Chiral Transition Research Articles

Split of the pseudocritical temperatures of chiral and confinement-deconfinement transitions by a temperature gradient

Searching of the critical endpoint (CEP) of the phase transition of quantum chromodynamics (QCD) matter in experiments is of great interest. The temperature in the fireball at a collider is location dependent, however, most theoretical studies address the scenario of uniform temperature. In this work, the effect of temperature gradients is investigated using lattice QCD approach. We find that the temperature gradient catalyzes chiral symmetry breaking, meanwhile the temperature gradient increases the Polyakov loop in the confined phase but suppresses the Polyakov loop in the deconfined phase. Furthermore, the temperature gradient decreases the pseudocritical temperature of chiral transition but increases the pseudocritical temperature of the confine-deconfine transition. It is also found that the temperature gradient can drive the system away from the singularity, implying that the CEP in the T−μ plane may move in the direction of the first-order phase transition in the phase diagram due to the temperature gradient. Published by the American Physical Society 2024

Resolving chiral transitions in one-dimensional Rydberg arrays with quantum Kibble-Zurek mechanism and finite-time scaling

Resolving chiral transitions in one-dimensional Rydberg arrays with quantum Kibble-Zurek mechanism and finite-time scaling

Theoretical study of the mechanism of 2F-molecular sieve domain chiral transition of Asn molecules

Abstract Using density functional theory at the level of oniom (b3lyp/6-31g (d, p): uff), we investigated the chiral transition process of the Asparagine molecule in 2F-MOL. Furthermore, a complete chiral transition path reaction potential energy surface was drawn by looking for the extreme value point structures including the transition state and intermediate. The results show that the hydrogen atom on the chiral carbon atom of S-Asparagine molecule can transfer to the other side of the carbon atom via the oxygen atoms of carboxyl atoms as a bridge, to achieve the chiral transition of Asparagine molecule from S-type to R-type. On this path there is four intermediate and five transition states. The biggest reaction energy barrier is 243.9089KJ/mol derived from the fourth transition state TS1-R-Asn@2F-MOL.

Organocatalysis for Enantioselective Decarboxylative Nucleophilic Addition Reactions

AbstractThe catalytic decarboxylation of malonic acid half oxy‐ and thioesters, β‐ketocarboxylic acids, and their related compounds is a straightforward, powerful, and atom‐economical strategy for the in‐situ formation of enolates, which are important and well‐studied synthons for various functional materials and natural products. This strategy, inspired by the biosynthesis of polyketides and fatty acids, is an attractive method for synthesizing enols from carboxyl compounds with less reactive α‐hydrogen atoms under mild conditions. In addition, these reactions are environmentally friendly and are of great interest to chemists because the use of a stoichiometric amount of base can be avoided, and the only byproduct is CO2. Thus far, remarkable progress has been made, especially in the field of organocatalytic enantioselective decarboxylation reactions, allowing for the stereocontrolled formation of new C−H, C−C, C−heteroatom, and C−X bonds. This review provides a comprehensive overview of organocatalytic enantioselective decarboxylation reactions and highlights the significant progress made since 2020. In particular, it focuses on chiral catalyst systems and transition states as key parameters for decarboxylation reactions.

Sedimentation dynamics of triply twisted Möbius bands: Geometry versus topology

We explore the sedimentation dynamics of triply twisted Möbius bands, each characterized by threefold rotational symmetry but distinguished by its construction and intrinsic geometrical properties. Three types of bands are considered: one with vanishing Gaussian curvature, constructed by isometrically deforming flat rectangular strips through bending without stretching; and two with negative Gaussian curvature, one being constructed by isometrically deforming helicoids. Experiment on these three types of bands, with a focus on varying aspect ratios, reveals a singular phenomenon: while the spin directions of bands not derived from helicoids spin in directions consistent with their inherent chirality, bands derived from helicoids exhibit an aspect-ratio-dependent spin, pointing to the existence of a critical aspect ratio at which geometric factors dominate over chiral influences. Supported by numerical simulations and a detailed analysis of the resistance tensors, we propose the unique response of bands derived from helicoids originates from a complex interaction among geometry, topology, and hydrodynamics. Two explanations are offered for the chiral transition observed in bands derived from helicoid. First, this transition may parallel the dynamics of superhelices, for which competing chiralities influence rotational behavior. Second, the unique geometrical properties of bands derived from helicoids, coupled with deviations between the rotation axis and the local symmetry axis, may underlie the observed aspect-ratio-dependent chiral transition. Our study underscores the significant role of geometrical and topological nuances in determining the behavior of chiral objects suspended in fluids. In addition to offering transformative potential across diverse fields, it promises advancements in mixing, separation processes, and innovative passive swimmers. Published by the American Physical Society 2024

Chiral Zero-Dimensional Transition Metal Halide Hybrid Perovskite with Ehanced Circular Dichroism and Magnetism

Chiral Zero-Dimensional Transition Metal Halide Hybrid Perovskite with Ehanced Circular Dichroism and Magnetism

Order of the SU(Nf)×SU(Nf) chiral transition via the functional renormalization group

Renormalization group flows of the SU(Nf)×SU(Nf) symmetric Ginzburg-Landau potential are calculated for a general number of flavors, Nf. Our approach does not rely on the ε expansion, but uses the functional renormalization group, formulated directly in d=3 spatial dimensions, with the inclusion of all possible (perturbatively) relevant and marginal operators, whose number is considerably larger than those in d=4. We find new, potentially infrared stable fixed points spanned throughout the entire Nf range. By conjecturing that the thermal chiral transition is governed by these “flavor continuous” fixed points, stability analyses show that for Nf≥5 the chiral transition is of second order, while for Nf=2, 3, 4, it is of first order. We argue that the UA(1) anomaly controls the strength of the first-order chiral transition for Nf=2, 3, 4, and makes it almost indistinguishable from a second-order one, if it is sufficiently weak at the critical point. This could open up a new strategy to investigate the strength of the UA(1) symmetry breaking around the critical temperature. Published by the American Physical Society 2024

Dark matter phenomenology and phase transition dynamics of the next-to-minimal composite Higgs model with a dilaton

In this paper, we conduct a comprehensive study of the next-to-minimal composite Higgs model (NMCHM) extended with a dilaton field χ (denoted as NMCHMχ). A pseudo-Nambu-Goldstone boson (pNGB) η, resulting from the SO(6)→SO(5) breaking, serves as a dark matter (DM) candidate. The inclusion of the dilaton field is helpful for evading the stringent constraints from dark matter direct detection, as it allows for an accidental cancellation between the amplitudes of DM-nucleon scattering, an outcome of the mixing between the dilaton and Higgs fields. The presence of the dilaton field also enriches the phase transition patterns in the early universe. We identify two types of phase transitions: (i) a 1-step phase transition, where the chiral symmetry and electroweak symmetry breaking (EWSB) occur simultaneously, and (ii) a 2-step phase transition, where the chiral symmetry breaking transition takes place first, followed by a second phase transition corresponding to EWSB. Since the first-order phase transitions can be strong due to supercooling in our model, we also examine the stochastic background of gravitational waves generated by these phase transitions. We find that these gravitational waves hold promise for detection in future space-based gravitational wave experiments, such as LISA, Taiji, BBO, and DECIGO. Published by the American Physical Society 2024

Tandem Mass Spectrometry Approaches for Differentiation and Quantification Pidotimod and Its Three Isomers in the Gas Phase.

Pidotimod is a chiral drug that possesses two chiral centers, resulting in three isomeric impurities (analytes, A). This study employs electrospray ionization ion trap mass spectrometry (ESI-MS) through collision-induced dissociation (CID) to investigate the chiral recognition of pidotimod and its three isomers to eliminate chromatographic separation. Three approaches were explored: (1) Protonated molecules in CID exhibited discriminative potential for diastereomers, with the ability to distinguish between S,S and R,R configurations, albeit with an Rchiral value of ~1.8. However, differentiation between R,S and S,R configurations was not achievable. (2) Alkali adductions (lithium and sodium) only discerned diastereomers. The Rchiral values of the diastereomers obtained from alkali adduct ions were significantly lower than those obtained from protonated ions. (3) Therefore, a third approach was used to address the challenge of distinguishing between R,S and S,R configurations, including the introduction of chiral references (ref) and transition metals (MII) to form metal-bound complexes [MII(A)(ref)-H]+. Additionally, we synthesized a novel ligand, 4-(N-tert-butoxycarbonyl [Boc]-L-prolinamido)phenol (denoted as ligand A), by modifying N-t-Boc-L-Pro with 2-aminophenol, which, in combination with CuII and NiII, enabled simultaneous differentiation of all four isomers. CuII complexes exhibited significant chiral selectivity between R,S and S,R configurations. Density functional theory calculations were performed to further elucidate the stereodynamic behavior and stoichiometry of these ions in the gas phase. These calculations revealed the interaction energy and coordination sites of the precursor ions in the gas phase, correlating well with MS/MS experiment results. Additionally, the logarithm of the CuII complexes' characteristic fragment ion abundance ratio demonstrated a strong linear relationship with enantiomeric excess (ee). This study presents a novel strategy for chiral drug quality control that eliminates chromatographic separation.

Investigation into the DNA's conformations and their conversions from the phase transition theory

The functions and transformation mechanisms of nucleic acids in their various states are of great importance in physiology and pathology. Based on the Landau model, this study reveals the mechanism of the existence of chirality and the transformation rules between different chiral conformations by studying the Duffing oscillation response of the local gauge potential on the DNA chain. The research results show that normal chiral DNA and DNA configuration transition behaviors exhibit regular nonlinear periodic oscillations. Moreover, the gauge potential value approaches zero at the B-Z junction site, which may add a criterion for detecting Z-forming sites. In addition, external force and damping play a key role in the chiral gauge potential of nucleic acids, and they can influence, regulate and even control the configuration transition of nucleic acids. Finally, we verified the rationality of our theory by combining x-ray crystal diffraction data of multiple configurations of DNA. This study provides new insights into the behavior and function of chiral DNA in organisms, and provides new possibilities for regulating DNA conformational transition in the future.

Nucleosomes play a dual role in regulating transcription dynamics

Transcription has a mechanical component, as the translocation of the transcription machinery or RNA polymerase (RNAP) on DNA or chromatin is dynamically coupled to the chromatin torsion. This posits chromatin mechanics as a possible regulator of eukaryotic transcription, however, the modes and mechanisms of this regulation are elusive. Here, we first take a statistical mechanics approach to model the torsional response of topology-constrained chromatin. Our model recapitulates the experimentally observed weaker torsional stiffness of chromatin compared to bare DNA and proposes structural transitions of nucleosomes into chirally distinct states as the driver of the contrasting torsional mechanics. Coupling chromatin mechanics with RNAP translocation in stochastic simulations, we reveal a complex interplay of DNA supercoiling and nucleosome dynamics in governing RNAP velocity. Nucleosomes play a dual role in controlling the transcription dynamics. The steric barrier aspect of nucleosomes in the gene body counteracts transcription via hindering RNAP motion, whereas the chiral transitions facilitate RNAP motion via driving a low restoring torque upon twisting the DNA. While nucleosomes with low dissociation rates are typically transcriptionally repressive, highly dynamic nucleosomes offer less of a steric barrier and enhance the transcription elongation dynamics of weakly transcribed genes via buffering DNA twist. We use the model to predict transcription-dependent levels of DNA supercoiling in segments of the budding yeast genome that are in accord with available experimental data. The model unveils a paradigm of DNA supercoiling-mediated interaction between genes and makes testable predictions that will guide experimental design.

Enhanced Replenishment of Active Lattice Oxygen Using Chiral Copper Oxide.

Effective catalytic performance of the transition metal oxide is attributed to high specific surface areas, abundant surface oxygen atoms, and balanced valence ratios. Although the chirality of the transition metal has attracted attention, most studies have focused on optical application. A few chiral transition metal oxides were used as electrocatalysts and photocatalysts. The influence of the chiral catalysts on the thermal catalysis process has been less explored. In this study, Mn-loaded chiral (M/l-CuO and M/d-CuO) and achiral CuO (M/a-CuO) were synthesized and compared in the catalytic oxidization of toluene. Spectrally analyzed Mn was well-dispersed on both chiral and achiral CuO. l-CuO and d-CuO showed nanoflower-like chirality. The angles between each (001) plane of CuO were the source of chirality. The toluene turnover frequency (TOF) of the samples was in the order of Mn/d-CuO (5.6 × 10-5 s-1) > Mn/l-CuO (4.4 × 10-5 s-1) > Mn/a-CuO (3.2 × 10-5 s-1) at 240 °C, consistent with the order of the oxygen replenishment rate. The as-prepared catalysts had similar ratios of lattice oxygen/surface adsorbed oxygen, Mn3+/Mn4+, and Cu+/Cu2+. A higher TOF was attributed to chirality, which increased the lattice oxygen replenishment speed from the gaseous phase to the solid surface. Our study indicates gas-solid catalysis from a structure-activity viewpoint.

CHIRAL SWITCHING CONTROL OF PHARMACEUTICAL SUBSTANCES

Objective: The aim of this study was to demonstrate that chiral switching should be recognized as a widespread phenomenon that extends beyond the production of pure enantiomeric drugs. Methods: To investigate the optical activity of substances from various chemical classes, enantiomers of chiral compounds (Sigma-Aldrich, USA) were chosen: valine and its racemic form (D-valine, L-valine, and racemic valine with optical purity ≥ 99%), L-ascorbic acid (content ≥ 99%), carbohydrates (D-glucose, D-galactose, L-galactose, contents ≥ 99.5%). Solutions were prepared using deuterium-depleted water (DDW–"light" water, D/H=4 ppm), natural deionized high-ohmic water (BD, D/H=140 ppm), and heavy water (99.9% D2O; Sigma-Aldrich). Optical activity was measured using the Atago POL-1/2 polarimeter. Results: One of the components in the racemic medication mixture can act as an inert agent, exhibit toxicity, or undergo undesirable biotransformation mechanisms, resulting in the formation of products with unknown properties. It has been established that a change in the deuterium/protium (D/H) ratio in water leads to a change in the equilibrium and kinetic characteristics of optically active compounds across various chemical classes, such as amino acids, carboxylic acids, and carbohydrates. An inequality was observed in the absolute values of the optical rotation of the L-and D-isomers of valine and galactose, depending on the D/H isotope ratio. The impact of chiral water clusters on optical rotation accounts for the sudden shift in the specific rotation of dilute solutions (less than 0.5%) of L-ascorbic acid in water, based on the D/H ratio. The influence of the isotopic composition of water was confirmed by studying the temperature-dependent mutarotation kinetics of D-glucose and L-and D-galactose in Arrhenius coordinates. The mutarotation process in natural high-resistivity water is characterized by an activation energy (Ea) of 40.8±1.4 kJ mol-1, while in deuterium-depleted water, Ea = 63.6±3.5 kJ mol-1. This results in a kinetic isotope effect for deuterium (KIED) of 1.6. Conclusion: Methodological approaches have been developed to control chiral switching based on the isotopic composition of water in vivo and in vitro. The study of changes in the optical activity of hierarchical structures in the human body, the influence of solvent properties on the mechanisms of optical rotation, as well as the use of KIED values, can be utilized to monitor various chiral transitions in vitro and living organisms.

Anisotropy and paramagnetism of QCD matter with an anomalous magnetic moment

We employ the Polyakov-loop enhanced Nambu–Jona-Lasinio model incorporating the quark anomalous magnetic moment to investigate the anisotropy structure and the renormalized magnetization of magnetized quark matter at finite temperature. The ultraviolet divergences and nonphysical oscillatory behavior are eliminated by the vacuum magnetic regularization scheme. With a parametrization of the anomalous magnetic moment that is proportional to the square of the chiral condensate, the renormalized magnetization is enlarged by the strong magnetic field so that the anisotropy becomes more apparent. The inflection point of the renormalized magnetization indicates the pseudocritical temperature for the chiral crossover. We find that the results with the anomalous magnetic moment are closer to the lattice quantum chromodynamics data. The connection between the paramagnetism and the chiral transition provides new insight into a magnetohydrodynamics description of hot and dense QCD matter produced in heavy-ion collisions.

Thermodynamics of the parity-doublet model: Symmetric nuclear matter and the chiral transition

Thermodynamics of the parity-doublet model: Symmetric nuclear matter and the chiral transition

Cavity Catalysis of an Enantioselective Reaction under Vibrational Strong Coupling.

Strong light-matter interaction is emerging as an exciting tool for controlling chemical reactions. Here, we demonstrate an L-proline-catalyzed direct asymmetric Aldol reaction under vibrational strong coupling. Both the reactants (4-nitrobenzaldehyde and acetone) carbonyl bands are coupled to an infrared photon and react in the presence of L-proline. The reaction mixture is eluted from the cavity, and the conversion yields and enantiomeric excess are quantified using NMR and chiral HPLC. The conversion yields increase by up to 90 % in ON-resonance conditions. Interestingly, a large increase in the conversion yield does not affect the enantiomeric excess. Further control experiments were carried out by varying the temperature, and we propose that the rate-limiting step may not be the deciding factor in enantioselectivity. Whereas the formation of the enamine intermediate is modified by cavity coupling experiments. For this class of enantioselective reactions, strong coupling does not change the enantiomeric excess, possibly due to the large energy difference in chiral transition states. Strong coupling can boost the formation of enamine intermediate, thereby favouring the product yield. This gives more hope to test polaritonic chemistry based on enantioselective reactions in which the branching ratios can be controlled.

Iridium-Catalyzed Asymmetric Hydrogenation of Heteroaromatics with Multiple N Atoms via Substrate Activation: An Entry to 4,5,6,7-Tetrahydropyrazolo[1,5-a]pyrimidine-3-carbonitrile Core of a Potent BTK Inhibitor.

The chiral 4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidine is the key core skeleton of potent Bruton's tyrosine kinase (BTK) inhibitor Zanubrutinib, and the catalyst-controlled asymmetric hydrogenation of planar multinuclear pyrimidine heteroarenes with multiple N atoms could provide an efficient route toward its synthesis. Owing to the strong aromaticity and poisoning effect toward chiral transition metal catalyst, asymmetric hydrogenation of pyrazolo[1,5-a]pyrimidines with multiple nitrogen atoms is still a challenge for synthesizing the chiral 4,5,6,7-tetrahydropyrazolo[1,5-a]-pyrimidine. Herein, an efficient iridium-catalyzed asymmetric hydrogenation of pyrazolo[1,5-a]pyrimidines has been developed using substrate activation strategy, with up to 99% ee. The decagram scale synthesis further demonstrated the potential and promise of this procedure in the synthesis of Zanubrutinib. In addition, a mechanistic study indicated that the hydrogenation starts with 1,2-hydrogenation.

DFT study on the Stereoselectivity of Asymmetric Synthesis of C, N‐Cyclic Azomethine Imines with Allyl Alkyl Ketones

AbstractBased on the density functional theory, the stereoselectivity of the asymmetric synthesis of tetrahydroisoquinolinopyrazole derivatives by the cycloaddition reaction of C, N‐cyclic azomethine imines with allyl alkyl ketones which was catalyzed using a chiral primary amine is studied theoretically. The results demonstrate that the four chiral transition states (TS‐1R2R, TS‐1R2S, TS‐1S2R and TS‐1S2S) are formed by the reaction of dienamine intermediate with C, N‐cyclic azomethine imine, and the reaction barrier of TS‐1R2S is in the lowest level (ΔG=6.98 kcal/mol). The consequence reveal that the 1R2S configuration product is formed by TS‐1R2S transition state. Non‐covalent interaction and electron density topology analysis show that the stereoselectivity of the chiral product is determined through van der Waals forces and hydrogen bond interaction of the transition state molecules.

Tunable Quantum Criticality in Multicomponent Rydberg Arrays.

Arrays of Rydberg atoms have appeared as a remarkably rich playground to study quantum phase transitions in one dimension. One of the biggest puzzles that was brought forward in this context are chiral phase transitions out of density waves. Theoretically predicted chiral transition out of period-four phase is still pending experimental verification mainly due to extremely short interval over which this transition is realized in a single-component Rydberg array. In this Letter, we show that multicomponent Rydberg arrays with extra experimentally tunable parameters provide a mechanism to manipulate quantum critical properties without breaking translation symmetry explicitly. We consider an effective blockade model of two component Rydberg atoms. Weak and strong components obey nearest- and next-nearest-neighbor blockades correspondingly. When laser detuning is applied to either of the two components the system is in the period-3 and period-2 phases. But laser detuning applied to both components simultaneously stabilizes the period-4 phase partly bounded by the chiral transition. We show that relative ratio of the Rabi frequencies of the two components tunes the properties of the conformal Ashkin-Teller point and allows us to manipulate an extent of the chiral transition. The prospects of multicomponent Rydberg arrays in the context of critical fusion is briefly discussed.

Enantioseparation of organometallic compounds by electromigration techniques.

Over time, chiral organometallic compounds have attracted great interest in several fields, with applications going across several disciplines of chemical, biological, medical, and material sciences. In the last decades, due to advancements in molecular design and computational modeling, the chemistry of chiral transition metal complexes had a remarkable flowering, with the development of new structures for applications in asymmetric synthesis, bioinorganic chemistry, and molecular recognition. In these fields, fast chiral analysis to determine the enantiomeric purity of organometallic structures prepared by asymmetric synthesis, and for high-throughput screening of analytes, catalysts, and reactions, is very important. Capillary electrophoresis and related techniques proved to be extremely versatile for chiral analysis, showing unsurpassed advantages compared to chromatography like low consumption of materials, production of limited amounts of waste, fast equilibration, and possibility to replace easily type and concentration of the chiral selector, among others. Furthermore, electromigration techniques may be useful to gain details about the stereochemistry of the enantiomers of new compounds and to study analyte-selector noncovalent interactions at molecular level. On this basis, this short review aims to provide the reader with a comprehensive view on the enantioseparation of organometallic compounds by electromigration techniques, examining the topic from the historical perspective and showing what was made in this field so far, an essential know-how for developing new and advanced applications in the next future.