Orbital Hall conductivity (OHC) is a central ingredient of orbitronics, yet how to control it microscopically remains largely unexplored. Here we identify a general mechanism in which tilted Weyl crossings formed by orbitally distinct bands generate a strongly asymmetric orbital Berry curvature (OBC) distribution, whose imbalance survives Brillouin-zone integration and yields a sizable OHC already at zeroth order. Using first-principles calculations, we show that monolayer PtBi2 realizes this mechanism and hosts a giant OHC dominated by a type-II Weyl point. A small biaxial tensile strain drives a type-II → type-I → type-II Weyl transition, leading to a reversible sign change of the OHC through the evolution of the OBC imbalance. This process is governed by the chiral orbital texture of the crossing bands and is further assisted by a strain-induced first-order structural phase transition through bonding reconstruction and polarization change. Our results establish Weyl engineering of orbital quantum geometry as a powerful route to generating and reversibly controlling OHC in polar multi-orbital materials.
Photon-initiated energy transfer dynamics was studied in two tetranuclear complexes, Ru(RuL)3 and Ru(LRu)3, and three dinuclear complexes, RuLRu, RuLOs, and OsLRu, assembling ruthenium or osmium ion centers by bridging ligand L {Ru and Os represent [Ru(bpy)2]2+and [Os(bpy)2]2+ portions, respectively, where by = 2,2-bipyridyl; L = 2-(4 '-methyl-2,2 '-bipyridin-4-yl)-1H-imidazo[4,5-f]-1,10-phenanthroline}. In the tetranuclear complexes, the four metallic components are linked by bridging ligand L connecting the ruthenium atom and the moiety [Ru(bpy)2]2+. The dinuclear and tetranuclear complexes show intense absorption throughout the UV-Vis region and display long-lived emission in the near-infrared region (NIR). The electrochemical studies reveal rich redox properties of the metal complexes, characterized by multiple reversible metal-based oxidation and ligandcentered reduction pairs. The excited state deactivation behavior of Ru(II) center demonstrates effective light-driven energy transfer in the heterodinuclear complexes, thereby generating osmium(II) NIR luminescence, which may be useful for the further development of NIR emission bioimagers. Emission and lifetime measurements reveal the efficient intramolecular energy transfer in homodinuclear and homotetranuclear complexes from Ru(II) ion center coordinated with Lphen to Ru(II) ion center coordinated with Lbpy. Interestingly, the homotetranuclear complexes emit intense luminescence. These multinuclear complexes efficiently absorb visible light by directing it from multiple chromophores to the subunit with the lowest excited in the excited state.
Hydrogen bonds are fundamental interactions that govern molecular aggregation. Although the O-H···O hydrogen bond is dominant in simple hydroxylic dimers, how this dominance is perturbed by substituents remains a key question. This study investigates the 2-butyn alcohol dimer using pulsed-jet Fourier transform microwave spectroscopy and theoretical calculations to quantitatively assess the impact of an alkynyl substituent on the dominant O-H···O hydrogen bond. The observed isomer is stabilized by a primary -H···O hydrogen bond and secondary O-H···π and C-H···π interactions. Quantum theory of atoms in molecules analysis revealed that the -H···O hydrogen bond energy contributes merely 55.0% to the total dimerization energy─the lowest value observed among a series of hydroxylic dimers, including water, alcohols, and phenols. This systematic comparative analysis reveals that introducing substituents, particularly those with π-systems or elongated alkyl chains, consistently reduces the energetic contribution ratio of the O-H···O hydrogen bond. The 2-butyn alcohol dimer, with its significantly weakened relative energy contribution ratio of the dominant hydrogen bond, approaches a threshold where the dominance of the O-H···O hydrogen bond could be challenged, providing a crucial perspective for understanding hierarchical molecular self-assembly.
In this study, we begin by revisiting the oscillatory behavior of radiative quantities-energy, angular momentum, and linear momentum-linked with initial eccentricities in binary black hole (BBH) mergers. By varying the mean anomaly l_0 across the parameter range [0,2π] from a post-Newtonian perspective, we establish an envelope that encapsulates the oscillations of these radiative quantities. Our analysis reveals that while the oscillations are influenced by the specific initial condition l_0, the effect of eccentricity contributes to the formation of this envelope. Subsequently, we model dynamical quantities such as peak luminosity L_peak, remnant mass M_rem, spin α_rem, and recoil velocity V_rem in circular orbits. Through polynomial modeling, we explore their relationships with mass ratios and correlations. Our results demonstrate the effectiveness of these polynomials in capturing the intricate relationships and correlations among these quantities in circular orbits. Furthermore, we synthesize and analyze dynamical quantities for both circular and eccentric orbits, revealing continuous variations within specific ranges corresponding to distinct mass ratios. These variations are influenced by continuous changes in initial eccentricity and the associated envelope, which can be extrapolated to encompass other mass ratios. By interpolating the maximum and minimum values of these dynamical quantities, we unveil considerably broad domains relative to circular orbits in both orbital and non-orbital BBH mergers. These domains provide robust constraints on the relationships between dynamical quantities, mass ratios, and their correlations. Finally, we discuss the extension of this eccentricity effect to spin alignment and spin precession configurations of BBHs.
Ochratoxin A(OTA)is ubiquitous in the food and feed fields.It has strong hepatotoxicity and nephrotoxicity,seriously threatening the health of humans and animals.Enzymatic degradation of mycotoxins is considered to be a promising method to control mycotoxin contaminations.In this study,a new ochratoxin A amidohydrolase from Microbulbifer thermotolerans(MiADH)was obtained.After heterologous expression in Escherichia coli and purification,the recombinant protein was studied regarding the hydrolysis activity,hydrolysis products,enzymatic properties,and substrate binding mode.MiADH can degrade OTA into ochratoxin α(OTα)and phenylalanine,demonstrating a detoxifying ability.It demonstrated the best performance at 70℃and pH 8.0,and Cu2+had the strongest inhibitory effect on the activity of MiADH.MiADH with good thermal stability exhibited huge potential for industrial application.Rational design guided by three-dimensional structural models and substrate docking analysis revealed the important amino acids affecting substrate binding and obtained multiple mutants with improved activity.Among these mutants,V324A had the highest activity,which was 4.2-fold that of the wild type.The identification of MiADH enriches the ochratoxin A degradation enzyme library and provides a new candidate enzyme for the biological detoxification of ochratoxin A in the food and feed industry.
The utilization of array detection technology is pivotal in augmenting the capability of laser ranging systems to detect echo signals. It can amplify the likelihood of successful detection. But there will be variations amongst the channels due to the array detector's inconsistency. A response time model is developed based on the detection mechanism of superconducting nanowire single photon detectors (SNSPD). This model is employed in conjunction with ground target calibration measurements to rectify time bias among the channels within the 4-channel Satellite Laser Ranging (SLR) system. The findings indicate that this method adeptly manages channel deviations and mitigates data fluctuations by rectifying the inherent range walk error of SLR measurement data, resulting in improved data quality. The average precision of satellite measurement data in the first half of 2024 increased by 2.962 . 962 mm .
This study presents a thorough comparative analysis between post-Newtonian (PN) and numerically relativistic (NR) waveforms in eccentric orbits, covering nonspinning and spin-aligned configurations. The comparison examines frequency, amplitude, and phase characteristics of various harmonic modes, including (l, m) = (2, 2), (2, 1), (3, 3), (3, 2), (4, 4), (5, 5) modes. The study utilizes eccentric PN waveforms based on 3PN quasi-Keplerian parametrization with 3PN radiative reaction, surpassing Newtonian quadrupole moment with higher-order moments. NR waveforms from RIT and SXS catalogs span mass ratios from 1/4 to 1, eccentricities up to 0.45, and durations exceeding 17000M across nonspinning and spin-aligned configurations. Focusing on the (2, 2) mode, frequency comparisons between quadrupole and higher-order moments of Psi 224 and h22 were conducted. Amplitude comparisons revealed superior accuracy in quadrupole moments of Psi 22 4 . Analysis of total 180 sets of eccentric waveforms showed increasing fitting residuals with rising eccentricity, correlating with smaller mass ratios. Comparisons of initial eccentricity from PN fitting, 3PN quasi-Keplerian parametrization, and RIT/SXS catalogs revealed alignment discrepancies. Frequency, phase, and amplitude comparisons of (2, 2) modes show consistent inspiral behavior between PN and NR, with divergences near merger for nonspinning PN and pre-200M for spin-aligned PN. Average errors of frequency, phase, and amplitude up to 200M premerger amplify with increasing eccentricity. Average errors for eccentricities of 0-0.2 are below 3% for frequency, 0.2 for phase, and 6% for amplitude. For eccentricities of 0.2-0.4, errors increase. The higher-order modes demonstrate consistent trends for frequency and phase, and with increased amplitude errors, underscoring the self-consistency of the PN fitting process. Fittings on three RIT eccentric waveforms with low mass ratios highlight deviation between PN and NR for such scenarios. Refinements in PN and NR accuracy, especially at higher orders, and small mass ratios are essential for precise gravitational wave templates in eccentric orbits, reducing systematic errors in parameter estimation and advancing gravitational wave detection.
The intrinsically disordered C-terminal domain (CTD) serves as a critical regulatory element in GPCR[1][1]–[3][2]. However, directly interrogating the CTD responses to different ligands is challenging due to its high flexibility, which renders it invisible to conventional structural biology techniques. To address the challenge, we developed a live-cell fluorescence imaging strategy that enables real-time visualization of CTD conformational transitions under physiological conditions. Our dual-mode approach integrates single-cell fluorescence lifetime imaging microscopy (FLIM) with single-molecule total internal reflection fluorescence microscopy (TIRFM), facilitating multi-scale analysis. Our data revealed that the dynamics of both full-length and truncated CTDs in the β2-adrenergic receptors are ligand-specific. By bridging single-molecule dynamics with ensemble cellular responses, our method uncovered previously inaccessible molecular mechanisms underlying receptor activation. This advance not only elucidates how GPCRs transduce ligand binding into functional outcomes but also establishes a versatile platform for drug discovery, enabling rapid assessment of ligand efficacy and receptor activity in physiological contexts. ### Competing Interest Statement The authors have declared no competing interest. National Key Research and Development Program of China, 2019YFA0709304 [1]: #ref-1 [2]: #ref-3
Two isostructural thiacalix[4]arene-capped Ln8 aggregates with a "hand in hand" structure, denoted as {Ln8(μ4-OH)2Cl2(TC4A)4(BCT)2(DMF)6--x(CH3OH)2+x(H2O)2}·mCH3OH·nDMF (Ln = Tb (1), Eu (2); H4TC4A = p-tert-butylthiacalix[4]arene; H2BCT = 3,5-bis(4'-carboxy-phenyl)-1,2,4-triazole; DMF = N,N'-dimethylformamide), were constructed from two sandwich-like Ln4-(TC4A)2 entities bridged via two BCT2- linkers. These aggregates present a layer-like structure on the ac plane, with poly-nuclear secondary building units (PSBUs) staggered and assembled in three-dimensional space. 1 exhibits green photoluminescence under 379 nm excitation, with an average decay time of approximately 1.15 ms. Notably, the metal-centered luminescence of 1 remains nearly stable even after replacing the DMF molecules with methanol. The structural stability of 1 in various solvents, along with its excellent photoluminescence properties after being immersed in water for several months, suggests that it could effectively resist luminescence quenching. This makes it a promising candidate for applications in anti-counterfeiting and luminescence detection. In contrast, 2 does not show visible luminescence under the irradiation of a portable ultraviolet lamp (λ = 326 nm), which could be attributed to the slight difference in ligand-based energy levels. Collectively, these findings enhance the understanding of the structural diversity and application scenarios of thiacalix[4]arene-capped Ln(III) aggregates.
Mycotoxin patulin poses serious threats to human health by contaminating food and food products; biological detoxification of patulin by using enzymes is a promising method, and the key is an effective enzyme. Here, a thermostable patulin-degrading lipase, AhEst from Acetomicrobium hydrogeniformans, is identified and characterized. It retains over 50% residual activity after heat treatment at 85 °C for 120 min, and its thermostability is the highest of known patulin-degrading enzymes. It converts patulin efficiently to a new low-toxicity product 2-(2-hydroxy-4-oxodihydro-2H-pyran-3(4H) -ylidene) acetic acid, different from the previously reported hydrolysis product. Structural modeling analysis reveals AhEst's catalytic triad and patulin hydrolysis mechanism. Variant AhEstE49A with higher catalytic efficiency is obtained by protein engineering on the substrate entrance tunnel; it can remove patulin in commercial apple juice at low enzyme load. The study of AhEst adds to the knowledge of patulin enzymatic degradation and provides a candidate for patulin biodetoxification in the food industry.
Altermagnets (AMs) are a recently identified class of unconventional collinear compensated antiferromagnets that exhibit momentum-dependent spin splitting despite having zero net magnetization. This unconventional magnetic order gives rise to a range of phenomena, including the anomalous Hall effect, chiral magnons, and nonlinear photocurrents. Here, using spin space group (SSG) symmetry analysis and first-principles calculations, we demonstrate an efficient strategy to control altermagnetism in two-dimensional multiferroics through ferroelectric polarization and interlayer sliding. For material realization, we find that monolayer and bilayer FeCuP2S6 exhibit finite spin splitting when ferroelectric sublattices are connected by nonsymmorphic screw-axis operations rather than pure translation or inversion symmetry. Interlayer sliding further enables reversible switching or suppression of spin splitting through modifications of the SSG. Our calculations further reveal that the anomalous Hall response serves as a direct probe of these spin-split states. These findings establish two-dimensional van der Waals multiferroics as promising platforms for realizing electrically controllable altermagnetism and advancing next-generation spintronic and magnetoelectric technologies.
Despite their potential, Cassegrain systems face challenges due to central obstruction, resulting in reduced emitting efficiency. Optical vortex (OV) beams, known for their unique orbital angular momentum (OAM) characteristics, show promise in enhancing transmission efficiency. However, the existence of central phase singularity in OV beams may limits their effectiveness in laser ranging. In this work, a solid 532 nm laser and a spatial light modulator (SLM) are used to produce the OV and hollow Gaussian beam (HGB). Per the requirements of our experiments, the transmission characteristics of OVs in the Fresnel region have been thoroughly investigated. Based on the healing properties of HGBs, Experimental validation is conducted using HGBs and OV beams under varying atmospheric turbulence levels, and stronger echo signals with HGBs are realized. Additionally, a simplified model simulating central obstruction challenges in Cassegrain systems is developed, HGB shows the superior performance of HGBs in improving transmission efficiency and enhancing echo signals. This research provides valuable insights for optimizing Cassegrain antenna systems and advancing laser ranging technology and highlighting the potential of HGBs as a promising solution for overcoming central obstruction challenges and improving overall system performance.
We analyze 192 sets of binary black hole merger data in eccentric orbits obtained from RIT, decomposing the radiation energy into three distinct phases through time: inspiral, late inspiral to merger, and ringdown. Our investigation reveals a universal oscillatory behavior in radiation energy across these phases, influenced by varying initial eccentricities. From a post-Newtonian perspective, we compare the orbital average of radiation energy with the non-orbital average during the inspiral phase. Our findings indicate that the oscillatory patterns arise from non-orbital average effects, which disappear when orbital averaging is applied. This orbital effect significantly impacts the mass, spin, and recoil velocity of the merger remnant, with its influence increasing as the initial eccentricity rises. Specifically, in the post-Newtonian framework, the amplitudes of oscillations for mass, spin, and recoil velocity at e_t_0 = 0.5 (initial temporal eccentricity of PN) are enhanced by approximately 10, 5, and 7 times, respectively, compared to those at e_t_0 = 0.1. For a circular orbit, where e_t_0 = 0.0, the oscillations vanish entirely. These findings have important implications for waveform modeling, numerical relativity simulations, and the characterization of binary black hole formation channels.
As scaling down to the nanoscale, the dramatically increased morphological deviation between nanostructures becomes a major challenge in implementing large‐scale nanodevices. On the other side of the coin, the often‐undesirable rich non‐repeatable randomness introduced during nanostructure growth and subsequent device fabrication is of great value in the implementation of physically unclonable functions (PUF), a booming innovative security primitive. Herein, it is shown that the self‐oriented organic nanowires grown on a faceted surface through a vapor transport process are advanced building blocks for the implementation of two novel PUFs. An optical PUF is first demonstrated by exploiting the unclonable morphological randomness of the self‐oriented nanowires (e.g., length, thickness, density, and location), which can provide an entity‐specific primary encryption for nanowire devices. Next, these nanowires are integrated into photodetector arrays directly on their growth substrate and accordingly enable an electrical PUF based on the inherent resistance variation between detector cells. Furthermore, by combining these two PUFs, a secondary encryption with higher security is proposed for information communication. The implementation of nanowire‐based PUFs not only opens a new device direction to exploit the annoying unclonable randomness of bottom‐up nanowires, but also provides innovative label‐free security primitives for emerging nanowire‐based devices and systems.
Controlling the vapor-deposited nanoribbons to grow along a consistent orientation will enable the desired in situ integration of functional devices, representing a major technological advance compared to post-growth processing strategies. In this work, n-type F 16 CuPc molecules are self-assembled into horizontally-oriented nanoribbons with a consistent growth axis after creating periodic hydrophobic nanogrooves on a sapphire surface. Consequently, electrodes are deposited directly on the growth substrate to enable in situ fabrication of photodetectors. Depending on the deposited electrodes, these horizontally-oriented nanoribbons are connected to form a monolithic photodetector with a large sensing area or an on-chip array of photodetectors with multiple detector units. This in situ integration strategy avoids potential structural damage and contamination from impurities associated with post-growth processing steps. Therefore, the vapor-deposited nanoribbons can retain their high quality during the device manufacturing process, which contributes to performance improvement. As a result, the in-situ integrated F 16 CuPc photodetectors exhibit a sensitive response in the ultraviolet-visible-near-infrared (UV-vis-NIR) region. The response time is on the order of tens of milliseconds, the fastest record ever for the F 16 CuPc-based photodetectors. Furthermore, statistics from an array of 6 × 6 photodetectors show little variation in their sensitivity and response time, and hence this in situ fabrication scheme will contribute to the implementation of on-chip integrated photodetectors with consistent performance based on bottom-up nanoribbons. Overall, this self-oriented growth provides a versatile option to achieve desired in-situ integrated functional devices based on bottom-up nanoribbons.
The large amount of waste synthetic polyester plastics has complicated waste management and also endangering the environment due to improper littering. In this study, a novel carboxylesterase from Thermobacillus composti KWC4 (Tcca) was identified, heterologously expressed in Escherichia coli, purified and characterized with various plastic substrates. Irregular grooves were detected on polybutylene adipate terephthalate (PBAT) film by scanning electron microscopy (SEM) after Tcca treatment, and Tcca can also hydrolyze short–chain diester bis(hydroxyethyl) terephthalate (BHET). The optimal pH and temperature for Tcca were 7.0 and 40 °C, respectively. In order to explore its catalytic mechanism and improve its potential for plastic hydrolysis, we modeled the protein structure of Tcca and compared it with its homologous structures, and we identified positions that might be crucial for the binding of substrates. We generated a variety of Tcca variants by mutating these key positions; the variant F325A exhibited a more than 1.4–fold improvement in PBAT hydrolytic activity, and E80A exhibited a more than 4.1–fold increase in BHET activity when compared to the wild type. Tcca and its variants demonstrated future applicability for the recycling of bioplastic waste containing a PBAT fraction.
Petrochemical-derived polyester plastics such as polyethylene terephthalate (PET) and polybutylene adipate terephthalate (PBAT) have been widely used. However, the difficulty to be degraded in nature (PET) or the long biodegradation cycle (PBAT) resulted in serious environmental pollution. In this connection, treating these plastic wastes properly becomes one of the challenges of environment protection. From the perspective of circular economy, biologically depolymerizing the waste of polyester plastics and reusing the depolymerized products is one of the most promising directions. Recent years have seen many reports on polyester plastics degrading organisms and enzymes. Highly efficient degrading enzymes, especially those with better thermal stability, will be conducive to their application. The mesophilic plastic-degrading enzyme Ple629 from the marine microbial metagenome is capable of degrading PET and PBAT at room temperature, but it cannot tolerate high temperature, which hampers its potential application. On the basis of the three-dimensional structure of Ple629 obtained from our previous study, we identified some sites which might be important for its thermal stability by structural comparison and mutation energy analysis. We carried out transformation design, and performed expression, purification and thermal stability determination of the mutants. The melting temperature (Tm) values of mutants V80C and D226C/S281C were increased by 5.2 ℃ and 6.9 ℃, respectively, and the activity of mutant D226C/S281C was also increased by 1.5 times compared with that of the wild-type enzyme. These results provide useful information for future engineering and application of Ple629 in polyester plastic degradation.
PET (polyethylene terephthalate) is one of the most important petrochemicals that is widely used in mineral water bottles, food and beverage packaging and textile industry. Because of its stability under environmental conditions, the massive amount of PET wastes caused serious environmental pollution. The use of enzymes to depolymerize PET wastes and upcycling is one of the important directions for plastics pollution control, among which the key is the depolymerization efficiency of PET by PET hydrolase. BHET (bis(hydroxyethyl) terephthalate) is the main intermediate of PET hydrolysis, its accumulation can hinder the degradation efficiency of PET hydrolase significantly, and the synergistic use of PET hydrolase and BHET hydrolase can improve the PET hydrolysis efficiency. In this study, a dienolactone hydrolase from Hydrogenobacter thermophilus which can degrade BHET (HtBHETase) was identified. After heterologous expression in Escherichia coli and purification, the enzymatic properties of HtBHETase were studied. HtBHETase shows higher catalytic activity towards esters with short carbon chains such as p-nitrophenol acetate. The optimal pH and temperature of the reaction with BHET were 5.0 and 55 ℃, respectively. HtBHETase exhibited excellent thermostability, and retained over 80% residual activity after treatment at 80 ℃ for 1 hour. These results indicate that HtBHETase has potential in biological PET depolymerization, which may facilitate the enzymatic degradation of PET.
The dynamics of membrane proteins that are well-foldedin waterand become functional after self-insertion into cell membranes isnot well understood. Herein we report on single-molecule monitoringof membrane association dynamics of the necroptosis executioner MLKL.We observed that, upon landing, the N-terminal region (NTR) of MLKLanchors onto the surface with an oblique angle and then is immersedin the membrane. The anchoring end does not insert into the membrane,but the opposite end does. The protein is not static, switching slowlybetween water-exposed and membrane-embedded conformations. The resultssuggest a mechanism for the activation and function of MLKL in whichexposure of H4 is critical for MLKL to adsorb on the membrane, andthe brace helix H6 regulates MLKL rather than inhibits it. Our findingsprovide deeper insights into membrane association and function regulationof MLKL and would have impacts on biotechnological applications.
The interface between organic nanowires and metal layers plays a key role in determining the photoresponse and noise characteristics of organic nanowires. Herein, nickel phthalocyanine (NiPc) nanowires are self-aligned along parallel nanogrooves on a sapphire surface, and then photodetectors are fabricated in situ without post-growth transfer and alignment steps. This in-situ fabrication eliminates unpredictable factors associated with postgrowth processing steps and allows us to focus on studying the influence of different nanowire-metal interfaces. Two different electrodes prepared by thermal evaporation deposition (TED) and etching-assisted transfer printing (ETP) are compared. While both electrodes ensure that NiPc nanowires exhibit a sensitive photoresponse in the 380-800 nm spectrum, the ETP electrodes result in higher sensitivity but an order of magnitude slower response due to the increased nanowire-metal interfacial capacitance. The noise power spectral density (PSD) confirms that for both photodetectors, the frequency-dependent 1/f noise dominates at frequencies below 10 kHz while the frequency-independent white noise increases significantly at higher frequencies. However, while the noise PSD of the photodetectors with TED electrodes remains stable with increasing temperature and bias, the noise PSD of the photodetectors with ETP electrodes increase by four to twelve orders of magnitude due to significantly increased electromigration and structural damage.