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ALSUntangled reviews alternative and off-label treatments for people living with amyotrophic lateral sclerosis (PALS). Here we review ozone therapy. Ozone therapy has possible mechanisms for slowing ALS progression based on its antioxidant, anti-inflammatory, and mitochondrial effects. A non-peer-reviewed report suggests that ozone treatment may slow progression in a mTDP-43 mouse model of ALS. One verified "ALS reversal" occurred on a cocktail of alternative treatments including ozone. There are no ALS trials using ozone to treat PALS. There can be potentially serious side effects associated with ozone therapy, depending on the dose. Based on the above information, we support an investigation of ozone therapy in ALS cell or animal models but cannot yet recommend it as a treatment in PALS.

ALSUntangled reviews alternative and off label treatments with a goal of helping patients make more informed decisions about them. Here we review ketogenic diets. We shows that these have plausible mechanisms, including augmenting cellular energy balance and reducing excitotoxicity, neuroinflammation and oxidative stress. We review a mouse model study, anecdotal reports and trials in ALS and other diseases. We conclude that there is yet not enough data to recommend ketogenic diets for patients with ALS, especially in light of the many side effects these can have.

ALSUntangled reviews alternative and off-label treatments for people with amyotrophic lateral sclerosis (PALS). Here we review glucocorticoids. Neuroinflammation plays a prominent role in amyotrophic lateral sclerosis (ALS) pathogenesis, so some hypothesize that glucocorticoids might be an effective ALS therapy through their immunosuppressive effects. In this paper, we review the available evidence for glucocorticoids in ALS, including one pre-clinical study with a genetic mouse model of ALS, nine case reports (ranging from 1 to 26 patients each), and four clinical trials. We also review the possible side effects (including steroid myopathy) and the costs of therapy. We graded the level of evidence as follows: Mechanism, D; Pre-Clinical, F; Cases, B; Trials, F; Risks, C. Our review of the current evidence concludes that glucocorticoids do not offer clinical benefit in ALS and confer serious risks. Thus, ALSUntangled does not recommend glucocorticoids as a treatment for ALS.

Several infections have been associated with motor neuron diseases resembling ALS, including species of viruses, bacteria, and parasites. Mycobacterium avium subspecies paratuberculosis (MAP), most known for its probable etiologic association with Crohn’s disease, has been suggested as another possible infectious cause of motor neuron disease. Two published case reports describe the successful treatment of ALS-like symptoms with antimycobacterial antibiotics. Both cases had atypical features. Based on these, we believe it would be reasonable to begin performing chest imaging in PALS who have features of their history or exam that are atypical for ALS such as pain, fevers, or eye movement abnormalities. If the chest imaging is abnormal, more specific testing for mycobacteria may be indicated. Until there is more clear evidence of an association between mycobacteria and ALS, we cannot endorse the widespread use of potentially toxic antimycobacterial antibiotics for PALS.

ALSUntangled reviews alternative and off-label treatments for people living with amyotrophic lateral sclerosis (PALS). Here we review butyrate and its different chemical forms (butyrates). Butyrates have plausible mechanisms for slowing ALS progression and positive pre-clinical studies. One trial suggests that sodium phenylbutyrate (NaPB) in combination with Tauroursodeoxycholic acid (TUDCA) can slow ALS progression and prolong survival, but the specific contribution of NaPB toward this effect is unclear. Butyrates appear reasonably safe for use in humans. Based on the above information, we support a trial of a butyrate in PALS, but we cannot yet recommend one as a treatment.

The hydrogen adsorption energetics on the surface of inorganic compounds can be used to predict electrolyte stability in Li-ion batteries and catalytic activity for selective oxidation of small molecules such as H2 and CH4. Using first-principles density functional theory (DFT), the hydrogen adsorption was found to be unfavorable on high-band-gap insulators, which could be attributed to a lower energy level associated with adsorbed hydrogen relative to the bottom of the conduction band. In contrast, the hydrogen adsorption was shown to be the most favorable on metallic and semiconducting compounds, which results from an electron transfer from adsorbed hydrogen to the Fermi level or the bottom of the conduction band. Of significance, computed hydrogen adsorption energetics on insulating, semiconducting, and metallic oxides; phosphates; fluorides; and sulfides were decreased by lowering the ligand p band center, while the energy penalty for ligand vacancy formation was increased, indicative of decreased surface reducibility. A statistical regression analysis, where 16 structural and electronic parameters such as metal-ligand distance, electronegativity difference, Bader charges, bulk and surface metal and ligand band centers, band gap, ligand band width, and work function were examined, further showed that the surface ligand p band center is the most accurate single descriptor that governs the hydrogen adsorption tendency, and additional considerations of the band gap and average metal-ligand distance further reconcile the differences among compounds with different ligands/structures, whose ligand bands are different in shape and width. We discuss the implications of these findings for passivating coatings and design of catalysts and the need for novel theoretical methods to accurately estimate these quantities from first principles. These results establish a universal design principle for future high-throughput studies aiming to design electrode surfaces to minimize electrolyte oxidation by dehydrogenation in Li-ion batteries and enhance the H-H and C-H activation for selective oxidation catalysis.

Surface chemistry modification of positive electrodes has been used widely to decrease capacity loss during Li-ion battery cycling. Recent work shows that coupled LiPF6 decomposition and carbonate dehydrogenation is enhanced by increased metal-oxygen covalency associated with increasing Ni and/or lithium de-intercalation in metal oxide electrode, which can be responsible for capacity fading of Ni-rich oxide electrodes. Here we examined the reactivity of lithium nickel, manganese, cobalt oxide (LiNi[subscript 0.6]Mn[subscript 0.2]Co[subscript 0.2]O[subscript 2], NMC622) modified by coating of Al[subscript 2]O[subscript 3], Nb[subscript 2]O[subscript 5] and TiO[subscript 2] with a 1 M LiPF[subscript 6] carbonate-based electrolyte. Cycling measurements revealed that Al[subscript 2]O[subscript 3]-coated NMC622 showed the least capacity loss during cycling to 4.6 VLi compared to Nb[subscript 2]O[subscript 5]-, TiO[subscript 2]- coated and uncoated NMC622, which was in agreement with smallest electrode impedance growth during cycling from electrochemical impedance spectroscopy (EIS). Ex-situ infrared spectroscopy of charged Nb[subscript 2]O[subscript 5]- and TiO[subscript 2]-coated NMC622 pellets (without carbon nor binder) revealed blue peak shifts of 10 cm[superscript −1], indicative of dehydrogenation of ethylene carbonate (EC), but not for Al[subscript 2]O[subscript 3]-coated NMC622. X-ray Photoelectron Spectroscopy (XPS) of charged TiO[subscript 2]-coated NMC622 electrodes (carbon-free and binder-free) showed greater salt decomposition with the formation of lithium-nickel-titanium oxyfluoride species, which was in agreement with ex-situ infrared spectroscopy showing greater blue shifts of P-F peaks with increased charged voltages, indicative of species with less F-coordination than salt PF[subscript 6][superscript −] anion on the electrode surface. Greater salt decomposition was coupled with the increasing dehydrogenation of EC with higher coating content on the surface. This work shows that Al[subscript 2]O[subscript 3] coating on NMC622 is the most effective in reducing carbonate dehydrogenation and accompanied salt decomposition and rendering minimum capacity loss relative to TiO[subscript 2] and Nb[subscript 2]O[subscript 5] coating.

Understanding the effect of electrode-electrolyte interface (EEI) on the kinetics of electrode reaction is critical to design high-energy Li-ion batteries. While electrochemical impedance spectroscopy (EIS) is used widely to examine the kinetics of electrode reaction in Li-ion batteries, ambiguities exist in the physical origin of EIS responses for composite electrodes. In this study, we performed EIS measurement by using a three-electrode cell with a mesh-reference electrode, to avoid the effect of counter electrode impedance and artefactual responses due to asymmetric cell configuration, and composite or oxide-only working electrodes. Here we discuss the detailed assignment of impedance spectra for LiCoO[subscript 2] as a function of voltage. The high-frequency semicircle was assigned to the impedance associated with ion adsorption and desorption at the electrified interface while the low-frequency semicircle was related to the charge transfer impedance associated with desolvation/solvation of lithium ions, and lithium ion intercalation/de-intercalation into/from LixCoO[subscript 2]. Exposure to higher charging voltages and greater hold time at high voltages led to no significant change for the high-frequency component but greater resistance and greater activation energy for the low-frequency circle. The greater charge transfer impedance was attributed to the growth of EEI layers on the charged LixCoO[subscript 2] surface associated with electrolyte oxidation promoted by ethylene carbonate dehydrogenation. Keywords: Batteries - Lithium, Electrode Kinetics, EIS, Electrode-Electrolyte Interface, Li-ion Batteries, BMW Group

The (electro)chemical reactions between positive electrodes and electrolytes are not well understood. We examined the oxidation of a LiPF6-based electrolyte with ethylene carbonate (EC) with layered lithium nickel, manganese, and cobalt oxides (NMC). Density functional theory calculations showed that the driving force for EC dehydrogenation on oxides, yielding surface protic species, increased with greater Ni content in NMC. Ex situ infrared and Raman spectroscopy revealed experimental evidence for EC dehydrogenation on charged NMC surfaces. Protic species on charged NMC surfaces from EC dehydrogenation could further react with LiPF6 to generate less-coordinated F species such as PF3O-like and lithium nickel oxyfluoride species on charged NMC particles and HF and PF2O2- in the electrolyte. Larger degree of salt decomposition was coupled with increasing EC dehydrogenation on charged NMC with increasing Ni or lithium deintercalation. An oxide-mediated chemical oxidation of electrolytes was proposed, providing new insights in stabilizing high-energy positive electrodes and improving Li-ion battery cycle life.

© 2017 by the authors. Flexible butyl interconnection segments are synthetically incorporated into an electronically conductive poly(pyrene methacrylate) homopolymer and its copolymer. The insertion of butyl segment makes the pyrene polymer more flexible, and can better accommodate deformation. This new class of flexible and conductive polymers can be used as a polymer binder and adhesive to facilitate the electrochemical performance of a silicon/graphene composite anode material for lithium ion battery application. They act like a "spring" to maintain the electrode mechanical and electrical integrity. High mass loading and high areal capacity, which are critical design requirements of high energy batteries, have been achieved in the electrodes composed of the novel binders and silicon/graphene composite material. A remarkable area capacity of over 5 mAh/cm2 and volumetric capacity of over 1700 Ah/L have been reached at a high current rate of 333 mA/g.

The cycling stability and the surface passivation qualities of a heterogeneous polycrystalline NiSi2/amorphous NixSiOy core-shell nanowires cycled in a Li ion half cell is reported. The nanowire morphology showed stable cycling and excellent charge rate capability having a stable capacity above 1700 mAh/g when cycled in a coin cell at 1/2 C and retaining a capacity of 300 mAhr/g when cycled at a 10 C charge rate. It is shown that the stable cycling is due to the passivation qualities of the oxide components within the amorphous shell which create a stable solid-electrolyte interphase (SEI) during charging which is reduced during discharging through the conductive pathway provided by the Ni doping in the shell and NiSi2 in the core. The NiSi2 core interacts with Li through intercalation retaining its rigid core even while Li charged, the overall dimensions of the structure mitigate any pulverization issues, and the conductive core along with the Ni doping disallow any Li trapping leading to high columbic efficiency.

We report the influence of nickel catalyst layer thickness when growing nickel silicide alloy nanowires below the liquefaction temperature through metal induced growth. Three different catalyst layer thicknesses show three different nanowire growth results that vary significantly the performance when used as an anode in a lithium ion solution. The thicker catalyst layers (70 nm) show pure NiSi nanowires which have an initial capacity of 1300 mAh g−1 that degrades to 550 mAh g−1 within 90 cycles. The thinner (30 nm thick) layer shows a heterogenous nanowire morphology comprising of a multicrystalline NiSi2 inside core and a Ni doped SiO amorphous shell with initial Li-ion capacity of 1727 mAh g−1 capacity that increases to 2468 mAh g−1 after 90 cycles. Samples with no catalyst layers were shown to grow pure silicon nanowires with poor surface coverage having an initial capacity of 1779 mAh g−1 that falls to 242 mAh g−1 after 90 cycles.

Graphene has amazing abilities due to its unique band structure characteristics defining its enhanced electrical capabilities for a material with the highest characteristic mobility known to exist at room temperature. The high mobility of graphene occurs due to electron delocalization and weak electron phonon interaction making graphene an ideal material for electrical applications requiring high mobility and fast response times. In this paper, we are going to focus on the benefits along with some of the limitations with using graphene in infrared (IR) devices, electro-optic (EO) devices, and field effect transistors (FET) for radio frequency (RF) applications.

We present here for the first time observations that grain boundaries in electrodeposited (ED) nanocrystalline (nc) Ni are predominantly of Σ3 character. The results presented are based on orientation imaging microscopy (OIM) performed to produce electron backscatter diffraction (EBSD) maps. This large volume fraction of coherent low sigma coincidence site lattice (CSL) boundaries appears to be consistent with the superior corrosion resistance of ED nc-Ni in comparison with its coarse-grained counterpart.

Graphene has amazing abilities due to its unique band structure characteristics de‐ fining its enhanced electrical capabilities for a material with the highest characteris‐ tic mobility known to exist at room temperature. The high mobility of graphene occurs due to electron delocalization and weak electron–phonon interaction, mak‐ ing graphene an ideal material for electrical applications requiring high mobility and fast response times. In this review, we cover graphene’s integration into infra‐ red (IR) devices, electro-optic (EO) devices, and field effect transistors (FETs) for ra‐ dio frequency (RF) applications. The benefits of utilizing graphene for each case are discussed, along with examples showing the current state-of-the-art solutions for these applications. Graphene has many outstanding properties due to its unique bonding and subse‐ quently band gap characteristics, having electronic carriers act as “massless” DiracFermions. The material characteristics of graphene are anisotropic, having phenomenal characteristic within a single sheet and diminished material character‐ istics between sheet with increasing sheet number and grain boundaries. We will discuss the integration of graphene into many electronic device applications. Graphene has the highest mobility values measured in a material at room tempera‐ ture, allowing integration into fast response time devices such as a high electron mobility transistor (HEMT) for RF applications. Graphene has shown promise in IR detectors by utilizing graphene in thermal-based detection applications.

Understanding electrode/electrolyte interface (EEI) is crucial for the development of high-energy batteries for electric vehicle applications. The EEI layer formation of negative electrode (also referred as Solid Electrolyte Interphase) is comprehensively studied [1,2], whereas the electrolyte decomposition and formation of the EEI layer at the positive electrodes are still unknown [3,4]. Especially, at high potentials, the role of oxygen in the transition metal oxide becomes critical, leading to the evolution of oxygen from the oxide lattice or the formation of highly reactive species like surface peroxide and superoxide, which can modify the nature of the EEI layer. Here, we show how EEI layer depends on different positive electrodes (LiCoO2 and NMC electrodes with different Ni content) and different electrolyte additives (diphenyl carbonate and adiponitrile) by using X-ray Photoelectron Spectroscopy (XPS). We also highlight the importance of using carbon-free, binder-free electrodes to unambiguously pinpoint the reactivity of the electrolyte at the positive electrode [5]. The analysis of the XPS results points to a strong dependency of the surface reactivity on different electrode and electrolyte composition. [1] E. Peled, J. Electrochem. Soc. 126, 2047 (1979). [2] D. Aurbach et al., J. Power Sources 81-82, 95 (1999). [3] K. Xu et al., Chem. Rev., 114, 11503 (2014). [4] M. Gauthier, T. Carney, A. Grimaud et al., J. Phys. Chem. Lett. 6, 4653 (2015). [5] M. Gauthier et al., in preparation.

Silicon (Si) with porous structure could possibly accommodate the large volume expansion of Si in lithium ion batteries, avoiding fast capacity fading during charge/discharge. Herein, we report a composite electrode made from porous Si with only 5 wt% conductive polymer binder. By limiting the lithiation level, we demonstrate a stable cycled cell with a greatly extended cycle life and high coulombic efficiency beyond 99.5%. Both the morphology study and electrochemical characterization suggest that electrodes are able to accommodate over 50% volume change without any capacity fading during cell operation.

There are several significant challenges that must be overcome for PEM fuel cell commercialization such as electrode flooding, carbon corrosion, and significant cost due to the high loading of the platinum catalyst. Thus, a new structure is proposed for the cathode catalyst support consisting of Si/TiOx core/shell nanowires with branched structures, which has the potential to reduce electrode flooding, increase stability, and dramatically reduce the required Pt loading. In this study, Pt-coated Si/TiOx core/shell nanowires with and without branches are compared. The Pt surface area on supports with branch structures was calculated to be more than 4 times larger than on supports without branch structures, while keeping the Pt loading at only about 0.1 mg/cm2 (for the samples with branched structures). SEM, XRD, AES, and TEM were used to characterize the morphologies and structures of the as-prepared samples. Branched Si/TiOx core/shell nanowire structures may be a promising catalyst support to enable commercialization of highly cost-efficient PEM fuel cells and to promote an era of clean energy usage.

A novel multi-walled carbon nanotube (MWNT) growth process is reported based on carbon incorporation in a nickel catalyst layer deposited via plasma-enhanced atomic layer deposition (PEALD) on silicon nanowires and silicon wafer substrates. As-deposited PEALD Ni films containing relatively high amounts of carbon (18 at.%) were observed to promote the growth of MWNTs upon post-deposition rapid thermal annealing. For these films the carbon originated from the ALD precursor ligand and MWNT growth occurred in the absence of a vapor-phase carbon feedstock. MWNT growth relied on the formation of nickel silicide at the PEALD Ni/Si interface which increased the local carbon concentration in the Ni film sufficiently to promote carbon saturation/precipitation at Ni catalyst grains and nucleate MWNT growth. Similar MWNT growth from annealed PEALD Ni films was not observed on SiO(2)-coated Si wafer substrates, consistent with the role of silicidation in the observed Ni-catalyzed MWNT growth on Si. This MWNT growth mode requires neither the catalytic decomposition of a gaseous hydrocarbon source nor the high-temperature pyrolysis of metallocene materials and purposely avoids a catalyst diffusion barrier at the Si substrate, commonly used in MWNT growth processes on Si.

Nanowire surface conduction channels have been fabricated and tested based on self-assembled Si nanowires (SiNWs) synthesized via VLS processing. Conduction channel formation utilized W and Ni silicidation. SiNWs were directly grown on silicon substrates via vapor-liquid-solid (VLS) growth process. The diameters of the SiNW templates ranged from approximately 5 to 120 nm. Nanowire synthesis via VLS growth was carried out using a SiH 4 / Ar mixture at 500 °C. TEM analysis confirmed crystalline VLS SiNWs. Ni evaporation and Ni and W atomic layer deposition (ALD) and post-deposition thermal processing were carried out for silicide formation. TEM-EDS results showed that ALD W was conformally deposited on the surface of SiNWs. In contrast, e-beam evaporated Ni was asymmetrically deposited on the template nanowire although the resultant silicide was nearly symmetric. Conformal Ni deposition and silicidation was successfully performed, however, using Ni ALD processing. Silicide nanowires were dispensed on Au-patterned Si wafers for electrical characterization and exhibited an improvement in electrical conductivity of eight orders of magnitude compared with that of as-grown VLS silicon nanowires.