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At least 775 records · Page 43

Single spin asymmetry in e+p → e′ +B↑ +X

We study an exotic type of single spin asymmetry in unpolarized electron-proton scattering, in which the outgoing electron momentum exhibits a left-right asymmetry relative to the transverse spin of the leading baryon B in the target fragmentation region. We lay out two theoretical frameworks for describing this effect: The twist-three fracture function at high-Q2 and the spin-dependent odderon in the high energy limit.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Topological carbon materials: A new perspective

Carbon has numerous one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) allotropic structures. The study of carbon materials has long been a major focus of material sciences and condensed matter physics. Recently, a number of topological semi-metallic carbon allotropes with vastly different topological phases have been predicted from first-principles, showing exceptionally clean and robust topological properties near the Fermi surfaces. Here, we provide a brief summary of the development of carbon allotropes from 1D to 3D. Then, we discuss topological properties of pure carbon materials, despite their exceedingly small spin–orbit coupling. Instead, the nearest-neighbor p z orbit interaction has been identified as the origin for the non-trivial topological properties, which vary due to different p z connectivity: zigzag, armchair, or pentagonal, as well as the interactions among further neighboring atoms. Next, we consider possible expansions of the topological properties of carbon materials to other light-element materials such as boron. Finally, we discuss future prospects in light of experimental feasibility and the recent surge in pursue of exotic carbon physics due to twisted graphene, which may also be viewed as a subset of the topological physics involving sp 2 /p z carbon.

36 MATERIALS SCIENCE↗

A nonlinear elasto-plastic bond model for the discrete element modeling of woody biomass particles

This work presents an experiment-informed, semi-empirical, elasto-plastic bond model for the discrete element modeling of woody biomass particles. The model renders nonlinear plastic deformation of materials when subjected to compression/tension, bending, and twisting, essential for accurately simulating the behavior of biomass in comminution. The model is implemented in an open-source DEM package LIGGGHTS and is assessed in a number of verification tests. The model is applied to simulate the fracturing test of notched loblolly pine blocks. Reduced bond strength is prescribed to the weak planes along the growth rings. It is found that the square-root formulation for describing the elasto-plastic normal bond contact delivers the best agreement with the experimental data over its linear and quadratic counterparts. Furthermore, the model predicts a strong anisotropic behavior of wood blocks with regard to the grain orientations, indicating that the cutting angle should be an important attribute for the optimization of biomass comminution.

42 ENGINEERING↗

Cancer/testis antigen LDHC promotes proliferation and metastasis by activating the PI3K/Akt/GSK-3β-signaling pathway and the in lung adenocarcinoma

The cancer/testis antigen lactate dehydrogenase-C4 (LDHC) is a specific isoenzyme of the LDH family that regulates invasion and metastasis in some malignancies; however, little is known regarding its role in progression of lung adenocarcinoma (LUAD). Thus, we investigated LDHC expression by immunohistochemistry, and analyzed its clinical significance in 88 LUAD specimens. The role and molecular mechanisms subserving LDHC in cellular proliferation, migration, and invasion were explored both in vitro and in vivo. As a result, we found that high LDHC expression was significantly correlated with clinicopathological features of aggressive LUAD and a poor prognosis. Overexpression of LDHC induced LUAD cells to produce lactate and ATP, increased their metastatic and invasive potential—, and accelerated xenograft tumor growth. We further demonstrated that overexpression of LDHC affected the expression of cell proliferation-related proteins (cyclin D1 and c-Myc) and epithelial-mesenchymal transition (EMT)-related proteins (MMP-2, MMP-9, E-cadherin, Vimentin, Twist, Slug, and Snail) both in vitro and in vivo. Finally, excessive activation of LDHC enhanced the phosphorylation levels of AKT and GSK-3β, revealing activation of the PI3K/Akt/GSK-3β oncogenic-signaling pathways. Treatment with a PI3K inhibitor reversed the effects of LDHC overexpression by inhibiting cellular proliferation, migration, and invasion, with diminished levels of p-Akt and p-GSK3β. PI3K inhibition also reversed cell proliferation-related and EMT-related proteins in LDHC-overexpressing A549 cells. In conclusion, LDHC promotes proliferation, migration, invasion, and EMT in LUAD cells via activation of the PI3K/Akt/GSK-3β pathway.

60 APPLIED LIFE SCIENCES↗

Downregulation of fascin in the first trimester placental villi is associated with early recurrent miscarriage

Highlights: • Fascin is downregulated in the placentae of pregnancies complicated by early recurrent miscarriage. • Knockdown of fascin decreased HTR-8/SVneo cells' proliferation, migration and invasion. • Fascin knockdown decreased phosphorylated ERK1/2 and phosphorylated STAT3 protein level in HTR-8/SVneo cells. • Hypoxia reoxygenation decreased fascin, N-Cadherin and Vimentin protein levels to affect HTR-8/SVneo cells' invasion. Inadequate trophoblast proliferation, shallow invasion and exaggerated rate of trophoblast apoptosis are implicated in early recurrent miscarriage (ERM). However, the mechanistic bases of this association have not been fully established. We aimed at investigating the involvement of fascin, an actin-bundling protein, in trophoblast activities and ERM. We found that fascin was downregulated in the cytotrophoblasts (CTBs) and distal cytotrophoblasts (DCTs) of ERM placentae. Knockdown of fascin altered cellular and nucleolar morphology, and inhibited the proliferation but increased apoptosis of trophoblastic HTR8/SVneo cells. Furthermore, fascin knockdown decreased the expression of transcription factors such as Snail1/2, Twist and Zeb1/2, mesenchymal molecules such as Vimentin and N-cadherin, and the protein expression of phosphorylated extracellular signal-regulated kinase 1/2 (ERK1/2) and phosphorylates signal transducer and activator of transcript 3 (STAT3). Exposure of HTR-8/SVneo cells to hypoxia reoxygenation (H/R) decreased fascin expression to affect the cells’ invasion. Our results indicate for the first time that the downregulation of fascin is involved in the pathogenesis of early recurrent miscarriage; and hence a potential therapeutic target against the disease.

60 APPLIED LIFE SCIENCES↗

TWIST2 inhibits EMT and induces oxidative stress in lung cancer cells by regulating the FGF21-mediated AMPK/mTOR pathway

Twist related protein 2 (TWIST2) plays an important role in bone development, tumorigenesis, tumour progression and epithelial mesenchymal transition (EMT). At present, there are few reports about the role of TWIST2 in lung cancer, which need to be further explored. Therefore, the purpose of this study is to explore the role and molecular mechanism of TWIST2 in the occurrence and development of lung cancer. The expression of TWIST2 in tissues of patients and cell lines was measured using RT-qPCR and western blotting. MTT and CCK8 assays were used to detect cell proliferation and viability. Western blotting was used to measure the expression of EMT-related proteins, including E-cadherin, N-cadherin, Vimentin and Slug. The results revealed that TWIST2 is lowly expressed in the tissues of lung cancer patients and cell lines. Further studies found that overexpression of TWIST2 significantly induced apoptosis and promoted the expression of E-cadherin, as well as inhibiting the expression of N-cadherin, Vimentin and Slug. More importantly, TWIST2 induced oxidative stress in lung cancer cells. In addition, TWIST2 regulated the FGF21 and AMPK/mTOR signalling pathway, which is involved in the molecular mechanism of the gene in lung cancer cells. We suggest that the mechanism of TWIST2 inhibition of the progression of lung cancer is by regulating the FGF21-mediated AMPK/mTOR signalling pathway.

60 APPLIED LIFE SCIENCES↗

Electron pulse train accelerated by a linearly polarized Laguerre–Gaussian laser beam

A linearly polarized Laguerre–Gaussian (LP-LG) laser beam with a twist index $l$ = –1 has field structure that fundamentally differs from the field structure of a conventional linearly polarized Gaussian beam. Close to the axis of the LP-LG beam, the longitudinal electric and magnetic fields dominate over the transverse components. This structure offers an attractive opportunity to accelerate electrons in vacuum. It is shown, using three-dimensional particle-in-cell simulations, that this scenario can be realized by reflecting an LP-LG laser off a plasma with a sharp density gradient. The simulations indicate that a 600 TW LP-LG laser beam effectively injects electrons into the beam during the reflection. The electrons that are injected close to the laser axis experience a prolonged longitudinal acceleration by the longitudinal laser electric field. The electrons form distinct monoenergetic bunches with a small divergence angle. The energy in the most energetic bunch is 0.29 GeV. The bunch charge is 6 pC and its duration is approximately 270 as. The divergence angle is just 0.57° (10 mrad). By using a linearly polarized rather than a circularly polarized Laguerre–Gaussian beam, our scheme makes it easier to demonstrate the electron acceleration experimentally at a high-power laser facility.

43 PARTICLE ACCELERATORS↗

Dynamics and bifurcations of laminar annular swirling and non-swirling jets

This paper presents bifurcation analyses characterising the nonlinear dynamics of fully developed laminar annular jets with respect to the centrebody diameter ${ {d}}$ , Reynolds number ${ {Re}}$ , and swirl ratio ${ {S}}$ . Similar flows appear in numerous applications and feature a vibrant range of topological and dynamical characteristics associated with phenomena including shear layer separation and vortex breakdown. Our results begin by describing the non-monotonic evolution of the axisymmetric jet's steady topology under varying ${ {S}}$ . In accord with earlier reports, the jet progresses through a sequence of wake, breakdown and wall jet regimes in a qualitatively similar manner across a wide span of ${ {d}}$ and ${ {Re}}$ values. In the wake regime, the non-swirling jet bifurcates to a plane-symmetric, but not axisymmetric, steady flow pattern beyond a ${ {d}}$ -dependent critical ${ {Re}}$ value. With further increase in ${ {Re}}$ , the steady non-swirling jet destabilises subsequently via multiple distinct Hopf bifurcations. Introducing ${ {S}}>0$ to the jet also induces unsteadiness by twisting the singly azimuthally periodic ( $|m|=1$ ) asymmetric wake structure and causing it to precess periodically in time about the central axis. Intermediate swirl stabilises this unsteady dynamics and restores the jet's axisymmetry. This stabilising effect is then reversed in the breakdown regime at higher ${ {S}}$ , where a variety of different $|m|=1$ and $|m|=2$ instabilities bifurcate from the steady flow as ${ {S}}$ is increased. Several instances of hysteresis and subcritical behaviour are reported and discussed, including one that manifests precessing vortex core oscillations.

Douglas, Christopher M. (ORCID:0000000259683315)↗

Evolution of an arched magnetized laboratory plasma in a sheared magnetic field

Arched magnetized structures are a common occurrence in space and laboratory plasmas. Results from a laboratory experiment on spatio-temporal evolution of an arched magnetized plasma ( $\beta \approx 10^{-3}$ , Lundquist number $\approx 10^{4}$ , plasma radius/ion gyroradius $\approx 20$ ) in a sheared magnetic configuration are presented. The experiment is designed to model conditions relevant to the formation and destabilization of similar structures in the solar atmosphere. The magnitude of a nearly horizontal overlying magnetic field was varied to study its effects on the writhe and twist of the arched plasma. In addition, the direction of the guiding magnetic field along the arch was varied to investigate its role in the formation of either forward- or reverse-S shaped plasma structures. The electrical current in the arched plasma was well below the current required to make it kink unstable. A significant increase in the writhe of the arched plasma was observed with larger magnitudes of overlying magnetic field. A forward-S shaped arched plasma was observed for a guiding magnetic field oriented nearly antiparallel to the initial arched plasma current, while the parallel orientation yielded the reverse-S shaped arched plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Inducing Ferrimagnetic Exchange in 1D-FeSe 2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe 2 ] 2

[Fe(en)(tren)][FeSe 2 ] 2 (en = ethylenediamine, C 2 H 8 N 2 , tren = tris(2-aminoethyl)amine, C 6 H 18 N 4 ) has been synthesized by a mixed-ligand solvothermal method. Its crystal structure contains heteroleptic [Fe(en)(tren)] 2+ complexes with distorted octahedral coordination, incorporated between 1D-FeSe 2 chains composed of edge–sharing FeSe 4 tetrahedra. The twisted octahedral coordination environment of the Fe–amine complex leads to partial dimerization of Fe–Fe distances in the FeSe 2 chains so that the FeSe 4 polyhedra deviate strongly from the regular tetrahedral geometry. 57 Fe Mössbauer spectroscopy reveals oxidation states of +3 for the Fe chain atoms and +2 for the Fe complex atoms. The close proximity of Fe atoms in the chains promotes ferromagnetic nearest neighbor interactions, as indicated by a positive Weiss constant, θ = +53.8(6) K, derived from the Curie–Weiss fitting. Magnetometry and heat capacity reveal two consecutive magnetic transitions below 10 K. DFT calculations suggest that the ordering observed at 4 K is due to antiferromagnetic intrachain interactions in the 1D-FeSe 2 chains. The combination of two different ligands creates an asymmetric coordination environment that induces changes in the structure of the Fe–Se fragments. Finally, this synthetic strategy opens new ways to explore the effects of ligand field strength on the structure of both Fe-amine complexes and surrounding Fe–Se chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pu(VI) Oxalate Crystal Structure and Evidence of Photoreduction to Pu(IV) Oxalate

We report the first crystal structure of a Pu(VI)-oxalate compound. This compound, [PuO 2 (C 2 O 4 )(H 2 O)]·2(H 2 O) (1), crystallizes in space group P21/c with a = 5.5993(3) Å, b = 16.8797(12) Å, c = 9.3886(6) Å, and β = 98.713(6)°. It is isostructural with the previously reported U(VI) compound, [UO 2 (C 2 O 4 )(H 2 O)]·2(H 2 O). Each plutonyl ion (PuO 2 2+ ) is coordinated in the equatorial plane by two side-on bidentate oxalates, creating an infinite chain along [001]. A coordinated water molecule and twisting of the oxalates lead to a distorted pentagonal bipyramidal geometry of the Pu. A photochemical degradation was observed for 1, which resulted in the formation of a secondary crystalline phase. The absorption spectrum of this secondary phase confirmed the presence of Pu(IV), but it did not match the spectrum of Pu(C 2 O 4 ) 2 ·6H 2 O, which is considered to be the primary product of Pu-oxalate precipitation. While compound 1 has previously been proposed to exist in solution, this is the first time it has been isolated via crystallization. Although redox interactions between Pu and oxalate have been documented in the literature, the present study is the first observation of a photochemical reduction of Pu(VI)-oxalate. Finally, this study has expanded on the limited understanding of the Pu(VI)-oxalate system, which is important for nuclear fuel cycle applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Ligand–Metal Complementarity in Rare-Earth and Actinide Chemistry

In this article, the rare-earths are comprised of scandium, yttrium, and the lanthanides (atomic numbers 21, 39, and 57–71). (1) While these elements are essential to modern life, they were historically characterized as simple, perhaps dull, compared to the rich multielectron chemistry of d-block metals in catalysts and enzymes. These descriptions were quite fair and largely true at the time that these elements were being discovered and the first compounds containing them were being synthesized, although much progress has been made to overturn this view of the rare earths. Similarly, discussions about actinide chemistry are sometimes limited to research pertinent to the nuclear industry, which, while comprising technologies vital to modern society, does not celebrate the fascinating chemical space that much of the actinide series occupies. These historic characterizations of most of the rare-earth and actinide elements persist in some textbooks, and we acknowledge that it is a helpful place to start; however, altogether these series comprise 32 elements-27% of the 118 known by 2024-and we suggest it would be an unfortunate twist of physics if such a large proportion of the Periodic Table were genuinely dull. Indeed, as this Inorganic Chemistry Forum Issue “Ligand-Metal Complementarity in Rare-Earth and Actinide Chemistry” highlights, the chemistry-let alone the physics, that is, spectroscopy and magnetism-of these elements is rich and depends on ligands!

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From +I to +IV, Alkalis to Actinides: Capturing Cations across the Periodic Table with Keggin Polyoxometalate Ligands

Coordination chemistry trends across the periodic table are often difficult to probe experimentally due to limitations in finding a versatile but consistent chelating platform that can accommodate various elements without changing its coordination mode. Herein, we present new metal/ligand systems covering a wide range of ionic radii, charges, and elements. Five different ligands derived from the Keggin structure (HBW 11 O 39 8– , PW 11 O 39 7– , SiW 11 O 39 8– , GeW 11 O 39 8– , and GaW 11 O 39 9– ) were successfully crystallized with six different cations (Na + , Sr 2+ , Ba 2+ , La 3+ , Ce 4+ , and Th 4+ ) and characterized by single-crystal X-ray diffraction. Twenty-five new compounds were obtained by using Cs + as the counterion, yielding a consistent base formula of Cs x [M(XW 11 O 39 ) 2 ]·nH 2 O. Despite having a similar first-coordination sphere geometry (i.e., 8-coordinated), the nature of the central cation was found to impact the long-range geometry of the complexes. This unique crystallographic data set shows that, despite the traditional consensus, the local geometry of the cation (i.e., metal–oxygen bond distance) is not enough to depict the full impact of the complexed metal ion. The bending and twisting of the complexes, as well as ligand–ligand distances, were all impacted by the nature of the central cation. We also observed that counterions play a critical role by stabilizing the geometry of the M(XW 11 ) 2 complex and directing complex–complex interactions in the lattice. We also define certain structural limits for this type of complex, with the large Ba 2+ ion seemingly approaching those limits. Finally, this study thus lays the foundation for capturing the coordination chemistry of other rarer elements across the periodic table such as Ra 2+ , Ac 3+ , Bk 4+ , Cf 3+ , etc.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational Spin-Orbit Coupling Contributions to Excited State Decay of Ligand-to-Ligand Charge Transfer States

Controlling excited state relaxation processes is important in a variety of photochemical and photophysical processes, including the generation of ground and excited state spin polarization for quantum information science applications. Here, we address how specific static distortions – based on vibrational spin-orbit active modes at C2v symmetry determined by group theory – in a series of low-symmetry ligand-to-ligand charge transfer complexes enable direct spin-orbit coupling contributions to T1 → S0 excited state decay. These results are used to address spin-vibronic coupling contributions to T1 → S0 decay in a high-symmetry (tBu2bpy)Pt(S,S) (tBu2bpy = 4,4’-di-tert-butyl-2,2’-bipyridine and S,S = benzene-1,2-dithiolate) ligand-to-ligand charge transfer complex with effective C2v symmetry, where T1 relaxation is both spin- and orbitally forbidden due to the direct spin-orbit coupling matrix element being zero by symmetry. Low-frequency vibrations that involve a pyridine-pyridine twisting motion within the bpy ligand generate large ∂/∂Qi values that will contribute significantly to T1 → S0 relaxation. The work advances ligand design strategies for the generation of tailored T1 → S0 relaxation rates, which can be utilized to optimize the generation of electron spin polarization in radical-elaborated ligand-to-ligand charge transfer complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LAN: A Materials Notation for Two-Dimensional Layered Assemblies

Two-dimensional (2D) layered materials offer intriguing possibilities for novel physics and applications. Before any attempt at exploring the materials space in a systematic fashion, or combining insights from theory, computation, and experiment, a formal description of information about an assembly of arbitrary composition is required. Here, we introduce a domain-generic notation that is used to describe the space of 2D layered materials from monolayers to twisted assemblies of arbitrary composition, existent or not yet fabricated. The notation corresponds to a theoretical materials concept of stepwise assembly of layered structures using a sequence of rotation, vertical stacking, and other operations on individual 2D layers. Its scope is demonstrated with several example structures using common single-layer materials as building blocks. This work overall aims to contribute to the systematic codification, capture, and transfer of materials knowledge in the area of 2D layered materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extracting Inelastic Scattering Cross Sections for Finite and Aperiodic Materials from Electronic Dynamics Simulations

Explicit time-dependent electronic structure theory methods are increasingly prevalent in the areas of condensed matter physics and quantum chemistry, with the broad-band optical absorptivity of molecular and small condensed-phase systems nowadays routinely studied with such approaches. Here, in this paper, it is demonstrated that electronic dynamics simulations can similarly be employed to study cross sections for the scattering-induced electronic excitations probed in nonresonant inelastic X-ray scattering and momentum-resolved electron energy loss spectroscopies. A method is put forth for evaluating the electronic dynamic structure factor, which involves the application of a momentum boost-type perturbation and transformation of the resulting reciprocal space density fluctuations into the frequency domain. Good agreement is first demonstrated between the dynamic structure factor extracted from these electronic dynamics simulations and the corresponding transition matrix elements from linear response theory. The method is then applied to some extended (quasi)one-dimensional systems, for which the wave vector becomes a good quantum number in the thermodynamic limit. Finally, the dispersion of many-body excitations in a series of hydrogen-terminated graphene flakes (and twisted bilayers thereof) is investigated to highlight the utility of the presented approach for capturing morphology-dependent effects in the inelastic scattering cross sections of nanostructured and/or noncrystalline materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substituent Effects on Transient, Carbodiimide-Induced Geometry Changes in Diphenic Acids

Nucleotide-induced conformational changes in motor proteins are key to many important cell functions. Inspired by this biological behavior, we report a simple chemically fueled system that exhibits carbodiimide-induced geometry changes. Bridging via transient anhydride formation leads to a significant reduction of the twist about the biaryl bond of substituted diphenic acids, giving a simple molecular clamp. The kinetics are well-described by a simple mechanism, allowing structure–property effects to be determined. The kinetic parameters can be used to derive important characteristics of the system such as the efficiencies (anhydride yields), maximum anhydride concentrations, and overall lifetimes. Transient diphenic anhydrides tolerate steric hindrance ortho to the biaryl bond but are significantly affected by electronic effects, with electron-deficient substituents giving lower yields, peak conversions, and lifetimes. Furthermore, the results provide useful guidelines for the design of functional systems incorporating diphenic acid units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polarized, V-Shaped, and Conjoined Biscoumarins: From Lack of Dipole Moment Alignment to High Brightness

Eleven conjoined coumarins possessing a chromeno[3,4-c]chromene-6,7-dione skeleton have been synthesized via the reaction of electron-rich phenols with esters of coumarin-3-carboxylic acids, catalyzed by either Lewis acids or 4-dimethylaminopyridine. Furthermore, Michael-type addition to angular benzo[f]coumarins is possible, leading to conjugated helical systems. Arrangement of the electron-donating amino groups at diverse positions on this heterocyclic skeleton makes it possible to obtain π-expanded coumarins with emission either sensitive to, or entirely independent of, solvent polarity with large Stokes shifts. Computational studies have provided a rationale for moderate solvatochromic effects unveiling the lack of collinearity of the dipole moments in the ground and excited states. Depending on the functional groups present, the obtained dyes are highly polarized with dipole moments of ~14 D in the ground state and ~20–25 D in the excited state. Strong emission in nonpolar solvents, in spite of the inclusion of a NO 2 group, is rationalized by the fact that the intramolecular charge transfer introduced into these molecules is strong enough to suppress intersystem crossing yet weak enough to prevent the formation of dark twisted intramolecular charge transfer states. Photochemical transformation of the dye possessing a chromeno[3,4-c]pyridine-4,5-dione scaffold led to the formation of a spirocyclic benzo[g]coumarin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗