ABSTRACT
NASICON-type solid electrolytes are suitable choices for solid state batteries considering safer and more stable electrochemical performance compared to other potential solid electrolytes. The present study investigates intrinsic defects and dopant incorporation energetics in the LiGe2(PO4)3 (LGP) electrode material using density functional theory-based calculations. The formation energies of intrinsic defects (Frenkel, Schottky and anti-sites) indicate that Li Frenkel pair formation is the most energetically feasible process. With an aim to improve the lithium ion conductivity and chemical stability by suitable doping, solution energies are calculated for various trivalent (M3+ = B3+, Al3+, Ga3+, Sc3+, In3+, Y3+, Gd3+, La3+) and tetravalent (M4+ = Si4+, Ti4+, Sn4+ and Zr4+) ions substituted at the Ge4+ site. The most favourable trivalent and tetravalent dopants are Al3+ and Ti4+, respectively. The changes in lattice parameters with doping are correlated with channel/bottleneck size for Li+ migration. Alkali atom doping at the Li+ site is energetically favourable whereas alkali-earth doping at the Li+ site is not. Analysis based on Bader charges and density of states delineates changes in chemical interactions between the dopant atoms and the host LGP.
ABSTRACT
Topological magnetic charges, arising due to the non-vanishing magnetic flux on spin ice vertices, serve as the origin of magnetic monopoles that traverse the underlying lattice effortlessly. Unlike spin ice materials of atomic origin, the dynamic state in artificial honeycomb spin ice is conventionally described in terms of finite size domain wall kinetics that require magnetic field or current application. Contrary to this common understanding, here we show that a thermally tunable artificial permalloy honeycomb lattice exhibits a perpetual dynamic state due to self-propelled magnetic charge defect relaxation in the absence of any external tuning agent. Quantitative investigation of magnetic charge defect dynamics using neutron spin echo spectroscopy reveals sub-ns relaxation times that are comparable to the relaxation of monopoles in bulk spin ices. Most importantly, the kinetic process remains unabated at low temperature where thermal fluctuation is negligible. This suggests that dynamic phenomena in honeycomb spin ice are mediated by quasi-particle type entities, also confirmed by dynamic Monte-Carlo simulations that replicate the kinetic behavior. Our research unveils a macroscopic magnetic particle that shares many known traits of quantum particles, namely magnetic monopole and magnon.
ABSTRACT
Hybrid organic-inorganic formate perovskites, AB(HCOO)3, are a large family of compounds that exhibit a variety of phase transitions and diverse properties, such as (anti)ferroelectricity, ferroelasticity, (anti)ferromagnetism, and multiferroism. While many properties of these materials have already been characterized, we are not aware of any study that focuses on the comprehensive property assessment of a large number of formate perovskites. A comparison of the properties of materials within the family is challenging due to systematic errors attributed to different techniques or the lack of data. For example, complete piezoelectric, dielectric, and elastic tensors are not available. In this work, we utilize first-principles density functional theory based simulations to overcome these challenges and to report structural, mechanical, dielectric, piezoelectric, and ferroelectric properties of 29 formate perovskites. We find that these materials exhibit elastic stiffness in the range 0.5-127.0 GPa; highly anisotropic linear compressibility, including zero and even negative values; dielectric constants in the range 0.1-102.1; highly anisotropic piezoelectric response with the longitudinal values in the range 1.18-21.12 pC/N; and spontaneous polarizations in the range 0.2-7.8 µC/cm2. Furthermore, we propose and computationally characterize a few formate perovskites that have not been reported yet.
ABSTRACT
Neuronal function and differentiation are tightly regulated by both genome and epigenome. Based on the environmental information the epigenetic changes occur. Neurodegeneration is the consequence of dysregulation of both the genome and epigenome. In this study, we saw different types of alterations of epigenome present in neuronal cells of different model organisms for neurodegenerative disorders. The epigenetic modifications including chromatin modification, DNA methylation, and changes in regulatory RNAs (miRNA) are having a great impact on neurodegenerative disorders as well as memory. The effects of these re-editing in the neuronal cells cause Alzheimer's disease, Parkinson's disease, Huntington's disease but an unusual form of neuroepigenetics has been seen in Prion Disease. Subsequently, for the development of treatment of these diseases, epigenetic modifications should be kept in mind. Although until now many reports came on drug discovery inhibiting histone deacetylases and DNA methyltransferases to reverse the epigenetic change but they lack targeted delivery and sometimes cause a cytotoxic effect on neuronal cells. In future, advancement in targeted and non-cytotoxic drugs should be the main focus for therapeutic treatment of the neurodegenerative disorders.(AU)
La función y diferenciación neuronales están reguladas en gran medida por el genoma y el epigenoma. Los estímulos ambientales producen cambios epigenéticos. La neurodegeneración es consecuencia de una alteración en el genoma y el epigenoma. Hemos analizado diferentes tipos de alteraciones del epigenoma presentes en células neuronales de diferentes modelos animales de enfermedad neurodegenerativa. Los cambios epigenéticos (modificación de la cromatina, metilación del ADN, cambios en los ARN reguladores [miARN]) tienen un impacto importante en las enfermedades neurodegenerativas y en la memoria. Dichos cambios en células neuronales causan diferentes enfermedades, como las de Alzheimer, Parkinson, y Huntington; sin embargo, las enfermedades priónicas muestran formas epigenéticas inusuales. Por tanto, el desarrollo de tratamientos para estas enfermedades debe considerar los cambios epigenéticos. Se han desarrollado diversos fármacos inhibidores de la histona deacetilasa y la ADN metiltransferasa, que revierten los cambios epigenéticos, pero no utilizan sistemas de liberación inteligente, por lo que a veces pueden producir efectos citotóxicos en las células neuronales. La investigación sobre tratamientos para las enfermedades neurodegenerativas debe centrarse en el desarrollo de fármacos no citotóxicos con sistemas de liberación inteligente.(AU)
Subject(s)
Humans , Epigenomics , DNA Methylation , Neurodegenerative Diseases , Neurology , Nervous System DiseasesABSTRACT
Neuronal function and differentiation are tightly regulated by both genome and epigenome. Based on the environmental information the epigenetic changes occur. Neurodegeneration is the consequence of dysregulation of both the genome and epigenome. In this study, we saw different types of alterations of epigenome present in neuronal cells of different model organisms for neurodegenerative disorders. The epigenetic modifications including chromatin modification, DNA methylation, and changes in regulatory RNAs (miRNA) are having a great impact on neurodegenerative disorders as well as memory. The effects of these re-editing in the neuronal cells cause Alzheimer's disease, Parkinson's disease, Huntington's disease but an unusual form of neuroepigenetics has been seen in Prion Disease. Subsequently, for the development of treatment of these diseases, epigenetic modifications should be kept in mind. Although until now many reports came on drug discovery inhibiting histone deacetylases and DNA methyltransferases to reverse the epigenetic change but they lack targeted delivery and sometimes cause a cytotoxic effect on neuronal cells. In future, advancement in targeted and non-cytotoxic drugs should be the main focus for therapeutic treatment of the neurodegenerative disorders.
Subject(s)
Alzheimer Disease , Neurodegenerative Diseases , Parkinson Disease , Humans , Epigenesis, Genetic , DNA Methylation , Neurodegenerative Diseases/genetics , Alzheimer Disease/genetics , Parkinson Disease/geneticsABSTRACT
A combination of first-principles calculations and cluster expansion method is used to study ordering of oxygen vacancies in PuO2-x and AmO2-x. Vacancy ordered stable/metastable structures of composition Pu8O15 (PuO1.875), Pu6O11 (PuO1.833), Pu8O14 (PuO1.75) and Am10O19 (AmO1.90), Am8O15 (AmO1.875), Am10O18 (AmO1.80), Am8O13 (AmO1.625) are identified in PuO2-x and AmO2-x, respectively, from cluster expansion calculations. A comparison of formation enthalpies of vacancy ordered and vacancy disordered structures shows that Am8O15 (AmO1.875) and Am8O13 (AmO1.625) are more stable by 52 and 55 meV per atom, respectively, compared to their disordered counterparts. Similarly, vacancy ordered Pu8O15 (PuO1.875) and Pu8O14 (PuO1.75) structures are more stable compared to the disordered structures by 10 and 8 meV per atom, respectively. In contrast, the disordered PuO1.625 structure is more stable compared to the cluster expansion generated structures. The vacancy ordered structures are mechanically stable and their bulk modulus, Young's modulus, shear modulus and Poisson's ratio are reported.
ABSTRACT
Purpose: Adolescence is a period of transformation in humans with changes in the neural physiology at subcortical and cortical levels. However, its significance on auditory processing skills and working memory skills and their association is yet to be well understood. Hence, the current study was designed to evaluate and establish the association between auditory processing skills and working memory abilities in adolescents. Method: A total of 125 adolescents within the age range of 10 to 15 years participated in the current study. All of them had normal hearing sensitivity and no associated obvious peripheral or central deficits. All the participants underwent auditory closure ability assessment using quick speech perception in noise test in Kannada, binaural integration ability assessment using dichotic CV test, and temporal processing assessment using gap detection test. Auditory working memory abilities were assessed using auditory digit span and digit sequencing. Results: Spearman correlation was done to assess the correlation between auditory processing skills and working memory abilities. Results revealed a significant negative correlation between most of the central auditory processing abilities and all the working memory spans. Conclusions: Findings of the current study indicate that individuals with poor working memory abilities have difficulty in auditory processing abilities.
ABSTRACT
Magnetic semiconductors are at the core of recent spintronics research endeavors. Chemically doped II-VI diluted magnetic semiconductors, such as (Zn1-x Cr x )Te, provide a promising platform in this quest. However, a detailed knowledge of the microscopic nature of magnetic ground state is necessary for any practical application. Here, we report on the synergistic study of (Zn1-x Cr x )Te single crystals using elastic neutron scattering measurements and density functional calculations. For the first time, our research unveils the intrinsic properties of ferromagnetic state in a macroscopic specimen of (Zn0.8Cr0.2)Te. The ferromagnetism is onset at T C â¼ 290 K and remains somewhat independent to modest change in the substitution coefficient x. We show that magnetic moments on Zn/Cr sites develop ferromagnetic correlation in the a-c plane with a large ordered moment of µ = 3.08 µ B. Magnetic moment across the lattice is induced via the mediation of Te sites, uncoupled to the number of dopant carriers as inferred from the density functional calculation. Additionally, the ab initio calculations also reveal half-metallicity in x = 0.2 composition. These properties are highly desirable for future spintronic applications.
ABSTRACT
Hybrid organic-inorganic perovskites [NH2NH3][X(HCOO)3] (X = Mn, Fe, Co) have a so-called "wine-rack" type of geometry that could give origin to the rare property of negative linear compressibility, which is an exotic and highly desirable material response. We use first-principles density functional theory computations to probe the response of these materials to hydrostatic pressure and predict that, indeed, all three of them exhibit negative linear compressibility above a critical pressure of 1 GPa. Calculations reveal that, under pressure, XO6 octahedra and -HCOO ligands remain relatively rigid while XO6 octahedra tilt significantly, which leads to highly anisotropic mechanical properties and expansion along certain directions. These trends are common for the three materials considered.
ABSTRACT
Hybrid organic-inorganic perovskites is a class of materials with diverse chemically tunable properties and outstanding potential for multifunctionality. We use first-principles simulations to predict room temperature ferroelectricity in a representative of the formate family, [NH_{2}NH_{3}][Co(HCOO)_{3}]. The ferroelectricity arises as a "by-product" of structural transition driven by the stabilization of the hydrogen bond. As a consequence the coupling with the electric field is relatively weak giving origin to large intrinsic coercive fields and making material immune to the depolarizing fields known for its detrimental role in nanoscale ferroelectrics. Insensitivity to the electric field and the intrinsic dynamics of the order-disorder transition in such material leads to the supercoercivity defined as significant increase in the coercive field with frequency. Room temperature polarization measurements provide further support for the predictions.
ABSTRACT
Tinnitus is associated with sensorineural hearing loss irrespective of its severity and configuration. Frequency discrimination training is a contemporary method used for the treatment of tinnitus. However, its efficacy in treating tinnitus associated with flat sensorineural hearing loss is not studied yet. The objectives were to assess (a) treatment effect across sessions on tinnitus percept using subjective questionnaires (b) association in the severity and handicap of tinnitus before and after FDT treatment. A total of 16 participants with mean age of 56 years, who had subjective tinnitus and flat sensorineural hearing loss ranging from mild to moderate were included in the study. However, only 11 participants completed the treatment regime. Each participant was provided FDT in a game format for 15 days. The Quantitative (tinnitus pitch and loudness in each session) and qualitative measurements (THI and TFI) were assessed in each participant. Friedman test revealed a significant reduction in handicap from tinnitus as reflected in THI and reduced functionality impairment from tinnitus as reflected in TFI across sessions. Besides, a significant association was observed in the Chi-square test in severity and handicap of tinnitus before and after therapy. A change in pitch and reduced loudness was noted in eight of 11 participants. Three of them had no tinnitus perception at the end of the treatment regime. The current study findings demonstrate the efficacy of FDT using a game module in treating tinnitus associated with flat sensorineural hearing loss. The perceived severity and handicap of tinnitus reduces as a function of treatment.
ABSTRACT
First-principles density functional theory computations are used to predict negative linear compressibility in hybrid organic-inorganic perovskite [NH2NH3][Co(HCOO)3]. Negative linear compressibility is a rare exotic response of a material to pressure associated with expansion along one or two lateral directions. Detailed structural analysis revealed that [NH2NH3][Co(HCOO)3] responds to pressure through tilting of its relatively rigid units, CoO6 polyhedra, and (HCOO)-1 ligand chain. The (HCOO)-1 units form a "wine-rack" geometry which is well described with the "strut-hinge" model. Within the model, the struts are formed by the rigid units, while hinges are their relatively flexible interconnects. Under pressure, the hinge angle increases which leads to the expansion along the direction subtended by the angle. Interestingly, at zero pressure the linear compressibilities in [NH2NH3][Co(HCOO)3] are all positive. As pressure increases, the lowest linear compressibility value turns negative and increases in magnitude. Comparison with the literature suggests that such a trend is likely to be common to this family of materials. Mechanical properties of [NH2NH3][Co(HCOO)3] are highly anisotropic.
ABSTRACT
Neuronal function and differentiation are tightly regulated by both genome and epigenome. Based on the environmental information the epigenetic changes occur. Neurodegeneration is the consequence of dysregulation of both the genome and epigenome. In this study, we saw different types of alterations of epigenome present in neuronal cells of different model organisms for neurodegenerative disorders. The epigenetic modifications including chromatin modification, DNA methylation, and changes in regulatory RNAs (miRNA) are having a great impact on neurodegenerative disorders as well as memory. The effects of these re-editing in the neuronal cells cause Alzheimer's disease, Parkinson's disease, Huntington's disease but an unusual form of neuroepigenetics has been seen in Prion Disease. Subsequently, for the development of treatment of these diseases, epigenetic modifications should be kept in mind. Although until now many reports came on drug discovery inhibiting histone deacetylases and DNA methyltransferases to reverse the epigenetic change but they lack targeted delivery and sometimes cause a cytotoxic effect on neuronal cells. In future, advancement in targeted and non-cytotoxic drugs should be the main focus for therapeutic treatment of the neurodegenerative disorders.
ABSTRACT
A combination of special quasi-random structure (SQS) analysis, density functional theory (DFT) based simulations and experimental techniques are employed in determining the transformation pathway for the disorderedγ-(U, Zr) phase (bcc structure) to transform into the chemically orderedδ-UZr2phase (C32, AlB2type structure). A novel Monte-Carlo based strategy is developed to generate SQS structures to study theßâωdisplacive phase transformation in A1-xBxbinary random alloy. Structures generated with this strategy and using DFT calculations, it is determined that (222)bccplane collapse mechanism is energetically unfavorable in chemically disordered environment at UZr2composition. A mechanically and dynamically stable 24 atom SQS structure is derived which serves as a structural model of chemically orderedδ-UZr2structure. Finally, a thermodynamic basis for the mechanism of theγtoδtransformation has been established which ensures chemical ordering is a precursor to the subsequent displacive transformation to form chemically orderedδ-UZr2structure.
ABSTRACT
Aggregation of proteins towards amyloid formation is a significant event in many neurodegenerative diseases. Low-molecular weight oligomers are considered to be the primary toxic agents in many of these maladies. Therefore, there is an increasing interest in understanding their formation and behavior. In this paper, we build on our previously established theoretical investigations on the interactions between Aß and lipids (L) that adopt off-pathway fibril formation under the control of L concentrations. Our previously developed competing game theoretic framework between the on- and off-pathway dynamics has been expanded to understand the underlying network topological structures in the reaction kinetics of amyloid formation. The mass-action based dynamical systems are solved to identify dominant pathways in the system with fixed initial conditions, and variations in the occurrence of these dominant pathways are identified as a function of various seeding conditions. The mechanistic approach is supported by thermodynamic free energy computations which helps identify stable reactions. The resulting analysis provides possible intervention strategies that can draw the dynamics away from the off-pathways and potential toxic intermediates. We also draw upon the classic literature on network thermodynamics to suggest new approaches to better understand such complex systems.
ABSTRACT
Piezoelectrics are critical functional components of many practical applications such as sensors, ultrasonic transducers, actuators, medical imaging, and telecommunications. So far, the best performing piezoelectrics are ferroelectric ceramics, many of which are toxic, heavy, hard, and cost-ineffective. Recently, a groundbreaking discovery of extraordinarily large piezoelectric coefficients in the family of organic-inorganic perovskites gave a hope for a cheaper, environmentally friendly, inexpensive, lightweight, and flexible alternative. However, the origin of such a response in organic-inorganic ferroelectrics whose spontaneous polarization is an order of magnitude smaller than for inorganic counterparts remains unclear. In our study, we employ first-principles simulations to predict that the mechanism associated with large piezoelectric constants is of extrinsic origin and associated with switching between the stable phase and a previously overlooked energetically competitive metastable phase that can be stabilized by the external stress. The phase switching changes the polarization direction and therefore produces a large piezoelectric response similar to PbZr_{1-x}Ti_{x}O_{3} near the morphotropic phase boundary. The existence of such metastable phases is likely to manifest as the dynamical molecular disorder above the Curie temperature and therefore could be intrinsic to the entire family of organic-inorganic ferroelectrics with such disorder.
ABSTRACT
BACKGROUND: Speech perception encompasses the perception of spectro-temporal cues. These cues include temporal envelope, temporal fine structure, and spectral shape of the signal. Extraction of these cues is essential for speech perception and, most importantly, for perceiving speech in the presence of noise (SPIN). Speech perception in noise scores improves with age in children and is crucial in their routine communications, including classroom learning. Though it is established that the speech perception in noise improves with age in children, the age at which SPIN scores become adult-like and the differences in the maturation pattern between the ears remains unclear. The present study aimed to assess and understand the maturation pattern of speech perception in noise abilities during adolescence. METHOD: The study included 146 participants who were divided into six crossectional age groups. Participants were in the age range of 10-15 years and adults of 18-19 years. SPIN was assessed for right and left ears for each of these sub-groups. The scores were compared across the different subgroups for both the ears. RESULTS: Results demonstrated that SPIN scores in the right ear were matured by the age of 10 years and were comparable with the right ear SPIN scores in adults. Pairwise comparison using Bonferroni's corrections for multiple comparisons of left ear SPIN scores revealed that SPIN scores in the left ear become adult-like between 13 and 14 years of age. DISCUSSION: Findings of the current study can be attributed to the morphological changes and differences in the developmental changes across the different regions of the cortex.
Subject(s)
Speech Perception , Adolescent , Adult , Child , Ear , Humans , Noise/adverse effectsABSTRACT
The structural, thermodynamic, electronic, and elastic properties of Th1-xUxO2 and Th1-xPuxO2 mixed oxides (MOX) have been calculated with Hubbard corrected density functional theory (DFT+U) to account for the strong 5f electron correlations. The ideal solid solution is approximated by special quasi-random structures and the U-ramping method is used to account for the presence of metastable states in the self-consistent field solution of the DFT+U approach. The mixing enthalpy (ΔHmix) is positive throughout the composition range of the Th1-xUxO2 MOX, consistent with a simple miscibility gap (at low temperature) phase diagram. The behavior of the Th1-xPuxO2 MOX is more complex, where ΔHmix is positive in the ThO2-rich region and negative in the PuO2-rich region. Electronic structure analysis shows that substitution of Th by U/Pu in ThO2 leads to a reduction of the average Th-O bond lengths, causing distortion in the crystal structure. The distortion in the crystal structure results in an increase in the conduction bandwidth and a reduction of the band-gap in the MOX. Good agreement of our DFT+U calculated elastic properties of ThO2, UO2 and PuO2 compounds with experiments leads to convincing prediction of these properties for Th1-xUxO2 and Th1-xPuxO2 MOX.
ABSTRACT
The design of stable and high performance metal free bifunctional electrocatalysts is a necessity in alkaline zinc-air batteries for oxygen reduction and evolution reaction. In the present work co-doped carbon materials have been developed from polymeric precursors with abundant active sites to achieve bifunctional activity. A 3-dimensional microporous nitrogen-carbon (NC) and co-doped nitrogen-sulfur-carbon (NSC) and nitrogen-phosphorus-carbon (NPC) were synthesized using poly(2,5-benzimidazole) as an N containing precursor. The obtained sheet like structure shows outstanding ORR and OER performance in alkaline systems with excellent stability compared to Pt/C catalyst. The doped heteroatom in the carbon is expected to have redistributed the charge around heteroatom dopants lowering the ORR potential and modifying the oxygen chemisorption mode thereby weakening the O-O bonding and improving the ORR activity and overall catalytic performance. The bifunctional activity (ΔE = E j=10 - E 1/2) of an air electrode for NPC, NSC, NC and Pt/C is 0.82 V, 0.87 V, 1.06 V and 1.03 V respectively, and the NPC value is smaller than most of the reported metal and non-metal based electrocatalysts. The ORR (from onset potential) and OER (10 mA cm-2) overpotential for NPC, NSC, and NC is (290 mV, 410 mV), (310 mV, 450 mV) and (340 mV, 600 mV) respectively. In the prepared catalyst the NPC exhibited higher ORR and OER activity (NPC > NSC > NC). The doping of P in NPC is found to have a great influence on the microstructure and therefore on the ORR and OER activity.
ABSTRACT
AIM: Linoleic acid (LA) is an essential fatty acid involved in the biosynthesis of arachidonic acid and prostaglandins. LA is known to induce obesity and insulin resistance. In this study, two concentrations of LA with or without added glucose (G) were fed to mice to investigate their effects on endocannabinoid (EC) biology. MATERIALS AND METHODS: Four groups of C57BL/6 mice were provided with diets containing 1% or 8% LA with or without added G (LAG) for 8 weeks. Body weights, food intake, circulating glucose and insulin levels were measured throughout the study. Following euthanasia, plasma, bowel and hepatic ECs, monoacylglycerol lipase and fatty acid amide hydroxylase protein levels (enzymes responsible for EC degradation) and transcriptional activity of PPARα in liver were quantified. Liver was probed for evidence of insulin receptor activity perturbation. RESULTS: Increasing dietary LA from 1% to 8% significantly increased circulating, small bowel and hepatic ECs. 1%LAG fed mice had lowest feed efficiency, and only liver levels of both ECs were reduced by addition of G. Addition of G to 1% LA diets resulted in elevated monoacylglycerol lipase and fatty acid amide hydroxylase protein levels (p < 0.001 and p < 0.001, respectively) in liver due to increased transcriptional activity of PPARα (p < 0.05). The reduced EC levels with addition of G also correlated with a measure of enhanced insulin action. CONCLUSION: In conclusion, body weight of mice is influenced by the source of calorie intake. Furthermore, tissue EC/g are dependent on tissue-specific synthesis and degradation that are modulated by dietary LA and G which also influence food efficiency, and down-stream insulin signalling pathways. The findings could potentially be useful information for weight management efforts in humans.