows: Dependent responses were particle size, polydispersity index, zeta potential, and entrapment efficiency. The optimized VLT-ETHs had a nanometric diameter (45.8 ± 0.5 nm), a negative surface charge (-51.4 ± 6.3 mV), and a high drug encapsulation (94.24 ± 0.2). The prepared VLT ethosomal gel (VLT-ethogel) showed a high peak plasma concentration and enhanced bioavailability in rats compared with the oral solution of valsartan presented in the higher AUC (0-∞). The AUC (0-∞) with oral treatment was 7.0 ± 2.94 (μg.h/mL), but the AUC (0-∞) with topical application of the VAL nanoethosomal gel was 137.2 ± 49.88 (μg.h/mL), providing the sustained release pattern of VLT from the tested ethosomal gel.

Spectroscopy of nanoantenna-covered Cu2O : Towards enhancing quadrupole transitions in Rydberg excitons

Plasmonic antennas channel incoming light into a confined near field that comes along with strong field gradients at the edges. Transverse field gradients are capable of driving quadrupole transitions in a more effective way than the weak longitudinal field gradient in dipolar light. Cuprous oxide Rydberg excitons with principal quantum number $n$ between 5 and 15 are several tens to a few hundreds of nanometers in diameter and can have different orbital angular momentum quantum numbers. Usually, only $P$- and $F$-excitons are electric dipole allowed, while $S$- and $D$-excitons remain dark. Here, we use 30-nm-wide and 60- to 110-nm-long plasmonic aluminum nanoantennas deposited on the cuprous oxide crystal surface to create transverse field gradients in similar spatial dimensions as the size of the Rydberg excitons. This way, light field and matter wave function overlap spatially and quadrupole transitions of $S$excitons are enhanced. The relative enhancement of the $S$-exciton oscillator strength with respect to the $P$-exciton oscillator accounts for a factor of up to 1.4.

Effect of Hf on the microstructure and martensitic transformation behavior in Ti–Pd–Hf alloy

We investigated the microstructure and the crystallography of martensite variants in Ti–Pd–Hf alloy using electron microscopy. The martensitic transformation temperature decreased with increasing amount of Hf substituted into the Ti50−xPd50Hfx alloy. No indication of a martensitic transformation was observed in the as-quenched Ti25Pd50Hf25 and Ti10Pd50Hf40 alloys, even when the samples were cooled to 150 K. The Ti40Pd50Hf10, Ti35Pd50Hf15, and Ti30Pd50Hf20 alloys were composed of a B19 orthorhombic phase having plate-like habit-plane variants consisting of both major and minor correspondence variants several hundred nanometers in width and several tens of micrometers in length at room temperature. Lattice-invariant shear of these alloys was a {111}B19 Type I twin. A solution-treated sample of the Ti25Pd50Hf25 alloy consisted of a B2 cubic matrix with local atomic displacement and lattice distortions, and rounded H-phase particles several tens of nanometers in diameter were precipitated inside the B2 matrix upon aging of the specimen at 823 K for 10.8 ks. The as-quenched Ti10Pd50Hf40 alloy contained rounded H-phase particles several tens of nanometers in diameter embedded in a B2 matrix at room temperature. The martensitic transformation temperature in the Ti50−xPd50Hfx alloy was drastically decreased by both the fully coherent nanosized H-phase particles and the short-range order originating from clustering of solute atoms.

Scalable Dry-Pressed Electrodes Based on Holey Graphene.

ConspectusHoley graphene (hG) is a structural derivative of graphene with arrays of through-thickness holes of a few to tens of nanometers in diameter, randomly distributed across the nanosheet surfaces. In most bulk preparation methods, the holes on hG sheets are preferentially generated from the pre-existing defects on graphene. Therefore, contrary to intuitive belief, hG is not necessarily more defective than the intact graphene. Instead, it retains essential parent properties, including high electrical conductivity, high surface area, mechanical robustness, and chemical inertness. Furthermore, the added holey structural motif imparts unique properties that are not present in unmodified graphene, making hG advantageous in numerous applications such as sensing, membranes, reinforcements, and electrochemical energy storage. In particular, the presence of holes enhances the mass transport through the nanosheet plane and thus significantly reduces tortuosity. This difference is a key advantage for using hG in energy storage applications where the transport of ions through the thickness becomes more hindered as the electrode thickness increases to meet practical energy density requirements.An unexpected discovery is that the holes of the hG sheets enable the dry hG powder to be directly compressed into robust monoliths. hG not only can be pressed into monoliths by itself but also can host other electrochemically active materials as a compressible matrix. This important yet unique property, which is not available for other carbon materials including intact graphene, significantly broadens the application horizon in energy storage applications. With the dry compressibility, electrodes with ultrahigh mass loading and thus ultrahigh areal capacity may be conveniently fabricated without toxic solvents or parasitic binders, which are required in conventional slurry-based approaches for electrode fabrication. The dry-press electrode preparation process can be completed within minutes regardless of mass loading. In comparison, high-mass-loading electrodes for advanced battery chemistries using conventional fabrication methods often need stringent and time-consuming process control. hG can also be combined with electrochemically active battery materials while maintaining dry compressibility. This has allowed the unprecedented, convenient manipulation of a wide variety of thick electrode compositions and architectures, which provides not only outstanding performance but also new physical insights for various battery chemistries.In this Account, we first present some basic observations on the dry compressibility of hG as well as the mechanistic investigations from atomistic modeling rationalizing this unique property. We then showcase the applications of neat and composite dry-pressed hG electrodes for various energy storage platforms including supercapacitors, lithium (Li) ion batteries, Li-O2 batteries, and Li-S/Se batteries. The preparation and performance of thick electrodes with practical mass loadings and unique electrode architecture manipulation, both enabled by the dry compressibility of hG, are highlighted and discussed.

All-Gas-Phase Synthesis of Heterolayered Two-Dimensional Nanohybrids Decorated with Metallic Nanocatalysts for Water Splitting.

Herein, a sequential gas-phase process involving air jet milling followed by chemical vapor deposition (CVD), is demonstrated to be an efficient strategy for the fabrication of heterolayered 2D nanohybrids (2DNHs) decorated with nanocatalysts. Tens of grams of the nanohybrids, which is a substantial quantity at the laboratory scale, are produced in the absence of solvents and water, and without the need for an extra purification procedure. Air jet milling enables the development of binary/ternary heterolayered structures consisting of graphene, WSe2 , and/or MoS2 via the gas-phase co-exfoliation of their bulk counterparts. Based on the X-ray photoelectron and Raman spectroscopy data, the heterolayers of the 2DNHs exert chemical and electronic effects on each other, while diminishing the interactions between same-component layers. Moreover, the electrochemically active surface area increases by >190% and the charge transfer resistance decreases by >35%. CVD is performed to introduce Pt and Ru nanoparticles with diameters of a few nanometers as additional electrocatalysts into the 2DNHs. The nanocatalyst-decorated 2DNHs show excellent performance for the production of hydrogen and oxygen gases in water-splitting cells. Notably, the proposed all-gas-phase processes allow for the large-scale production of functional 2DNHs with minimal negative environmental impact, which is crucial for the commercialization of nanomaterials.

Long-term aging of CVD grown 2D-MoS2 nanosheets in ambient environment

A chemically vapor deposited MoS2 nanosheets (NSs) is aged in the laboratory at ambient and at 40% average humidity for ~36 months. Nanorods of few microns in length and few nanometers in diameter are found to grow from the MoS2 seeds. They have been growing as a result of the chemical reaction between the MoS2 NSs and ambient O2 and moisture, they exhibit an amorphous phase structure in the stoichiometric form of MoO3. Density functional theory simulations further reveal the role of H2O and O2 in the transformation of the MoS2 NSs. The adsorption energy of O2 molecules on the MoS2 sites is Ead = −1.09 eV as compared to lowest absolute Ead = −0.10 eV of H2O indicating the favorable adsorption of O2 and subsequent Mo oxidation. This study provides valuable insight into the aging phenomenon of MoS2 exposed to O2 and moisture which might limit their application.

Pore Evolution Characteristics of Marine Organic-Rich Shale Based on a Pyrolysis Simulation Experiment

The pore evolution characteristics of organic-rich shale under semiclosed and open-system conditions were investigated through a pyrolysis simulation experiment conducted on marine low-maturity shale. The results show that the experimental samples of the two systems mainly developed organic pores, clay mineral intergranular pores, and brittle mineral dissolution pores during the evolution process. The shale porosity showed a non-linear growth trend with the thermal maturity increase. However, the porosity increase rate of the semiclosed system was higher than that of the open system. The pore structure characterization parameters of the experimental samples under the two systems were quite different. The samples of the semiclosed system developed wedge- or V-shaped pores with a diameter of several tens of nanometers, while those of the open system developed more small throats with a diameter of several nanometers to ink bottle-type and closed pores of tens of nanometers. For the marine organic-rich shale, the organic matter (OM) evolution was mainly affected by the formation pressure. In summary, a semiclosed system with a higher formation pressure is more conducive to the development of organic pores and the pore structure than an open system with a lower formation pressure. The best stage of pore evolution and development is the overmature stage.

Metal Nanoparticles on Lipophilic Nanographenes.

Utilization of graphitic domains on nanographenes (NGs) for anchoring metal nanoparticles (NPs) can open the door for their applications in catalysis. Reported examples employ hydrophilic graphene oxides as substrates, making it difficult to coexist with organic substrates in organic solvents. The title NGs are metal NP-doped lipophilic NGs (M-NG1). Various metal cations form NPs with a diameter of a few to tens of nanometers on the basal plane. Owing to the lipophilic nature of NG1, M-NG1 is prepared by the reduction of the basal plane with sodium in THF followed by the addition of metal salts. Au-NPs on NG1 allow anchoring an organic thiol carrying an anthracene fluorophore, which is a proof of concept of composite materials utilizing the surface of NGs. The assessment of the catalytic function of Pd-NG1 reveals that chlorobenzene and bromobenzene yield a coupling product, and fluorobenzene also undergoes the reactions, demonstrating the catalytic function of Pd-NG1.

Integration of Nanographenes and Organic Chemistry - Toward Nanographene-based Two-Dimensional Materials.

Graphene and its relatives have received considerable attention from the fields of physics and chemistry since the isolation of pristine graphene sheets. Nanographenes (NGs) are graphene fragments that are a few to tens of nanometers in diameter. Compared to graphene and its relatives, such as graphene oxides, NGs can be handled more easily, and their large π surface and oxygen functional groups on the edge allow postsynthetic modifications. The study of NGs is gradually shifting from the development of synthetic procedures to postsynthetic modification. From the structural point of view, NGs can be regarded as two-dimensional carbon polymers. Their unique structures and affinity for organic molecules make NGs excellent scaffolds for two-dimensional materials, which are now an important topic in organic and polymer chemistry. In this conceptual article, we introduce the position of NGs from the perspective of two-dimensional substances and briefly review both the structural features of NGs and the effects of functionalization on their physical properties. These are valuable when producing reasonable strategies for their postsynthetic modifications.

Nanocracks in nature and industry.

Nanocracks in nature and industry.

Gas-Diffusion Coefficient in Organic Matter Affects Estimation of Shale-Gas Reservoirs

This article, written by JPT Technology Editor Chris Carpenter, contains highlights of paper SPE 201653, “On the Inference of Gas Diffusion Coefficient in Organic Matter of Shale Gas Reservoirs,” by Esmail Eltahan, SPE, Mehran Mehrabi, and Kamy Sepehrnoori, SPE, The University of Texas at Austin, et al. The paper has not been peer reviewed. US shale reservoirs are tight and inherently heterogeneous, with an abundant presence of kerogenic material. Modeling fluid flow in shale reservoirs is complex because of flow physics such as pressure flow and diffusion. Many field-performance forecasts underestimate production from these reservoirs constantly because most current models ignore important governing physics. This study provides new insights on diffusion in organic matter to correct a main source of underestimation of gas production in shale-gas models. In the complete paper, the authors implement a multiscale diffusion model to estimate gas-diffusion coefficient in organic matter. Background Pores in shale-gas resources, which are on the order of a few to tens of nanometers in diameter, are much smaller than pores in conventional resources. At such small pore size, the ratio of surface area to pore volume becomes large, giving importance to transport mechanisms that depend on the surface area. According to other researchers, in addition to the free gas, considerable amounts of gas molecules will exist on the surface of organic material (adsorbed gas) and inside the solid matrix of kerogen (dissolved gas). Although typically neglected in conventional gas resources, the adsorbed and dissolved gas should receive attention in the case of shale-gas resources because of an abundance of organic material and substantial pore surface area. Gas production from shale is largely facilitated by maximizing the contact a well creates with the formation. In practice, the contact is established by numerous hydraulic fractures along a wellbore that extends for a lengthy horizontal distance in the formation. The induced-fracture networks grant direct access to the free gas in organic and inorganic pores as well as the adsorbed and dissolved gas through organic pores. Gas is depleted in the same manner as it is stored (in laboratory experiments, but in reverse order). Free gas is expanded first, creating local pressure sinks that force adsorbed gas to detach from the pore surface. As the desorption process continues, the number of unoccupied spots on the pore walls increases. Local concentration disruptions occur at those spots, which cause the dissolved gas to diffuse back into the pores. The contribution of dissolved gas in field cases has been reported in several studies, which provides motivation to study the physics of dissolved-gas diffusion on the pore scale and to develop consistent predictive models on the mesoscale. In a previous work by the authors, they presented a mathematical model for the evolution of dissolved gas that considers detailed pore geometry. However, the authors write that they have shown that pore geometry has minor influence, in contrast to the involved diffusion-length scales. Thus, the key components of previously obtained insights are used to build a simple model. The proposed model is considerably simpler in implementation, yet descriptive of the key components that govern dissolved-gas evolution. The mathematical model and its associated equations are detailed in the complete paper.

Thyme-Loaded Nanofibrous Dressing for Skin Wound Healing: A Combination of Chinese Traditional Medicine with Cutting-Edge Technology

The skin has vital functions and its defects and damages must be properly treated and healed. Chinese traditional herbal medicine has a long history in skin wound healing, and its merging with novel approaches (nanotechnology) has resulted in more promising results. The current study aimed to combine the biological properties of a long-lasting Chinese traditional herbal medicine (Thyme) with cutting-edge technology (electrospinning) to the fabricated interactive and bioactive wound dressing. The extract of Thyme was obtained and added into the polymeric solution and converted to the nanofibrous wound dressing. The SEM analysis revealed that the fabricated nanofibers were intact without deformity with an acceptable nanometric diameter. The release kinetics evaluation showed that 80±4% of the extract was released from the nanofibers during the first 24 h. Hemolysis lower than 8% for all nanofibers revealed hemocompatibility in the fabricated wound dressings. The in vitro studies confirmed the cytocompatibility of the nanofibers. The applied animal studies exhibited that the Thyme-loaded nanofibrous dressing enhanced the wound-healing process in a dose-dependent manner. These findings demonstrate the combination of Chinese traditional herbal medicine with modern cutting-edge technology, resulting in an interactive nanofibrous mat with promising potential as the wound dressing material.

Nanoscale energy deposition frequencies evaluation using GATE simulation tools

Over the last decade, cancer treatment with radiation therapy has evolved significantly due to the improvements in Treatment Planning Systems (TPS). Ideally, these algorithms can determine the dose distribution at the macroscopic scale. However, due to the lack of knowledge, these approaches remain impractical to model radiation side effects at the nanometric scale. This study presents the validation of Monte Carlo (MC) algorithms as a novel approach to model the nanodosimetric effects of radiation therapy particles on real DNA molecule models. A simulation of two simple volumes irradiated by a proton beam is performed to demonstrate the ability of the mixed Geant4-DNA physics model to describe extremely low-energy particle interactions compared to the simple standard Electromagnetic options three physic list. Furthermore, the nanodosimetric effects on the DNA molecule are simulated based on the calculations of the energy frequency deposited by both electron and proton beams in cylinders of three distinct nanometric diameters sizes corresponding to the block elements of the nucleus cell (10 bp, nucleosome, and chromatin fiber). Finally, following the results of this study, the energy deposition frequency in nanoscale cylinders simulated based on the Gate MC code is in good agreement with the results of the series of MOCA codes previously published in the literature.

Development of Cathodes for Aluminum-Ion and Aluminum-Air Batteries Using Pulsed Electrodeposition

Electrical energy storage has emerged as a critical component in North America’s clean energy transformation. Vehicle electrification and integration of renewables such as wind and solar power into the grid have further underlined the importance of affordable, environmentally friendly energy storage platforms. Rechargeable batteries are now considered to be viable options for large-scale energy storage with lithium-ion and redox flow batteries leading the charge. Over the past decades, aluminum-ion batteries have experienced a renaissance on account of their high volumetric energy density, superior cycleability, enhanced stability and significant cost benefits compared with other commercially available secondary batteries. Aluminum-air batteries also hold significant promise as primary energy storage platforms, but they suffer from thermodynamics and kinetics hurdles, leading to inferior performance. To address these issues, researchers have focused on optimizing different cell components, including anodes, cathodes, and electrolytes.It is well established that nano-structuring battery components would markedly improve their short- and long-term performance by enhancing reaction kinetics. One of the major impediments to wide-scale commercialization of Al-ion batteries continues to be its inferior capacity and cycle stability compared with commercially available secondary batteries. Part of these issues can be ascribed to the failure of cathode materials currently being investigated and used. As for primary Al-air batteries, conventional air cathodes do not perform very well either; and there are many reasons as to why the incorporation of such air cathodes into Al-air batteries would lead to inferior performance or premature failure; the most important of which is low catalytic activity.To address a number of these issues, pulsed current electrodeposition was employed to deposit nano-catalysts such nickel, silver, platinum and oxides of manganese on different support materials, including carbon paper and cloth, titania nanotubes, and stainless steel and nickel meshes. The influence of various electrodeposition parameters, including peak current density, duty cycle, type of waveform and pulse frequency, on resulting layers were systematically investigated. In most cases, nanocatalysts about 2-40 nm in diameter were obtained. Various electrochemical tests were utilized to characterize the resulting layers. A simple mathematical model based on progressive nucleation also was developed to predict the influence of the aforementioned electrodeposition parameters on the resulting nano-catalyst layers. The model was further refined by considering all contributing factors towards growth current, including diffusion, ohmic and charge transfer phenomena as well as changing diffusion coefficients, during electrodeposition. According to the model, at high peak deposition current densities and low duty cycles (5% or less), the ramp-down waveform yielded the highest nucleation rates, confirming the experimental findings in which nanoparticles generated with the above waveform produced the smallest average grain size, ranging from 2-10 nanometer in diameter for platinum and silver nanocatalysts on carbon cloths and titania nanotubes, and 10-50 nm in diameter for nickel nanoparticles deposited on stainless steel and nickel meshes and titania nanotubes.

Phase-separating RNA-binding proteins form heterogeneous distributions of clusters in subsaturated solutions

Macromolecular phase separation is thought to be one of the processes that drives the formation of membraneless biomolecular condensates in cells. The dynamics of phase separation are thought to follow the tenets of classical nucleation theory, and, therefore, subsaturated solutions should be devoid of clusters with more than a few molecules. We tested this prediction using invitro biophysical studies to characterize subsaturated solutions of phase-separating RNA-binding proteins with intrinsically disordered prion-like domains and RNA-binding domains. Surprisingly, and in direct contradiction to expectations from classical nucleation theory, we find that subsaturated solutions are characterized by the presence of heterogeneous distributions of clusters. The distributions of cluster sizes, which are dominated by small species, shift continuously toward larger sizes as protein concentrations increase and approach the saturation concentration. As a result, many of the clusters encompass tens to hundreds of molecules, while less than 1% of the solutions are mesoscale species that are several hundred nanometers in diameter. We find that cluster formation in subsaturated solutions and phase separation in supersaturated solutions are strongly coupled via sequence-encoded interactions. We also find that cluster formation and phase separation can be decoupled using solutes as well as specific sets of mutations. Our findings, which are concordant with predictions for associative polymers, implicate an interplay between networks of sequence-specific and solubility-determining interactions that, respectively, govern cluster formation in subsaturated solutions and the saturation concentrations above which phase separation occurs.