Asymmetric Coupling Research Articles

Origin of the up/down poloidal asymmetric dependence of ELM control in ITER-like RMP configuration in KSTAR

Recent edge-localized modes (ELM) control experiments via resonant magnetic perturbation (RMP) in KSTAR have shown a strong up/down poloidal asymmetric coupling dependence. Specifically, in lower single null (LSN) plasmas at q95 ≳ 5, the lower two-row (middle/bottom) RMPs among ITER-like three-row (top/middle/bottom) in-vessel control coils (IVCC) in KSTAR were more effective in suppressing ELM-crashes than the upper two-row (top/middle) RMPs. In contrast, at q 95 ∼ 4, the upper two-row RMPs turned out to be more effective than the lower counterpart. Since the ITER baseline scenario is planned to operate at q 95 ∼ 3, the understanding of the origin of such up/down poloidal asymmetric coupling dependence, as well as the prediction about ITER-relevant conditions at a lower q 95, would be quite important and potentially impactful to the RMP ELM control in ITER. A linear, resistive, single-fluid MHD code MARS-F has been utilized to address and model the up/down poloidal asymmetric RMP coupling dependence. Specifically, based on two contrasting exemplary discharges with up/down poloidal (i) asymmetric at q 95 ∼ 4 and (ii) symmetric behavior at q 95 ∼ 5, among tens of otherwise similar discharges, a systematic MARS-F modeling has been thoroughly conducted. As a result, the plasma response investigation suggests that the X-point displacement (ξ X), rather than any other figures of merit, would be a directly relevant metric for the up/down poloidal asymmetric coupling in RMP-driven, ELM-crash suppression in KSTAR. Based on a sensitivity study of the edge safety factor in MARS-F modeling, the ξ X variation follows the same quantitative trend as observed in experiments. However, no or little plasma pressure dependence has been found, though ξ X increases with plasma pressure. At the ITER-relevant low q 95 ∼ 3 in a scaled KSTAR equilibrium, such modeling predicts the upper two-row RMPs would be more favorable in suppressing the ELM-crashes than the lower counterpart.

Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Couplings: Just a Change of the Reduction System?

ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp3) carbon centers. Numerous novel approaches have been reported to rapidly construct chiral carbon-carbon bonds through nickel-catalyzed asymmetric couplings between electrophiles and nucleophiles or asymmetric reductive cross-couplings of two different electrophiles. Building upon these advances, our group has been devoted to interrogating dual nickel- and photoredox-catalyzed asymmetric reductive cross-coupling reactions.In our endeavors over the past few years, we have successfully developed several dual Ni-/photoredox-catalyzed asymmetric reductive cross-coupling reactions involving organohalides. While some probably think that this system is just a change of the reduction system from traditional metal reductants to a photocatalysis system, a question that we also pondered at the beginning of our studies, both the achievable reaction types and mechanisms suggest a different conclusion: that this dual catalysis system has its own advantages in the chiral carbon-carbon bond formation. Even in certain asymmetric reactions where the photocatalysis regime functions only as a reducing system, the robust reducing capability of photocatalysts can effectively accelerate the regeneration of low-valent nickel species, thus expanding the selectable scope of chiral ligands. More importantly, in many transformations, besides reducing nickel catalysts, the photocatalysis system can also undertake the responsibility of alkyl radical formation, thereby establishing two coordinated, yet independent catalytic cycles. This catalytic mode has been proven to play a crucial role in achieving diverse asymmetric coupling reactions with great challenges.In this Account, we elucidate our understanding of this system based on our experience and findings. In the Introduction, we provide an overview of the main distinctions between this system and traditional Ni-catalyzed asymmetric reductive cross-couplings with metal reductants and the potential opportunities arising from these differences. Subsequently, we outline various chiral carbon-carbon bond-forming types obtained by this dual Ni/photoredox catalysis system and their mechanisms. In terms of chiral C(sp3)-C(sp2) bond formation, extensive discussion focuses on the asymmetric arylations of α-chloroboronates, α-trifluoromethyl alkyl bromides, α-bromophosphonates, and so on. In the realm of chiral C(sp3)-C(sp) bond formation, asymmetric alkynylations of α-bromophosphonates and α-trifluoromethyl alkyl bromides have been presented herein. Regarding C(sp3)-C(sp3) bond formation, we take the asymmetric alkylation of α-chloroboronates as a compelling example to illustrate the great efficiency of this dual catalysis system. This summary would enable a better grasp of the advantages of this dual catalysis system and clarify how the photocatalysis regime facilitates enantioselective transformations. We anticipate that this Account will offer valuable insights and contribute to the development of new methodologies in this field.

Chiral α-Aminophosphonates as Ligands in Copper-Catalyzed Asymmetric Oxidative Coupling of 2-Naphthols.

Chiral α-aminophosphonates with adjacent carbon and phosphonate stereogenic centers have been employed as ligands in the copper-catalyzed oxidative coupling of 2-naphthols, resulting in the production of chiral BINOLs in favorable yields and moderate to good enantiomeric excess. This represents the first application of chiral P-based ligands to enable such a transformation. The synthesis of these chiral α-aminophosphonate ligands offers a significant advantage over approaches that typically necessitate elaborate synthetic processes for chiral ligand production.

Non-perturbative dynamics of flat-band systems with correlated disorder

Abstract We develop a numerical method for the time evolution of Gaussian wave packets on flat-band lattices in the presence of correlated disorder. To achieve this, we introduce a method to generate random on-site energies with prescribed correlations. We verify this method with a one-dimensional (1D) cross-stitch model, and find good agreement with analytical results obtained from the disorderdressed evolution equations. This allows us to reproduce previous findings, that disorder can mobilize 1D flat-band states which would otherwise remain localized. As explained by the corresponding disorder-dressed evolution equations, such mobilization requires an asymmetric disorder-induced coupling to dispersive bands, a condition that is generically not fulfilled when the flat-band is resonant with the dispersive bands at a Dirac point-like crossing. We exemplify this with the 1D Lieb lattice. While analytical expressions are not available for the two-dimensional (2D) system due to its complexity, we extend the numerical method to the 2D α-T 3 model, and find that the initial flat-band wave packet preserves its localization when α = 0, regardless of disorder and intersections. However, when α ≠ 0, the wave packet shifts in real space. We interpret this as a Berry phase controlled, disorder-induced wave-packet mobilization. In addition, we present density functional theory calculations of candidate materials, specifically Hg1-xCdxTe. The flat-band emerges near the Γ point (k =0) in the Brillouin zone.

A U-band cascaded quadruplet quartz glass SIW filter based on double row vias coupling window

A U-band Substrate Integrated Waveguide (SIW) Cascaded Quadruplet (CQ) filter is designed based on low-cost quartz glass planar integrated circuits process with limited depth-to-diameter ratio and via spacing, which challenge the control accuracy of coupling coefficients. To address this issue, a double-row vias coupling structure control strategy is proposed to enhance the precision of coupling coefficient control. Cascaded quadruplet topology based on the proposed coupling structure with asymmetric coupling window is designed to improve the passband selectivity and harmonic suppression. The filter exhibits −3dB relative bandwidth of 4.6 % (1.94 GHz) at a central frequency of 42.2 GHz, insertion loss of 4.2 dB and rectangular coefficient (−20 dB BW/−3dB BW) of 1.47.

From Liouville to Landauer: Electron transport and the bath assumptions made along the way

A generalized quantum master equation approach is introduced to describe electron transfer in molecular junctions that spans both the off-resonant (tunneling) and resonant (hopping) transport regimes. The model builds on prior insights from scattering theory but is not limited to a certain parameter range with regard to the strength of the molecule–electrode coupling. The framework is used to study the simplest case of energy and charge transfer between the molecule and the electrodes for a single site noninteracting Anderson model in the limit of symmetric and asymmetric coupling between the molecule and the electrodes. In the limit of elastic transport, the Landauer result is recovered for the current by invoking a single active electron Ansatz and a binary collision approximation for the memory kernel. Inelastic transport is considered by allowing the excitation of electron–hole pairs in the electrodes in tandem with charge transport. In the case of low bias voltages where the Fermi levels of the electrodes remain below the molecular state, it is shown that the current arises from tunneling and the molecule remains neutral. However, once the threshold is reached for aligning the fermi level of one electrode with the molecular orbital, a small amount of charge transfer occurs with a negligible amount of hopping current. While inelasticity in the current has a minimal impact on the shape of the current–voltage curve in the case of symmetric electrode coupling, the results for a slight asymmetry in coupling demonstrate complete charge transfer and a significant drop in current. These results provide encouraging confirmation that the framework can describe charge transport across a wide range of electrode–molecule coupling and provide a unique perspective for developing new master equation treatments for energy and charge transport in molecular junctions. An extension of this work to account for inelastic scattering from electron–vibrational coupling at the molecule is straightforward and will be the subject of subsequent work.

Palladium-catalyzed asymmetric carbene coupling en route to inherently chiral heptagon-containing polyarenes.

Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial. However, originate chirality from the distorted structure around heptagon-containing polyarenes is largely overlooked, the enantioselective construction of all-carbon heptagon-containing polyarenes remains a challenge. Herein, we present a highly enantioselective synthesis route for fabricating all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross-coupling of benzyl bromides and N-arylsulfonylhydrazones. A wide range of nonplanar, saddle-shaped tribenzocycloheptene derivatives are efficiently prepared in high yields with excellent enantioselectivities using this approach. In addition, stereochemical stability experiments show that these saddle-shaped tribenzocycloheptene derivatives have high inversion barriers.

Stereoretentive enantioconvergent reactions

Enantioconvergent reactions are pre-eminent in contemporary asymmetric synthesis as they convert both enantiomers of a racemic starting material into a single enantioenriched product, thus avoiding the maximum 50% yield associated with resolutions. All currently known enantioconvergent processes necessitate the loss or partial loss of the racemic substrate’s stereochemical information, thus limiting the potential substrate scope to molecules that contain labile stereogenic units. Here we present an alternative approach to enantioconvergent reactions that can proceed with full retention of the racemic substrate’s configuration. This uniquely stereo-economic approach is possible if the two enantiomers of a racemic starting material are joined together to form one enantiomer of a non-meso product. Experimental validation of this concept is presented using two distinct strategies: (1) a direct asymmetric coupling approach, and (2) a multicomponent approach, which exhibits statistical amplification of enantiopurity. Thus, the established dogma that enantioconvergent reactions require substrates that contain labile stereogenic units is shown to be incorrect.

Non-Hermitian Moiré Valley Filter.

A valley filter capable of generating a valley-polarized current is a crucial element in valleytronics, yet its implementation remains challenging. Here, we propose a valley filter made of a graphene bilayer which exhibits a 1D moiré pattern in the overlapping region of the two layers controlled by heterostrain. In the presence of a lattice modulation between layers, electrons propagating in one layer can have valley-dependent dissipation due to valley asymmetric interlayer coupling, thus giving rise to a valley-polarized current. Such a process can be described by an effective non-Hermitian theory, in which the valley filter is driven by a valley-resolved non-Hermitian skin effect. Nearly 100% valley polarization can be achieved within a wide parameter range and the functionality of the valley filter is electrically tunable. The non-Hermitian topological scenario of the valley filter ensures high tolerance against imperfections such as disorder and edge defects. Our work opens a new route for efficient and robust valley filters while significantly relaxing the stringent implementation requirements.

From Ground-State to Excited-State Activation Modes: Flavin-Dependent "Ene"-Reductases Catalyzed Non-natural Radical Reactions.

Enzymes are desired catalysts for chemical synthesis, because they can be engineered to provide unparalleled levels of efficiency and selectivity. Yet, despite the astonishing array of reactions catalyzed by natural enzymes, many reactivity patterns found in small molecule catalysts have no counterpart in the living world. With a detailed understanding of the mechanisms utilized by small molecule catalysts, we can identify existing enzymes with the potential to catalyze reactions that are currently unknown in nature. Over the past eight years, our group has demonstrated that flavin-dependent "ene"-reductases (EREDs) can catalyze various radical-mediated reactions with unparalleled levels of selectivity, solving long-standing challenges in asymmetric synthesis.This Account presents our development of EREDs as general catalysts for asymmetric radical reactions. While we have developed multiple mechanisms for generating radicals within protein active sites, this account will focus on examples where flavin mononucleotide hydroquinone (FMNhq) serves as an electron transfer radical initiator. While our initial mechanistic hypotheses were rooted in electron-transfer-based radical initiation mechanisms commonly used by synthetic organic chemists, we ultimately uncovered emergent mechanisms of radical initiation that are unique to the protein active site. We will begin by covering intramolecular reactions and discussing how the protein activates the substrate for reduction by altering the redox-potential of alkyl halides and templating the charge transfer complex between the substrate and flavin-cofactor. Protein engineering has been used to modify the fundamental photophysics of these reactions, highlighting the opportunity to tune these systems further by using directed evolution. This section highlights the range of coupling partners and radical termination mechanisms available to intramolecular reactions.The next section will focus on intermolecular reactions and the role of enzyme-templated ternary charge transfer complexes among the cofactor, alkyl halide, and coupling partner in gating electron transfer to ensure that it only occurs when both substrates are bound within the protein active site. We will highlight the synthetic applications available to this activation mode, including olefin hydroalkylation, carbohydroxylation, arene functionalization, and nitronate alkylation. This section also discusses how the protein can favor mechanistic steps that are elusive in solution for the asymmetric reductive coupling of alkyl halides and nitroalkanes. We are aware of several recent EREDs-catalyzed photoenzymatic transformations from other groups. We will discuss results from these papers in the context of understanding the nuances of radical initiation with various substrates.These biocatalytic asymmetric radical reactions often complement the state-of-the-art small-molecule-catalyzed reactions, making EREDs a valuable addition to a chemist's synthetic toolbox. Moreover, the underlying principles studied with these systems are potentially operative with other cofactor-dependent proteins, opening the door to different types of enzyme-catalyzed radical reactions. We anticipate that this Account will serve as a guide and inspire broad interest in repurposing existing enzymes to access new transformations.

Effects of asymmetric coupling and boundary on the dynamic behaviors of a random nearest neighbor coupled system

Effects of asymmetric coupling and boundary on the dynamic behaviors of a random nearest neighbor coupled system

Asymmetric Hydrogenative Coupling of Indoles with Unsaturated Ketones Enabled by Copper/Ruthenium Relay Catalysis

AbstractA relay catalytic system is developed for the asymmetric hydrogenative coupling of indoles with α,β-unsaturated ketones, affording enantioenriched chiral γ-indole alcohols with broad substrate scope and excellent enantioselectivities (32 examples, up to >99% ee). Mechanistic studies suggest that the relay catalytic system consists of copper-catalyzed alkylation and ruthenium-catalyzed asymmetric hydrogenation.

Final epidemic size of a two-community SIR model with asymmetric coupling.

Communities are commonly not isolated but interact asymmetrically with each other, allowing the propagation of infectious diseases within the same community and between different communities.To reveal the impact of asymmetrical interactions and contact heterogeneity on disease transmission, we formulate a two-community SIR epidemic model, in which each community has its contact structure while communication between communities occurs through temporary commuters. We derive an explicit formula for the basic reproduction number , give an implicit equation for the final epidemic size z, and analyze the relationship between them. Unlike the typical positive correlation between and z in the classic SIR model, we find a negatively correlated relationship between counterparts of our model deviating from homogeneous populations. Moreover, we investigate the impact of asymmetric coupling mechanisms on . The results suggest that, in scenarios with restricted movement of susceptible individuals within a community, does not follow a simple monotonous relationship, indicating that an unbending decrease in the movement of susceptible individuals may increase . We further demonstrate that network contacts within communities have a greater effect on than casual contacts between communities. Finally, we develop an epidemic model without restriction on the movement of susceptible individuals, and the numerical simulations suggest that the increase in human flow between communities leads to a larger .

Clustering Component Synchronization of Nonlinearly Coupled Complex Networks via Pinning Control

In this paper, the problem of clustering component synchronization of nonlinearly coupled complex networks with nonidentical nodes and asymmetric couplings is investigated. A pinning control strategy is designed to achieve the clustering component synchronization with respect to the specified components. Based on matrix analysis and stability theory, clustering component synchronization criteria are established. Two numerical simulations are also provided to show the effectiveness of the theoretical results.

Chalcogenide TE-Pass Waveguide Polarizer and Polarization Beam Splitter Base on Asymmetric Directional Coupling

Chalcogenide TE-Pass Waveguide Polarizer and Polarization Beam Splitter Base on Asymmetric Directional Coupling

All-fiberized sorter for nondestructively splitting the orbital angular momentum modes

Orbital angular momentum (OAM) mode sorter is crucial for various OAM (de)multiplexing applications. However, it is challenging to sort the OAM mode without destroying its helical phase. Here, an all-fiber non-destructive OAM mode sorter is proposed for splitting the high purity (>90%) OAM beam with specific topological charge, polarization state and wavelength. By controlling the asymmetrical microfiber coupling region, only the specific OAM mode satisfies the phase matching condition. The all-fibered OAM sorter is optimized to splitting the third order OAM mode with the maximum coupling efficiency 91.02% and the purity 94.71%. The Multiple modes sorter can be realized through the multistage cascaded structure. The proposed all-fiber OAM sort will be a prospective component to expand the OAM beam fiber system.

Heat currents in a two channel Marcus molecular junction

We present a theoretical analysis of heat transfer in a single-molecule junction where the bridge is simulated by a three-state model with two possible transport channels for electrons. Interactions between electrons on the bridge and phonons in the nuclear environment are supposed to be strong, so that Marcus-type processes predominate in the electron transport. It is shown that asymmetric coupling between the bridge states and electrodes and/or asymmetric distribution of the bias voltage over the system together with characteristics of the environmental reorganization and relaxation processes accompanying electron transport may result in qualitative changes in the behavior of steady state heat currents. These changes are controlled by the same mechanism as NDR effect manifested in the charge current under similar conditions. Also, we analyze the energy balance in single-molecule junctions assuming that energy levels of the molecule are slowly driven by an external force.

Nickel-Catalyzed Asymmetric Borylative Coupling of 1,3-Dienes with Aldehydes

AbstractThe nickel-catalyzed borylative coupling of aldehydes and 1,3-dienes with diboron reagents offers an efficient method for synthesizing valuable homoallylic alcohols from easily accessible starting materials. However, achieving enantioselectivity in this reaction has been a significant challenge. We discuss our recent report on the first example of a nickel-catalyzed enantioselective borylative coupling of aldehydes with 1,3-dienes, employing a chiral spiro-phosphine–oxazoline ligand. Notably, by utilizing (E)-1,3-dienes or (Z)-1,3-dienes, we can reverse the diastereoselectivity, yielding either anti- or syn-products, respectively.

Observation of non-Hermitian skin effect in thermal diffusion

The paradigm shift of Hermitian systems into the non-Hermitian regime profoundly modifies inherent property of the topological systems, leading to various unprecedented effects such as the non-Hermitian skin effect (NHSE). In the past decade, the NHSE has been demonstrated in quantum, optical and acoustic systems. Beside those wave systems, the NHSE in diffusive systems has not yet been observed, despite recent abundant advances in the study of topological thermal diffusion. In this work, we design a thermal diffusion lattice based on a modified Su-Schrieffer-Heeger model and demonstrate the diffusive NHSE. In the proposed model, the asymmetric temperature field coupling inside each unit cell can be judiciously realized by appropriate configurations of structural parameters. We find that the temperature fields trend to concentrate toward the target boundary which is robust against initial excitation conditions. We thus experimentally demonstrated the NHSE in thermal diffusion and verified its robustness against various defects. Our work provides a platform for exploration of non-Hermitian physics in the diffusive systems, which has important applications in efficient heat collection, highly sensitive thermal sensing and others.

Nonuniformly twisted states and traveling chimeras in a system of nonlocally coupled identical phase oscillators

We explore the model of a population of nonlocally coupled identical phase oscillators on a ring (Abrams and Strogatz 2004 Phys. Rev. Lett. 93 174102) and describe traveling patterns. In the continuous in space formulation, we find families of traveling wave solutions for left-right symmetric and asymmetric couplings. Only the simplest of these waves are stable, which is confirmed by numerical simulations for a finite population. We demonstrate that for asymmetric coupling, a weakly turbulent traveling chimera regime is established, both from an initial standing chimera or an unstable traveling wave profile. The weakly turbulent chimera is a macroscopically chaotic state, with a well-defined synchronous domain and partial coherence in the disordered domain. We characterize it through the correlation function and the Lyapunov spectrum.