bluuebunny/crossref_metadata_2025 huggingface dataset:
ON INFLUENCE OF H/D EXCHANGE ON SOLVENT ISOTOPE EFFECTS IN THERMODYNAMIC (ENTHALPIC) CHARACTERISTICS OF SOLVATION OF PROTON-DONATING NON-ELECTROLYTES
Authors: Ivanov Evgeniy V. , Abrosimov V.K.
Published: July 2018

Some features of the solvent H/D-isotope effect method are discussed in the frame of development of ideas about the solvation mechanism including the structural and thermodynamic characteristics concept being proposed by G.A. Krestov and its followers. We have found it necessary to debate the possibility of employing the H2O-by-D2O isotope substitution for thermodynamic studying of binary aqueous systems containing a proton-donating organic non-electrolyte. In this regard, the two main aspects of the problem are discussed: (i) how the H-D exchange affects the thermodynamic (enthalpic) solvent isotope effects and (ii) how such effects dependent on the partial or complete pre-deuteration of a solute molecule. All potentially exchangeable protons (of N-H, O-H,) in heavy water are replaced by deuterons, but the fast exchange of D between D2O and the C-H (in methyl and methylen groups) does not occur. Herewith the extent to which proton-donor sites in complex molecules are stabilized by intramolecular hydrogen bonding remains uncertain, making it difficult to assess details of H-D exchange mechanisms in the hydration process. It is important to note that the H-D-isotope exchange is accompanied by changes in the molecular composition both the solute and solvent (due to forming HDO) in the nearest environment. This affects the thermodynamic (mole-additive) parameters of solvation process in heavy water as well as the corresponding isotope effects. The problem can be partly overcome by using the deuterium-substitution in a solute molecule. In this case, the molar mass of each solution component does not change but we should not forget here on the effect of secondary H/D isotope substitution in the solute. From a purely thermodynamic view, we can focus only on the analysis of H/D isotope effects in characteristics of its sublimation or vaporization. Herewith H- and D-bonded systems have the same distinctions in the (zero-point) vibration energy as in individual components. It because the specified isotope effects can be rather directly related to the condensed-phase partition functions which may be written down under the assumption of isotope-independent potential energy surface (within the precision of Born-Oppenheimer “adiabatic” approximation).
PROPERTIES OF 1-BUTYL-3-METHYLIMIDAZOLIUM BROMIDE IONIC LIQUID AND ITS BLENDS WITH WATER AND BROMIDES OF SILVER, COPPER AND TANTALUM
Authors: Grishina Elena P. , Ramenskaya Ludmila M.
Published: July 2018

Ionic liquids with N,N¢-dialkylimidazolium cation characterized now as "green" solvents are investigated intensively to find their practical application. In this research the physical-chemical, electrochemical and corrosion properties of 1-butyl-3-methylimidazolium bromide (BMImBr) and its blends with water and bromides of silver (I), cupper (II) and tantalum (V) were studied. BMImBr is a hygroscopic ionic liquid and in depending on a water content can exists as a solid, liquid, metastable supercooled melt, and two-phase system – liquid and crystalline hydrate of BМImBr´0.5Н2О composition. At 1:1 components ratio the structural transformation of the melt (СН2О<50 mol%) « the solution (СН2О>50 мол.%) was observed. The BMImBr ionic liquid is a good solvent towards bromides of silver (I), cupper (II) and tantalum (V). These salts destroy the inter- and intramolecular interactions of BMImBr and generate the complex metal-containing ions with Br- anion of ionic liquid. As a result the glass temperature and the density increased, the melting point decreased and on isotherms of dynamic viscosity and specific electro conductivity a distinct minimum was observed at the low concentration range of the salt. Electrochemical window of BMImBr is 1.9 V and it is limited by bromide ions oxidation in the anodic potential range and by imidazolium cations reduction in the cathodic potential range. Additions of the water and the metals salt are an electrochemical active. In their presence the redox processes proceeds inside of the electrochemical window and the discharge-ionization process is the limiting steps. From IL studied the thin films of silver and copper can be deposited with good adhesion on metal substrates including tantalum and titanium. Investigated ionic liquids are a corrosive fluid, and corrosion of the metal increases dramatically in the presence of the same cations.
SYNTHESES OF ω -Н-PERFLUORINE CARBOXYLIC ACIDS BY OXIDATION OF ALCOHOL-TELOMERS H(CF2CF2)nCH2OH
Authors: Dmitriev Iliya A. , Glazunov Alexey V. , Semeikin Alexandr S. , Golubchikov Oleg A. , Prigorelov Gennagiy A.
Published: July 2018

Methods of synthesis of ω-Н-perfluorine carboxylic acids by oxidation of alcohol-telomers of H(CF2CF2)nCH2OH (n = 1 – 4) composition were developed. Physical-chemical properties of poly fluorinated alcohols and carboxylic acids were determined.
INDIUM EXTRACTION FROM SOLUTIONS WITH MODIFIED ALUMINOSILICATES
Authors: Timofeev Konstantin L. , Maltsev Gennadiy I. , Sviridov Alexeiy V.
Published: July 2018

The aim of this work was to study the adsorption of indium from aqueous solutions on modified highly dispersed aluminosilicates for the recovery of indium from technological solutions. The adsorption isotherms of indium, iron and zinc from multi component solutions on modified by di(2-ethylhexyl) phosphoric acid montmorillonite were obtained. It was shown that adsorption processes can be reliably described by models of Langmuir and Freundlich (R2  =  0.96–0.99). The shape of the isotherms is determined both by the surface properties of the sorbent and forms of presence of metal ions in aqueous solutions. The highest value of Langmuir constant Kads = 422.65 for reagent "Metоsol" was obtained for ions of indium, which indicates the preferential affinity of the sorbing mineral to this element, since the corresponding figures for the ions Fe2+ (1.09) and Zn2+ (0.78) are close to unity. At sorption of metal ions from model solution in the range of acidity of 1-20 g/dm3 of H2SO4 the extraction of indium remains unchanged at ~70 %, and iron – is reduced from 39 to 15% of the initial content. With the further increase of acidity to 100 g/dm3 of H2SO4, the recovery of indium is reduced to 40 %; iron down to 14 %. In the examined range of concentration of sulfuric acid the extraction of zinc is from 6.0 to 7.5 percent. The value of the static exchange capacity for the studied metals are mmol/g: 0.39–0.23 of indium; 0.11–0.04 of iron(III); 0.05–0.04 of zinc. A rank of affinity of reagent "Metоsol" to extract the metal ions from solution with pre-reduced iron(III)  was In3+ > Fe2+ > Zn2+ which determines the feasibility of its use for the selective adsorption of indium from the complex composition of technological solutions of zinc production.
MOLECULAR STRUCTURE AND VIBRATION SPECTRA OF PIVALIC ACID
Authors: Pogonin Alexander E. , Pimenov Oleg A. , Zhabanov Yuriy A.
Published: July 2018

The metal carboxylates such as metal pivalates (salts of the pivalic acid (CH3)3CCOOH) attract a great interest as most promising precursors for chemical vapor deposition (CVD) technology. The possibility to use these substances in the CVD technology is specified by their good thermal stability and high volatility. For modeling of chemical reactions with metal pivalates in the gas-phase and the data on molecular structure will be very useful, in particularly information about effect of central metal ion to geometry of pivalic ligands. In the frame of this task the structures of metal pivalate molecules and pivalic acid (H(piv)) in a gas phase should be finding. The aim of present work is theoretical investigation of the geometry and IR-spectrum of H(piv) using density functional theory (DFT) methods. All calculations were performed using the Gaussian 03 program. The optimization of geometry and quadratic force field calculations were carried out using DFT functionals B3LYP, PBE, PBE0 and BP86 with correlation-consistent triple-ζ valence cc-pVTZ basis sets for O, C, and H. Appropriate assignment of vibrational modes was carried out by the potential energy distribution (PED) analysis among internal coordinates using the SHRINK program. According to DFT computations, the H(piv) molecule has an equilibrium structure of Cs symmetry with Гvib=26A'+19A''. The theoretical and experimental IR-spectra are satisfactorily agreed. The comparison of the ten intensities of highest bands in spectra allowed determining linear correlation between peaks position in experimental and modeling IR-spectra. It should be note the complicated composition of vibrational modes.
CRYSTALLOGRAPHIC ORIENTATION INFLUENCE ON SECONDARY ELECTRON EMISSION COEFFICIENT OF A SINGLE CRYSTAL OF SYNTHETIC DIAMOND
Authors: Sadovoy Vladimir Yu. , Blank Vladimir D. , Terentiev Sergey A. , Teteruk Dmitriy V. , Troschiev Sergey Yu.
Published: July 2018

Dependence of secondary electron emission coefficient on the chosen crystallographic orientation for a synthetic single crystal diamond of type IIb, grown up by method of a temperature gradient, was investigated. The type IIb of single crystal diamond was chosen because of wide applicability in different areas of microelectronics and the semiconductor properties. Quantitative measurements of secondary electron emission coefficients with energy of primary beam about 7 keV and above for various crystallographic orientations was carried out: the highest coefficient of secondary electronic emission are recorded for the direction (100), cubic sector, and also in intergrowth area that is confirmed by a picture of distribution of the luminescence intensity for various sectors of a single crystal received by means of true secondary electrons detector of scanning electron microscope. The results for (100) area are outstanding: 8.18 at primary beam energy of 7 keV, 10.13 at 10 keV, 49.78 at 30 keV. The results for intergrowth area are similar: 10.10 at primary beam energy of 7 keV, 13.56 at 10 keV, 64.41 at 30 keV. The crystallographic directions (111) have shown secondary electron emission coefficient 4-6 times lower in comparison with (100) and intergrowth area: 2.54 on the average at primary beam energy of 7 keV, 2.75 at 10 keV, 10.03 at 30 keV. The non-standard behavior of secondary electron emission coefficient at the high energy primary beam for all orientations of single crystal diamond is shown: increase in secondary electron emission coefficient with increase in energy of primary beam. At the moment the reason of such behavior is not clear up to the end and since this fact causes a great interest of researchers, considerably expands applicability of the existing devices and detectors due to replacement of a functional element on diamond one, and also opens big opportunities for formation of new field of microelectronics, this facts demand further in-depth study by means of various methods of the structural and surface analysis.
BARIC DEPENDENCE OF LATTICE PROPERTIES FOR DIAMOND
Authors: Magomedov Makhach N.
Published: July 2018

Based on the pairwise interatomic potential of Mi-Lennard-Jones and the Einstein's model of crystal the state equation P(V/V0, T) and the baric dependencies of the lattice properties for diamond were obtained. The calculations were performed along two isotherms: T = 300 and 3000 K and until to P = 10000 kbar (i.e. until to the relative volume V/V0 = 0.5). The baric dependencies for the following properties were obtained: isothermal elastic modulus, isochoric and isobaric heat capacities and thermal expansion coefficient. Good agreement with experimental data was obtained.
Growth under cold conditions in a wide perennial ryegrass panel is under tight physiological control
Authors: Förster Lena , Grant Jim , Michel Thibauld , Ng Carl , Barth Susanne
Published: July 2018

Background. Perennial ryegrass is a cool-season grass species from the family Poaceae and is widely cultivated in temperate regions because it exhibits rapid growth and establishment, and possesses high forage quality. The extension of the growing season in Ireland in spring and autumn is a breeding target to make farming more profitable since a rass-fed diet based on grazing is the cheapest way of nutrition for ruminants. Methods. Fifty-seven perennial ryegrass accessions were screened for their ability to grow under typical Irish spring conditions as taken from long term emperature records in controlled climate chambers. They were grown in low temperature (8°C/2°C day/night) and control conditions (15°C/8°C day/night) in three consecutive independent experiments. Fresh weight, height, clorophyll content and electrolyte leakage were measured, and these parameters were used to rank plant performance under low temperature growth conditions. Results. The results showed that height, yield and electrolyte leakage are xcellent measures for the impact of cold stress tolerance. Little variation in growth was seen undercold stress, but a wide variety of responses were observed under control conditions. Discussion. Our results suggest that cold stress is under tight physiological control. Interestingly, the various genotypes responded differentially to more amenable control conditions, indicating that a quick response to more amenable growth conditions is a better target for breeding programmes.
Arid1a restrains Kras-dependent changes in acinar cell identity
Authors: Livshits Geulah , Alonso-Curbelo Direna , Morris John P , Koche Richard , Saborowski Michael , Wilkinson John Erby , Lowe Scott W
Published: July 2018

Mutations in members of the SWI/SNF chromatin remodeling family are common events in cancer, but the mechanisms whereby disruption of SWI/SNF components alters tumorigenesis remain poorly understood. To model the effect of loss of function mutations in the SWI/SNF subunit Arid1a in pancreatic ductal adenocarcinoma (PDAC) initiation, we directed shRNA triggered, inducible and reversible suppression of Arid1a to the mouse pancreas in the setting of oncogenic KrasG12D. Arid1a cooperates with Kras in the adult pancreas as postnatal silencing of Arid1a following sustained KrasG12D expression induces rapid and irreversible reprogramming of acinar cells into mucinous PDAC precursor lesions. In contrast, Arid1a silencing during embryogenesis, concurrent with KrasG12D activation, leads to retention of acinar cell fate. Together, our results demonstrate Arid1a as a critical modulator of Kras-dependent changes in acinar cell identity, and underscore an unanticipated influence of timing and genetic context on the effects of SWI/SNF complex alterations in epithelial tumorigenesis.
KCNE1 tunes the sensitivity of KV7.1 to polyunsaturated fatty acids by moving turret residues close to the binding site
Authors: Larsson Johan E , Larsson H Peter , Liin Sara I
Published: July 2018

The voltage-gated potassium channel KV7.1 and the auxiliary subunit KCNE1 together form the cardiac IKs channel, which is a proposed target for future anti-arrhythmic drugs. We previously showed that polyunsaturated fatty acids (PUFAs) activate KV7.1 via an electrostatic mechanism. The activating effect was abolished when KV7.1 was co-expressed with KCNE1, as KCNE1 renders PUFAs ineffective by promoting PUFA protonation. PUFA protonation reduces the potential of PUFAs as anti-arrhythmic compounds. It is unknown how KCNE1 promotes PUFA protonation. Here, we found that neutralization of negatively charged residues in the S5-P-helix loop of KV7.1 restored PUFA effects on KV7.1 co-expressed with KCNE1 in Xenopus oocytes. We propose that KCNE1 moves the S5-P-helix loop of KV7.1 towards the PUFA-binding site, which indirectly causes PUFA protonation, thereby reducing the effect of PUFAs on KV7.1. This mechanistic understanding of how KCNE1 alters KV7.1 pharmacology is essential for development of drugs targeting the IKs channel.
To be or not to be
Authors: Zhang Zhe , Hessmann Elisabeth
Published: July 2018

Chromatin remodeling processes can drive acinar cell fate decisions.
Illusory resizing of the painful knee is analgesic in symptomatic knee osteoarthritis
Authors: Stanton Tasha R. , Gilpin Helen R. , Edwards Louisa , Moseley G. Lorimer , Newport Roger
Published: July 2018

Background

Experimental and clinical evidence support a link between body representations and pain. This proof-of-concept study in people with painful knee osteoarthritis (OA) aimed to determine if: (i) visuotactile illusions that manipulate perceived knee size are analgesic; (ii) cumulative analgesic effects occur with sustained or repeated illusions.

Methods

Participants with knee OA underwent eight conditions (order randomised): stretch and shrink visuotactile (congruent) illusions and corresponding visual, tactile and incongruent control conditions. Knee pain intensity (0–100 numerical rating scale; 0 = no pain at all and 100 = worst pain imaginable) was assessed pre- and post-condition. Condition (visuotactile illusion vs control) × Time (pre-/post-condition) repeated measure ANOVAs evaluated the effect on pain. In each participant, the most beneficial illusion was sustained for 3 min and was repeated 10 times (each during two sessions); paired t-tests compared pain at time 0 and 180s (sustained) and between illusion 1 and illusion 10 (repeated).

Results

Visuotactile illusions decreased pain by an average of 7.8 points (95% CI [2.0–13.5]) which corresponds to a 25% reduction in pain, but the tactile only and visual only control conditions did not (Condition × Time interaction: p = 0.028). Visuotactile illusions did not differ from incongruent control conditions where the same visual manipulation occurred, but did differ when only the same tactile input was applied. Sustained illusions prolonged analgesia, but did not increase it. Repeated illusions increased the analgesic effect with an average pain decrease of 20 points (95% CI [6.9–33.1])–corresponding to a 40% pain reduction.

Discussion

Visuotactile illusions are analgesic in people with knee OA. Our results suggest that visual input plays a critical role in pain relief, but that analgesia requires multisensory input. That visual and tactile input is needed for analgesia, supports multisensory modulation processes as a possible explanatory mechanism. Further research exploring the neural underpinnings of these visuotactile illusions is needed. For potential clinical applications, future research using a greater dosage in larger samples is warranted.
Territórios-rede e territórios-zona do narcotráfico na metrópole de Belém
Authors: Couto Aiala Colares
Published: July 2018

A Amazônia vem nestas últimas décadas se destacado enquanto uma área geográfica de grande importância para a conexão global do crime. Nesse contexto, as cidades da Amazônia, sobretudo, as metrópoles de Belém e Manaus, onde territorialidades alternativas vêm se configurando como substrato espacial. Este artigo tem como proposta objetiva analisar os territórios-rede e territórios-zona do narcotráfico na metrópole de Belém. Esta pesquisa é parte dos resultados de tese de doutorado defendida no Programa de Pós-Graduação em Desenvolvimento Sustentável do Trópico Úmido. A metodologia utilizada neste trabalho se baseou em pesquisa bibliográfica, análise documental, trabalhos de campo e observações sistemáticas. Os territórios do narcotráfico em Belém são configurações geográficas que marcam a história dos conflitos urbanos na atualidade.

Abstract

NETWORK-TERRITORIES AND ZONE-TERRITORIES OF NARCOTRAFFIC ON THE METROPOLIS OF BELÉM

In the past decades, Amazon has emerged as a geographical area of great importance for the global connection of crime. In this context, the cities of the Amazon, above all, the metropolises Belém and Manaus, where alternative territorialities are becoming a spacial substrate. This article has the objective of analyze the network-territories and zone territories of narcotraffic in the metropolis of Belém. This research is part of the result from a doctoral thesis defended in the Postdoctoral Program in Sustainable Development of the Humid Tropics. This work’s methodology is based on bibliographic research, documentary analysis, field work and systematic observations. The territories of narcotraffic in Belém are geographical configurations that mark the history of today’s urban conflicts.
Carnaval de Salvador: o declínio da festa mercantil
Authors: Siqueira Dias Clímaco Cesar
Published: July 2018

O carnaval da cidade de Salvador, importante metrópole brasileira, sempre foi uma das mais expressivas festas de rua do País e pesquisá-lo é algo necessário, pelo fato de este conter muitas das dinâmicas socioespaciais do lugar. Este artigo faz um breve histórico, desde o surgimento da festa até o momento atual, e se detém no período da profissionalização, iniciado na década de 1990, que transforma a festa em uma atividade econômica, fonte de grandes lucros para o segmento de artistas e produtores culturais que fizeram sucesso nacional com o ritmo denominado axé music, integrado à cultura de massas. Tal período foi marcado por uma grande projeção da festa no cenário nacional, mas hegemonizado por um segmento, o bloco de trio comandado por estrelas musicais. Esse modelo, por ser produtor de muitas desigualdades, também produziu muitos conflitos, sobretudo no choque da cultura de massas com a cultura popular, e, atualmente, vive uma crise, que é derivada dos acúmulos dessas exclusões e desigualdades. Existem alguns cenários para o futuro, mas ainda não existem tendências consolidadas.

Abstract

SALVADOR`S CARNIVAL: THE DECLINE OF MERCANTILE PARTY

The carnival in the city of Salvador, important Brazilian city, has always been one of the most expressive public celebrations in this country and is necessary to research it, because this manifestation contains many socio spatial dynamics of the place. This paper draws a brief historical, since the beggining of the party to this days, and concentrates in the professionalization period, started in the 1990’s, that turned the party into an economic activity, source of great profits for performing artists and producers that experienced national success with the musical genre axé music, integrated to the mass culture. That period is known by a great projection of the party in national mainstream, but hegemonized by a segment, i.e. the bloco de trio (large group of people that follows a moving performing stage set up in the top of a large truck, called Trio Elétrico, in a musical parade by the city streets, protected by a line held by private guards). This model, by being producer of many inequalities, also produced many conflicts, mostly in the clashes between mass culture and popular culture and, nowadays, experience a crisis that is a resultant of accumulation of exclusion an inequality. There are a few scenarios for the future, but there are still no consolidate tendencies.
Nanoscale Potential Fluctuations in Zirconium Oxide and the Flash Memory Based on Electron and Hole Localization
Authors: Gritsenko Vladimir A. , Novikov Yuriy N. , Perevalov Timofey V. , Kruchinin Vladimir N. , Aliev Vladimir S. , Gerasimova Alina K. , Erenburg Simon B. , Trubina Svetlana V. , Kvashnina Kristina O. , Prosvirin Igor P. , Lanza Mario
Published: July 2018

X‐ray photoelectron spectroscopy, extended X‐ray absorption fine structure spectroscopy (EXAFS), X‐ray absorption near edge structure (XANES) spectroscopy, spectral ellipsometry, and quantum‐chemistry calculations are used to examine the atomic and electronic structure of nonstoichiometric amorphous ZrOx slightly enriched with zirconium. The experimental data show that the ZrOx material consists of stoichiometric ZrO2, metallic Zr, and zirconium suboxides ZrOy. A model of nanoscale spatial potential fluctuations in ZrOx is substantiated. In this model, the potential fluctuations for electrons and holes arise due to the local bandgap energy fluctuations in the range from 0 to 5.4 eV. A ZrOx‐based flash memory element with giant retention time is proposed.
Collective Structural Relaxation in Phase‐Change Memory Devices
Authors: Le Gallo Manuel , Krebs Daniel , Zipoli Federico , Salinga Martin , Sebastian Abu
Published: July 2018

Phase‐change memory devices are expected to play a key role in future computing systems as both memory and computing elements. A key challenge in this respect is the temporal evolution of the resistance levels commonly referred to as “resistance drift.” In this paper, a comprehensive description of resistance drift as a result of spontaneous structural relaxation of the amorphous phase‐change material toward an energetically more favorable ideal glass state is presented. Molecular dynamics simulations provide insights into the microscopic origin of the structural relaxation. Based on those insights, a collective relaxation model is proposed to capture the kinetics of structural relaxation. By linking the physical material parameters governing electrical transport to such a description of structural relaxation, an integrated drift model that is able to predict the current–voltage characteristics at any instance in time even during nontrivial temperature treatments is obtained. Accurate quantitative matching with experimental drift measurements over a wide range of time (10 decades) and temperature (160–420 K) is demonstrated.
Flexible Thermoelectric Generators with Ultrahigh Output Power Enabled by Magnetic Field–Aligned Metallic Nanowires
Authors: Chen Yani , He Minhong , Tang Junhui , Bazan Guillermo C. , Liang Ziqi
Published: July 2018

Emerging organic–inorganic thermoelectric nanocomposites (TENCs) are promising candidates for the realization of high‐performance flexible thermoelectric generators (TEGs), yet there is an absence of effective means to precisely regulate the film morphology of TENCs. Here, the use of a magnetic field to improve thermoelectric performance of solution fabricated n‐type metallic TENCs is reported. Of particular relevance is that the magnetic field gives rise to aligned Co nanowires (NWs) within a poly(vinylidene fluoride) (PVDF) matrix. Such oriented TENCs exhibit significantly increased electrical conductivity in comparison to identical nanocomposites that are randomly oriented. As a result, the best power factor of oriented Co NWs (80 wt%)/PVDF TENCs reaches 523 µW m−1 K−2 at 320 K, which is among the highest reported n‐type TENCs. By pairing these n‐type TENCs with benchmark p‐type poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) thin films, the fabrication of flexible and planar TEGs that yield a maximum output voltage and power of 26.4 mV and 5.2 µW when ∆T = 50 K, respectively, is reported.
Narrow Heater Bottom Electrode‐Based Phase Change Memory as a Bidirectional Artificial Synapse
Authors: La Barbera Selina , Ly Denys R. B. , Navarro Gabriele , Castellani Niccolò , Cueto Olga , Bourgeois Guillaume , De Salvo Barbara , Nowak Etienne , Querlioz Damien , Vianello Elisa
Published: July 2018

Phase change memory can provide a remarkable artificial synapse for neuromorphic systems, as it features excellent reliability and can be used as an analog memory. However, this approach is complicated by the fact that crystallization and amorphization differ radically: crystallization can be realized in a very gradual manner, very similarly to synaptic potentiation, while the amorphization process tends to be abrupt, unlike synaptic depression. Addressing this non‐biorealism of amorphization requires system‐level solutions that have considerable energy cost or limit the generality of the approach. This work demonstrates experimentally that an adaptation of the memory structure associated with an initialization electrical pulse followed by a sequence of identical fast pulses can overcome this challenge. A single device can then naturally implement gradual long‐term potentiation and depression, much like synapses in biology. This study evidences through statistical measurements the reproducibility of the approach, discusses its physical origin, as well as the importance of the device architecture and of the initial electrical pulse. Through the use of system‐level simulation, it is shown that this device is especially adapted to a neuroscience‐inspired learning. These results highlight how nanodevices can be suitable for bioinspired applications while retaining the qualities of industrial technology.
Clonal immunoglobulin λ light‐chain gene rearrangements detected by next generation sequencing in POEMS syndrome
Authors: Kawajiri‐Manako Chika , Mimura Naoya , Fukuyo Masaki , Namba Hiroe , Rahmutulla Bahityar , Nagao Yuhei , Togasaki Emi , Shimizu Ryoh , Oshima‐Hasegawa Nagisa , Tsukamoto Shokichi , Mitsukawa Shio , Takeda Yusuke , Ohwada Chikako , Takeuchi Masahiro , Iseki Tohru , Misawa Sonoko , Yokote Koutaro , Tsuiji Makoto , Kuwabara Satoshi , Sakaida Emiko , Kaneda Atsushi , Nakaseko Chiaki
Published: July 2018

Polyneuropathy, organomegaly, endocrinopathy, M‐protein, and skin changes (POEMS) syndrome is a rare plasma cell dyscrasia characterized by polyneuropathy, organomegaly, endocrinopathy, extravascular fluid overload, M protein, and a myriad of skin changes. The pathogenesis is poorly understood, but monoclonal plasma cells are λ‐restricted and these immunoglobulin λ light chain variable (IGLV) region genes are derived from only two germlines, either IGLV1‐44 or 1‐40. Here we analyzed the clonal IGLV gene rearrangements of genomic DNA samples of bone marrow mononuclear cells using next‐generation sequencing (NGS) to understand the clonal composition of IGLV genes in patients with POEMS syndrome (n = 30). The dominant IGLV gene rearrangement of POEMS syndrome‐specific germline sequences were significantly increased in 11 POEMS patients (36.7%; IGLV1‐44: n = 9, IGLV1‐40: n = 2). In some cases, IGLV gene rearrangement clone was not detected as significant increase but was detected using cDNA samples by heteroduplex (HD) analysis and Sanger sequencing, suggesting that the quite small number of monoclonal plasma cells may produce large quantity of mRNA of monoclonal proteins. However, significant increase of dominant clone sizes was not directly linked to the initial disease status. On the other hand, in cases with significantly increased dominant clones, they decreased and increased accompanying with disease remission and relapse. These data demonstrate that monoclonal plasma cells are related to the pathogenesis of POEMS syndrome.
CHCHD10 variants in amyotrophic lateral sclerosis: Where is the evidence?
Authors:   Project MinE ALS Sequencing Consortium
Published: July 2018

Objective

After the initial report of a CHCHD10 mutation in mitochondrial disease with features resembling amyotrophic lateral sclerosis (ALS), CHCHD10 mutations have been considered to be a frequent cause for ALS. However, the exact pathogenicity and clinical significance of these mutations remain unclear. Here, we aimed to determine the role of CHCHD10 mutations in ALS.

Methods

We analyzed 4,365 whole genome sequenced ALS patients and 1,832 controls from 7 different countries and examined all nonsynonymous single nucleotide variants in CHCHD10. These were tested for association with ALS, independently and in aggregate using several genetic burden tests (including sequence kernel association test [SKAT], optimal unified test [SKAT‐O], and Firth logistic regression).

Results

We identified 3 new variants in cases, but only 1 was ALS‐specific. Also, 1 control‐specific mutation was identified. There was no increased burden of rare coding mutations among ALS patients compared to controls (p = 0.86, p = 0.86, and p = 0.88 for SKAT, SKAT‐O, and Firth, respectively). The few carriers with potential pathogenic CHCHD10 mutations exhibited a slowly progressive ALS‐like phenotype with atypical features such as myopathy and deafness.

Interpretation

CHCHD10 mutations seem to be a far less prevalent cause of pure ALS than previously suggested, and instead appear related to more complex phenotypes. There appears to be insufficient evidence for the pathogenicity of most previously reported variants in pure ALS. This study shows that routine testing for CHCHD10 mutations in pure ALS is not recommended and illustrates the importance of sufficient genetic and functional evidence in establishing pathogenicity of genetic variants. Ann Neurol 2018;83:110–116
Neurofilament light: A candidate biomarker of presymptomatic amyotrophic lateral sclerosis and phenoconversion
Authors: Benatar Michael , Wuu Joanne , Andersen Peter M. , Lombardi Vittoria , Malaspina Andrea
Published: July 2018

Objective

To evaluate neurofilament light (NfL) as a biomarker of the presymptomatic phase of amyotrophic lateral sclerosis (ALS).

Methods

The study population includes 84 individuals at risk for developing ALS, 34 controls, 17 ALS patients, and 10 phenoconverters (at‐risk individuals observed both before and after the emergence of clinically manifest disease). At‐risk individuals are enrolled through Pre‐Symptomatic Familial ALS (Pre‐fALS), a longitudinal natural history and biomarker study of individuals who are carriers of any ALS‐associated gene mutation (in SOD1, C9orf72, TARDBP, FUS, VCP, etc), but who, at the time of enrollment, demonstrated no clinical symptoms or signs (including electromyographic evidence) of manifest disease. NfL in serum and cerebrospinal fluid (CSF) were quantified using an electrochemiluminescence immunoassay.

Results

Serum and CSF NfL are substantially higher in ALS patients compared to controls and at‐risk individuals and remain relatively stable over time. Among phenoconverters, however, NfL levels were elevated (ie, above the range observed in controls) as far back as ∼12 months preceding the emergence of the earliest clinical symptoms or signs of disease.

Interpretation

Serum (and CSF) NfL are informative biomarkers of presymptomatic ALS, providing a new tool to quantify presymptomatic disease progression and to potentially predict the timing of clinical phenoconversion. As such, quantification of NfL may aid the design and implementation of early therapeutic intervention for affected individuals and/or disease prevention trials for individuals at short‐term risk of developing ALS. Ann Neurol 2018 Ann Neurol 2018;83:130–139
Identifying therapeutic targets from spontaneous beneficial brain lesions
Authors: Joutsa Juho , Shih Ludy C. , Horn Andreas , Reich Martin M. , Wu Ona , Rost Natalia S. , Fox Michael D.
Published: July 2018

Brain damage can occasionally result in paradoxical functional benefit, which could help identify therapeutic targets for neuromodulation. However, these beneficial lesions are rare and lesions in multiple different brain locations can improve the same symptom. Using a technique called lesion network mapping, we show that heterogeneous lesion locations resulting in tremor relief are all connected to common nodes in the cerebellum and thalamus, the latter of which is a proven deep brain stimulation target for tremor. These results suggest that lesion network mapping can identify the common substrate underlying therapeutic lesions and effective therapeutic targets. Ann Neurol 2018;83:153–157
Durch Nanopartikel vermittelter immunogener Zelltod ermöglicht und verstärkt die Immuntherapie gegen Krebs
Authors: Duan Xiaopin , Chan Christina , Lin Wenbin
Published: July 2018

Immuntherapien gegen Krebs, die körpereigene Immunsysteme auf das Erkennen, Angreifen und Auslöschen von Tumorzellen vorbereiten oder dazu stimulieren und dabei gesunden Zellen nur minimale Schäden zufügen, haben in den letzten Jahren vielversprechende klinische Ergebnisse erbracht. Dennoch bieten die meisten dieser immuntherapeutischen Strategien nur einer kleinen Gruppe an Patienten einen Nutzen und bringen für einige Patienten systemische Autoimmuneffekte mit sich. Modalitäten, die einen immunogenen Zelltod (ICD) herbeiführen, töten nicht nur Krebszellen direkt ab, sondern lösen auch gegen ein breites Spektrum an soliden Tumoren gerichtete Immunantworten aus. Solche Strategien zum Herbeiführen impfungsähnlicher Funktionen könnten verwendet werden, um ein “kaltes” Tumor‐Mikroumfeld in ein immunogenes, “heißes” Tumor‐Mikroumfeld umzuwandeln, was synergistisch mit Immuntherapien gegen Krebs zusammenzuwirken würde und dadurch die Antwortrate unter den Patienten sowie die Behandlungsergebnisse verbessern könnte. Dieser Kurzaufsatz behandelt Nanopartikel‐basierte Behandlungsmodalitäten, die ICD auslösen und verstärken können, um Immuntherapien gegen Krebs zu unterstützen.
Iron(II)‐Catalyzed Site‐Selective Functionalization of Unactivated C(sp3)−H Bonds Guided by Alkoxyl Radicals
Authors: Guan Honghao , Sun Shutao , Mao Ying , Chen Lei , Lu Ran , Huang Jiancheng , Liu Lei
Published: July 2018

An alkoxyl radical guided strategy for site‐selective functionalization of unactivated methylene and methine C−H bonds enabled by an FeII‐catalyzed redox process is described. The mild, expeditious, and modular protocol allows efficient remote aliphatic fluorination, chlorination, amination, and alkynylation of structurally and electronically varied primary, secondary, and tertiary hydroperoxides with excellent functional‐group tolerance. The application for one‐pot 1,4‐hydroxyl functionalization of non‐oxygenated alkane substrates initiated by aerobic C−H oxygenation is also demonstrated.
Measuring the Relative Reactivity of the Carbon–Hydrogen Bonds of Alkanes as Nucleophiles
Authors: Olmos Andrea , Gava Riccardo , Noverges Bárbara , Bellezza Delia , Jacob Kane , Besora Maria , Sameera W. M. Chamil , Etienne Michel , Maseras Feliu , Asensio Gregorio , Caballero Ana , Pérez Pedro J.
Published: July 2018

We report quantitative measurements of the relative reactivities of a series of C−H bonds of gaseous or liquid CnH2n+2 alkanes (n=1–8, 29 different C−H bonds) towards in situ generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with strong electrophiles suffering from C−C cleavage processes, which precluded direct comparison of the relative reactivities of alkane C−H bonds.
Thioether‐Functionalized Corn Oil Biosorbents for the Removal of Mercury and Silver Ions from Aqueous Solutions
Authors: Dunn Robert O. , Bantchev Grigor B. , Doll Kenneth M. , Ascherl Kim L. , Lansing James C. , Murray Rex E.
Published: July 2018

Heavy‐metal contamination is one of the most important environmental problems faced in the world, particularly in developing countries. Metals such as silver and mercury from drinking water, food, and air sources can accumulate in living organisms and present significant health concerns. Meanwhile, the demand for these metals in many industries continues to increase. In the present study, thioether‐functionalized corn oil (TFCO) from a photoinitiated thiol‐ene synthesis was utilized to remove Ag+ and Hg2+ ions from an aqueous solution. An aqueous solution containing AgNO3 and Hg[NO3]2 was prepared and contacted directly with TFCO. After vortex mixing for 60 s, the experiment ran for 351 min with the aqueous phase being periodically sampled for the analysis of metal ions (M
n+). Results showed that 88.9% of Ag+ and 99.6% of Hg2+ ions were removed from the aqueous phase by the TFCO. Mass balances indicated that the total M
n+ concentration in the oil phase was 13.890 g kg−1 under the conditions studied. TFCO exhibited higher selectivity for removing Hg2+ than for Ag+ ions. Analysis of the adsorption kinetics showed that a pseudosecond‐order model may be used to determine the rate of Ag+ ion sorption by the oil phase. The presence of the Hg2+ ions interfered with the adsorption of Ag+ ions from the aqueous solution.
Hydrolytic and thermal degradation of polyethylene glycol compatibilized poly(lactic acid)‐nanocrystalline cellulose bionanocomposites
Authors: Zhang Ping , He Yi‐Yao , Gao De , Cai Yingfeng , Liu Bingren
Published: July 2018

This study investigates the effect of nanocrystalline cellulose (NCC) and polyethylene glycol (PEG) on the hydrolytic degradation behavior of poly(lactic acid) (PLA) bio‐nanocomposites compared with that of neat PLA, under specific environmental condition, namely at 37°C in a pH 7.4 phosphate buffer medium for a time period up to 60 days. The water absorption, mass loss, molecular weight, and the morphologies of nanocomposites before and after degradation were explored. Thermogravimetric analysis (TGA) was used to study the thermal decomposition of the PLA/NCC/PEG nanocomposites before and after degradation. The results showed that the presence of hydrophilic NCC and PEG significantly accelerated the hydrolytic degradation of PLA, which was related to the rapid dissolution of PEG causing easy access of water molecules to the composites and initiating fast hydrolytic chain scission of PLA. The thermal degradation temperatures of the nanocomposites slightly decreased due to the poor thermal stability of NCC in comparison with that of the neat PLA. After degradation, the thermal stability of the separated PLA from nanocomposites significantly decreased because the molecular decreased during the hydrolytic process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2019,136, 46933.
Mitochondrial DNA analyses of Donax trunculus (Mollusca: Bivalvia) population structure in the Iberian Peninsula, a bivalve with high commercial importance
Authors: Fernández‐Pérez Jenyfer , Nantón Ana , Arias‐Pérez Alberto , Freire Ruth , Martínez‐Patiño Dorotea , Méndez Josefina
Published: July 2018

The wedge clam, Donax trunculus (Linnaeus, 1758), is an ecologically and economically important species found in the warm waters of the Atlantic and Mediterranean areas. Donax trunculus has been suffering from a severe population decline in some wild stocks of the Iberian Peninsula, and genetic monitoring of wild populations can provide valuable information to support conservation measures and management policies.

In this study, mitochondrial 16S rDNA (16S) and cytochrome b (Cytb) gene variation was examined at 18 localities across the Iberian Peninsula to test whether the patterns of genetic diversity, population structure, and demographic inferences previously deduced by using microsatellites are supported by these molecular markers.

Samples (N = 557) were collected from 18 localities of the Iberian Peninsula and attention was paid to the north‐western Atlantic area, where wild stocks have diminished greatly. Analysis of molecular variance, fixation index (FST), and demographic inferences were estimated based on mitochondrial DNA. Since D. trunculus shows doubly uniparental inheritance, both types of mitochondrial DNA (F and M) were analysed.

A high level of genetic diversity was detected using the haplotype diversity dataset, showing different geographic patterns.

FST values for the M type revealed significant differentiation between populations on both sides of the Almeria–Oran front, and between the locality from the Alboran Sea (FU) and localities from the Atlantic Ocean. However, the F type did not detect the differentiation of FU. This makes the M genome sequences more suitable for investigating genetic structure of D. trunculus populations.

Management and recovering strategies of this important resource should consider the genetic structure observed.

Several strategies for conservation and management of this commercial and ecologically important bivalve are proposed.
Age‐related changes in hepatic expression and activity of drug metabolizing enzymes in male wild‐type and breast cancer resistance protein knockout mice
Authors: Zheng Haihui , Wang Liping , Zeng Sijing , Chen Jiamei , Wang Haojia , Yu Jia , Gong Xia , Jiang Huangyu , Yang Xia , Qi Xiaoxiao , Wang Ying , Lu Linlin , Hu Ming , Zhu Lijun , Liu Zhongqiu
Published: July 2018

This study aimed to reveal age‐related changes in the expression and activity of seven hepatic drug metabolizing enzymes (DMEs) in male wild‐type and breast cancer resistance protein knockout (Bcrp1−/−) FVB mice. The protein expression of four cytochrome P450 (Cyps) (Cyp3a11, 2d22, 2e1, and 1a2), and three UDP‐glucuronosyltransferases (Ugts) (Ugt1a1, 1a6a, and 1a9) in liver microsomes of wild‐type and Bcrp1−/− FVB mice at different ages were determined using a validated ultra high performance liquid chromatography with tandem mass spectrometry (UHPLC–MS/MS) method. The activities and mRNA levels of these DMEs were measured using the probe substrates method and real‐time PCR, respectively. In the liver of wild‐type FVB mice, Cyp3a11, 2d22, 2e1, 1a2, Ugt1a1, and 1a6a displayed maximum protein levels at 6–9 weeks of age. Cyp1a2, Ugt1a1, 1a6a, and 1a9 showed maximum activities at 6–9 weeks of age, whereas Cyp3a11, 2d22, and 2e1 showed maximum activities in 1–3‐week‐old mice. Additionally, most of the DMEs showed maximum mRNA levels in 17‐week‐old mice liver. Compared with wild‐type FVB mice, the protein levels of these DMEs showed no significant changes in Bcrp1−/− FVB mice liver. However, the activity of Cyp2e1 was increased and that of Cyp2d22 was decreased. In conclusion, the seven hepatic DMEs in FVB mice liver showed significant alterations in an isoform‐specific manner with increased age. Although the protein levels of these DMEs showed no significant changes, the activities of Cyp2e1 and 2d22 were changed in Bcrp1−/− mice.
The Effects of Surface Modifications on the Electrochemical Properties of LiMn2−xNixO4 (0 ≤ x ≤ 0.5) as Cathode Materials for Secondary Lithium Batteries
Authors: Kwon Neung , Jeong Yeon Uk , Choi Sang‐Il , Kim Sung Yeol , Lee Yong Joong
Published: July 2018

In an attempt to achieve a higher energy density of secondary lithium batteries, cathode materials with higher potentials are investigated. LiMn2−xNixO4 samples are synthesized by a solid‐state reaction in a controlled atmosphere. While the energy density and cycle life have improved with higher Ni contents in the phase, the electrical conductivity has decreased. In order to improve the rate capability of cells, surface modifications of the cathode material are carried out by a wet chemical method. Surface modified samples show improved rate capability and cyclability compared to the unmodified samples.
Selective C−C Hydrogenolysis of Alkylbenzenes to Methylbenzenes with Suppression of Ring Hydrogenation
Authors: Yanatake Shin , Nakaji Yosuke , Betchaku Mii , Nakagawa Yoshinao , Tamura Masazumi , Tomishige Keiichi
Published: July 2018

Selective reduction of alkylbenzenes, which are supplied by refining heavy hydrocarbons, to methylbenzenes by selective C−C hydrogenolysis was accomplished by Ru/CeO2 catalyst. Hydrogenolysis of ethylbenzene was carried out with gas‐phase fixed‐bed flow reactor and various noble metal catalysts. The catalyst with high Ru loading (4 wt%) on CeO2 support pre‐calcined at high temperature (1073 K; Ru(4)/CeO21073 catalyst) showed both good activity and selectivity to toluene. The yield of toluene reached 65 %‐C in the conditions of 533 K and H2 partial pressure of 0.075 MPa. Hydrogenolysis of other alkylbenzenes including p‐ethyltoluene, propylbenzene and cumene was also carried out. Hydrogenolysis of Caryl‐Calkyl bond and hydrogenation of benzene ring was slow in all substrate cases. Hydrogenolysis of p‐ethyltoluene can give p‐xylene as the main product (highest yield: 53 %‐C). These high yields of methylbenzenes make a marked contrast to the traditional bifunctional hydrocracking systems which preferably dissociate Caryl‐Calkyl bond in alkylbenzenes. Characterization of Ru catalysts suggests that the block‐shaped Ru particles with small size (<2 nm) in Ru(4)/CeO21073 give good catalytic performance. Too strong interaction between Ru species and CeO2 support induced by decreasing the loading amount rather gives ring‐hydrogenation activity and decreases methylbenzenes selectivity.