Inverse Mechanism Research Articles

Computational Study on the Photo‐Induced Antibiotic Activity of an Azoquinolone with Promising Applications in Photopharmacology

Azocompounds are among the most important group of molecular photoswitches due to their multiple applications in various scientific areas. We studied the thermal and photochemical reactions of an azocompound with photo‐induced antibiotic properties using ab‐initio calculations based on Kohn‐Shan, Spin‐Flip and time‐dependent Density Functional Theory. Our primary goal is to understand the absorption spectra and isomerization pathways governing the molecule’s light‐controlled antibiotic activity. The nuclear ensemble approach was used for the most stable trans and cis isomers, and the absorption spectra were calculated and fitted to predict the cis/trans isomer ratios in the carboxylate form, using experimental measurements as a reference. We stablished that rotation is involved in the most favorable cis⇄cis and trans⇄trans thermal isomerization pathways, while the inversion mechanism is the most likely for cis⇄trans isomerizations. We found that the photochemical trans→cis isomerization follows a consistent mechanism across all trans isomers, involving excitation to S2(ππ*), an in‐plane ultrafast internal conversion to S1(nπ*), followed by rotation of the azo bond up to a twisted S1(nπ*)/S0 conical intersection. We used a custom approach to evaluate the most favorable decay pathway from the S1(nπ*)/S0 conical intersections to trans and cis photoproducts using static calculations.

Decays Z → eaeb in a 3-3-1 model with neutral leptons

Abstract We investigate the 3-3-1 model with neutral leptons, a specific extension of the 3-3-1 models that includes heavy neutral leptons, which are sufficient to accommodate the neutrino oscillation data via the inverse seesaw mechanism. We will point out that this model can simultaneously explain the lepton flavor violating decays of the Z and Standard Model-like Higgs bosons into different charged leptons Z, h → e a e b , as well as the charged lepton decays e b → e a γ, in agreement with the recent experimental data. In addition, the numerical results show strong correlations among the decay rates of the Z and h bosons predicted by this model. Specifically, some of these rates are nearly linearly dependent on each other. Consequently, the decay channels can be theoretically determined if one of them is detected in experiments.

Light-dependent switching between two flagellar beating states selects versatile phototaxis strategies in microswimmers

Microorganisms have evolved sophisticated sensor-actuator circuits to perform taxis in response to various environmental stimuli. How any given circuit can select between different taxis responses in noisy vs. saturated stimuli conditions is unclear. Here, we investigate how Euglena gracilis can select between positive vs. negative phototaxis under low vs. high light intensities, respectively. We propose three general selection mechanisms for phototactic microswimmers, and biophysical modeling demonstrates their effectiveness. Perturbation and high-speed imaging experiments show that of these three mechanisms, the "photoresponse inversion mechanism" is implemented in E. gracilis: a fast, light-intensity-dependent switching between two flagellar beat states responsible for swimming and turning causes positive vs. negative phototaxis at low vs. high light intensity via run-and-tumble vs. helical klinotaxis strategies, respectively. This coordinated beat-switching mechanism then also accounts for a larger set of previously reported E. gracilis behaviors; furthermore, it suggests key design principles for other natural as well as synthetic microswimmers.

Resonant conversion of gravitational waves in neutron star magnetospheres

High-frequency gravitational waves are the subject of rapidly growing interest in the theoretical and experimental community. In this work we calculate the resonant conversion of gravitational waves into photons in the magnetospheres of neutron stars via the inverse Gertsenshtein mechanism. The resonance occurs in regions where the vacuum birefringence effects cancel the classical plasma contribution to the photon dispersion relation, leading to a massless photon in the medium which becomes kinematically matched to the graviton. We set limits on the amplitude of a possible stochastic background of gravitational waves using X-ray and IR flux measurements of neutron stars. Using Chandra (2–8 keV) and NuSTAR (3–79 keV) observations of RX J1856.6-3754, we set strain limits hclim≃10−26–10−24 in the frequency range 5×1017 Hz≲f≲2×1019 Hz. Our limits are many orders of magnitude stronger than existing constraints from individual neutron stars at the same frequencies. We also use recent JWST observations of the Magnetar 4U 0142+61 in the range 2.7×1013 Hz≲f≲5.9×1013 Hz, setting a limit hclim≃5×10−19. These constraints are in complementary frequency ranges to laboratory searches with CAST, OSQAR and ALPS II. We expect these limits to be improved both in reach and breadth with a more exhaustive use of telescope data across the full spectrum of frequencies and targets. Published by the American Physical Society 2024

Mechanism of Subsurface Deformation Transmission and Geomechanical Response Inversion in Carbon Capture and Storage Project: Integrating Small Baseline Subset-Interferometric Synthetic Aperture Radar, Mechanical Experiments, and Numerical Simulation

Summary In the context of carbon capture and storage (CCS) engineering, ensuring the stability of the caprock is paramount to mitigating CO2 leakage, thus constituting a pivotal engineering challenge in CO2 geological sequestration. With the injection of CO2, pore pressure accumulates within the reservoir, bringing forth risks including diminished effective stress within the formation, surface deformation, occurrence of microseismic events, and potential caprock failure. Therefore, it is necessary to explore the geomechanical issues in CCS projects. This study focuses on the Daqingzijing in the Jilin Oilfield as the study area, utilizing the small baseline subset (SBAS)-interferometric synthetic aperture radar (InSAR) method to conduct a deformation time-series analysis in the well group area under injection and production conditions. The results reveal variations in deformation sensitivity among the sites, with surface displacements correlated to fluid injection and production, demonstrating temporal delays. At the H79 North block, the time effect is relatively minimal, with rapid propagation of formation deformation. Surface displacement in the H46 block appeared 4 months later than behind cumulative fluid volume changes. By conducting triaxial creep tests on shallow mudstone samples from the Songliao Basin under various triaxial stress states, a constitutive creep equation for caprock rocks was obtained. The numerical models of elastic and creep constitutive equations were established. The results show that the creep model exhibits superior accuracy by comparing with InSAR monitoring data (the root mean square error values of elastic and creep constitutive geomechanical models were 6.7 mm and 1.7 mm, respectively). Additionally, based on the experimental and simulation results, this study explores the transfer mechanisms of formation deformation and the inverse relationship between deformation and pore pressure. This study provides theoretical support for the geomechanical safety analysis in corresponding CCS projects.

Inverse transfer mechanisms in multinucleon transfer reactions

Inverse transfer mechanisms in multinucleon transfer reactions

Bonding Interactions Can Drive Topological Phase Transitions in a Zintl Antiferromagnetic Insulator

AbstractWhile ∼30% of materials are reported to be topological, topological insulators are rare. Magnetic topological insulators (MTI) are even harder to find. Identifying crystallographic features that can host the coexistence of a topological insulating phase with magnetic order is vital for finding intrinsic MTI materials. Thus far, most materials that are investigated for the determination of an MTI are some combination of known topological insulators with a magnetic ion such as MnBi2Te4. Motivated by the recent success of EuIn2As2, the role of chemical pressure on topologically trivial insulator is investigated, Eu5In2Sb6 via Ga substitution. Eu5Ga2Sb6 is predicted to be topological but is synthetically difficult to stabilize. The intermediate compositions between Eu5In2Sb6 and Eu5Ga2Sb6 are observed through theoretical works to explore a topological phase transition and band inversion mechanism. The band inversion mechanism is attributed to changes in Eu–Sb hybridization as Ga is substituted for In due to chemical pressure. Eu5In4/3Ga2/3Sb6 is also synthesized, the highest Ga concentration in Eu5In2‐xGaxSb6, and report the thermodynamic, magnetic, transport, and Hall properties. Overall, the work paints a picture of a possible MTI via band engineering and explains why Eu‐based Zintl compounds are suitable for the co‐existence of magnetism and topology.

Heavy neutrino as dark matter in a neutrinophilic U(1) model

We study the prospect of heavy singlet neutrinos as a dark matter (DM) candidate within a neutrinophilic U(1) model, where the Standard Model (SM) is extended with a U(1) gauge symmetry, and neutrino mass and oscillation parameters are explained through an inverse see-saw mechanism. The lightest of the heavy neutrinos plays the role of the DM, while the newly introduced scalars and the extra gauge boson Z′\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$Z'$$\\end{document} act as mediators between the dark sector and the SM sector. We show the range of model parameters where this DM candidate can be accommodated in the Weakly Interacting Massive Particle (WIMP) or Feebly Interacting Massive Particle (FIMP) scenario. The observed DM relic density (DMRD) is achieved via the new gauge boson and singlet scalar portals in the WIMP scenario, whereas within the FIMP scenario, these two particles assume a distinct yet pivotal role in generating the observed DMRD.

Phenomenology of 3-3-1 models with a radiative inverse seesaw mechanism

We propose two models based on the SU(3)C×SU(3)L×U(1)X gauge symmetry, each incorporating distinct inverse seesaw mechanisms for generating neutrino masses at the radiative level. Therefore, neutrino masses are suppressed by the radiative nature of the mass generation mechanism, which occurs after the spontaneous breaking of the global lepton number symmetry. Both scenarios discussed here are characterized by the presence of vectorlike charged leptons, which are involved in generating the masses of the Standard Model charged leptons. These additional vectorlike fermions also contribute to the anomalous magnetic moments of the muon. We perform a detailed analysis of the scalar sectors, show that these models can successfully accommodate the observed baryon asymmetry through resonant leptogenesis, and compute the rates of charged lepton flavor-violating decays, such as μ→eγ. We discuss the constraints of the model arising from these processes and those associated with the nonunitarity of the lepton mixing matrix. Published by the American Physical Society 2024

(g−2)e,μ anomalies and decays h, Z→ebea in 3-3-1 models with inverse seesaw neutrinos

The lepton flavor violating (LFV) decays h,Z→ebea, and eb→eaγ are discussed in a class of general 3-3-1 models adding heavy neutral leptons and singly charged Higgs bosons to accommodate experimental data of neutrino oscillation and (g−2)ea anomalies of charged leptons through the inverse seesaw mechanism. We show that the models with the minimal number of inverse seesaw neutrinos cannot reach the 1σ range of (g−2)μ data due to the experimental upper bounds on decay rates of (τ→μγ) and (μ→eγ). Features of LFV decays are presented in detail, focusing on the regions of parameter space satisfying the 1σ ranges of (g−2)e,μ data. Published by the American Physical Society 2024

Bipolar Membrane Capacitive Deionization for the Selective Capture of Lithium Ions from Brines and Conversion to Lithium Hydroxide

Meeting the increasing demand for lithium in vehicle electrification and renewable energy storage requires innovations in lithium-ion (Li+) separations. Traditional solar evaporation methods for lithium recovery are slow and consume tremendous volumes of water and secondary chemicals (acids and bases). This study introduces a bipolar membrane capacitive deionization (BPM-CDI) unit for direct lithium extraction and LiOH production without the external addition of acids and bases. Utilizing de-lithiated lithium-iron-phosphate (LFP) coated carbon cloth electrodes, the BPM-CDI unit demonstrates selective Li+ capture over competing ions. Molecular dynamics simulations and H-cell experiments elucidate pH inversion mechanisms during Li+ release, yielding LiOH. The BPM-CDI platform efficiently removes Li+ from synthetic brines featuring 8x higher Mg2+ concentrations (200 ppm Mg2+) and 26x higher Na+ concentrations (682 ppm Na+), achieving a LiOH concentration of 124 ppm (36 ppm Li+) after 8 cycles of recirculation. Post-mortem analysis confirms electrode integrity and stability. BPM-CDI integrated with selective electrodes is a promising electrochemical separation-reactor platform for lithium recovery while producing LiOH.

Thermoplastic Elastomers and Their Physical Gels Electrospun into Tunable Microfibrous Nonwoven Mats: Structure Formation and Property Enhancement

AbstractThermoplastic elastomers (TPEs) based on styrenic block copolymers constitute excellent examples of self‐networking macromolecules that are employed in a wide range of contemporary technologies as molded parts. In such applications, these TPEs exist as dense (nonporous) films or other shapes. Here, it is first demonstrated that a series of commercial TPEs possessing comparable compositions can be electrospun from solution to form microfibers that are arranged into nonwoven mats that are breathable. An important consideration for microfiber formation is the copolymer molecular weight, which regulates i) the viscosity of the parent solution prior to electrospinning, ii) the ability of these copolymers to self‐assemble during electrospinning, iii) the microfiber morphology, and iv) the mechanical properties of the resultant microfibers. The addition of a midblock‐selective aliphatic oil to these TPEs yields thermoplastic elastomer gels (TPEGs), wherein the copolymer morphology and mechanical properties become highly composition‐tunable. Electrospinning TPEGs from a binary oil+solvent solution introduces a micelle inversion mechanism that begins with an oil‐rich micellar core and ends with a styrene‐rich micellar core, required for network stabilization, as the solvent dries during microfiber solidification. This work has implications for the production of controllably low‐modulus microfibrous materials possessing modestly improved toughness but exceptional extensibility and enhanced optical transparency.

Synthesis of Polycyclic Olefinic Monomers from Norbornadiene for Inverse Vulcanization: Structural and Mechanistic Consequences.

The preparation of high-sulfur content organosulfur polymers has generated considerable interest as an emerging area in polymer science that has been driven by advances in the inverse vulcanization polymerization of elemental sulfur with organic comonomers. While numerous new inverse vulcanized polysulfides have been made over the past decade, insights into the mechanism of inverse vulcanization and structural characterization of the high-sulfur-content copolymers remain limited in scope. Furthermore, the exploration of new molecular architectures for organic comonomer synthesis remains an important frontier to enhance the properties of these new polymeric materials. In the current report, the first detailed study on the synthesis and inverse vulcanization of polycyclic rigid comonomers derived from norbornadiene was conducted, affording a quantitative assessment of polymer microstructure for these organopolysulfides and insights into the inverse vulcanization polymerization mechanism for this class of monomers. In particular, a stereoselective synthesis of the endo-exo norbornadiene cyclopentadiene adduct (Stillene) was achieved, which enabled direct comparison with the known exo-exo norbornadiene dimer (NBD2) previously used for inverse vulcanization. Reductive degradation of these sulfur copolymers and detailed structural analysis of the recovered sulfurated organic fragments revealed that remarkable exo-stereospecificity was achieved in the inverse vulcanization of elemental sulfur with both these polycyclic dienyl comonomers, which correlated to the robust thermomechanical properties associated with organopolysulfides made from NBD2 previously. Melt processing and molding of these sulfur copolymers were conducted to fabricate free-standing plastic lenses for long-wave infrared thermal imaging.

Seismotectonic study in the Sierras de Velasco, Ambato, and Ancasti, Eastern Sierras Pampeanas of Argentina

In this work, we study the seismic activity and tectonic regime in the region of the Sierras de Velasco, Ambato and Ancasti, belonging to the Sierras Pampeanas. These areas exhibit notable seismic activity, posing a considerable risk for populations in the region. We relocated the most important seismic events of the last twenty years and obtained their focal mechanisms. We reviewed the field evidence of neotectonic deformation, and measured kinematic indicators on Quaternary faults interpreted as seismogenic. Based on this information, we discuss the link between seismogenic sources and the most relevant morphostructural features. Our findings reveal that the seismicity is dominated by reverse focal mechanisms, exhibiting nodal planes with strikes that align with the main structures. This indicates that the main range-bounding faults are the most important seismogenic structures in the area. Some events have strike-slip movements, likely associated with the reactivation of basement fabrics. Additionally, in the Pirquitas area, we observed a normal focal mechanism, oriented perpendicular to the main structures. Our results contribute to a better understanding of current deformation dynamics and of seismic hazard in the region, and underscore the need for more detailed studies.

"On-the-Fly" Nonadiabatic Dynamics Simulation on the Ultrafast Photoisomerization of a Molecular Photoswitch Iminothioindoxyl: An RMS-CASPT2 Investigation.

Iminothioindoxyl (ITI) is a new class of photoswitch that exhibits many excellent properties including well-separated absorption bands in the visible region for both conformers, ultrafast Z to E photoisomerization as well as the millisecond reisomerization at room temperature for the E isomer, and switchable ability in both solids and various solvents. However, the underlying ultrafast photoisomerization mechanism at the atomic level remains unclear. In this work, we have employed a combination of high-level RMS-CASPT2-based static electronic structure calculations and nonadiabatic dynamics simulations to investigate the ultrafast photoisomerization dynamics of ITI. Based on the minimum-energy structures, minimum-energy conical intersections, linear interpolation internal coordinate paths, and nonadiabatic dynamics simulations, the overall photoisomerization scenario of ITI upon excitation is established. Upon excitation around 416 nm, the molecule will be excited to the S2 state considering its close energy to the experimentally measured absorption maximum and larger oscillator strength, from which ultrafast decay of S2 to S1 state can take place efficiently with a time constant of 62 fs. However, the photoisomerization is not likely to complete in the S2 state since the dihedral associated with the Z to E isomerization changes little during the relaxation. Upon relaxing to the S1 state, the molecule will decay to the S0 state ultrafast with a time constant of 232 fs. In contrast, the decay of the S1 state is important for the isomerization considering that the dihedral related to the isomerization of the hopping structures is close to 90°. Therefore, the S1/S0 intersection region should be important for the isomerization of ITI. Arriving at the S0 state, the molecule can either go back to the original Z reactant or isomerize to the E products. At the end of the 500 fs simulation time, the E configuration accounts for nearly 37% of the final structures. Moreover, the photoisomerization mechanism is different from the isomerization mechanism in the ground state; i.e., instead of the inversion mechanism in the ground state, the photoisomerization prefers the rotation mechanism. Our results not only agree well with previous experimental studies but also provide some novel insights that could be helpful for future improvements in the performance of the ITI photoswitches.

Inverse compensation mechanism-based adaptive fuzzy-neural fault-tolerant control for an uncertain quadrotor UAV

Actuator faults, system uncertainties, and external disturbances can affect tracking control performance of the quadrotor UAV, and even cause the instability of the system. To address this issue, an adaptive fuzzy-neural fault-tolerant control (AFNFTC) scheme is proposed for the quadrotor UAV integrated with inverse compensation strategy and fuzzy neural networks (FNNs) technology. Firstly, we design an inverse compensation mechanism to address actuator faults and utilize the approximation capabilities of the FNNs to compensate for system uncertainties. Then, based on the Lyapunov direct method, the AFNFTC scheme is designed to ensure the stability of the quadrotor UAV. Under the proposed scheme, the closed-loop system for the quadrotor UAV is proven to be uniformly bounded, and the tracking error of the quadrotor UAV is demonstrated to converge to a small compact set ultimately by appropriately selecting design parameters. Finally, the feasibility and effectiveness of the proposed scheme is validated through simulation results.

Composite dark matter and neutrino masses from a light hidden sector

We study a class of models in which the particle that constitutes dark matter arises as a composite state of a strongly coupled hidden sector. The hidden sector interacts with the Standard Model through the neutrino portal, allowing the relic abundance of dark matter to be set by annihilation into final states containing neutrinos. The coupling to the hidden sector also leads to the generation of neutrino masses through the inverse seesaw mechanism, with composite hidden sector states playing the role of the singlet neutrinos. We focus on the scenario in which the hidden sector is conformal in the ultraviolet, and the compositeness scale lies at or below the weak scale. We construct a holographic realization of this framework based on the Randall-Sundrum setup and explore the implications for experiments. We determine the current constraints on this scenario from direct and indirect detection, lepton flavor violation and collider experiments and explore the reach of future searches. We show that in the near future, direct detection experiments and searches for μ → e conversion will be able to probe new parameter space. At colliders, dark matter can be produced in association with composite singlet neutrinos via Drell Yan processes or in weak decays of hadrons. We show that current searches at the Large Hadron Collider have only limited sensitivity to this new production channel and we comment on how the reconstruction of the singlet neutrinos can potentially expand the reach.

Chiral Inversion of Au40(SR)24 Nanocluster Driven by Rotation of Gold Tetrahedra in the Kekulé-like Core.

Studying the chiral characteristics and chiral inversion mechanisms of gold nanoclusters is important to promote their applications in the field of chiral catalysis and chiral recognition. Herein, we investigated the chiral inversion process of the Au40(SR)24 nanocluster and its derivatives using density functional theory calculations. The results showed that the chiral inversion process can be achieved by rotation of tetrahedra units in the gold core without breaking the Au-S bond. This work found that Au40 nanoclusters protected by different ligands have different chiral inversion mechanisms, and the difference is mainly attributable to the steric effects of the ligands. Moreover, the chiral inversion of the derivative clusters (Au34, Au28, and Au22) of the Au40 nanocluster can also be accomplished by the rotation of the Au4 tetrahedra units in the gold core. The energy barrier in the chiral inversion process of gold nanoclusters increases with the decrease of Au4 tetrahedra units in the gold core. This work identifies a chiral inversion mechanism with lower reaction energy barriers and provided a theoretical basis for the study of gold nanocluster chirality.

A Ground-Based Electrostatically Suspended Accelerometer.

In this study, we have developed an electrostatically suspended accelerometer (ESA) specifically designed for ground use. To ensure sufficient overload capacity and minimize noise resulting from high suspension voltage, we introduced a proof mass design featuring a hollow, thin-walled cylinder with a thin flange fixed at the center, offering the highest surface-area-to-mass ratio compared to various typical proof mass structures. Preload voltage is directly applied to the proof mass via a golden wire, effectively reducing the maximum supply voltage for suspension. The arrangement of suspension electrodes, offering five degrees of freedom and minimizing cross-talk, was designed to prioritize simplicity and maximize the utilization of electrode area for suspension purposes. The displacement detection and electrostatic suspension force were accurately modeled based on the structure. A controller incorporating an inverse winding mechanism was developed and simulated using Simulink. The simulation results unequivocally demonstrate the successful completion of the stable initial levitation process and suspension under ±1g overload.

Phenomenological aspects of the fermion and scalar sectors of a S4 flavored 3-3-1 model

We proposed a viable and predictive model based on the SU(3)C×SU(3)L×U(1)X gauge symmetry, supplemented by the global U(1)Lg symmetry, the S4 family symmetry and several auxiliary cyclic symmetries, which successfully reproduces the experimentally observed SM fermion mass and mixing pattern. The tiny active neutrino masses are generated through an inverse seesaw mechanism mediated by right-handed Majorana neutrinos. The model is consistent with the SM fermion masses and mixings and successfully accommodates the current Higgs diphoton decay rate constraints as well as the constraints arising from oblique S, T and U parameters and we studied the meson mixing due to flavor changing neutral currents mediated by heavy scalars, finding parameter space consistent with experimental constraints.