Asymmetric Environment Research Articles

ROBOT-ASSISTED TARGETED GAIT TRAINING.

Millions of people are affected yearly by "runner's knee" and osteoarthritis, which is thought to be related to impact force. Millions are also affected by chronic falling, who are usually both difficult to identify and train. While at first glance, these topics seem to be entirely disconnected, there appears to be a need for a device that would address both issues. This paper proposes and investigates the use of the Variable Stiffness Treadmill (VST) as a targeted training device for the different populations described above. The VST is the authors' unique robotic split-belt treadmill that can reduce the vertical ground stiffness of the left belt, while the right belt remains rigid. In this work, heart rate and energy expenditure are measured for healthy subjects in the challenging asymmetric environment created by the VST and compared to a traditional treadmill setting. This study shows that this asymmetric environment results in an increase in heart rate and energy expenditure, an increase in activity in the muscles about the hip and knee, and a decrease in impact force at heel strike. Compliant environments, like those created on the VST, may be a beneficial tool as they can: reduce high-impact forces during running and walking, significantly engage the muscles surrounding the hip and knee allowing for targeted training and rehabilitation, and assist in identifying and training high fall-risk individuals.

Fluorescent and electronic properties of Dysprosium acylpyrazolone complexes along with their synthesis and structural features

Six distorted square antiprismatic eight coordinated Dysprosium acylpyrazolone complexes were synthesized having the compositions [Dy(L1)3(EtOH)(H2O)] (DyL1), [Dy(L2)3(EtOH)(H2O)] (DyL2), [Dy(L3)3(EtOH)(H2O)] (DyL3), [Dy(L4)3(EtOH)(H2O)] (DyL4), [Dy(L5)3(EtOH)(H2O)] (DyL5), and [Dy(L6)3(H2O)(EtOH)] (DyL6). The structure of all six complexes was examined using ESI-mass, FT-IR, UV–Vis, powder XRD, and thermogravimetric methods. According to the single crystal analysis of DyL4A, the complex was found eight coordinated (DyO8) with a distorted square antiprismatic geometry. The comparison of stimulated powder pattern of DyL4A crystal and experimental powder x-ray data helps to confirm the geometry of other complexes. In the solid-state emission spectra, the transition 4F9/2→6H13/2, which is close to the yellow region of the visible spectrum (∼510–530 nm), exhibits hypersensitivity. The variance in intensity between electric-dipole and magnetic-dipole transition suggests a less asymmetric environment. The solvent effect has been thoroughly investigated through a comparative analysis of electronic spectra in different solvents. The intensity of emission spectra, Y/B ratio, and antenna effect energy diagram were examined from solid-state emission spectra.

Hydrothermally synthesized rod shaped Y2O3:Eu3+ as red emitter

Rod shape Y2O3:Eu3+ were synthesized by using simple hydrothermal method. Characterizations of the samples were done with X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Increase of Eu3+ concentration in Y2O3 renders shift in Eu – O charge transfer band (CTB) to lower energy. PL emission indicates the asymmetric nature of Eu3+ surroundings. The calculated values of second order crystal field parameter corroborate the asymmetric environment of Eu3+. The improvement in the luminescence with the increase annealing temperature is realized from PL emission and decay lifetime studies. The quantum yield for Y2O3:Eu3+ (13 at.%) under 255 nm excitation is found to be 10 %.

Decentralized Inverse Transparency with Blockchain

Employee data can be used to facilitate work, but their misusage may pose risks for individuals. Inverse transparency therefore aims to track all usages of personal data, allowing individuals to monitor them to ensure accountability for potential misusage. This necessitates a trusted log to establish an agreed-upon and non-repudiable timeline of events. The unique properties of blockchain facilitate this by providing immutability and availability. For power asymmetric environments such as the workplace, permissionless blockchain is especially beneficial as no trusted third party is required. Yet, two issues remain: (1) In a decentralized environment, no arbiter can facilitate and attest to data exchanges. Simple peer-to-peer sharing of data, conversely, lacks the required non-repudiation. (2) With data governed by privacy legislation such as the GDPR, the core advantage of immutability becomes a liability. After a rightful request, an individual’s personal data need to be rectified or deleted, which is impossible in an immutable blockchain. To solve these issues, we present Kovacs , a decentralized data exchange and usage logging system for inverse transparency built on blockchain. Its new-usage protocol ensures non-repudiation, and therefore accountability, for inverse transparency. Its one-time pseudonym generation algorithm guarantees unlinkability and enables proof of ownership, which allows data subjects to exercise their legal rights regarding their personal data. With our implementation, we show the viability of our solution. The decentralized communication impacts performance and scalability, but exchange duration and storage size are still reasonable. More importantly, the provided information security meets high requirements. We conclude that Kovacs realizes decentralized inverse transparency through secure and GDPR-compliant use of permissionless blockchain.

CEO Political Ideology and Voluntary Forward-Looking Disclosure

Abstract This study investigates whether the management earnings forecasts of Republican and Democratic CEOs differ due to systematic differences in their information disclosure preferences. We find that Republican CEOs prefer a less asymmetric information environment than Democrat CEOs, and thus make more frequent, timelier, and more accurate disclosures than Democrat CEOs. Results using the propensity score matched sample and difference-in-differences analysis show that our results are unlikely to be driven by potential endogeneity. Our results are robust to controlling for various CEO characteristics and are stronger for firms with higher levels of institutional ownership and litigation risk.

In-depth 27Al NMR investigation of Al(C6F5)3 and its complexes with Lewis bases

For the first time, a correct 27Al chemical shift and W1/2 for 134 ppm Al(C6F5)3 as the most widely used Al-based ‘super-electrophilic’ Lewis acid was determined. A step-by-step proper way for acquisition and processing challenging 27Al spectra is suggested, which is applicable for any organo-aluminium compounds with asymmetric environment of Al. Using this procedure, several Lewis pairs of Al(C6F5)3 with N,O,S,P-centered Lewis bases were characterized.

Dynamic association of stock market volatility, foreign portfolio investment and macroeconomic indicators by taking the impact of structural breaks

In an asymmetric information environment, investors diversify their investments to minimize risk and maximize their wealth. Such diversification ranges from one market to another market and from one country to another country. Investors prefer foreign portfolio investment over foreign direct investment because of the economy's turmoil, changes in macroeconomic indicators, and market liberation. This study analyzes the dynamic relationship among stock market volatility, foreign portfolio investment, and macroeconomic indicators (foreign exchange rate, interest rate, and Gross Domestic Product) using the dynamic long-run Auto-regressive Distributed Lag (ARDL) model concerning the Pakistan environment. This study also considers the impact of multiple structural breaks, representing variables' endogenous and exogenous shocks. The secondary data is used from Oct. 01, 2009, to Sept. 30, 2019, with monthly frequency. The results indicate a co-integration between SMV, FPI, FXR, IR, and GDP. In short-run analyses, the error correction term is statistically significant, while in the long run, the SMV, FPI, and FXR are not impacted. As no evidence of volatility has been found between SMV and FPI, unidirectional or bi-directional policies can be devised to further attract the new FPI for strengthening the foreign reserves, the balance of payments, and other macroeconomic variables. Additionally, investors should update their knowledge based on considering the endogenous and exogenous shocks on the SMV.

Hydrothermal Synthesis of Rod Shaped Red Emitting Gd2O3:Eu3+ Phosphor.

Simple hydrothermal method can be applied for synthesizing rod shape Gd2O3:Eu3+ phosphors. X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy are used for the characterizations of samples. Increase of Eu3+ concentration in Gd2O3:Eu3+ can cause red shift in the charge transfer band (CTB) of Eu - O. The nature of Eu3+ surroundings is asymmetric. It is ascertained from PL emission studies. The calculation of second order crystal field parameter from PL spectra corroborates the asymmetric environment of Eu3+. PL emission and decay lifetime studies confirm the existence of quenching due cross-relaxation. The quantum yield for Y2O3:Eu3+ (19 at.%) under 265 nm excitation is found to be 7%.

NMR Signatures and Electronic Structure of Ti Sites in Titanosilicalite-1 from Solid-State 47/49Ti NMR Spectroscopy.

Although titanosilicalite-1 (TS-1) is among the most successful oxidation catalysts used in industry, its active site structure is still debated. Recent efforts have mostly focused on understanding the role of defect sites and extraframework Ti. Here, we report the 47/49Ti signature of TS-1 and molecular analogues [Ti(OTBOS)4] and [Ti(OTBOS)3(OiPr)] using novel MAS CryoProbe to enhance the sensitivity. While the dehydrated TS-1 displays chemical shifts similar to those of molecular homologues, confirming the tetrahedral environment of Ti consistent with X-ray absorption spectroscopy, it is associated with a distribution of larger quadrupolar coupling constants, indicating an asymmetric environment. Detailed computational studies on cluster models highlights the high sensitivity of the NMR signatures (chemical shift and quadrupolar coupling constant) to small local structural changes. These calculations show that, while it will be difficult to distinguish mono- vs dinuclear sites, the sensitivity of the 47/49Ti NMR signature should enable distinguishing the Ti location among specific T site positions.

Various results on some asymmetric types of density

The structures of symmetric connectedness and dually, antisymmetric connectedness were described and studied before, especially in terms of graph theory as the corresponding counterparts of the connectedness of a graph and the connectedness of its complementary graph. By taking into consideration the deficiencies of topological density in the context of symmetric and antisymmetric connectedness, two special kinds of density in the theory of non-metric $T_0$-quasi-metrics were introduced in the previous studies under the names symmetric density and antisymmetric density. In this paper, some crucial and useful properties of these two types of density are investigated with the help of the major results and (counter)examples peculiar to the asymmetric environment. Besides these, many further observations about the structures of symmetric and antisymmetric-density are dealt with, especially in the sense of their combinations such as products and unions through various theorems in the context of $T_0$-quasi-metrics. Also, we examine the question of under what kind of quasi-metric mapping these structures will be preserved.

Bismuth-based halide double perovskite Cs2KBiCl6: Disorder and luminescence

A new bismuth-based halide double perovskite Cs2KBiCl6 was isolated successfully through solid-state reactions and investigated using X-ray and neutron diffraction. Rather than an ordered structure, the crystal structure consists of shifted Cs, K, Bi, and Cl sites from the ideal positions with fractional occupancy in compensation, leading to variable local coordination of Cs+ ions, as revealed by 133Cs solid-state nuclear magnetic resonance spectroscopy. Cs2KBiCl6 displays volume hysteresis at 5–298 K range upon heating and cooling. The Cs2KBiCl6 has a direct bandgap of 3.35(2) eV and red-shift luminescence of around 600 nm upon Mn doping compared with the Na analogue. The stabilization of disordered structure in Cs2KBiCl6 is related to two factors including the large-sized K+ cation which prefers to coordinate with more than six Cl−, and the Bi3+ with 6s2 lone pair which has a preference for a local asymmetric environment. These findings could have general application and help to understand the structure and property of halide perovskites.

Stark splitting and spectroscopic properties improvement of Yb3+-doped phosphate glass with SiO2 modification

This study focuses on the Stark splitting and spectroscopic properties of Yb3+-doped phosphate glass with SiO2 modification. Stark splitting levels were calculated through deconvolution absorption and emission spectra. The coordination environment of Yb3+ ions was investigated to explain the enlarged Stark splitting. Spectroscopic parameters were given to characterized the effect of SiO2 on spectroscopic properties. The increased crystal field parameter and more asymmetric coordination environment lead to the enlargerd Stark splitting with the increase of SiO2 content. The constantly enhanced absorption cross-section, emission cross-section, and systematic factor values suggest that spectroscopic properties were improved through the addition of SiO2. The glass with 9 mol% SiO2 addition has largest Stark splitting and optimum spectroscopic performances, indicating that it is most likely to be applied to laser application.

Asymmetric Growth of Monolayer Graphene on Cu Foil by Space‐Confined CVD

AbstractChemical vapor deposition (CVD) is the most efficient method for growing graphene while its performance heavily relies on the growth environment. In this work, we examine the growth of continuous monolayer graphene films using CVD in an asymmetric environment by placing the Cu foil substrate on a specially designed semicircular quartz boat with grooves. We find that the asymmetry plays a key role in the growth of graphene and the quality of graphene on the bottom surface of Cu foil is higher than that on the top surface. This difference is attributed to different oxygen and carbon source concentration on the two surfaces of Cu foil, which leads to different nucleation density, grain size, and growth rate. COMSOL simulation confirms this hypothesis and reveals that the lower gas flow velocity on the bottom is responsible for the higher oxygen content and less carbon source supply, promoting higher‐quality graphene. Based on this asymmetric mechanism, we achieve stable and efficient batch production of high‐quality graphene using a special substrate support. Our method has guiding significance for the stable and batch growth of high‐quality graphene or other two dimensional (2D) materials in spatial design strategies.

Symmetric Electronic Structures of Active Sites to Boost Bifunctional Oxygen Electrocatalysis by MN4+4 Sites Directly from Initial Covalent Organic Polymers

AbstractTransition metal‐nitrogen‐carbon (M‐N‐C) catalysts with CoN4 centers have attracted great attention as a potential alternative to precious metal catalysts for bifunctional oxygen electrocatalysis. However, the asymmetric charge environment of the active site of MN4 obtained by conventional pyrolysis strategy makes the unbalanced adsorption of oxygen molecules, which restricts the activities of both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, a series of well‐defined quasi‐phthalocyanine conjugated 2D covalent organic polymer (COPBTC‐M) is developed with MN4+4 active sites through a pyrolysis‐free strategy. Compared to CoN4 site, the additional subcentral N4 atoms in MN4+4 site in COPBTC‐Co catalyst balance the charge environment and form a symmetric charge distribution, which changes the antibonding orbital of the active metal and regulate the oxygen species adsorption, thus improving the activity of the bifunctional oxygen electrocatalysis. In Silico screening demonstrates that cobalt has the best ORR and OER activity for COPBTC‐M with MN4+4 sites, which can be attributed to the fewer anti‐bonding orbital below the Fermi level, which weakens the oxygen species adsorption. Both theoretical and experimental results verify that the COPBTC‐Co possesses unique CoN4+4 active sites and the harmonious coordinating environment can lead to superior bifunctional oxygen catalytic activity with a high bifunctional oxygen catalytic activity (ΔE [Ej10 – E1/2] = 0.76 V), which is comparable with the benchmark Pt/C‐IrO2 pairs. Accordingly, the as‐assembled Zn–air battery exhibits a maximum power density of 157.7 mW cm −2 with stable operation for >100 cycles under an electric density of 10 mA cm −2. This study provides a characteristic understanding of the intrinsic active species toward MNx centers and could inspire new avenues for designation of advanced bifunctional electrocatalysts that catalyze ORR and OER processes simultaneously.

Laser-Induced Chirality of Plasmonic Nanoparticles Embedded in Porous Matrix.

Chiral plasmonic nanostructures have emerged as promising objects for numerous applications in nanophotonics, optoelectronics, biosensing, chemistry, and pharmacy. Here, we propose a novel method to induce strong chirality in achiral ensembles of gold nanoparticles via irradiation with circularly-polarized light of a picosecond Nd:YAG laser. Embedding of gold nanoparticles into a nanoporous silicate matrix leads to the formation of a racemic mixture of metal nanoparticles of different chirality that is enhanced by highly asymmetric dielectric environment of the nanoporous matrix. Then, illumination with intense circularly-polarized light selectively modifies the particles with the chirality defined by the handedness of the laser light, while their "enantiomers" survive the laser action almost unaffected. This novel modification of the spectral hole burning technique leads to the formation of an ensemble of plasmonic metal nanoparticles that demonstrates circular dichroism up to 100 mdeg. An unforeseen peculiarity of the chiral nanostructures obtained in this way is that 2D and 3D nanostructures contribute almost equally to the observed circular dichroism signals. Thus, the circular dichroism is neither even nor odd under reversal of direction of light propagation. These findings will help guide the development of a passive optical modulator and nanoplatform for enhanced chiral sensing and catalysis.

Contract design for a closed-loop supply chain considering information asymmetry of remanufacturing process innovation

PurposeAsymmetric cost information exists between a supplier and a manufacturer regarding the manufacturer's process innovation for remanufacturing (PIR), which may hurt the supplier's profit. The authors therefore seek to develop a menu of nonlinear pricing contracts for channel information sharing.Design/methodology/approachBased on principal–agent theory, the supplier, acting as a Stackelberg leader, designs a menu of nonlinear pricing contracts to impel the manufacturer to disclose its private cost information on PIR (i.e. PIR efficiency). In addition, the authors compare the equilibrium outcomes under asymmetric and symmetric information to examine the effects of asymmetric PIR information on the production policies and profits of the supplier and the manufacturer.FindingsThe proposed contract menu encourages th4e manufacturer to spontaneously share PIR efficiency information with the supplier. Asymmetric PIR information may distort the output of new products upward or downward, but the output of remanufactured products may only be distorted downward. In addition, the manufacturer with high PIR efficiency gains information rent, and interestingly, the increase in the probability of low PIR efficiency amplifies its information rent. Finally, an asymmetric information environment may increase the threshold for the manufacturer to enter remanufacturing.Originality/valueThe authors probe the issue of the supplier's contract design by jointly considering remanufacturing, process innovation and information asymmetry. The paper expands the influencing mechanism of process innovation information in the remanufacturing field. The authors also observe new results that may offer guidance to decision makers.

Occupant’s thermal responses to asymmetric radiant thermal environment with warm wall and cool ceiling, Part A: Overall thermal responses

A radiant ceiling cooling (CC) system integrated with a mechanical ventilation system, which can improve human thermal comfort and reduce HVAC system energy consumption simultaneously, has been extensively applied in the modern office building with glass curtain walls. In a ceiling cooling room with a glass curtain wall, the horizontal and vertical asymmetric radiation caused by the warm wall and cool ceiling may result in different thermal responses of human body. Therefore in this paper, occupant’s thermal responses in a simulated ceiling cooling office room with mixing ventilation (MV) or underfloor air distribution (UFAD) were investigated by a combination of subjective and objective experiments. Indoor operative temperature was increased from 23.0 °C to 30.0 °C as the surface temperatures of warm wall and cool ceiling were from 30.0 °C to 40.0 °C and from 14.0 °C to 27.0 °C. The results showed that the indoor thermal environment with CC + MV or CC + UFAD was comfortable and acceptable as the indoor operative temperature was from 25.0 °C to 27.0 °C. The thermal neutral operative temperature in the room was 25.6 °C with CC + MV and 26.4 °C with CC + UFAD, and the corresponding thermal neutral skin temperatures was 33.4 °C and 33.7 °C, respectively. Moreover, the thermal comfort stability of indoor operative temperature was close to 0.30 °C−1 with CC + MV or CC + UFAD, and the corresponding thermal comfort stability of mean skin temperature was 0.90 °C−1–0.94 °C−1. There were clearly linear relationships between thermal sensation or thermal preference and indoor operative temperature or mean skin temperature, and these relationships may be beneficial for the intelligent control of a radiant ceiling cooling system combined with a mechanical ventilation system.

Exploiting Molecular Symmetry to Quantitatively Map the Excited-State Landscape of Iron-Sulfur Clusters.

Cuboidal [Fe4S4] clusters are ubiquitous cofactors in biological redox chemistry. In the [Fe4S4]1+ state, pairwise spin coupling gives rise to six arrangements of the Fe valences ("valence isomers") among the four Fe centers. Because of the magnetic complexity of these systems, it has been challenging to understand how a protein's active site dictates both the arrangement of the valences in the ground state as well as the population of excited-state valence isomers. Here, we show that the ground-state valence isomer landscape can be simplified from a six-level system in an asymmetric protein environment to a two-level system by studying the problem in synthetic [Fe4S4]1+ clusters with solution C3v symmetry. This simplification allows for the energy differences between valence isomers to be quantified (in some cases with a resolution of <0.1 kcal/mol) by simultaneously fitting the VT NMR and solution magnetic moment data. Using this fitting protocol, we map the excited-state landscape for a range of clusters of the form [(SIMes)3Fe4S4-X/L]n, (SIMes = 1,3-dimesityl-imidazol-4,5-dihydro-2-ylidene; n = 0 for anionic, X-type ligands and n = +1 for neutral, L-type ligands) and find that a single ligand substitution can alter the relative ground-state energies of valence isomers by at least 103 cm-1. On this basis, we suggest that one result of "non-canonical" amino acid ligation in Fe-S proteins is the redistribution of the valence electrons in the manifold of thermally populated excited states.

ASAA: Multihop and Multiuser Channel Hopping Protocols for Cognitive-Radio-Enabled Internet of Things

The devices of Internet of Things (IoT) are integrated and interconnected by using the traditional wireless communication technology. Unavailability of spectrum sharing occurs in traditional wireless communication due to the presence of a massive number of IoT devices. Thus, Cognitive Radio Network (CRN) is introduced as a promising technology to utilize the spectrum efficiently. Channel Hopping Sequence (CHS) is used to establish communication among CRN users. However, the majority of CHS mechanisms only focus on multi-user single-hop scenarios, which can lead to bottleneck and throughput degradation problems. It is also found that few existing CHS mechanisms still have a low percentage of rendezvous that can cause difficulties for the Secondary Users (SUs) to communicate. Thus, it is a challenge to design efficient CHS for establishing fast communication among SUs under multi-user, multi-hop scenarios and asymmetric asynchronous environments. In this paper, Asymmetric Synchronous and Asymmetric Asynchronous (ASAA) Channel Hopping (CH) algorithms are designed for the multi-user CRN-enabled IoT devices to share the unused spectrum in the multi-hop scenario. The Multi-User Asymmetric Synchronous (MUAS) and Multi-User Asymmetric Asynchronous (MUAA) protocols are designed in the proposed ASAA channel hopping mechanism. The simulation results show that the proposed ASAA CHS algorithms outperform the existing CHS mechanisms in terms of throughput, Channel Loading (CL), Channel Utilization (CU), Maximum Time To Rendezvous (MTTR), Average Time to Rendezvous (ATTR) and Maximum Inter Rendezvous Interval (MIRI).

Three Processor Allocation Approaches towards EDF Scheduling for Performance Asymmetric Multiprocessors

With the rapid development of high-performance computing and parallel computing technology, by virtue of its cost-effectiveness, strong scalability, and easy programming, the multiprocessor system has gradually become the mainstream computing platform. Meanwhile, a growing number of researchers pay attention to the performance of multiprocessor systems, especially the task scheduling problem, which has an important impact on the system performance. Most of the current research works on task scheduling algorithms are based on the homogeneous computing environment. On the contrary, research works focusing on more complex performance asymmetric multiprocessor environments still remain rare. In this paper, we compare the effects of three earliest deadline first algorithms under different processor allocation strategies on performance asymmetric multiprocessors. We propose an efficient schedulability analysis for an allocation strategy that assigns high-priority tasks to the slowest idle processor. Experimental results show that the strategy of allocating processors with optimum speeds for high-priority tasks can schedule more task sets than the other two allocation strategies. The strategy that prioritizes the slowest processors for high-priority tasks has the smallest number of task migrations, and the strategy has the highest effective processor utilization.