Antiparallel Orientation Research Articles

Deciphering the Conformations of Glutathione Oxidized Peptide: A Comparative NMR Study in Solution and Solid-State Environments.

Glutathione (GSH) and its oxidized dimer (GSSG) play an important role in living systems as an antioxidant, balancing the presence of reactive oxygen species (ROS). The central thiol (-S-S-) bond in GSSG can undergo free rotation, providing multiple conformations with respect to the S-S bridge. The six titratable sites of GSSG, which are influenced by pH variations, affect these conformations in solution, whereas in solids, additionally crystal packing effects come into play. In view of differing reports about the structure of GSSG in literature, we have here conducted an extensive reexamination of its conformations using NMR, and contrasting results have been obtained for solution and solid state. In solution, the existence of more than one antiparallel orientation of the monomer unit with different hydrogen bonding schemes has been indicated by NOE and amide temperature coefficient results. On the other hand, in the solid-state, a 1H-1H double-quantum (DQ) to 13C single-quantum (SQ) correlation study has confirmed a parallel orientation, consistent with the reported X-ray crystal structure. Experimentally assigned solid-state NMR resonances have been validated using GIPAW calculations incorporated in the Quantum ESPRESSO package.

Determination of molecular arrangement in extremely uniaxial solid thin films of a linear bisazo dye

Abstract The molecular arrangement of the extremely uniaxial thin film was determined using X-ray analysis, including grazing incidence wide-angle X-ray scattering. The highly oriented film was obtained by depositing a bisazo dye onto an aligned polytetrafluoroethylene (PTFE) layer via vacuum evaporation, as shown previously. The X-ray analysis indicated that the molecules are arranged in parallel or antiparallel orientations within the unit cell. Moreover, their long axes are parallel to each other within the grains, which are uniformly oriented throughout the film. These results confirm the driving force of the orientation reported previously using a molecular dynamics model: dye molecules trapped along the atomic grooves between adjacent PTFE chains serve as nuclei for crystal growth. In addition, the long molecular axes remain parallel to the rubbing direction, although some grains are inclined in the short-axis direction. This molecular arrangement in the film could contribute to a high degree of uniaxial orientation.

Electronic and magnetic properties of Janus ZrSSe monolayer doped with V impurity and VX3(X = C, N, O, and F) clusters

In this work, doping with V impurity and VX3 (X = C, N, O, and F) clusters is proposed to modify the electronic and magnetic properties of Janus ZrSSe monolayer. Pristine ZrSSe monolayer is an indirect-gap semiconductor two-dimensional (2D) material with energy gap of 0.73 eV. This value is reduced to 0.13 eV under effects of single Zr vacancy, which corresponds to the reduction of the order of 82.19%. V impurity magnetizes significantly ZrSSe monolayer, inducing feature-rich magnetic semiconductor nature. Herein, the magnetism with a total magnetic moment of 1.00 μ B is produced mainly by V-3d orbital. Investigations indicate that the antiferromagnetic state with zero total magnetic moment is stable when V impurities are located close to each other. Further separating impurities causes the antiferromagnetic-to-ferromagnetic state transition, such that a total magnetic moment of 2.00 μ B is obtained. ZrSSe monolayer is metallized by doping with VC3, VN3 and VF3 clusters. In the first two cases, the non-magnetic nature is preserved. Meanwhile, significant magnetization with a total magnetic moment of 3.00 μ B is achieved by VF3 cluster substitution. Similarly, VO3 cluster induces significant magnetic properties in ZrSSe monolayer with a total magnetic moment of 1.00 μ B , which are originated mainly from the antiparallel spin orientation between V atom and Se atoms closest to the doping sites. Herein, VO3 cluster substitution in ZrSSe monolayer makes new magnetic semiconductor 2D material. The Bader charge analysis indicates that all four clusters attract charge from the host monolayer. Our work may introduce efficient approaches to modify the ZrSSe monolayer electronic and magnetic properties towards spintronic and optoelectronics applications.

Synergistic effects of vacancy and doping at Ge sublattices on the electronic and magnetic properties of new Janus Ge2PAs monolayer

Recently, 2D materials based on IV-V group have attracted great attention because of their interesting physical properties. In this work, Janus Ge2PAs monolayer with good stability is predicted using first-principles calculations. Our simulations assert its non-magnetic semiconductor nature with an indirect band gap of 1.11(1.75)eV obtained by PBE(HSE06)-based calculations. Further, vacancy defects and doping with transition metals (TMs = Cr and Mn) are explored in order to induce novel physical aspects. It is found significant magnetization of Janus Ge2PAs monolayer induced by Ge vacancies with total magnetic moments between 1.58 and 1.97 μB, where magnetism is produced mainly by atomic species around the defect sites. Herein, single Ge vacancy metalizes the monolayer, while the half-metallicity is obtained by creating a pair Ge vacancies. Regardless doping site, feature-rich diluted magnetic semiconductor and half-metallic behaviors are also obtained in Janus Ge2PAs monolayer by doping with Cr and Mn atom, respectively. In these case, TM impurities originate mainly the system magnetism with total magnetic moments between 2.00 and 3.03 μB. In addition, the coexistence of Ge vacancy and doping is also investigated. The calculated spin density shows an antiparallel spin orientation of Cr dopant and its neighboring atoms, meanwhile a parallel spin orientation is observed for Mn impurity and its neighboring atoms. Consequently, small total magnetic moment of 0.53 μB is obtained by the synergistic effects of doping with Cr and Ge vacancy, meanwhile the coexistence of Mn dopant and Ge vacancy generates a larger value of 4.88/4.89 μB. In all cases, the origin of electronic and magnetic properties is unraveled. Our results introduce new prospective spintronic 2D materials made from a new Janus Ge2PAs monolayer.

Accelerating and breaking adaptive nano-colloids (

Unlike conventional colloids showing random mobility because of Brownian motion, active colloids contain nanomotors that translate chemical or physical triggers into directed movement. Whereas the acceleration of such particles works well, it is difficult to decelerate them by request. Compared to the existing literature on microscaled swimmers/robots, the main question of the current paper is whether nanoscaled colloids (<100 nm) can also be actively controlled despite the stronger relevance of rotational diffusion at such dimensions. We developed nanoparticles comprising two independent mechanisms for propulsion: a chemical engine associated with a Janus-type modification of organosilica nanoparticles and physical locomotion because of a superparamagnetic core inside these particles. Both triggers can be used independently to initiate the particles' directed and anisotropic movement. The magnetic forces can be tuned, most importantly concerning the angle defining the chemical acceleration. Superposition and a boost state are adopted for a parallel alignment. However, when the magnetic field acting on the particles is turned to an antiparallel orientation, a rapid deceleration can be observed, and the colloids halt.

Two-dimensional electrons at mirror and twistronic twin boundaries in van der Waals ferroelectrics

Semiconducting transition metal dichalcogenides (MX2) occur in 2H and rhombohedral (3R) polytypes, respectively distinguished by anti-parallel and parallel orientation of consecutive monolayer lattices. In its bulk form, 3R-MX2 is ferroelectric, hosting an out-of-plane electric polarisation, the direction of which is dictated by stacking. Here, we predict that twin boundaries, separating adjacent polarisation domains with reversed built-in electric fields, are able to host two-dimensional electrons and holes with an areal density reaching ~ 1013cm−2. Our modelling suggests that n-doped twin boundaries have a more promising binding energy than p-doped ones, whereas hole accumulation is stable at external surfaces of a twinned film. We also propose that assembling pairs of mono-twin films with a ‘magic’ twist angle θ* that provides commensurability between the moiré pattern at the interface and the accumulated carrier density, should promote a regime of strongly correlated states of electrons, such as Wigner crystals, and we specify the values of θ* for homo- and heterostructures of various TMDs.

Stacking interaction and opto-electronic properties of star-shaped benzotrithiophene and its extended derivatives

Benzotrithiophene and its derivatives obtained by fusing the aromatic rings at the peripheral sites are modelled using density functional methods for exploring their optoelectronic properties. The studies showed that absorption maximum shifted towards higher wavelengths with the extension of rings, irrespective of the functional used. The above molecules adopt anti-parallel orientations in their stacked dimer. The analysis of the stacked dimers revealed that they interact via van der Waals forces. The charge transport properties are found to vary with the orientation of the molecules. The studies showed that the designed molecules act as electron transporters in their anti-parallel orientation.

Optical imaging of ferroelectric domains in periodically poled lithium niobate using ferroelectric liquid crystals

Ferroelectric liquid crystals exhibiting a chiral smectic C* phase are deposited on z cut periodically poled lithium niobate substrates and investigated by polarized optical microscopy. While the pure substrates placed between crossed polarizers and observed in transmission appear dark, uniformly aligned liquid crystal films deposited on these substrates show alternating domains with varying brightness. This effect can be attributed to the well-known coupling between the direction of the spontaneous polarization and the optical axis in the birefringent ferroelectric smectic C* phase. Quantitative measurements of the tilt angle between the local optical axis and the smectic layer normal confirm antiparallel orientations of spontaneous polarization of the liquid crystal from domain to domain, as expected by the periodic poling of the lithium niobate substrate. This effect provides a valuable non-destructive method of optical inspection of the quality of periodically poled ferroelectric substrates, which plays an important role in achieving quasi-phase-matching in non-linear optical applications.

Establishing mechanisms for nonlinear collector tribodynamics of magnetization under ferroresonance regimes

The paper considers a parallel electromagnetic oscillating circuit with a nonlinear inductance under conditions of excitation of ferroresonances. Physical mechanisms of dynamic self-regulation of the system of spin magnetic moments of ferromagnetic and ferrimagnetic dielectrics in the surrounding magnetic field are established. It is shown that upon entering the magnetic saturation regime, the effect of dynamic antiferroresonance is observed, due to the cyclic reversal of magnetization in the internal magnetic field. This effect has a collector character and corresponds to the maximum potential energy of the magnetic moment in the field and the antiparallel orientation of the moment with respect to the field. Such regimes are realized in thermodynamically non-equilibrium conditions and are correlated with unstable equilibrium positions of the corresponding mechanical analogues. The resulting forms of oscillations correlate with the dynamics of an inverted pendulum and have a significantly non-harmonic character. Autosynchronization of frequencies and nonlinear mixing of such forms with quasi-static modes imitating the time form of external excitation of oscillations were revealed. It is shown that the nonlinearity of ferromagnetic elements self-limits the height of resonance maxima. And on the other hand, it contributes to the cascade transport of energy by the spectrum of disturbances, which can have negative consequences when exciting low-frequency ferroresonances in power grids. The effect of dynamic antiferroresonance has the opposite direction to the known quasi-static behavior of the system of spin magnetic moments in an external field and must be taken into account when calculating and operating electrical systems with nonlinear inductances. Examples of collector self-oscillating modes similar in their physical mechanisms in nonlinear contact tribodynamics systems are given

Effect of Ferromagnet/Organic Semiconductor Interface Defect States on Tunnel Magnetoresistance of Hybrid Magnetic Tunnel Junctions

Herein, analytical modeling of Fe3O4/x(≈1.1 nm)/Co (x = rubrene, C60, and bathocuproine (BCP)) magnetic tunnel junctions (MTJs) has been performed using rubrene, C60, and BCP as organic spacer layers. The simulation is considered as nonequilibrium Green's function assuming spin precession at ferromagnet/organic semiconductor (FM/OSC) interface defect states. The voltage‐dependent resistances for both parallel (RP) and antiparallel (RAP) orientations have been observed to be dependent on spin injection from FM/OSC defect states. Pinning well‐dependent defect state depths have been associated with band misalignment‐induced lattice distortion at FM/OSC interface of the devices. The large tunnel magnetoresistance (TMR) response for rubrene‐based MTJ device has been attributed to a higher change of FM/OSC defect state depths with voltage. High TMR may have reduced spin torque‐dependent spin precession, leading to lower spin transfer torque for the rubrene device. Hence, engineering of defect states at the FM/OSC interface may lead to the successful realization of enhanced TMR in organic spacer MTJs for high‐performance spintronic memory applications.

Superconducting spintronic heat engine

Heat engines are key devices that convert thermal energy into usable energy. Strong thermoelectricity, at the basis of electrical heat engines, is present in superconducting spin tunnel barriers at cryogenic temperatures where conventional semiconducting or metallic technologies cease to work. Here we realize a superconducting spintronic heat engine consisting of a ferromagnetic insulator/superconductor/insulator/ferromagnet tunnel junction (EuS/Al/AlOx/Co). The efficiency of the engine is quantified for bath temperatures ranging from 25 mK up to 800 mK, and at different load resistances. Moreover, we show that the sign of the generated thermoelectric voltage can be inverted according to the parallel or anti-parallel orientation of the two ferromagnetic layers, EuS and Co. This realizes a thermoelectric spin valve controlling the sign and strength of the Seebeck coefficient, thereby implementing a thermoelectric memory cell. We propose a theoretical model that allows describing the experimental data and predicts the engine efficiency for different device parameters.

Hydrogen bonds and elastic anisotropy of nitrile molecular crystals: an investigation from first-principles

ABSTRACT Atomistic calculations based on semi-classical dispersion-corrected density functional theory were performed to investigate bonding and elastic properties of low temperature polymorphs of three nitrile molecular crystals. For that purpose, the DFT-PBE-D3ijk method, which account for both pair and three-body interactions, was applied. The analysis of Hirshfeld surfaces demonstrated that the (C-N…H) hydrogen bonds are the strongest and the dominant ones in the three nitrile molecular crystals. The latter were found to share a common structural feature, consisting of an antiparallel orientation of the terminal nitrile groups at their constituent molecules. Our prediction of the elastic properties demonstrated that malonitrile has the highest Young modulus and succinonitrile has the lower one. The three nitrile crystals are expected to have similar resistance to volume variation while succinonitrle is predicted to exhibit the lowest resistance to shape change. Otherwise, succinonitrile was found to be ductile while malononitrile and acetonitrile were shown to be brittle. Elasticity anisotropy analysis demonstrated that the directions of maximum Young’s modulus are always nearly parallel to the direction of alignment of strong (C-H…N) hydrogen bonds in the three nitrile crystals. The present analyses are relevant for understanding the structure and the properties of more complex high temperature phases.

Coherent Magnons with Giant Nonreciprocity at Nanoscale Wavelengths.

Nonreciprocal wave propagation arises in systems with broken time-reversal symmetry and is key to the functionality of devices, such as isolators or circulators, in microwave, photonic, and acoustic applications. In magnetic systems, collective wave excitations known as magnon quasiparticles have so far yielded moderate nonreciprocities, mainly observed by means of incoherent thermal magnon spectra, while their occurrence as coherent spin waves (magnon ensembles with identical phase) is yet to be demonstrated. Here, we report the direct observation of strongly nonreciprocal propagating coherent spin waves in a patterned element of a ferromagnetic bilayer stack with antiparallel magnetic orientations. We use time-resolved scanning transmission X-ray microscopy (TR-STXM) to directly image the layer-collective dynamics of spin waves with wavelengths ranging from 5 μm down to 100 nm emergent at frequencies between 500 MHz and 5 GHz. The experimentally observed nonreciprocity factor of these counter-propagating waves is greater than 10 with respect to both group velocities and specific wavelengths. Our experimental findings are supported by the results from an analytic theory, and their peculiarities are further discussed in terms of caustic spin-wave focusing.

Competition of Moiré Network Sites to Form Electronic Quantum Dots in Reconstructed MoX2/WX2 Heterostructures.

Twisted bilayers of two-dimensional semiconductors offer a versatile platform for engineering quantum states for charge carriers using moiré superlattice effects. Among the systems of recent interest are twistronic MoX2/WX2 heterostructures (X = Se or S), which undergo reconstruction into preferential stacking domains and highly strained domain wall networks, determining the electron/hole localization across moiré superlattices. Here, we present a catalogue of options for the formation of self-organized quantum dots and wires in lattice-reconstructed marginally twisted MoX2/WX2 bilayers with a relative lattice mismatch δ ≪ 1 for twist angles ranging from perfect alignment to θ ∼ 1°. On the basis of multiscale modeling taking into account twirling of domain wall networks, we analyze bilayers with both parallel and antiparallel orientations of their unit cells and describe crossovers between different positioning of band edges for electrons and holes across moiré superlattices when θ < δ and θ > δ.

Massive Molecular Motion in Crystal Leads to an Unexpected Helical Covalent Polymer in a Solid-state Polymerization.

We designed a proline-derived monomer with azide and alkene functional groups to enable topochemical ene-azide cycloaddition (TEAC) polymerization. In its crystal, the monomer forms supramolecular helices along the 'a' axis through various non-covalent interactions. Along the 'c' axis, the molecules arrange themselves head-to-tail in a wave-like pattern, positioning the azide and alkene groups of adjacent molecules in close proximity and anti-parallel orientation, complying with Schmidt's criteria for topochemical reaction. This prearranged configuration was expected to facilitate smooth topochemical polymerization, resulting in a 1,4-triazoline-linked polymer. Upon heating, the monomer underwent TEAC polymerization in a remarkable single-crystal-to-single-crystal fashion, but, to our surprise, it yielded an unexpected covalent helical polymer linked by 1,5-disubstituted triazoline units. Remarkably, the crystal avoids the ready-to-react arrangement for polymerization, but connects monomer molecules within the supramolecular helix through the cycloaddition of azide and alkene groups, even though they are not in close proximity nor in the expected orientation. This unexpected path, involving a substantial 134° rotation of the alkene group, yields hitherto unknown 1,5-disubstituted triazoline product regiospecifically. This study serves as a cautionary reminder that relying solely on topochemical postulates for predicting reactivity can sometimes be misleading.

Experimental characterization of four ionization chamber types in magnetic fields including intra-type variation

Background and purposeFor dosimetry in magnetic resonance (MR) guided radiotherapy, assessing the magnetic field correction factors of air-vented ionization chambers is crucial. Novel MR-optimized chambers reduce MR-imaging artefacts, enhancing their quality assurance utility. This study aimed to characterize two new MR-optimized ionization chambers with sensitive volumes of 0.07 and 0.016cm3 regarding magnetic field correction factors and intra-type variation and compare them to their conventional counterparts. Material and methodsFive chambers of each type were evaluated in a water phantom, using a clinical linear accelerator and an electromagnet, as well as a 1.5 T MR-linac system. The magnetic field correction factor kB→,Q, addressing the change of response caused by a magnetic field, was assessed together with its intra-type variation. MR-optimized and conventional chambers were compared using a Mann-Whitney U-Test. ResultsConsidering 1.5 T and a perpendicular chamber orientation, we observed significant differences in the magnetic field-induced change in chamber reading between the two 0.016cm3 chamber versions (p = 0.03). For a 7MV beam, MR-optimized chambers (0.016/0.07 cm3) showed kB→,Q values of 1.0426(66) and 1.0463(44), compared to 1.0319(53) and 1.0480(41) of their conventional counterparts. In anti-parallel orientation, kB→,Q was 1.0012(69) and 0.9863(49) for the MR-optimized chambers. The average intra-type variation of kB→,Q over all chamber types was 0.3%. ConclusionMagnetic field correction factors were successfully determined for four ionization chamber types, including two new MR-optimized versions, allowing their use in MR-linac absolute dosimetry. Evaluation of the intra-type variation enabled the assessment of their contribution to the uncertainty of tabulated kB→,Q.

A systematic study of TMO n (TM = V, Cr, Mn, and Fe; n = 3 and 6) clusters embedded in a PtS2 monolayer.

Doping-based magnetism engineering is an effective approach to synthesize new multifunctional two-dimensional (2D) materials from their non-magnetic counterparts. In this work, doping with TMO n clusters (TM = V, Cr, Mn, and Fe; n = 3 and 6) is proposed to induce feature-rich electronic and magnetic properties in a PtS2 monolayer. The pristine monolayer is a non-magnetic semiconductor with an indirect energy gap of 1.81 (2.67) eV as obtained from PBE(HSE06)-based calculations. PtS3-type multivacancies magnetize significantly the monolayer, inducing the emergence of half-metallicity. In this case, a total magnetic moment of 1.90 μB is obtained and magnetic properties are produced mainly by atoms around the vacancy sites. Meanwhile, the PtS2 monolayer is metallized by creating PtS6-type multivacancies without magnetization. Depending on the type of TMO n cluster, either a feature-rich diluted magnetic semiconductor or half-metallic nature is induced, which is regulated mainly by the incorporated clusters. Except for the FeO6 cluster, TM atoms and O atoms exhibit an antiparallel spin orientation, resulting in total magnetic moments between 1.00 and 4.00 μB. Meanwhile, the parallel spin ordering gives a large total magnetic moment of 5.99 μB for the FeO6-doped monolayer. Furthermore, Bader charge analysis indicates that all the clusters attract charge from the host monolayer that is mainly due to the electronegative O atoms. Our results may introduce cluster doping as an efficient way to create new spintronic 2D materials from a non-magnetic PtS2 monolayer.

From Feast to Famine: A Systematic Study of Accretion onto Oblique Pulsars with 3D GRMHD Simulations

Disk-fed accretion onto neutron stars can power a wide range of astrophysical sources ranging from X-ray binaries, to accretion-powered millisecond pulsars, ultraluminous X-ray sources, and gamma-ray bursts. A crucial parameter controlling the gas–magnetosphere interaction is the strength of the stellar dipole. In addition, coherent X-ray pulsations in many neutron star systems indicate that the star's dipole moment is oblique relative to its rotation axis. Therefore, it is critical to systematically explore the 2D parameter space of the star's magnetic field strength and obliquity, which is what this work does, for the first time, in the framework of 3D general-relativistic magnetohydrodynamics. If the accretion disk carries its own vertical magnetic field, this introduces an additional factor: the relative polarity of the disk and stellar magnetic fields. We find that depending on the strength of the stellar dipole and the star–disk relative polarity, the neutron star's jet power can either increase or decrease with increasing obliquity. For weak dipole strength (equivalently, high accretion rate), the parallel polarity results in a positive correlation between jet power and obliquity, whereas the antiparallel orientation displays the opposite trend. For stronger dipoles, the relative-polarity effect disappears, and jet power always decreases with increasing obliquity. The influence of the relative polarity gradually disappears as obliquity increases. Highly oblique pulsars tend to have an increased magnetospheric radius, a lower mass accretion rate, and enter the propeller regime at lower magnetic moments than aligned stars.

Tuning of the antiferromagnetic-type interaction in photo-excited single-decker porphyrin-lanthanide complexes with different crown capping ligands.

The magnetic interaction between the total angular momentum (J) of the 4f electrons in a lanthanide ion and the orbital angular momentum (L) of a porphyrin in the photo-excited states of 5,10,15,20-tetraphenylporphyrinato Dy(III) complexes capped with a crown ether with one of two different symmetries, 12-crown-4 or 1-aza-12-crown-4, was investigated by temperature- and magnetic dependent magnetic circular dichroism (VT-VH MCD). The analysis was conducted on the complexes with different non-aromatic ligands to investigate how different symmetries of the non-aromatic ligands have an impact on the electronic interaction causing an anti-parallel orientation of J and L. The magnitude of the J-L interaction was determined from simulation-based fitting to experimental ratios. While in both cases an antiferromagnetic-type interaction between J and L was identified, an asymmetric non-aromatic ligand resulted in an increased magnitude of the J-L interaction.

Theory for nonlinear conductivity switching in semiconducting organic ferroelectrics.

In this work, the ferroelectric and semiconducting properties of the organic semiconducting ferroelectric benzotrithiophene tricarboxamide (BTTTA), and especially their nonlinear coupling, are theoretically investigated. BTTTA is an exponent of a small class of semiconducting organic ferroelectrics for which experiments have established a surprising polarization direction dependence of the bulk conductivity at finite fields. First, molecular dynamics (MD) simulations are used to investigate the occurrence and, under the influence of an external electric field, the inversion of the macroscopic electric dipole that forms along the axis of supramolecular columns of BTTTA. The MD results are consistent with the experimentally observed ferroelectric behavior of the material. Building on the MD results, a QM/MM scheme is used to investigate the charge carrier mobility in the quasi-1D BTTTA stacks in the linear and non-linear regimes. Indeed, at finite electric fields, a clear resistance switching effect was observed in the form of a hole mobility that is a factor ∼2 larger for antiparallel orientations of the polarization and field than for a parallel orientation. This phenomenon can be understood as a microscopic ratchet that is based on the non-equilibrium interaction between the (oriented) dipoles and the (direction of the) charge transport.