Dominant family control reduces Type I agency conflicts because of monitoring efficiencies, while increasing Type II agency conflicts because of the family’s voting power. Additionally, Type II agency conflicts could be exacerbated if the family agents managed the firm solely for the family’s benefit. The two different types of agency conflicts were examined in a sample of 499 public Indian family businesses during the years 2006 to 2015. Family-controlled and non-family-managed firms appeared to be optimally configured to minimize both types of agency conflicts. The absence of management control appeared to alleviate some of the dissipative agency conflict effects of dominant family ownership.
A dissolution followed by recrystallization from a deuterated solvent allows the site-selective deuteration of labile protons in molecular solids. High yields of deuteration obtained by this approach facilitates the structure elucidation of powdered solids by solid-state NMR spectroscopy, for example, by acquiring 1D 2H and 2D 2H-1H correlation NMR spectra with short experimental times. Along these lines, we present a cross-polarization 2H-1H isotope correlation spectroscopy (CP-iCOSY) approach for the characterization of deuterated amino acids and pharmaceutical compounds. We show that the high field NMR (28.2 T) coupled with fast magic-angle spinning (MAS) overcomes the sensitivity and resolution barrier for acquiring 2H MAS spectra, enabling the rapid detection of 2H peaks in a few seconds to minutes. Specifically, two-dimensional 2H-1H CP-iCOSY experiment allows the local structures and through-space interactions in a partially deuterated compounds to be elucidated. Analysis of partially deuterated L-histidine·HCl·H2O and dopamine.HCl is presented, whereby the detection of 2D peaks corresponding to 2H-1H pairs separated by >4 Å demonstrates the sensitivity and resolution power of the presented approach for the characterization of solid-state packing interactions. 2D ssNMR results are corroborate by NMR crystallography analysis using Gauge Including Projector Augmented Wave (GIPAW) approach. Molecular-level analysis enabled by this study is of considerable interest for further investigation of labile sites in a variety of molecular solids, reactive surfaces and interfaces, and supramolecular assemblies.
Having its genome makes the mitochondrion a unique and semiautonomous organelle within cells. Mammalian mitochondrial DNA (mtDNA) is a double-stranded closed circular molecule of about 16 kb coding for 37 genes. Mutations, including deletions in the mitochondrial genome, can culminate in different human diseases. Mapping the deletion junctions suggests that the breakpoints are generally seen at hotspots. '9-bp deletion' (8271-8281), seen in the intergenic region of cytochrome c oxidase II/tRNA Lys , is the most common mitochondrial deletion. While it is associated with several diseases like myopathy, dystonia, and hepatocellular carcinoma, it has also been used as an evolutionary marker. However, the mechanism responsible for its fragility is unclear. In the current study, we show that Endonuclease G, a mitochondrial nuclease responsible for nonspecific cleavage of nuclear DNA during apoptosis, can induce breaks at sequences associated with '9-bp deletion' when it is present on a plasmid or in the mitochondrial genome. Through a series of in vitro and intracellular studies, we show that Endonuclease G binds to G-quadruplex structures formed at the hotspot and induces DNA breaks. Therefore, we uncover a new role for Endonuclease G in generating mtDNA deletions, which depends on the formation of G4 DNA within the mitochondrial genome. In summary, we identify a novel property of Endonuclease G, besides its role in apoptosis and the recently described elimination of paternal mitochondria during fertilisation.
Regulation of enzyme activity is key to the adaptation of cellular processes such as signal transduction and metabolism in response to varying external conditions. Synthetic molecular glues have provided effective systems for enzyme inhibition and regulation of protein-protein interactions. So far, all the molecular glue systems based on covalent interactions operated in equilibrium conditions. To emulate dynamic far-from-equilibrium biological processes, we introduce herein a transient supramolecular glue with controllable lifetime. The transient system uses multivalent supramolecular interactions between guanidium group-bearing surfactants and adenosine triphosphates (ATP), resulting in bilayer vesicle structures. Unlike the conventional fuels for non-equilibrium assemblies, ATP here plays the dual role of providing a structural component for the assembly as well as presenting active functional groups to “glue” enzymes on the surface.
Hydroxyapatite (HAP) composite coatings on bio-implants have become very significant materials for orthopaedic applications. The additives in the HAP matrix can improve the wear resistance, mechanical strength, weak bonding and brittleness of the HAP. The present work reports comprehensive investigations of experimental and computational studies for commonly used bio-reinforcing agents, functionalized carbon nanotubes (CNT), graphene oxide (GrO) and hexagonal boron nitride (hBN), with HAP. The synergistic effect of lubrication of hBN and strong bonding between HAP and hBN resulted in a lower friction-of-coefficient (0.23) and reduced dissipation energy (4.6 Â 10 À4 J) for electrophoretically deposited HAP-hBN composite coating when compared to HAP-CNT, HAP-GrO and bare HAP. Furthermore, the high wear resistance with reduced wear volume (1.65 Â 10 À3 mm 3) and wear rate (1.83 Â 10 À3 mm 3 N À1 m À1) of the HAP-hBN composite coating exhibited its remarkable tribological properties for use in bone implants. Moreover, in order to facilitate some lucid insights into the interfacial bonding and nonbonding interactions (i.e. stability), structural, and electronic features of the HAP and HAP-based composite models (HAP-hBN, HAP-GrO, and HAP-CNT), comprehensive DFT are carried out. Remarkably, the HAP-BN composite model was stabilized by multiple CaN bonding interactions. With the employment of the electronic structure calculations approach, the HAP-hBN composite model was found to be the most stable among all three dimer complexes (HAP-hBN, HAP-GrO, and HAP-CNT), which was supported by the supramolecular approach (i.e. binding energy), QTAIM and NCI-plot tools. The biological studies of the HAP-hBN coating showed that the cell viability and antibacterial activity were greater than 80%, which shows the perfect bioactivity of the coating. Thus, the HAP-hBN composite coating with perfect hydrophilicity, wear resistance, biocompatibility and strong bonding compared to HAP-CNT and HAP-GrO can be used as an ideal implant material for bone tissue engineering.,
The current study aims to investigate the role of cultural values in shaping Sustainable consumption behavior in a non‐Western setting. The primary data on cultural orientation and consumption of Information and Communication Technology (ICT) products is collected from about 347 Indian consumers. Four consumption culture dimensions—Environmental Fatalism, Comfort‐centric Outlook, Spiritual Outlook, and Techno‐criticism—were derived from primary data using factor analysis. Consumption culture dimensions are shown to have a direct influence on sustainable consumption behavior and indirect influence through personal environmental stewardship. Environmental Fatalism and Comfort‐centric Outlook showed negative relationship, while Spiritual Outlook had a positive relationship with Sustainable Consumption Behavior—Techno‐criticism was found to be insignificant. Further analysis revealed that Personal Environmental Stewardship partially mediates the relationship between consumption culture dimensions and sustainable consumption behavior. The study findings extend the existing theoretical knowledge by offering a model that can be leveraged to validate the influence of cultural variables, including general attitudes toward waste and technology, on sustainable consumption behavior of high environmental impacts and spanning multiple consumption phases. Results from our study provide practical insights for educators, marketers, campaign managers and religious leaders to develop pedagogical practice and design culturally‐relevant messaging to activate norms relevant for pro‐environmental behaviors. The current study is among the first to focus on (i) an impact‐based operationalization of sustainable consumption behavior and (ii) the consumption area of electronics. Further, the current study also contributes to a rather nascent stream of research embedded in non‐Western contexts.
Highway proximity is essential to the economic growth of establishments and productivity of freight operations. The present study is motivated by the discernible gap in knowledge about the potential impacts of highway proximity on freight flow patterns of establishments. This knowledge gap impedes accurately estimating the potential benefits associated with infrastructure investments, especially related to freight-specific facility planning in developing countries. This paper investigates highway proximity impacts on freight establishments’ travel and shipment patterns using a comparative experiment approach. A total of 17 explanatory variables reflecting the freight flow pattern of an establishment have been considered. Proximity impact is evaluated by comparing the means of these explanatory variables among establishments closer to the highway, termed the “Influence” group, and those farther from the highway, defined as the “Control” group. Spatial and kernel analyses are carried out to determine the cut-off distance for demarcating samples into Influence and Control groups. The propensity score matching technique is subsequently used to create matched samples for a one-to-one comparison between the Influence group and Control group establishments. Results suggest that the Influence group typically consists of older establishments with larger business areas, generates many small-sized trips, and is associated with lower tonnage generation, expenditure, and shipment size than the Control group. The study findings are expected to have important implications on the infrastructure investment decision process and planning of freight operations.
The tannery industries have become an important part of societal growth; however, these processes have produced huge volumes of effluents containing heavy metals, particularly Cr(VI) oxyanions. The study is crucial and cost-effective for reducing the chromium (VI) from industrial wastewater. In order to meet the sustainable development goal (SDG) objective 6.3, the capacity of Sambucus nigra L. to adsorb heavy metal is established with the purpose of eradicating hazardous chemical contamination and reducing pollution. In this study, discontinuous tests were carried out to determine the efficiency of Cr(VI) sorption on leaves of Sambucus nigra L. Adsorption factors such as pH, temperature, adsorbent dosage, and contact time were evaluated. At a dosage of 3 g/L and pH 2, an efficiency of 98.22% was achieved under favorable conditions. The equilibrium and kinetic models that best fitted the experimental data are non-linear Freundlich and; pseudo-second order, and intra-particle diffusion, respectively. The thermodynamic parameters of the adsorption process, including Gibbs free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰), were measured at 291, 303, 323, and 343 K, indicating that the phenomena was spontaneous and endothermic. The chemical analyses and surface morphology of the adsorbent were analyzed using SEM (scanning electron microscopy), EDS (energy dispersive spectroscopy), FTIR (Fourier transform infra-red), XRD (X-ray diffraction), and ICP-OES (inductively coupled plasma optical-emission spectroscopy) techniques. The results showed that Sambucus nigra L. has a significant removal efficiency of Cr(VI) in the contaminated solutions, establishing adsorbent as a low cost, readily available, and environmentally friendly and ensuring its potential for industrial usage. Graphical abstarct.
Ni-YSZ-based electrodes are well-established in the field of solid oxide technologies. Ni/YSZ-based architectures have well-known performance and mechanical properties besides well-established manufacturing processes. Solid oxide-based CO2 electrolysis on Ni-YSZ at high temperature requires the presence of H2 in the CO2 inlet stream. It is believed that in pure CO2 streams the reaction fails due to oxidation of the Ni-YSZ electrode. Using operando Raman spectroscopy and online mass spectroscopy, we have shown that CO2 can in fact be reduced on the Ni-YSZ surface. Our measurements, reveal that Ni-YSZ oxidizes to NiOx-YSZ within a pure CO2 stream. CO2 electrolysis is possible on this oxide surface via a surface oxygen and vacancy-mediated mechanism similar to those observed within other oxide cathodes such as CeOx. The deactivation of the electrode coincides with strongly reducing conditions and at current densities > 400 mA/cm2, NiOx is completely reduced coinciding with complete stoppage of CO production. Cu-impregnation into Ni-YSZ was demonstrated to mitigate the deactivation issue by forming a more stable surface oxide on Ni which continued to carry out CO2 reduction under strongly reducing conditions. The new electrode demonstrated improved kinetics and stability against carbon deposition via Bouduard reaction.
Even as four-dimensional (4D) printing of biomaterials evolves as a fascinating technology to engineer complex and dynamic biomimetic parts, the utility of 4D printed hydrogels in addressing clinical needs in vivo has not been established. In this study, a hydrogel system was engineered from tailored concentrations of alginate and methyl cellulose with defined swelling behaviors, which demonstrated excellent printability in extrusion-based three-dimensional (3D) printing and programmed shape deformations post-printing. Shape deformations of the spatially patterned hydrogels with defined infill angles were computationally predicted for a variety of 3D printed structures, which were subsequently validated experimentally. The gels were further coated with gelatin-rich nanofibers by airbrushing to augment cell attachment and growth. 3D printed hydrogel sheets with pre-programmed infill patterns rapidly self-rolled into hollow tubes in vivo to serve as nerve guiding conduits for repairing sciatic nerve defects in a rat model. These 4D printed hydrogels minimized the complexity of surgeries by tightly clamping the resected ends of the nerves to assist in the healing of peripheral nerve damage, as revealed by histological evaluation and functional assessments for up to 45 days. This work demonstrates that 3D printed hydrogels can be designed for programmed shape changes by swelling in vivo to yield 4D printed tissue constructs for the repair of peripheral nerve damage with a potential to be extended in other areas of regenerative medicine.
We highlight the enhanced electronic and optical functionalization in the hybrid heterojunction of one-dimensional (1D) tellurene with a two-dimensional (2D) monolayer of graphene and MoS2 in both lateral and vertical geometries. The structural configurations of these assemblies are optimized with a comparative analysis of the energetics for different positional placements of the 1D system with respect to the hexagonal 2D substrate. The 1D/2D coupling of the electronic structure in this unique assembly enables the realization of the three different types of heterojunctions, viz. type I, type II, and Z-scheme. The interaction with 1D tellurene enables the opening of a band gap of the order of hundreds of meV in 2D graphene for both lateral and vertical geometries. With both static and time-dependent first-principles analysis, we indicate their potential applications in broadband photodetection and absorption, covering a wide range of visible to infrared (near-IR to mid-IR) spectrum from 380 to 10 000 nm. We indicate that this 1D/2D assembly also has bright prospects in green-energy harvesting.
We challenge the predominant viewpoint in the literature that employee silence is inherently harmful. We theorize that employees can engage in strategic silence, or the intentional withholding of untimely ideas or concerns, in order to raise issues that resonate better with managers when they do speak up. More specifically, we propose that employees’ voice is deemed higher quality by managers, and as a result, earns them higher performance evaluations and rewards, when those employees also engage in strategic silence. In a qualitative study (Study 1), we document the dimensions and real-life examples of strategic silence. In two multi-source survey-based field studies (Study 2a and Study 2b) and a pre-registered online experiment (Study 3), we demonstrate support for our theoretical model. Through our findings, we highlight that strategic silence is a functional and useful type of silence that employees use to gain more positive appraisal of their voice from managers.
Various concentrations of Sm (1, 2, 3, 4, and 5 at%) doped SnO2 thin films were synthesized by the sol-gel spin coating method and investigated the structural, optical, and electrical properties. According to X-ray diffraction studies, all deposited films exhibited the polycrystalline rutile tetragonal structure. The average crystallite size decreased with Sm doping concentration in SnO2, while the dislocation density and lattice strain values were increased. Both XPS and Raman spectra confirm that Sm³⁺ enters the host SnO2. The higher average optical transmittance is above 86% in pure SnO2, while Sm: SnO2 films exhibit a decreasing trend with the increase of Sm doping concentration and reached up to 77% in 5 at% Sm: SnO2 film. The optical bandgap energy increased with the increase of Sm doping concentration up to 3 at % Sm: SnO2 film (4.23 eV) which is attributed to the Moss-Burstein (MB) effect and then slightly decreased for 4 at% and 5 at% Sm: SnO2 films. Further, the room temperature sheet resistance and resistivity values were found to decrease with the increase of Sm doping concentration up to 3 at % Sm: SnO2 film then it slightly increased in 4 and 5 at% Sm: SnO2 films. Additionally, the efficiency parameter figure of merit (φ) for all the deposited films was calculated.
Ring‐expansion strategies are valuable synthetic tools that take benefit of existing ring structures and evade the unfavorable enthalpic‐and entropic effects that arise with end‐to‐end cyclizations. One potentially important class of such reactions is the Dowd–Beckwith reaction. In their Review article (DOI: 10.1002/chem.202202025), Hari et al. discuss the origin and advancement of the Dowd–Beckwith reaction with particular focus on its application to complex natural products synthesis.
In this research, we study the air cargo loading problem that aims to assign cargo containers to appropriate loading positions within a freight carrier aircraft. Here, as we deal with an aircraft that has been specially reconfigured into a freight aircraft from originally a passenger aircraft, this leads to a novel air cargo loading problem that is subject to four types of constraints, namely: assignment constraints; maximum position weight limits and zero fuel weight limit considerations; center of gravity (CG) envelope limiting conditions, which are based on the aircraft weight and fluctuating CG during the fueling process; respecting panel weight limits (a legacy constraint from the passenger aircraft structure), which are related to the CG envelope; and finally, lateral imbalance limits for double-row cargo configurations. We minimize the deviation from an optimal CG value, which is determined based on fuel economy and safety restrictions. This problem is formulated as a 0-1 mixed-integer nonlinear programming model, which is subsequently linearized, and four different types of aircraft configurations are utilized to test our formulation. The results indicate that significant improvements can be achieved as compared to a more traditionally used method in the freight cargo industry. Finally, we highlight a user-oriented, functional, and graphically appealing decision support tool, based on the proposed optimization framework, that has been developed and deployed at a major air cargo operator in Singapore.
Although the Climate Forecast System version‐2 (CFSv2) model simulates an overall dry bias in boreal summer mean rainfall over Indian land, the deficiency is particularly prominent over northwest India. The prevailed dryness limits the interannual prediction skill of the Indian Summer Monsoon Rainfall (ISMR) and its subseasonal variability because of poor representation of latent heating due to weak moist convection and the resulting circulation. Here, we show that land surface vegetation plays a crucial role in determining the dry bias in the CFSv2 model. We replaced the land surface model’s existing vegetation type over India with that derived from recent satellite‐based observations. The modifications helped improve the seasonal mean rainfall over northwest India by 6%. The improvements are especially noticeable during the monsoon season’s onset (14%) and withdrawal (10%) phases. Simulations with modified vegetation advanced the onset dates over Kerala, central India, and northwest India closer to that observed. This improvement in the mean onset dates is most prominent over northwest India. Such improvement was possible due to a substantial reduction of long rainfall hiatus after onset over Kerala in the simulation with modified vegetation. The modification makes the spatial orientation of monsoon onset isochrones more realistic. We found that although the vertically integrated moisture flux is eastward over most of the Indian monsoon region during its onset phase, its intraseasonal components are westward. In other words, at the intraseasonal time scale, moisture propagates against the prevailing low‐level westerlies. This intraseasonal eddy moisture transport advances onset from the Bay of Bengal toward the far northwest parts of the Indian land. The representation of such intraseasonal moisture seepage in the model updated with satellite‐derived vegetation types was improved. Our study indicates the necessity of greater attention to land surface representations for improved predictions of onset dates.
Rheoprocessing of Al alloys has grabbed attention for quite some time now, due to its potential to deliver sound engineering components with superior strength to weight ratio, when coupled with the gravity and pressure die casting techniques. However, effective implementation of the adopted rheoprocessing technique requires in-depth investigation of microstructure evolution mechanism, to meet the demand of producing semi-sold slurry having sought after morphological features of constituent primary solid (Al). A cooling slope is used here to perform rheoprocessing of the A356 Al alloy, to generate semi-solid slurry of the said alloy, for Rheo-pressure die casting process. Rapid oil quenching technique has been employed to investigate the physics behind slurry microstructure formation, while flowing down the cooling slope. Correlations are developed, based on the repetitive experimental results, between the melt flow length and shape, size, density of constituent α-Al grains of the slurry in view of establishing process control. Correlation model has also been developed to address the interdependency of particle size and shape, which serves as the quality characteristics of the semi-solid slurry for practical appliances. Insight is obtained on the effect of grain refiner addition on slurry microstructure evolution, during rheoprocessing using cooling slope. Moreover, solute rejection phenomena occur during cooling slope rheoprocessing of the slurry, and final globularization of microstructural features during isothermal holding stage has also been studied in this work.
One of the primary goals of supply chain management is to reduce supply–demand mismatch (SDM). Product variety explosion is a common occurrence across industries and is one of the primary sources of demand uncertainty, resulting in SDM and the associated costs. Researchers and practitioners have investigated the role of process flexibility in addressing SDM caused by product variety. This study investigates the impact of product modularity on the benefits of process flexibility. It answers the critical question: “Does introducing modularity in product structure lead to reduced process flexibility requirements?”. As flexibility investment is costly, the reduced requirement in the presence of product modularity positively impacts financially constrained manufacturing firms (e.g., those belonging to the SME sector or start-up ecosystem). Two stochastic optimization problems are formulated, one with two products and one with multiple products. The results show that in the presence of product modularity, the optimal production policy handles demand uncertainty better and thus reduces SDM cost more than the integrated product case. Further, the need for investment in process flexibility decreases in the presence of modularity. In the multi-product formulation, the researchers investigate the d-chain process flexibility structure requirement. In the presence of product modularity, a 2-chain process flexibility structure is sufficient to almost achieve the performance of a full flexibility structure, in contrast to integrated product scenarios where at least 3 to 4-chains are required.
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