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At least 415 records · Page 23

Synthesis, characterization, and controlled release antibacterial behavior of antibiotic intercalated Mg–Al layered double hydroxides

Graphical abstract: The antibiotic anion released from Mg–Al LDHs provides a controlled release antibacterial activity against the growth of Micrococcus lysodeikticus in 3.5% NaCl solution. Highlights: ► Antibiotic anion intercalated LDHs were synthesized and characterized. ► The ion-exchange one is responsible for the release process. ► The diffusion through particle is the release rate limiting step. ► LDHs loaded with antibiotic anion have high antibacterial capabilities. -- Abstract: Antibiotic–inorganic clay composites including four antibiotic anions, namely, benzoate (BZ), succinate (SU), benzylpenicillin (BP), and ticarcillin (TC) anions, intercalated Mg–Al layered double hydroxides (LDHs) were synthesized via ion-exchange. Powder X-ray diffraction and Fourier transform infrared spectrum analyses showed the successful intercalation of antibiotic anion into the LDH interlayer. BZ and BP anions were accommodated in the interlayer region as a bilayer, whereas SU and TC anions were intercalated in a monolayer arrangement. Kinetic simulation of the release data indicated that ion-exchange was responsible for the release process, and the diffusion through the particles was the rate-limiting step. The antibacterial capabilities of LDHs loaded with antibiotic anion toward Micrococcus lysodeikticus growth were analyzed using a turbidimetric method. Significant high inhibition rate was observed when LDH nanohybrid was introduced in 3.5% NaCl solution. Therefore, this hybrid material may be applied as nanocontainer in active antifouling coating for marine equipment.

36 MATERIALS SCIENCE↗

Effect of Dy/Nd double layer on coercivity in Nd-Fe-B thin films

The Nd-Fe-B (t{sub NFB} = 30 nm)/[Dy (t{sub Dy} nm)/Nd (t{sub Nd} nm)] (t{sub Dy/Nd} = 20 nm) (thickness t{sub Dy} = 0–10 nm) thin films were deposited on Al{sub 2}O{sub 3}(0001) substrate and subsequently in-situ annealed at 470 °C. As-deposited Nd-Fe-B thin films with a highly perpendicular orientation of c-axis were deposited by introducing bcc-Mo(111) single crystal buffer layer. After post-annealing, the grain size of the Nd-Fe-B/Dy/Nd thin films with the t{sub Dy} = 10 nm and t{sub Nd} = 10 nm becomes large due to the Dy and the Nd atoms thermal diffusion, while DyFe{sub 2} and Dy oxide compounds are formed in Nd-Fe-B layers, which is confirmed by means of a combination of atomic force microscopy observation and X-ray diffraction measurement. The H{sub c} of Nd-Fe-B/Dy/Nd thin films with the t{sub Dy} = 10 nm and t{sub Nd} = 10 nm was approximately the same value of the Nd-Fe-B thin films without Dy/Nd double layer annealed at 470 °C. On the other hand, H{sub c} is enhanced to be about 22.1 kOe in the annealed Nd-Fe-B/Dy/Nd films with the t{sub Dy} = 0.8 nm and t{sub Nd} = 19.2 nm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Layered double hydroxides with atomic-scale defects for superior electrocatalysis

Atomic composition tuning and defect engineering are effective strategies to enhance the catalytic performance of multicomponent catalysts by improving the synergetic effect; however, it remains challenging to dramatically tune the active sites on multicomponent materials through simultaneous defect engineering at the atomic scale because of the similarities of the local environment. Here in this paper, using the oxygen evolution reaction (OER) as a probe reaction, we deliberately introduced base-soluble Zn(II) or Al(III) sites into NiFe layered double hydroxides(LDHs), which are one of the best OER catalysts. Then, the Zn(II) or Al(III) siteswere selectively etched to create atomic M(II)/M(III) defects, which dramatically enhanced the OER activity. At a current density of 20 mA·cm -2 , only 200 mV overpotential was required to generate M(II) defect-rich NiFe LDHs, which is the best NiFe-based OER catalyst reported to date. Density functional theory(DFT) calculations revealed that the creation of dangling Ni–Fe sites (i.e., unsaturated coordinated Ni–Fe sites) by defect engineering of a Ni–O–Fe site at the atomic scale efficiently lowers the Gibbs free energy of the oxygen evolution process. This defect engineering strategy provides new insights into catalysts at the atomic scale and should be beneficial for the design of a variety of catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deconstruction of Lignin Model Compounds and Biomass-Derived Lignin using Layered Double Hydroxide Catalysts

Lignin is an underutilized value stream in current biomass conversion technologies because there exist no economic and technically feasible routes for lignin depolymerization and upgrading. Base-catalyzed deconstruction (BCD) has been applied for lignin depolymerization (e.g., the Kraft process) in the pulp and paper industry for more than a century using aqueous-phase media. However, these efforts require treatment to neutralize the resulting streams, which adds significantly to the cost of lignin deconstruction. To circumvent the need for downstream treatment, here we report recent advances in the synthesis of layered double hydroxide and metal oxide catalysts to be applied to the BCD of lignin. These catalysts may prove more cost-effective than liquid-phase, non-recyclable base, and their use obviates downstream processing steps such as neutralization. Synthetic procedures for various transition-metal containing catalysts, detailed kinetics measurements using lignin model compounds, and results of the application of these catalysts to biomass-derived lignin will be presented.

09 BIOMASS FUELS↗

The Skylab barium plasma injection experiments. II - Evidence for a double layer

Television observations of a barium-plasma flux tube extending from near 4500 km to near 10,000 km during a magnetic substorm and dawn-sector auroral display indicated several interesting anomalous events. Beyond 5500 km, there was a rapid increase in brightness accompanied by flux-tube splitting and diffusion, leaving behind a truncated single flux tube. From the orientation of the flux tube compared with theoretical field models, the presence of a substantial field-aligned current sheet is deduced. A suggested explanation of these phenomena is given in terms of a plasma potential double layer.

Wescott, E. M.↗

Revisiting density functionals for the primitive model of electric double layers

Density functional theory (DFT) calculations are typically based on approximate functionals that link the free energy of a multi-body system of interest with the underlying one-body density distributions. Whereas good performance is often proclaimed for new developments, it is difficult to vindicate the theoretical merits relative to alternative versions without extensive comparison with the numerical results from molecular simulations. Besides, approximate functionals may defy statistical-mechanical sum rules and result in thermodynamic inconsistency. Here we compare systematically several versions of density functionals for ionic distributions near a charged surface using the primitive model of electric double layers. We find that the theoretical performance is sensitive not only to the specific forms of the density functional but also to the range of parameter space and the precise properties under consideration. In general, incorporation of the thermodynamic sum rule into the DFT calculations shows significant improvements for both electrochemical properties and ionic distributions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

NASA Discipline Exobiology↗

Double layers in contactor plasmas

The concept of using a hollow cathode to establish a low impedance contact between a spacecraft and the ambient plasma continues to gain in popularity, and is often then referred to as a plasma contactor. A growing number of studies indicate that large contact currents can be supported with small potential difference between the contactor and the ambient plasma. Results will be presented from a simple one-dimensional spherical model that obtains potentials from the solution of Poisson's equation, and particle densities from a turning point formalism that includes particle angular momentum. The neglect of collisions and magnetic field limits the realism. However, the results illustrate the effect of double layers that can form at the interface between contactor and ambient plasmas, when there is any voltage differential between the contactor and the ambient. The I-V characteristic of this model shows the usual space charge depends upon collection when the contactor flux is lower than some threshold; independence of I from variation in V when the flux is slightly greater than that threshold, and (numerical ?) instability for excessive flux suggesting the possibility of negative resistance. Even if a real I-V characteristic does not exhibit negative resistance, flat spots or high resistance regions may still be troublesome (or useful) to the total circuit.

Cooke, David L.↗

Some aspects of double layer formation in a plasma constrained by a magnetic mirror

The shift from wave-generated anomalous resistivity toward the more large-scale effects of magnetic confinement of current carrying plasmas was inspired by the more extensive data on auroral particle distribution functions that were made available, data that may often seem consistent with a dissipation-free acceleration of auroral electrons over an extended altitude range. Efforts to interpret these data have brought new vigor to the concept that a smooth and static electric field can be self-consistently generated by suitable pitch angle anisotropies among the high altitude particle populations, different for electrons and ions, and that such an electric field is both necessary and sufficient to maintain the plasma in a quasi-neutral steady state. Certain aspects of this concept are reviewed and criticized, both from a general theoretical standpoint and from the standpoint of what is known about the magnetospheric environment. It is argued that this concept has flaws and that the actual physical problem is considerably more complicated, requiring a more complex electric field, possibly including double layer structures.

Lennartsson, W.↗

Structure and Dynamics of Polymeric Canopies in Nanoscale Ionic Materials: An Electrical Double Layer Perspective

Nanoscale ionic materials (NIMs) are an emerging class of materials consisting of charged nanoparticles and polymeric canopies attaching to them dynamically by electrostatic interactions. Using molecular simulations, we examine the structure and dynamics of the polymeric canopies in model NIMs in which the canopy thickness is much smaller than the nanoparticle diameter. Without added electrolyte ions, the charged terminal groups of polymers adsorb strongly on charged walls, thereby electrostatically “grafting” polymers to the wall. These polymers are highly stretched. They rarely desorb from the wall, but maintain modest in-plane mobility. When electrolyte ion pairs are introduced, the counterions adsorb on the wall, causing some electrostatically “grafted” polymers to desorb. The desorbed polymers, however, are less than the adsorbed counter-ions, which leads to an overscreening of wall charges. The desorbed polymers’ charged terminal groups do not distribute uniformly across the canopy but are depleted in some regions; they adopt conformation similar to those in bulk and exchange with the “grafted” polymers rapidly, hence dilating the canopy and accelerating its dynamics. We understand these results by taking the canopy as an electrical double layer, and highlight the importance of the interplay of electrostatic and entropic effects in determining its structure and dynamics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V 2 O 5 Double Layers

The 5/6s 2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V 2 O 5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s 2 cations situated in interlayer sites between condensed [V 4 O 10 ] n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered M x V 2 O 5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s 2 –O 2p-hybridized mid-gap states mediated by second-order Jahn–Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V–V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V–V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg 0.5 V 2 O 5 and δ-Tl 0.5 V 2 O 5 , respectively, as compared to 7 K for δ-Pb 0.5 V 2 O 5 . In δ-Pb 0.5 V 2 O 5 , the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V 4 O 10 ] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron-acoustic solitons and double layers in the inner magnetosphere: ELECTRON-ACOUSTIC SOLITONS

The Van Allen Probes observe generally two types of electrostatic solitary waves (ESW) contributing to the broadband electrostatic wave activity in the nightside inner magnetosphere. ESW with symmetric bipolar parallel electric field are electron phase space holes. The nature of ESW with asymmetric bipolar (and almost unipolar) parallel electric field has remained puzzling. To address their nature, we consider a particular event observed by Van Allen Probes to argue that during the broadband wave activity electrons with energy above 200 eV provide the dominant contribution to the total electron density, while the density of cold electrons (below a few eV) is less than a few tenths of the total electron density. We show that velocities of the asymmetric ESW are close to velocity of electron-acoustic waves (existing due to the presence of cold and hot electrons) and follow the Korteweg-de Vries (KdV) dispersion relation derived for the observed plasma conditions (electron energy spectrum is a power law between about 100 eV and 10 keV and Maxwellian above 10 keV). The ESW spatial scales are in general agreement with the KdV theory. We interpret the asymmetric ESW in terms of electron-acoustic solitons and double layers (shocks waves).

79 ASTRONOMY AND ASTROPHYSICS↗

Ion-cyclotron turbulence and diagonal double layers in a magnetospheric plasma

A survey of current concepts regarding electrostatic ion-cyclotron turbulence (theory and experiment), and regarding inclined double potential layers in the magnetospheric plasma is presented. Anomalous resistance governed by electrostatic ion-cyclotron turbulence, and one-dimensional and two-dimensional models of double electrostatic layers in the magnetospheric plasma are examined.

Liperovskiy, V. A.↗

Lithium aluminum–layered double hydroxide chlorides ( LDH ): Formation enthalpies and energetics for lithium ion capture

Layered aluminum double hydroxide chloride sorbents, LiCl∙Al 2 (OH)6. n H 2 O, Li-LDH, have shown promising application in selective Li extraction from geothermal brines. Maintaining LiCl uptake capacity and retaining a long cycle life are critical to widespread application of sorbent materials. To elucidate the energetics of Li capture, enthalpies of LDH with different Li content have been measured by acid solution calorimetry. The formation enthalpies generally become less exothermic as the Li content increases, which indicates that Li intercalation destabilizes the structure, and the enthalpies seem to approach a limit after the Li content x = 2Li/Al exceeds 1. To improve stability, metal doping of the aluminum LDH structure with iron was performed. Introduction of a metal with greater electron density but a similar ionic radius was postulated to improve the stability of the LDH crystal structure. Here, the calorimetric results from Fe-doped LDH samples corroborate this as they are more exothermic than LDH-lacking Fe. This suggests that Fe doping is an effective way to stabilize the LDH phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion Through Single And Double Layer Shields And Induced Voltages From Low Frequency Electromagnetic Environments

The diffusion through shells consisting of either a single conducting or double conducting layers are examined. Exterior drives resulting from Electromagnetic Radiation (EMR), Electromagnetic Pulse (EMP), nearby (indirect) lightning, and DC (low frequency) magnetic fields are used. Both the interior field and the induced voltage from a maximally oriented and sized single turn loop are estimated. It is shown that the loop voltage with the empty cavity bounds the case where the center region is excluded by a conducting object. The cases of interior magnetic and electric fields from an exterior magnetic drive and the interior electric field from an exterior electric drive are both solved; the magnetic interior field from an exterior magnetic drive is the only case that results in a nonzero low frequency penetration.

42 ENGINEERING↗

Hollow nanoparticles with hybrid double layers

The present invention discloses the morphology of hollow, double-shelled submicrometer particles generated through a rapid aerosol-based process. The inner shell is an essentially hydrophobic carbon layer of nanoscale dimension (5-20 nm), and the outer shell is a hydrophilic silica layer of approximately 5-40 nm, with the shell thickness being a function of the particle size. The particles are synthesized by exploiting concepts of salt bridging to lock in a surfactant (CTAB) and carbon precursors together with iron species in the interior of a droplet. This deliberate negation of surfactant templating allows a silica shell to form extremely rapidly, sealing in the organic species in the particle interior. Subsequent pyrolysis results in a buildup of internal pressure, forcing carbonaceous species against the silica wall to form an inner shell of carbon. The incorporation of magnetic iron oxide into the shells opens up applications in external stimuli-responsive nanomaterials.

John, Vijay T.↗

Resistive switching of a TaO{sub x}/TaON double layer via ionic control of carrier tunneling

Resistance random access memory (RRAM) is an attractive candidate for future non-volatile memory due to its superior features. As the oxide thickness is scaled down, the charge transport mechanism is also subject to the transition from hopping to tunneling dominant process, which is critically related to the interfacial electronic band structure. A TaO{sub x}/TaON double layer-based RRAM is fabricated and characterized in this work. Upon TaON insertion at the lower interface, the improved switching behavior is observed. The TaON at the bottom electrode interface blocks oxygen vacancy percolation due to strong N-O bonds and also modifies interfacial band alignment to lower the injected electron energy from bottom electrode due to higher tunneling barrier height than that of TaO{sub x}/Pt. This study suggested that a defect-minimized insertion layer like TaON with a proper interfacial band alignment is pivotal in RRAM for the effective ionic control of carrier tunneling resulting in non-linear I-V behavior with improved properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗