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Enhanced sampling algorithms are indispensable when working with highly disconnected multimodal distributions. An important application of these is the conformational exploration of particular internal degrees of freedom of molecular systems. However, despite the existence of many commonly used enhanced sampling algorithms to explore these internal motions, they often rely on system-dependent parameters, which negatively impact efficiency and reproducibility. Here, we present fully adaptive simulated tempering (FAST), a variation of the irreversible simulated tempering algorithm, which continuously optimizes the number, parameters, and weights of intermediate distributions to achieve maximally fast traversal over a space defined by the change in a predefined thermodynamic control variable such as temperature or an alchemical smoothing parameter. This work builds on a number of previously published methods, such as sequential Monte Carlo, and introduces a novel parameter optimization procedure that can, in principle, be used in any expanded ensemble algorithms. This method is validated by being applied on a number of different molecular systems with high torsional kinetic barriers. We also consider two different soft-core potentials during the interpolation procedure and compare their performance. We conclude that FAST is a highly efficient algorithm, which improves simulation reproducibility and can be successfully used in a variety of settings with the same initial hyperparameters. [ABSTRACT FROM AUTHOR]

To investigate the impact of fractional parameters on the thermodynamic behaviors of quantum systems, we incorporate fractional quantum mechanics into the cycle of a quantum Stirling heat engine and examine the influence of fractional parameters on regeneration and efficiency. We propose a novel approach to control the thermodynamic cycle that leverages the fractional parameter structure and evaluates its effectiveness. Our findings reveal that by tuning the fractional parameter, the region of the cycle with the perfect regeneration and the Carnot efficiency can be expanded. [ABSTRACT FROM AUTHOR]

The COVID-19 pandemic highlighted the pivotal role of transportation-related controls and vaccination in mitigating widespread infections. However, the substantial costs associated with these interventions necessitate a nuanced equilibrium between control measures and infection risks. This study, driven by the recognition of spatial heterogeneities in mobility networks and epidemic vulnerability, presents an optimal control framework for two control measures—vaccine distribution and transportation restrictions—within a metapopulation structure. The overarching goal is to minimize the total costs derived from the implementation of control measures and health and opportunity loss from infection. Our findings highlight the effectiveness of transportation control and vaccine distribution in reducing both total costs and infection rates. Notably, the efficacy of these control measures exhibits regional variations, and the simultaneous implementation of both measures emerges as the most effective and economically viable strategy. The synergy effect between vaccine distribution and transportation restrictions is also a key observation in our simulations, showcasing their complementary roles in pandemic control. By considering the spatial nuances of mobility networks and infection vulnerability, this framework provides a flexible and region-specific strategy to optimize the allocation of resources for pandemic control, ultimately striking a balance between efficacy and economic feasibility. • Pandemic control via joint strategy of transportation and vaccination. • Metapopulation model captures spatial heterogeneity for cost-effective controls. • Offers cost-minimization analysis for balancing health and economy. • Finds synergy in vaccination and travel restrictions. • Validates the approach with case study, guiding future pandemic strategies. [ABSTRACT FROM AUTHOR]

Two closely related yet distinctly different cationic clusters, [Dy52Ni44(HEIDA)36(OH)138(OAc)24(H2O)30]10+ (1) and [Dy112Ni76(HEIDA)44(EIDA)24(IDA)4(OH)268(OAc)48(H2O)44]4+ (2) (HEIDA=N‐(2‐hydroxyethyl)iminodiacetate), each featuring a multi‐shell core of Platonic and Archimedean polyhedra, were obtained. Depending on the specific conditions used for the co‐hydrolysis of Dy3+ and Ni2+, the product can be crystallized out as one particular type of cluster or as a mixture of 1 and 2. How the reaction process was affected by the amount of hydrolysis‐facilitating base and/or by the reaction temperature and duration was investigated. It has been found that a reaction at a high temperature and/or for an extended period favors the formation of the compact and thermodynamically more stable 1, while a brief reaction with a large amount of the base is good for the kinetic product 2. By tuning these intertwining conditions, the reaction can be regulated toward a particular product. [ABSTRACT FROM AUTHOR]

The synthesis of sulfoxide‐functionalized NHC ligand precursors were carried out by direct and mild oxidation from corresponding thioether precursors with high selectivity. Using these salts, a series of cationic [Ru(II)(η6‐p‐cymene)(NHC‐SO)Cl]+ complexes were obtained in excellent yields by the classical Ag2O transmetallation route. NMR analyses suggested a chelate structure for the metal complexes, and X‐ray diffractometry studies of complexes 4 b, 4 c, 4dBArF and 4 e unambiguously confirmed the preference for the bidentate (κ2‐C,S) coordination mode of the NHC‐SO ligands. Interestingly, only one diastereomer, in the form of an enantiomeric pair, was observed both in 1H NMR and in the solid state for the complexes. DFT calculations showed a possible intrinsic energy difference between the two pairs of diastereomer. The calculated energy barriers suggested that inversion of the sulfoxide is only plausible from the higher energy diastereomer together with bulky substituents. Inverting the configuration at the Ru center instead shows a lower and accessible activation barrier to provide the most stable diastereomer through thermodynamic control, consistent with the observation of a single species by 1H NMR as a pair of enantiomers. All these complexes catalyse the β‐alkylation of secondary alcohols. Complex 4dPF6 bearing an NHC‐functionalised S‐Ad group has been further studied with different primary and secondary alcohols as substrates, showing high reactivity and high to moderate β‐ol‐selectivities. [ABSTRACT FROM AUTHOR]

Compounds containing the thiophene moiety find several applications in physics and chemistry, such as electrical conduction, which depends on specific conformations to properly exhibiting the desired properties. In turn, chalcogen bonding has found to modulate the conformation of some N‐thiophen‐2‐ylfomamides. Since halogens participate in a kin interaction (halogen bonding) and are abundant in agrochemicals, pharmaceuticals, and materials, we have quantum‐chemically explored the interaction between organic halogen and thiophene as a conformational modulator in some model compounds. Although such interaction indeed appears, as demonstrated by atoms in molecules and natural bond orbital analysis, it is inefficient to control the conformational equilibrium. An energy decomposition analysis scheme demonstrated that halomethane and thiophene tend to move away from one another due to a core component (Pauli repulsion and exchange), which is mainly due to a deformation term. Therefore, chalcogen bonds with halogens appear weaker than with other chalcogens. [ABSTRACT FROM AUTHOR]

Protonated and methylated bis‐acridinium tweezers built around a 2,6‐diphenylpyridyl and an electron enriched 2,6‐di(p‐anisyl)pyridyl spacer have been synthesized. These tweezers can self‐assemble in their corresponding homodimers and the associated thermodynamic parameters have been probed in organic solvents. The switching properties of the tweezers have been exploited in biphasic transfer experiments showing the shift of the equilibria towards the homodimers. Moreover, the thermodynamic parameters of the formation of the reduced methylated homodimers investigated by electrochemical experiments revealed the dissociation of the dimers. Thus, in addition to solvent and temperature, the pH and redox responsiveness of the acridinium units of the tweezers make it possible to modulate to a larger extent the monomer‐dimer equilibria. [ABSTRACT FROM AUTHOR]

Motional Stark effect polarimetry is a key diagnostic for plasma fusion research since its usage on PBX-M. The MSE diagnostic measures the radial magnetic pitch angle profile in a plasma from a neutral beam by observation of Stark split D-alpha emission from atoms excited by collision with ions and electrons in the plasma. The pitch angle measurement is used with equilibrium reconstruction codes to determine the q-profile for studies of plasma stability, confinement, and transport. Historically, the algorithm was used in a post-processing fashion. The goal of our work was to apply this method in real time and pass the results to the plasma control system computer for real-time equilibrium reconstruction and control. [ABSTRACT FROM AUTHOR]

Carvone belongs to the chemical family of terpenoids and is the main component of various plant oils. Carvone and its hydrogenated products are used in the flavouring and food industries. A quantitative thermodynamic analysis of the general network of carvone hydrogenation reactions was performed based on the thermochemical properties of the starting carvone and all possible intermediates and end products. The enthalpies of vaporisation, enthalpies of formation, entropies and heat capacities of the reactants were determined by complementary measurements and a combination of empirical, theoretical and quantum chemical methods. The energetics and entropy change in the hydrogenation and isomerisation reactions that take place during the conversion of carvone were derived, and the Gibbs energies of the reactions were estimated. It was shown that negative Gibbs energies are recorded for all reactions that may occur during the hydrogenation of carvone, although these differ significantly in magnitude. This means that all these reactions are thermodynamically feasible in a wide range from ambient temperature to elevated temperatures. Therefore, all these reactions definitely take place under kinetic and not thermodynamic control. Nevertheless, the numerical Gibbs energy values can help to establish the chemoselectivity of catalysts used to convert carvone to either carvacarol or to dihydro- and terahydrocarvone, either in carvotanacetone or carveol. [ABSTRACT FROM AUTHOR]

This study investigated the physical aging behavior of commodity polymers, specifically polystyrene (PS) and poly(methyl methacrylate) (PMMA), across various molecular weights (MWs). Using ellipsometry, we examine the physical aging behavior of bulk polymer films supported on silicon across a wide range of quench depths below glass transition temperature. At shallow quench depths, where the physical aging behavior is thermodynamically controlled, we observe that the physical aging rate for both PS and PMMA increases with decreasing MW. The MW dependence of the physical aging rate in the thermodynamic‐control region is hypothesized to originate from the MW dependence of the fractional free volume. In support of this hypothesis, we observe that the difference in thermal expansivity between the rubbery state and the glassy state (αrubbery − αglassy), which has been demonstrated to be positively related to fractional free volume, exhibits a similar MW dependence as the physical aging behavior. This correlation lends support to the free volume model of physical aging. Building on the free volume model, we propose a method to tune the physical aging behavior, demonstrating that incorporating flexible chain ends alters the physical aging behavior in a manner akin to reducing MW. Highlights: Polystyrene and poly(methyl methacrylate) have maximum physical aging rates at specific quench depths.Physical aging behavior is thermodynamically or kinetically controlled.With thermodynamic control, the aging rate increases with a reduction in molecular weight.With thermodynamic control, the aging rate correlates with free volume.Aging behavior can be tuned by blending with low MW polymer with highly flexible chain ends. [ABSTRACT FROM AUTHOR]

A bis-ferrocene macrocycle was synthesized by reversible acylhydrazone formation under thermodynamic control, starting from a ferrocene functionalized with hydrazide and protected aldehyde moieties. A hydrogen sulfate anion acts as a template to direct the synthesis specifically toward the macrocyclic dimer, due to a weak but selective binding interaction. This work highlights the utility of dynamic combinatorial chemistry as an approach to macrocycle synthesis. [ABSTRACT FROM AUTHOR]

A novel sub‐sampling method has been used to isolate the dynamic effects of the response of the North Atlantic Oscillation (NAO) and the Siberian High (SH) from the total response to projected Arctic sea‐ice loss under 2°C global warming above preindustrial levels in very large initial‐condition ensemble climate simulations. Thermodynamic effects of Arctic warming are more prominent in Europe while dynamic effects are more prominent in Asia/East Asia. This explains less‐severe cold extremes in Europe but more‐severe cold extremes in Asia/East Asia. For Northern Eurasia, dynamic effects overwhelm the effect of increased moisture from a warming Arctic, leading to an overall decrease in precipitation. We show that the response scales linearly with the dynamic response. However, caution is needed when interpreting inter‐model differences in the response because of internal variability, which can largely explain the inter‐model spread in the NAO and SH response in the Polar Amplification Model Intercomparison Project. Plain Language Summary: The projected loss of Arctic sea‐ice under 2°C global warming will cause large warming in the Arctic region and climate and weather anomalies outside the Arctic. The warming in the Arctic will mean warmer airmasses coming from the Arctic and also more moisture from the open Arctic Ocean. Furthermore, it will also change atmospheric circulation. These effects together will determine the impacts of Arctic warming. In this study, we introduce a novel sub‐sampling method to isolate atmospheric circulation change in response to the Arctic warming. The method involves selecting members of simulations from the experiment with future Arctic sea‐ice conditions, the average of which is equal to the average of the members of simulations in the experiment with present‐day Arctic sea‐ice conditions. We found that atmospheric circulation change in European regions is relatively weak so that warming effects will dominate the climate and weather response there. On the other hand, atmospheric circulation change will dominate the climate and weather response in East Eurasia. We also found that stronger atmospheric circulation changes will generally increase the response to the Arctic warming. We suggest caution when assessing whether different responses in different models can be interpreted as true differences in model physics. Key Points: A novel sub‐sampling method is introduced to isolate the role of dynamics in the response to projected Arctic sea‐ice lossA dynamical Siberian High response dominates the temperature response over East Eurasia while that of the North Atlantic Oscillation is weakInter‐model differences in Polar Amplification Model Intercomparison Project likely contain a large fraction of internal variability due to the unconstrained dynamic effects [ABSTRACT FROM AUTHOR]

Dynamic bonds can facilitate reversible formation and dissociation of connections in response to external stimuli, endowing materials with shape memory and self-healing capabilities. Temperature is an external stimulus that can be easily controlled through heat. Dynamic covalent bonds in response to temperature can reversibly connect, exchange, and convert chains in the polymer. In this review, we introduce dynamic covalent bonds that operate without catalysts in various temperature ranges. The basic bonding mechanism and the kinetics are examined to understand dynamic covalent chemistry reversibly performed by equilibrium control. Furthermore, a recent synthesis method that implements dynamic covalent coupling based on various polymers is introduced. Dynamic covalent bonds that operate depending on temperature can be applied and expand the use of polymers, providing predictions for the development of future smart materials. [ABSTRACT FROM AUTHOR]

The preparation of novel structures of light-diffusing particles is currently a research focus in the field of light-diffusing materials. This study, conducted by the common melt-blending process, controlled thermodynamic and kinetic factors to distribute smaller-sized organic silica bead (OSB) particles at the interface between a polycarbonate (PC) matrix and spherical island-phase styrene–acrylonitrile copolymer (SAN) for the in situ formation of compound eye-like microspheres with SAN as "large eyes" and OSBs as "small eyes". Through the multiple-scattering effects of these compound eye-like microspheres, these light-diffusing materials significantly improved the haze, scattering range, and light-shielding capabilities while maintaining high transmittance. Specifically, the PC/SAN-OSB light-scattering materials achieved a haze of 100% with an OSB content of only 0.17%, maintaining a transmittance of 88%. Compared with the PC/OSB system with the same level of haze, the addition of OSB was reduced by 88%. Therefore, this study achieved exceptionally effective light-diffusing materials through a simple, environmentally friendly, and low-cost preparation method, suitable for the scalable production of light-diffusing materials in new display and lighting fields. [ABSTRACT FROM AUTHOR]

The success of solid-state synthesis often hinges on the first intermediate phase that forms, which determines the remaining driving force to produce the desired target material. Recent work suggests that when reaction energies are large, thermodynamics primarily dictates the initial product formed, regardless of reactant stoichiometry. Here, we validate this principle and quantify its constraints by performing in situ characterization on 37 pairs of reactants. These experiments reveal a threshold for thermodynamic control in solid-state reactions, whereby initial product formation can be predicted when its driving force exceeds that of all other competing phases by =60 milli-electron volt per atom. In contrast, when multiple phases have a comparable driving force to form, the initial product is more often determined by kinetic factors. Analysis of the Materials Project data shows that 15% of possible reactions fall within the regime of thermodynamic control, highlighting the opportunity to predict synthesis pathways from first principles. [ABSTRACT FROM AUTHOR]

Open-access policies for coastal recreation areas in France can negatively impact landscape quality and lead to crowding. Our main objective is to simulate the effects of using public policies to regulate access to these sites. We estimate a repeated random utility model to explain the choice of participating and visiting coastal sites with a congestion variable. Since congestion is a result of a Nash equilibrium and is likely to be endogenous, an instrumental variable approach is used to both estimate congestion at the visitation equilibrium and control for its endogeneity. We use data from a survey of visitors to 43 coastal sites in western France (Brittany). When congestion is instrumented, it becomes a deterrent attribute in the choice of visiting a coastal area. We then simulate alternative access management policies and find that a mix of parking fees and increased walking distances at site entrances have the greatest effect on reducing congestion. [ABSTRACT FROM AUTHOR]

Emergent exotic phenomena in the self-assembled process of vertically aligned nanocomposite (VAN) thin film remain under intensive studies. Insight exploration on the self-assembled formation from the combination of two different phases of materials is not only important to optimize the physical properties yields from those combined materials, but also open up a new avenue to discover new materials with the VAN system. In this work, the thermodynamic control of the self-assembled formation of BiFeO3-CoFe2O4 (BFO-CFO) VAN thin film has been confirmed by studying the effects of substrate temperature during the growth process by pulsed laser deposition (PLD) technique. The structural examination results on the samples, which were growing with various substrate temperatures highlight the importance of the thermodynamic factor to control the crystalline structure of BFO phase and CFO pillar size, which then affect the physical properties and further its practical applications. For instance, we can control the size of the CFO pillar using a temperature substrate to find appropriate spin magnetic switching in the CFO pillar for memory device applications. This study also sheds light on the relationship between thermodynamics and elastic strain energy on the formation of self-assembled matrix-pillars of the BFO-CFO VAN which is important for device fabrication. [ABSTRACT FROM AUTHOR]

Dynamic combinatorial chemistry (DCC) leverages a reversible reaction to generate compound libraries from constituting building blocks under thermodynamic control. The position of this equilibrium can be biased by addition of a target macromolecule towards enrichment of bound ligands. While DCC has been applied to select ligands for a single target protein, its application to identifying chimeric molecules inducing proximity between two proteins is unprecedented. In this proof‐of‐concept study, we develop a DCC approach to select bifunctional proteolysis targeting chimeras (PROTACs) based on their ability to stabilize the ternary complex. We focus on VHL‐targeting Homo‐PROTACs as model system, and show that the formation of a VHL2 : Homo‐PROTAC ternary complex reversibly assembled using thiol‐disulfide exchange chemistry leads to amplification of potent VHL Homo‐PROTACs with degradation activities which correlated well with their biophysical ability to dimerize VHL. Ternary complex templated dynamic combinatorial libraries allowed identification of novel Homo‐PROTAC degraders. We anticipate future applications of ternary‐complex directed DCC to early PROTAC screenings and expansion to other proximity‐inducing modalities beyond PROTACs. [ABSTRACT FROM AUTHOR]

The mid-Piacenzian warm period (MPWP, ~3.264–3.025 Ma) has gained widespread interest due to its partial analogy with future climate. However, quantitative data–model comparison of East Asian Summer Monsoon (EASM) precipitation during the MPWP is relatively rare, especially due to problems in decoding the imprint of physical processes to climate signals in the records. In this study, pollen-based precipitation records are reconstructed and compared to the multi-model ensemble mean of the Pliocene Model Intercomparison Project Phase 2 (PlioMIP2). We find spatially consistent precipitation increase in most simulations but a spatially divergent change in MPWP records. We reconcile proxy data and simulation by decomposing physical processes that control precipitation. Our results 1) reveal thermodynamic control of an overall enhancement of EASM precipitation and 2) highlight a distinct control of thermodynamic and dynamical processes on increases of tropical and subtropical EASM precipitation, reflecting the two pathways of water vapor supply that enhance EASM precipitation, respectively. [ABSTRACT FROM AUTHOR]

The current work proposes a numerical model for analysing the inertial migration of cylindrical-shaped rigid particles in pulsatile flow. The particle is non-neutrally buoyant, and the numerical model is built using a feedback forcing-based immersed boundary scheme. For shifting particle equilibrium position towards the channel centre, an opposing flow control force is applied. The relationship between control force and parameters such as particle diameter, Reynolds number, and density ratio is thoroughly investigated and reported here. The magnitude of the control force increases with Reynolds number and decreases with particle diameter. With density ratio, on the other hand, the magnitude of the control force first drops and then rises. Based on the results of the parametric study a prediction model for the control force is developed with the help of a linear regression algorithm. [ABSTRACT FROM AUTHOR]

With the advancement of urbanization, super high-rise buildings have become an integral part of modern cities. However, these structures face significant challenges due to thermal expansion effects in complex environments, especially considering the substantial impact of temperature-induced thermal expansion of concrete on the stability and safety of buildings. Although existing research has made some progress in exploring thermal expansion effects and their control strategies, traditional methods have limitations in addressing the complexities of super high-rise buildings. This study first solves the thermal expansion coefficient of concrete in super high-rise building structures based on an effective medium theory, providing a more precise calculation method from a microscopic perspective. Secondly, it proposes and validates a set of thermodynamic control strategies for super high-rise building structures to effectively manage the stress and deformation issues caused by temperature changes. The findings of this study will offer scientific support for the design and maintenance of super high-rise buildings, enhancing their overall safety and economic efficiency. [ABSTRACT FROM AUTHOR]

This study analyzes the samarium diiodide‐promoted cyclizations of 5‐arylpentan‐2‐ones to dearomatized bicyclic products utilizing density functional theory. The reaction involves a single electron transfer to the carbonyl group, which occurs synchronously with the rate determining cyclization event, and a second subsequent proton‐coupled electron transfer. These redox reactions are accurately computed employing small core pseudo potentials explicitly involving all f‐electrons of samarium. Comparison of the energies of the possible final products rules out thermodynamic control of the observed regio‐ and diastereoselectivities. Kinetic control via appropriate transition states is correctly predicted, but to obtain reasonable energy levels the influence of the co‐solvent hexamethylphosphortriamide has to be estimated by using a correction term. The steric effect of the bulky samarium ligands is decisive for the observed stereoselectivity. Carbonyl groups in para‐position of the aryl group change the regioselectivity of the cyclization and lead to spiro compounds. The computations suggest again kinetic control of this deviating outcome. However, the standard mechanism has to be modified and the involvement of a complex activated by two SmI2 moieties is proposed in which two electrons are transferred simultaneously to form the new C−C bond. Computation of model intermediates show the feasibility of this alternative+ mechanism. [ABSTRACT FROM AUTHOR]

Multi-Agent Reinforcement Learning (MARL) has shown strong advantages in urban multi-intersection traffic signal control, but it also suffers from the problems of non-smooth environment and inter-agent coordination. However, most of the existing research on MARL traffic signal control has focused on designing efficient communication to solve the environment non-smoothness problem, while neglecting the coordination between agents. In order to coordinate among agents, this paper combines MARL and the regional mixed-strategy Nash equilibrium to construct a Deep Convolutional Nash Policy Gradient Traffic Signal Control (DCNPG-TSC) model, which enables agents to perceive the traffic environment in a wider range and achieves effective agent communication and collaboration. Additionally, a Multi-Agent Distributional Nash Policy Gradient (MADNPG) algorithm is proposed in this model, which is the first time the mixed-strategy Nash equilibrium is used for the improvement in the Multi-Agent Deep Deterministic Policy Gradient algorithm traffic signal control strategy to provide the optimal signal phase for each intersection. In addition, the eco-mobility concept is integrated into MARL traffic signal control to reduce pollutant emissions at intersections. Finally, simulation results in synthetic and real-world traffic road networks show that DCNPG-TSC outperforms other state-of-the-art MARL traffic signal control methods in almost all performance metrics, because it can aggregate the information of neighboring agents and optimize the agent's decisions through gaming to find an optimal joint equilibrium strategy for the traffic road network. [ABSTRACT FROM AUTHOR]

Self‐assembling systems in nature display remarkable complexity with assemblies of different sub‐units to generate functional species. Synthetic analogues of such systems are a challenge, often requiring the ability to bias distributions that are under thermodynamic assembly control. Using lantern‐type MOCs (metal‐organic cages) as a prototypical self‐assembling system, herein we explore the role that steric bulk plays in controlling the exchange rate of ligands in paddlewheel‐based assemblies, and thus the stability of cages, in competitive self‐assembling scenarios. The effective lifetime of the lantern‐type MOCs varies over an order of magnitude depending on the steric bulk proximal to the metal nodes with lifetimes of the cages ranging from tens of minutes to several hours. The bulk of the coordinating solvents likewise reduces the rate of ligand exchange, and thus yields longer‐lived species. Understanding this subtle effect has implications for controlling the stability of complex assemblies in competitive environments with implications for guest release and application. [ABSTRACT FROM AUTHOR]

Cariprazine—the only single antipsychotic drug in the market which can handle all symptoms of bipolar I disorder—involves trans-4-substituted cyclohexane-1-amine as a key structural element. In this work, production of trans-4-substituted cyclohexane-1-amines was investigated applying transaminases either in diastereotope selective amination starting from the corresponding ketone or in diastereomer selective deamination of their diasteromeric mixtures. Transaminases were identified enabling the conversion of the cis-diastereomer of four selected cis/trans-amines with different 4-substituents to the corresponding ketones. In the continuous-flow experiments aiming the cis diastereomer conversion to ketone, highly diastereopure trans-amine could be produced (de > 99%). The yield of pure trans-isomers exceeding their original amount in the starting mixture could be explained by dynamic isomerization through ketone intermediates. The single transaminase-catalyzed process—exploiting the cis-diastereomer selectivity of the deamination and thermodynamic control favoring the trans-amines due to reversibility of the steps—allows enhancement of the productivity of industrial cariprazine synthesis. Stereoselective production of trans-4-substituted cyclohexane-1-amines—including a key intermediate in the synthesis of antipsychotic drug cariprazine—remains challenging. Here, the authors develop a process catalyzed by a single transaminase to produce trans-4-substituted cyclohexane-1-amines from the corresponding cis/trans-diastereomeric mixtures via a cis-deamination approach in continuous-flow, to achieve a dynamic cis-to-trans isomerization. [ABSTRACT FROM AUTHOR]

Three non-symmetrical segmental ligand strands L4 can be wrapped around a linear sequence of one Zn2+ and two trivalent lanthanide cations Ln3+ to give quantitatively directional [ZnLn2(L4)3]8+ triple-stranded helicates in the solid state and in solution. NMR speciations in CD3CN show negligible decomplexation at a millimolar concentration and the latter helicate can be thus safely considered as a preorganized C3-symmetrical HHH-[(L43Zn)(LnA)(2−n)(LnB)n]8+ platform in which the thermodynamic properties of (i) lanthanide permutation between the central N9 and the terminal N6O3 binding sites and (ii) exchange processes between homo- and heterolanthanide helicates are easy to access (Ln = La, Eu, Lu). Deviations from statistical distributions could be programmed by exploiting specific site recognition and intermetallic pair interactions. Considering the challenging La3+ : Eu3+ ionic pair, for which the sizes of the two cations differ by only 8%, a remarkable excess (70%) of the heterolanthanide is produced, together with a preference for the formation of the isomer where the largest lanthanum cation lies in the central N9 site ([(La)(Eu)] : [(Eu)(La)] = 9 : 1). This rare design and its rational programming pave the way for the preparation of directional light-converters and/or molecular Q-bits at the (supra)molecular level. [ABSTRACT FROM AUTHOR]

In this paper, a zero-sum differential game is formulated and solved in which a mobile Evader seeks to escape from within a circle at whose origin lies a stationary, turn-constrained Turret. The scenario is a variant of the famous Lady in the Lake game in which the shore-constrained Pursuer has been replaced with the Turret. As in the former, it is assumed that the Turret's maximum angular rate is greater than the linear velocity of the Evader. Since two outcomes are possible, a Game of Kind arises - either the Evader wins by reaching the perimeter of the circle, or the Turret wins by aligning with the latter's position. A barrier surface partitions the state space into two regions corresponding to these two outcomes and a Game of Degree is solved within each region. The solutions to the Games of Degree are comprised of the Value functions (i.e., the equilibrium value of the cost/utility as a function of the state) and the saddle-point equilibrium control policies for the two players. Like the Lady in the Lake game, the equilibrium policy of the Evader is not uniquely defined where it has angular rate advantage over the Turret. Unlike the Lady in the Lake game, the losing region for the Evader is present for all speed ratios, and there is an additional semi-permeable surface separating center- and shore-bound Evader trajectories. The solution depends heavily upon the speed ratio of the agents; in particular, there are two speed ratio regimes with distinctive solution structures. [ABSTRACT FROM AUTHOR]

A limited participation economy models the real-world phenomenon that some economic agents have access to more of the financial market than others. We prove the global existence of a Radner equilibrium with limited participation, where the agents have exponential preferences and derive utility from both running consumption and terminal wealth. Our analysis centers around a coupled quadratic backward stochastic differential equation (BSDE) system whose equations describe the economic agents' stochastic control solutions and equilibrium prices. We define a candidate equilibrium in terms of the BSDE system solution and prove through a verification argument that the candidate is a Radner equilibrium with limited participation. Finally, we prove that the BSDE system has a unique solution in S ∞ × bmo . This work generalises the model of Basak and Cuoco (Rev. Financ. Stud. 11:309–341, 1998) to allow a stock with a general dividend stream and agents with stochastic income streams and exponential preferences. We also provide an explicit example. [ABSTRACT FROM AUTHOR]

As a modern power grid that integrates advanced communication technology, sensor measurement technology, and intelligent control technology, the smart grid has good economy, reliability, and stability. Building a strong smart grid has important strategic significance for developing the national economy and improving Comprehensive National Power. The balance of electricity supply and demand, as a physical feature of the power system, determines the energy matching relationship between generation and consumption. Unreasonable power generation may lead to unmet electricity demand, as well as excess electricity and waste of resources. The energy storage has solved the problem of imbalance between supply and demand in most environments. The energy storage equipment provides a buffer space for electric energy, effectively adjusts the time unevenness of power grid load, realizes peak shaving and valley filling, and reduces the operation cost of the power grid. Taking the aboveground energy storage power station as the research object, the 3-D unsteady model of the small and medium-sized compressed energy storage system was established by using the FLUENT simulation software, and the correctness was verified through experimental methods. The influence of different environmental temperatures, chamber inflation flow rate, the thermodynamic characteristics of the surface condition and working chamber of the and energy storage were studied. The results show that the environmental temperature and expansion flow of oil storage chamber have important effects on its thermodynamic characteristics, while the surface conditions of oil storage chamber wall have little effect on its thermodynamic characteristics. [ABSTRACT FROM AUTHOR]

The main objective of the paper is to analyze how policymakers influence the random oligopolistic market equilibrium problem. To this purpose, random optimal control equilibrium conditions are introduced. Since the random optimal regulatory tax is characterized by a stochastic inverse variational inequality, existence and well-posedness results on such an inequality are proved. At last a numerical example is discussed. [ABSTRACT FROM AUTHOR]

This article presents a comprehensive computational chemistry experiment designed for senior undergraduate students majoring in chemistry. The experiment utilizes quantum chemical calculations to study a typical Diels-Alder reaction found in organic chemistry textbooks. It provides a microscopic physical picture of the reaction process, as well as quantitative information on the thermodynamic and kinetic properties of the reaction, elucidating the fundamental concepts of thermodynamic control and kinetic control in chemical reactions. The objective of this experiment is to cultivate students' basic skills in using computational chemistry methods to investigate chemical problems and deepen their understanding of the relationship between molecular structure and properties. Additionally, the experiment serves as a specific example of dialectical materialism worldview and methodology education for students, emphasizing the importance of recognizing the universality of contradictions and developing the ability to analyze and solve practical chemical problems using a holistic and developmental perspective. [ABSTRACT FROM AUTHOR]

Control of the intermolecular aggregation of organic π‐conjugated molecules as chromophores is crucial for tuning their physical properties such as light absorption/emission, and energy and charge transfer. Lots of advances have been achieved in control of intermolecular aggregation of organic chromophores in solid states where an indefinitely large number of molecules are involved. However, much less understanding has been gained at a mesoscale of aggregates formed by well‐defined organization of a deterministic number of chromophores, which has been realized in natural photosynthetic systems but still remains rare in manmade materials. Here, we report both the kinetic and the thermodynamic control of the supramolecular aggregation of a near‐infrared cyanine dye, PPcy, and its derivatives confined in colloidal nanoparticles stabilized by surfactants in aqueous media. Our results demonstrate that both the aggregation number, the aggregation state and the optical properties of the PPcy chromophores are controllable through optimization of the alkyl and polymer chains tethered from PPcy, the effective concentration of the chromophore inside each particle, and the surfactants utilized to stabilize the colloids in water. [ABSTRACT FROM AUTHOR]

Bearing technology must be supported to attain high-speed and high-efficiency rotating applications. Previous research focused on performance enhancement and optimization, rather than comparative studies among magnetic bearings. This study presents the design and comparison of five magnetic bearing types for high-speed rotating applications: an 8-pole conventional heteropolar, fork-type heteropolar, hybrid fork-type homopolar, and hybrid homopolar magnetic bearings. For quantitative evaluation, mechanical parameters were selected to ensure a uniform coil volume and current supply. The heteropolar magnetic bearings employed 35PN440 steel, whereas the homopolar magnetic bearings utilized pure solid iron. The bias currents were determined based on the respective material properties. The driving circuits were compared by comparing models with and without permanent magnets. The magnetic flux density was assessed at equilibrium and maximum control current, and the loss characteristics were evaluated at 30 000 rpm. Linear control regions were identified by analyzing the relationships between the electromagnetic force, current, and displacement. As a result, the most suitable magnetic bearing for high-speed rotating applications is proposed. [ABSTRACT FROM AUTHOR]

Multiphase flow phenomena are ubiquitous in real-life applications, and the pseudopotential-based lattice Boltzmann multiphase simulation method has gained extensive usage in fields such as fuel cells, energy storage materials, and boiling heat transfer. Over the past two decades, significant improvements have been made to the pseudopotential model. These advancements have greatly enhanced its accuracy in simulating various processes. In this paper, we employ a numerical stability-based unit conversion scheme to ensure an accurate representation of real-world material properties. Additionally, we introduce a more precise non-ideal two-parameter gas state equation Modified Peng-Robinson (MPR) that closely aligns with experimental data, surpassing the commonly used single-parameter Peng-Robinson state equations. Furthermore, we compare the accuracy of the two-state equations for polar and non-polar substances, finding improved accuracy for non-polar substances and a higher degree of fidelity for polar substances when using the MPR equation. We analyze the constant correction coefficients chosen for thermodynamic consistency regulation from the perspectives of vapor-liquid interface thickness and numerical stability, both when held constant and when employing a dynamic correction approach that balances vapor-liquid interface width, numerical stability, and thermodynamic consistency. Finally, we validate to ensure its practical applicability. [ABSTRACT FROM AUTHOR]

In this paper, we aim to optimize the two different social objectives of opinion optimization at equilibrium by controlling some individuals. This is usually called "Stackelberg games", in which a centralized authority is allowed to assign the strategies to a subset of individuals. The Stackelberg strategies of the centralized authority are the algorithms to select a subset of individuals and decide the actions for them in order to palliate the cost caused by the selfish behavior of the uncontrolled individuals. We give some combinatoral algorithms and linear program rounding algorithms as Stackelberg strategies for approximately optimizing the objective of utilitarian social cost (on special cases) and the objective of total expressed opinion (on general directed graphs), respectively. [ABSTRACT FROM AUTHOR]

The chemokine Cxcl1 plays a crucial role in recruiting neutrophils in response to infection. The early events in chemokine-mediated neutrophil extravasation involve a sequence of highly orchestrated steps including rolling, adhesion, arrest, and diapedesis. Cxcl1 function is determined by its properties of reversible monomer–dimer equilibrium and binding to Cxcr2 and glycosaminoglycans. Here, we characterized how these properties orchestrate extravasation using intravital microscopy of the cremaster. Compared to WT Cxcl1, which exists as both a monomer and a dimer, the trapped dimer caused faster rolling, less adhesion, and less extravasation. Whole-mount immunofluorescence of the cremaster and arrest assays confirmed these data. Moreover, the Cxcl1 dimer showed impaired LFA-1–mediated neutrophil arrest that could be attributed to impaired Cxcr2-mediated ERK signaling. We conclude that Cxcl1 monomer–dimer equilibrium and potent Cxcr2 activity of the monomer together coordinate the early events in neutrophil recruitment. [ABSTRACT FROM AUTHOR]

The folding of proteins into intricate three‐dimensional structures to achieve biological functions, such as catalysis, is governed by both kinetic and thermodynamic controls. The quest to design artificial enzymes using minimalist peptides seeks to emulate supramolecular structures existing in a catalytically active state. Drawing inspiration from the nuanced process of protein folding, our study explores the enzyme‐like activity of amphiphilic peptide nanosystems in both equilibrium and non‐equilibrium states, featuring the formation of supramolecular nanofibrils and nanosheets. In contrast to thermodynamically stable nanosheets, the kinetically trapped nanofibrils exhibit dynamic characteristics (e.g. rapid molecular exchange and relatively weak intermolecular packing), resulting in a higher hydrolase‐mimicking activity. We emphasize that a supramolecular microenvironment characterized by an optimal local polarity, microviscosity, and β‐sheet hydrogen bonding is conducive to both substrate binding and ester bond hydrolysis. Our work underscores the pivotal role of both thermodynamic and kinetic control in impacting biomimetic catalysis and sheds a light on the development of artificial enzymes. [ABSTRACT FROM AUTHOR]

Macrocyclic and medium‐sized ring ketones, lactones and lactams can all be made from common acryloyl imide starting materials through divergent, one‐pot cascade ring‐expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII)‐catalysed dihydoxylation, rearrangement through a four‐atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ring expansion. In the dihydroxylation series, three‐ or four‐atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control. [ABSTRACT FROM AUTHOR]

Understanding what controls vertical motion profile shape is fundamental to understanding tropical precipitation patterns. Two controls have been previously studied: the thermodynamic profiles of the environment and the dynamics imposed by sea surface temperature (SST) patterns. To fit these two perspectives together, we focus on two regions with distinctly top and bottom‐heavy vertical motion: The Western Pacific and the Central Eastern Pacific. These regions have roughly the same column‐integrated water, precipitation, and column‐integrated horizontal moisture advection, however the shape in the West is top heavy while the East is bottom heavy. The top‐heaviness angle is introduced to describe this difference. To study thermodynamic controls on vertical motion profile shape, we use weak temperature gradient simulations. We are able to simulate the shape differences between our two regions from the thermodynamics. We then show that the dry static stability and the underlying SST are the most important for the vertical motion shape differences between our two regions. We show that the qualitative shape differences can be explained using a simple entraining plume model. The entraining plume model accepts the temperature and moisture profiles as inputs and outputs the plume's buoyancy, which is directly related to the vertical motion profile shape. We find that increasing the dry static stability leads to bottom‐heaviness. We hypothesize that the SST gradients lead to a cooler equilibrium lower tropospheric temperature compared with no gradient, and this leads to a more conducive thermodynamic environment to bottom‐heaviness. Hence the dynamics control top‐heaviness through influencing the thermodynamic profiles. Plain Language Summary: In the tropics, the vertical velocity is related to the amount of rainfall in a region. There are large differences in the vertical velocity at different heights in different regions, which are important to the rainfall distribution. When upward vertical motion is faster lower in the atmosphere, the vertical motion is bottom‐heavy. When it is faster higher in the atmosphere, the vertical motion is top‐heavy. Some work indicates that these differences come from temperature profile differences and how adjacent regions change the moisture profile. Alternative work suggests that top‐heaviness depends on the distribution of sea surface temperatures (SST). We use a model that predicts vertical motion to reconcile these two. We simulate top and bottom‐heavy vertical motion profiles from just the differences in the thermodynamics of two regions. We then check what parts of the thermodynamics are most important to the vertical motion profile shape by changing one at a time and seeing how vertical motion changes. We find that temperature and SST are the most important factors, with bottom‐heaviness being due to having a lower sea surface and a more stable temperature profile. We hypothesize that the SST distribution affects the temperature profile, which leads to more bottom‐heaviness. Key Points: Climatological bottom‐heavy versus top‐heavy vertical motion profiles in the boxes examined can be simulated from temperature profilesThese thermodynamic controls of vertical motion can be understood using a simple entraining plume modelThe influence of SST gradients on vertical motion can be simulated via effects on the temperature profile [ABSTRACT FROM AUTHOR]

Problem: This study analyzed the contribution of DRB1, DQB1, and DPB1 HLA class II alleles and resulting 3‐locus haplotypes to the overall risk of idiopathic recurrent pregnancy loss (RPL). Method of study: The study participants included 188 Tunisian participants comprising 84 women with established diagnoses of RPL, and 104 matched multiparous females as controls. Genotyping of HLA alleles was done by PCR‐SSP. Results: The allelic frequencies of DPB1, DRB1, and DQB1 were consistent with Hardy‐Weinberg equilibrium among control subjects. Among class II alleles, DRB1*04:01:01 (p =.03), DRB1*08:01:01 (p =.04), and DPB1*01:01:01 (p =.04) were positively associated, whereas DPB1*04:01:01 (p =.012) and DPB1*14:01:01 (p =.006) were negatively associated with risk of RPL. The association of DRB1 and DPB1 alleles with RPL was lost after correction for multiple comparisons. The prevalence of the seven determined DQB1 alleles was not significantly different among case and control groups. Higher prevalence of DRB1*07:01:01∼ DQB1*02:01:01∼DPB1*04:01:01 (0.0417 vs. 0.000; p =.049) coupled with lower prevalence of DRB1*13:01:01∼DQB1*06:01:01∼DPB1*02:01:01 (0.0167 vs. 0.1000; p =.014) haplotypes was noted in women with RPL, thus could be considered as an RPL at‐risk and RPL‐protective haplotype, respectively. Conclusion: The study establishes weak/no contribution of class II alleles and corresponding 3‐locus haplotypes to the altered risk of RPL among Tunisian women and does not confirm previous findings on other Arab‐speaking populations of an HLA association with RPL. [ABSTRACT FROM AUTHOR]

The present study focuses on formulating, developing, and characterizing nanoemulsions (NE) of antifungal drug (Itraconazole) for its better thermodynamic stability. This way it is expected to be better utilized as a carrier for the transdermal delivery of the drug against Candida albicans infection. The solubility of the drug in various oils was investigated, leading to the identification of an oil phase (clove oil) that not only met the desired solubility criteria but also is reported to exhibit an antifungal effect. The subsequent step involves constructing a pseudo-ternary phase diagram and performing associated mathematical calculations to achieve a thermodynamically stable NE, utilizing the titration method at a constant temperature. The 4:1 ratio of Smix (a mixture of polysorbate 80 as a surfactant and polyethylene glycol 400 as a co-surfactant) was selected based on the largest area of transparency. This study aims to give an insight into the importance of pseudo ternary phase diagram construction and its evaluation, as a significant means for the development of NE. Furthermore, the optimized formulation was chosen and evaluated for key parameters, such as droplet size, polydispersity index, zeta potential, and viscosity. The results exhibited promising characteristics in terms of droplet size and zeta potential indicating the stability of the formulation which can be further explored for suitable dermal drug delivery. [ABSTRACT FROM AUTHOR]

Members of the Anelloviridae family dominate the blood virome, emerging early in life. The anellome, representing the variety of anelloviruses within an individual, stabilizes by adulthood. Despite their supposedly commensal nature, elevated anellovirus concentrations under immunosuppressive treatment indicate an equilibrium controlled by immunity. Here, we investigated whether anelloviruses are sensitive to the immune activation that accompanies a secondary infection. As a model, we investigated 19 health care workers (HCWs) with initial SARS-CoV-2 infection, with blood sampling performed pre and post infection every 4 weeks in a 3-month-follow-up during the early 2020 COVID-19 pandemic. A concurrently followed control group (n = 27) remained SARS-CoV-2-negative. Serum anellovirus loads were measured using qPCR. A significant decrease in anellovirus load was found in the first weeks after SARS-CoV-2 infection, whereas anellovirus concentrations remained stable in the uninfected control group. A restored anellovirus load was seen approximately 10 weeks after SARS-CoV-2 infection. For five subjects, an in-time anellome analysis via Illumina sequencing could be performed. In three of the five HCWs, the anellome visibly changed during SARS-CoV-2 infection and returned to baseline in two of these cases. In conclusion, anellovirus loads in blood can temporarily decrease upon an acute secondary infection. [ABSTRACT FROM AUTHOR]

In this study, we use the Whole Atmosphere Community Climate Model, forced by present-day atmospheric composition and coupled to a Slab Ocean Model, to simulate the state of the climate under grand solar minimum forcing scenarios. Idealized experiments prescribe time-invariant solar irradiance reductions that are either uniform (percentage-wise) across the total solar radiation spectrum (TOTC) or spectrally localized in the ultraviolet (UV) band (SCUV). We compare the equilibrium condition of these experiments with the equilibrium condition of a control simulation, forced by perpetual solar maximum conditions. In SCUV, we observe large stratospheric cooling due to ozone reduction. In both the Northern Hemisphere (NH) and the Southern Hemisphere (SH), this is accompanied by a weakening of the polar night jet during the cold season. In TOTC, dynamically induced polar stratospheric cooling is observed in the transition seasons over the NH, without any ozone deficit. The global temperature cooling values, compared with the control climate, are 0.55 ± 0.03 K in TOTC and 0.39 ± 0.03 K in SCUV. The reductions in total meridional heat transport outside of the subtropics are similar in the two experiments, especially in the SH. Despite substantial differences in stratospheric forcing, similarities exist between the two experiments, such as cloudiness; meridional heating transport in the SH; and strong cooling in the NH during wintertime, although this cooling affects two different regions, namely, North America in TOTC and the Euro–Asian continent in SCUV. [ABSTRACT FROM AUTHOR]

The paper presents the research of temperature change in the investigated medium during dynamic expansion of gas (CO2) generated in reservoir conditions, diffusion of carbon dioxide into the displacing uid and their in uence on the displacement process. In-situ gas generation can provide a way to control the non- equilibrium fractal state at the interface under displacement in a porous medium. The change from fractal growth to non-fractal growth can be characterised as a function of density and viscosity ratios. This effect is shown in the increase of hydrocarbon displacement coefficient due to the equalisation of densities of displacing and displaced agents as a consequence of the increase in gas saturation of the uid. [ABSTRACT FROM AUTHOR]

A new promising N‐methyl‐D‐glucamine modified polyvinyl chloride via methyl glycinate linker (PVC‐MG‐NMDG) was designed to extract boron from tourmaline ore from the Sikait area in the South Eastern Desert of Egypt, which assays 10.43% B2O3. Specifications for PVC‐MG‐NMDG composite were executed successfully utilizing sundry approaches, such as FT‐IR, XPS, GC–MS, TGA, BET, EDX, 13C‐NMR, 1H‐NMR, ICP‐OES, and XRD, which assure an acceptable synthesis of PVC‐MG‐NMDG. Optimized factors like pH, agitation time, primary boron concentration, composite dose, co‐ions, eluting agents, and temperature have been improved. At ambient temperature, pH 9, 10 min of agitation, and 0.0138 mol/L boron ions (150 ppm), the PVC‐MG‐NMDG composite has a 25 mg/g maximal uptake. The extraction‐distribution isotherm modeling suggests that the Langmuir model, with a theoretical value of 25.38 mg/g, more closely matches the practical value of 25 mg/g than the Freundlich model. The adsorption kinetics of boron ions by PVC‐MG‐NMDG were predicted with high accuracy using a pseudo‐second order kinetic model, yielding a theoretical retention capacity of 27.93 mg/g. The extraction process was predicted, as shown by thermodynamic calculations, exothermic, spontaneous, and optimal extraction at low temperature; the thermodynamic factors controlling ΔS (−0.04 kJ/mol), ΔH (−13.74 kJ/mol), and ∆G values rise from −1.82 kJ/mol at 298 K to −0.19 kJ/mol at 338 K. Boron ions can be eluted from the overloaded composite by 0.5 M H2SO4 with a 95% efficiency rate. It was established that PVC‐MG‐NMDG composite reveals a worthy separation factor to most co‐ions and gives a good separation power. Boric acid with a boron content of 17.23% and purity of 98.56% can be obtained through alkali fusion with NaOH flux and subsequent adsorption using a PVC‐MG‐NMDG composite. Highlights: A New modified polyvinyl chloride (PVC‐MG‐NMDG) was successfully prepared.The characteristics of new composite were verified via different techniques.The new composite reached its maximum boron absorption of 25 mg/g at 25°C.The extraction as an exothermic, spontaneous process at low temperature.The new composite has been applied to a real sample of Sikait tourmaline ore. [ABSTRACT FROM AUTHOR]

We design a geometric Brownian information engine by considering overdamped Brownian particles inside a two-dimensional monolobal confinement with irregular width along the transport direction. Under such detention, particles experience an effective entropic potential which has a logarithmic form. We employ a feedback control protocol as an outcome of error-free position measurement. The protocol comprises three stages: measurement, feedback, and relaxation. We reposition the center of the confinement to the measurement distance (xp) instantaneously when the position of the trapped particle crosses xp for the first time. Then, the particle is allowed for thermal relaxation. We calculate the extractable work, total information, and unavailable information associated with the feedback control using this equilibrium probability distribution function. We find the exact analytical value of the upper bound of extractable work as ( 5 3 − 2 l n 2) k B T. We introduce a constant force G downward to the transverse coordinate (y). A change in G alters the effective potential of the system and tunes the relative dominance of entropic and energetic contributions in it. The upper bound of the achievable work shows a crossover from ( 5 3 − 2 l n 2) k B T to 1 2 k B T when the system changes from an entropy-dominated regime to an energy-dominated one. Compared to an energetic analog, the loss of information during the relaxation process is higher in the entropy-dominated region, which accredits the less value in achievable work. Theoretical predictions are in good agreement with the Langevin dynamics simulation studies. [ABSTRACT FROM AUTHOR]

Fencing, a sport emphasizing the equilibrium and movement control of participants, forms the focal point of inquiry in the current study. The research endeavors to assess the efficacy of a novel system designed for real-time monitoring of fencers' balance and movement control, augmented by modules incorporating visual feedback and haptic feedback, to ascertain its potential for performance enhancement. Over a span of five weeks, three distinct groups, each comprising ten fencers, underwent specific training: a control group, a cohort utilizing the system with a visual real-time feedback module, and a cohort using the system with a haptic real-time feedback module. Positive outcomes were observed across all three groups, a typical occurrence following a 5-week training regimen. However, noteworthy advancements were particularly discerned in the second group, reaching approximately 15%. In contrast, the improvements in the remaining two groups were below 5%. Statistical analyses employing the Wilcoxon signed-rank test for repeated measures were applied to assess the significance of the results. Significance was solely ascertained for the second group, underscoring the efficacy of the system integrated with visual real-time feedback in yielding statistically noteworthy performance enhancements. [ABSTRACT FROM AUTHOR]

Parabens (or esters of 4-hydroxybenzoic acid) are widely used as effective preservatives in cosmetic and pharmaceutical products. They are manufactured by the esterification of 4-hydroxybenzoic acid with the corresponding alcohol, these reactions taking place under thermodynamic control. It has turned out that the available thermodynamic data are in disarray. Thermochemical properties of a homological series of the alkyl 4-hydroxybenzoates (alkyl = methyl, ethyl, n-propyl and n-butyl) were studied by combustion calorimetry, transpiration, static method and DSC. The following experimental results were derived for alkyl 4-hydroxybenzoates (alkyl, Δ cr g H m o (298.15 K) and Δ f H m o (cr, 298.15 K, in kJ⋅mol−1)): methyl, 107.9 ± 0.4 and − 563.6 ± 1.1; ethyl, 111.5 ± 0.4 and − 597.6 ± 1.2; n-propyl, 115.8 ± 0.5 and − 621.3 ± 1.7; and n-butyl, 122.9 ± 1.5 and − 651.8 ± 1.9. Experimental enthalpies of sublimation, vaporisation, fusion and enthalpies of formation in the crystalline state were derived. The vaporisation enthalpies of alkyl 4-hydroxybenzoates were tested for consistency and analysed for structure–property relationships. The composite quantum chemical methods G3MP2 and G4 were used to calculate the theoretical gas-phase enthalpies of formation in good agreement with the experiment. The data sets for each thermodynamic property were evaluated and recommended for thermochemical calculations. This study provides valuable insights into the thermodynamic properties of parabens and can help in the development of more accurate models to predict their behaviour in various applications. [ABSTRACT FROM AUTHOR]

Catalysts that distinguish between electronically distinct carbon-hydrogen (C–H) bonds without relying on steric effects or directing groups are challenging to design. In this work, cobalt precatalysts supported by N-alkyl-imidazole–substituted pyridine dicarbene (ACNC) pincer ligands are described that enable undirected, remote borylation of fluoroaromatics and expansion of scope to include electron-rich arenes, pyridines, and tri- and difluoromethoxylated arenes, thereby addressing one of the major limitations of first-row transition metal C–H functionalization catalysts. Mechanistic studies established a kinetic preference for C–H bond activation at the meta-position despite cobalt-aryl complexes resulting from ortho C–H activation being thermodynamically preferred. Switchable site selectivity in C–H borylation as a function of the boron reagent was thereby preliminarily demonstrated using a single precatalyst. [ABSTRACT FROM AUTHOR]

To control the plasma shape during a tokamak discharge, it is necessary to calculate the plasma shape in real-time. The rate requirements for the shape calculations are especially high for tokamaks with a small radius, such as Globus-M2 (St. Petersburg, Russia). A real-time magnetic plasma control system for the Globus-M2 tokamak with flux and current distribution identification (FCDI) algorithm for the plasma equilibrium reconstruction in feedback is presented. The control system contains discrete one-dimensional and matrix proportional-integral-derivative controllers synthesized by the matrix inequality method using the plasma LPV model calculated on experimental data, and carries out the coordinated control of the plasma position and shape as well as the compensation for the scattered field of the central solenoid. The FCDI algorithm is improved for the operation in the real-time mode, and makes it possible to reconstruct the plasma shape in 20 µs. The digital control system with a feedback algorithm was simulated on a real-time test bench, consisting of two Speedgoat Performance Real-Time Target Machines (RTTM), and demonstrated the average Task Execution Time (TET) value in 67 µs. [ABSTRACT FROM AUTHOR]