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Asymmetric catalysis involving a sulfoxide electrophile intermediate presents an efficient methodology for accessing stereogenic-at-sulfur compounds, such as sulfinate esters, sulfinamides, etc., which have garnered increasing attention in modern pharmaceutical sciences. However, as the aza-analog of sulfoxide electrophiles, the asymmetric issues about electrophilic sulfinimidoyl species remain largely unexplored and represent a significant challenge in sulfur stereochemistry. Herein, we exhibit an anionic stereogenic-at-cobalt(III) complex-catalyzed asymmetric synthesis of chiral sulfinamides via chiral sulfinimidoyl iodide intermediates. Mechanistic investigations reveal that the catalytic cycle is initiated by asymmetric oxidative iodination, generating sulfinimidoyl iodides. These active intermediates subsequently undergo an enantiospecific nucleophilic substitution with water, affording a diverse array of enantioenriched sulfinamides. Notably, these sulfinamides exhibit promising antifungal activities against Sclerotinia sclerotiorumand serve as ideal platform molecules facilitating the stereospecific transformation into various stereogenic aza-sulfur compounds.

Large Stokes shift red fluorescent proteins (LSS-RFPs) are of growing interest for multicolor bioimaging applications. However, their photochemical mechanisms are not fully understood. Here, we employed the QM(XDW-CASPT2//CASSCF)/MM method to investigate the excited-state proton transfer and photoisomerization processes of the LSS-RFP mKeima starting from its cis neutral isomer. Upon excitation to the bright S1state in the Franck–Condon region, mKeima relaxes to a metastable minimum-energy state. From this short-lived species, two competing deactivation pathways are available: the excited-state proton transfer in the S1state, and the S1decay via the S1/S0conical intersection as a result of the cis–trans photoisomerization. In comparison, the former is a dominant excited-state relaxation pathway, leading to the cis anionic isomer of mKeima in the S1state. This anionic intermediate then undergoes cis–trans photoisomerization after overcoming a barrier of approximately 10 kcal/mol in the S1state, which is followed by an excited-state decay via the S1/S0conical intersection region. The efficient nonadiabatic decay of the cis anionic isomer of mKeima in the S1state inhibits the radiative process, leading to a weak emission around 520 nm observed experimentally. These findings shed important mechanistic light on the experimental observations and provide valuable insights that could help in the design of LSS-RFPs with superior fluorescence properties.

In this paper, a signal-guided masked autoencoder (S-MAE) based semi-supervised learning framework is proposed for high-precision positioning with limited labeled channel impulse response (CIR) samples. To release the overfiting effect of the neural network under insufficient labeled samples, we design a two-stage training strategy based on the proposed S-MAE model, which can be divided into pre-training and fine-tuning stage. In the pre-training stage, we design an effective masking pattern in the antenna domain to learn the latent representation of CIR by utilizing a large number of unlabeled CIR samples. Besides, we introduce the channel attention mechanism to enhance the feature extraction ability in the S-MAE. In the fine-tuning stage, we use limited labeled CIR samples to fine-tune the pre-training model in a manner of supervised learning, where the long short term memory (LSTM) network is introduced to realize the mapping from CIR to user coordinates. Experiment results show that: 1) for the case of limited labeled samples, the proposed S-MAE model has superior positioning accuracy compared to conventional positioning models. 2) For the case of non-ideal CIR scenarios, the robustness performance of the S-MAE is better than that of other benchmark models. 3) The performance gain of the proposed S-MAE under different masking patterns/ratios on the CIR sample is presented, which verifies the effectiveness of the proposed masking strategy.

The phosphoinositide 3-kinase (PI3K)–Akt axis is one of the most frequently activated pathways and is demonstrated as a therapeutic target in Kirsten rat sarcoma viral oncogene homolog (KRAS)-mutated colorectal cancer (CRC). Targeting the PI3K–Akt pathway has been a challenging undertaking through the decades. Here we unveiled an essential role of E3 ligase SMAD ubiquitylation regulatory factor 1 (Smurf1)-mediated phosphoinositide-dependent protein kinase 1 (PDK1) neddylation in PI3K–Akt signaling and tumorigenesis. Upon growth factor stimulation, Smurf1 immediately triggers PDK1 neddylation and the poly-neural precursor cell expressed developmentally downregulated protein 8 (poly-Nedd8) chains recruit methyltransferase SET domain bifurcated histone lysine methyltransferase 1 (SETDB1). The cytoplasmic complex of PDK1 assembled with Smurf1 and SETDB1 (cCOMPASS) consisting of PDK1, Smurf1 and SETDB1 directs Akt membrane attachment and T308 phosphorylation. Smurf1 deficiency dramatically reduces CRC tumorigenesis in a genetic mouse model. Furthermore, we developed a highly selective Smurf1 degrader, Smurf1-antagonizing repressor of tumor 1, which exhibits efficient PDK1–Akt blockade and potent tumor suppression alone or combined with PDK1 inhibitor in KRAS-mutated CRC. The findings presented here unveil previously unrecognized roles of PDK1 neddylation and offer a potential strategy for targeting the PI3K–Akt pathway and KRAS mutant cancer therapy.

The release control of organic dye pollutants has become a global issue, and improper disposal of red mud(RM) can also cause environmental pollution. In this paper, a novel composite material, RM-SC-HA, was prepared to adsorb MB (methylene blue) from dye wastewater by co-hydrothermal treatment using RM, sucrose, and humic acid as raw materials. RM-SC-HA is simple to prepare and has better adsorption of MB in dye wastewater. The results supported the proposed secondary (R2= 0.99) kinetic model, which states that chemisorption is the primary form of adsorption. The maximum amount of adsorption, which was achieved by Langmuir's isothermal model, was 417.12 mg/g. In addition, the adsorption mechanism can be attributed to the role of electrostatic interactions, hydrogen bonding, π-π stacking and void diffusion. When RM-SC-HA was used to treat simulated industrial wastewater samples, the removal rate was also maintained at a high level(About 90 %). In addition, RM-SC-HA has good magnetic properties and reusability. Its magnetic properties (saturation magnetization value of 2.49 emu/g) make it easy to separate from water under an applied magnetic field. The present study provides an efficient novel MB adsorbent and promotes the practical application of modified RM composites in water purification.

Based on the financial data of A-share listed companies in China from 2016 to 2020, this study examines the impact of market integration on corporate participation in rural revitalization and its mechanisms. The findings indicate that market integration significantly enhances corporate enthusiasm for participating in rural revitalization. The mechanism tests show that market integration primarily promotes corporate participation in rural revitalization by facilitating labor mobility and alleviating financing constraints for enterprises. Heterogeneity analysis reveals that the effects are more pronounced among enterprises in the eastern region, state-owned enterprises, and those registered in non-poverty areas. Thus, further advancement of market integration is advocated to promote corporate participation in rural revitalization through enhancing labor mobility and easing financing constraints.

Halide interstitial defects severely hinder the optoelectronic performance of metal halide perovskites, making research on their passivation crucial. We demonstrate, using ab initio nonadiabatic molecular dynamics simulations, that hydrogen vacancies (Hv) at both N and C atoms of the methylammonium (MA) cation in MAPbI3efficiently passivate iodine interstitials (Ii), providing a self-passivation strategy for dealing with the Hvand Iidefects simultaneously. Hvat the N site (Hv-N) introduces a defect state into the valence band, while the state contributed by Hvat the C site (Hv-C) evolves from a shallow level at 0 K to a deep midgap state at ambient temperature, exhibiting a high environmental activity. Both Hv-Nand Hv-Care strong Lewis bases, capable of capturing and passivating Iidefects. Hv-Cis a stronger Lewis base, bonds with Iibetter, and exhibits a more pronounced passivation effect. The charge carrier lifetimes in the passivated systems are significantly longer than in those containing either Hvor Ii, and even in pristine MAPbI3. Our demonstration of the Hvand Iidefect self-passivation in MAPbI3suggests that systematic control of the relative concentrations of Hvand Iican simultaneously eliminate both types of defects, thereby minimizing charge and energy losses. The demonstrated defect self-passivation strategy provides a promising means for defect control in organic–inorganic halide perovskites and related materials and deepens our atomistic understanding of defect chemistry and charge carrier dynamics in solar energy and optoelectronic materials.

It has been established experimentally that aromatic thioketones possess several inherently unique photophysical properties, some of which are highly sensitive even to common hydrocarbon solvents. However, the deeper reasons and the underlying mechanisms remain unclear up to date. In this study, the multistate complete active space second-order perturbation theory (MS-CASPT2) has been utilized to investigate the five lowest-lying electronic states (S0, T1, S1, T2, and S2) of 4H-1-benzopyran-4-thione (BPT) in acetonitrile and hydrocarbons. The results show that the S1, T1, and T2states of BPT are close in energy so that the T2-state-mediated S1→ T2→ T1and T1→ T2→ S1transitions could occur in tens of picoseconds, which exhibits little dependence on the formation of the BPT–solvent complexes and on the bulk-solvent effect. This explains why thermally activated delayed fluorescence from the S1state has been observed for many aromatic thioketones in both inert media and hydrocarbons. Meanwhile, our calculations show that the intracomplex noncovalent interactions could be automatically adjusted by the redistribution of π-electrons in the flexible aromatic rings. This allows the S2→ S1internal conversion to occur efficiently in the vicinity of the two-state conical intersection, which results in the remarkable changes in the S2-state lifetimes and fluorescence quantum yields of many aromatic thioketones from inert media to hydrocarbon solvents. The aforementioned inherent photophysical properties could be qualitatively understood by a simple model of frontier molecular orbitals. This model could be used to understand photophysical properties of other aromatic compounds (such as aldehydes, ketones, amines, and carboxylic acids) in different solvents.

Quantum mechanical tunneling (QMT) has long been recognized as crucial for understanding chemical reaction mechanisms, particularly in reactions involving light atoms like hydrogen. However, recent findings have expanded this understanding to include heavy-atom tunneling reactions. In this report, we present the observation of two heavy-atom tunneling reactions involving the spontaneous conversions from end-on bonded beryllium ozonide complexes, OBeOOO (A) and BeOBeOOO (C), to their corresponding side-on bonded ozonide isomers, OBe(η2-O3) (B) and BeOBe(η2-O3) (D), respectively, in a cryogenic neon matrix. This discovery is supported by the weak temperature dependence of the rate constants and unusually large 16O/18O kinetic isotope effects. Quantum chemistry calculations reveal extremely low barriers (<1 kcal/mol) for both ring-closure reactions. Additionally, instanton theory calculations on both reactions unveil that the tunneling processes involve the concerted motion of all four oxygen atoms.

An $(n, k, d; r)_{q}$ -locally repairable code (LRC) is called a Singleton-optimal LRC if it achieves the Singleton-type bound. Analogous to the classical MDS conjecture, the maximal length problem of Singleton-optimal LRCs has attracted a lot of attention in recent years. In this paper, we give an improved upper bound for the length of q-ary Singleton-optimal LRCs with disjoint repair groups such that $(r+1)\mid n$ based on the parity-check matrix approach. In particular, for any Singleton-optimal $(n, k, d; r)_{q}$ -LRCs, we show that: 1) $n\le q+d-4$ , when $r=2$ and $d=3e+8$ with $e\ge 0$ ; 2) $n\leq (r+1)\left \lfloor {{\frac {2(q^{2}+q+1)}{r(r+1)} +e+1}}\right \rfloor $ , when $d\ge 8$ and $\max \left \{{{3,\frac {d-e-6}{e+1}}}\right \}\le r\le \frac {d-e-3}{e+1}$ for any $0\le e\le \left \lfloor {{\frac {d-6}{4} }}\right \rfloor $ . Furthermore, we establish equivalent connections between the existence of Singleton-optimal $(n,k,d;r)_{q}$ -LRCs for $d=6, r=3$ and $d=7, r=2$ with disjoint repair groups and some subsets of lines in finite projective space with certain properties. Consequently, we prove that the length of q-ary Singleton-optimal LRCs with minimum distance $d=6$ and locality $r=3$ is upper bounded by $O(q^{1.5})$ . We construct Singleton-optimal $(8\le n\le q+1,k,d=6,r=3)_{q}$ -LRC with disjoint repair groups such that $4\mid n$ and determine the exact value of the maximum code length for some specific q. We also prove the existence of $(n, k, d=7; r=2)_{q}$ -Singleton-optimal LRCs for $n \approx \sqrt {2}q$ .

Vectorial dual-bent functions have recently attracted some researchers’ interest as they play a significant role in constructing partial difference sets, association schemes, bent partitions, and linear codes. In this paper, we further study vectorial dual-bent functions $F: V_{n}^{(p)}\rightarrow V_{m}^{(p)}$ , where $2\leq m \leq \frac {n}{2}$ , and $V_{n}^{(p)}$ denotes an n-dimensional vector space over the prime field $\mathbb {F}_{p}$ . For certain vectorial dual-bent functions (called vectorial dual-bent functions with Condition A), we present a more concise characterization in terms of partial difference sets than the one given in Wang et al. (2023), and give new characterizations in terms of amorphic association schemes, linear codes, and generalized Hadamard matrices, respectively. When $p=2$ , we characterize vectorial dual-bent functions with Condition A in terms of bent partitions. Through the relationship between vectorial dual-bent functions and bent partitions, new characterizations of certain bent partitions in terms of amorphic association schemes, linear codes, and generalized Hadamard matrices are obtained. For a vectorial dual-bent function $F: V_{n}^{(p)}\rightarrow V_{m}^{(p)}$ with $F(0)=0, F(x)=F(-x)$ , where $2\leq m \leq \frac {n}{2}$ , we give a necessary and sufficient condition under which the preimage set partition of F induces an association scheme. By using two classes of vectorial dual-bent functions, more association schemes are obtained.

The structural, photophysical, and photochemical properties of Ln(depma)(hmpa)2(NO3)3(Ln = La, Ce, Nd, Sm, Eu, Tb, Ho, Er, and Yb) complexes 1-Lnwere investigated with a multidisciplinary approach involving synthesis, photocycloaddition-based crystal engineering, spectroscopic analytical techniques and quantum chemical ab initio calculations. Depending on the Ln3+ion the isostructural 1-Lncomplexes exhibit quite different behavior upon excitation at 350–400 nm. Some 1-Lncomplexes (Ln = La, Ce, Sm, Tb, Yb) emit a broad and strong band near 533 nm arising from paired anthracene moieties, whereas others (Ln = Nd, Eu, Ho, Er) do not. 1-Euis not emissive at all, whereas 1-Nd, 1-Ho, and 1-Erexhibit a Ln3+based luminescence. Upon irradiation with 365 nm ultraviolet (UV) light 1-Ln(Ln = La, Ce, Sm, Tb, Yb) dimerize by means of a photochemically induced [4 + 4] cycloaddition of the anthracene moieties, whereas 1-Ln(Ln = Nd, Eu, Ho, Er) remain monomers. We propose three models, based on the matching of the energy levels between the Ln3+ion and the paired or dimerized anthracene units in the energy-resonance crossing region, as well as on internal conversion-driven and intersystem crossing-driven energy transfer, which explain the Ln3+ion regulated photophysics and photochemistry of the 1-Lncomplexes.

This work reports on the synthesis of a unique nickel oxide/carboxylated reduced graphene oxide (NiO/c-rGO) nanocomposites electrochemical sensor for the detection of quercetin (QCT). The successful integration of NiO nanoparticles into the c-rGO matrix was confirmed by the characterization and synthesis of both the NiO nanoparticles and c-rGO. After that, the glassy carbon electrode (GCE) was treated with the NiO/c-rGO nanocomposite, which produced a modified GCE with improved electrochemical characteristics. The NiO/c-rGO modified GCE showed a wide linear-range of 0.5 to 750 µM and a low detection limit of 0.016 µM, indicating high sensitivity towards QCT. Additionally, the sensor exhibited excellent selectivity, with very little interference from examined kinds of analytes, both organic and inorganic. Additionally, the sensor’s long-term stability was demonstrated by its steady redox reaction to QCT, with a sensitivity of roughly 96.68% over a 33-day period. The suggested sensor’s use was evaluated by measuring differential pulse voltammetry on real samples, including onions, apple juice, honey, and green tea. These samples’ QCT recovery rates, which varied from 96.00 to 99.40%, showed the precision, dependability, and potency of the suggested sensor. Based on these results, the NiO/c-rGO nanocomposite may be a great material to use in the creation of stable, highly sensitive, and selective electrochemical sensors for QCT detection. The food, pharmaceutical, and clinical diagnostics industries might all benefit greatly from this. This work enhances the field of electrochemical sensor technology and paves the way for the development of further sensors using similar nanocomposites.

The hot-rolled microstructure of medium Mn steel has coarse grains and severe elemental segregation, resulting in low strength and plasticity. Constructing a multiphase structure, refining the microstructure, and regulating elemental segregation enhance the mechanical properties. In this study, liquid nitrogen treatment created a layered distribution of austenite and martensite. Warm rolling was then used to reduce layer thickness and refine grain structure. After liquid nitrogen and warm rolling treatments, the strength and plasticity of medium Mn steel increased to 1270 MPa and 23.3%, respectively, far exceeding the hot-rolled state (724 MPa, 12.8%). Warm rolling also triggers austenite reverted transformation (ART) and introduces high-density dislocations, further improving austenite stability. This strengthening effect is higher than that from intercritical annealing alone. Improved austenite stability delays the transformation induced plasticity (TRIP) effect, preventing brittle fracture and enhancing deformation coordination between layers, significantly increasing the plastic deformation capacity of medium Mn steel.

The activation of halogens (X = Cl, Br, I) by N2O5is linked to NOxsources, ozone concentrations, NO3reactivity, and the chemistry of halide-containing aerosol particles. However, a detailed chemical mechanism is still lacking. Herein, we explored the chemistry of the N2O5···X–systems at the air–water interface. Two different reaction pathways were identified for the reaction of N2O5with X–at the air–water interface: the formation of XNO2or XONO, along with NO3–. In the case of the Cl–system, the ClNO2generation pathway is more favorable, while for the Br–and I–systems, the formation of BrONO and IONO is barrierless, making them the predominant products. Furthermore, the mechanisms of formation of X2from XNO2and XONO were also investigated. The high energy barriers of reactions and the high free energies of the products compared to those of the reactants indicate that ClNO2is stable at the air–water interface. Contrary to the widely held belief regarding X2producing from the reaction of XNO2with X–, our calculations demonstrate that BrONO and IONO initially form stable BrONO···Br–and IONO···I–complexes, which then subsequently react with Br–and I–to form Br3–and I3–, respectively. Finally, Br3–and I3–decompose to form Br2and I2.These findings have significant implications for experimental interpretation and offer new insights into halogen cycling in the atmosphere.

The photochemistry of nitrous acid (HONO), encompassing dissociation into OH and NO as well as the reverse association reaction, plays a pivotal role in atmospheric chemistry. Here, we report the direct observation of nitrosyl-O-hydroxide (HOON) in the photochemistry of HONO, employing matrix-isolation IR and UV–vis spectroscopy. Despite a barrier of approximately 30 kJ/mol, HOON undergoes spontaneous rearrangement to the more stable HONO isomer through quantum mechanical tunneling, with a half-life of 28 min at 4 K. Kinetic isotope effects and instanton theory calculations reveal that the tunneling process involves the concerted motion of the NO moiety (65.2%) and the hydrogen atom (32.3%). Our findings underscore the significance of HOON as a key intermediate in the photolytic dissociation–association cycle of HONO at low temperatures.

We simulated hot-electron relaxation in black phosphorus using the nonadiabatic molecular dynamics (NA-MD) approach with a non-Condon effect in momentum space beyond the harmonic approximation. By comparing simulations at the Γ point in a large supercell with those using a few k-points in a smaller supercell─while maintaining the same number of electronic states within the same energy range, we demonstrate that both setups yield remarkably consistent energy relaxation times, regardless of the initial state energy. This consistency arises from the complementary effects of supercell size in real space and the number of k-points in the reciprocal space. This finding confirms that simulations at a single k-point in large size supercells are an effective approximation for NA-MD with a non-Condon effect. This approach offers significant advantages for complex photophysics, such as intervalley scattering and indirect bandgap charge recombination, and is particularly suitable for large systems without the need for a harmonic approximation.

Different from the previous neutral reaction solvent system, this work explores the synthesis of Al-oxo rings in ionic environments. Deep eutectic solvents (DESs) formed by quaternary ammonium salts hydrogen bond acceptor (HBA) and phenols hydrogen bond donor (HBD) further reduce the melting point of the reaction system and provide an ionic environment. Further, the quaternary ammonium salt was chosen as the HBA because it contains a halogen anion that matches the size of the central cavity of the molecular ring. Based on this thought, five Al8ion pair cocrystals were synthesized via “DES thermal”. The general formula is Q+⊂ {Cl@[Al8(BD)8(μ2-OH)4L12]} (AlOC-180–AlOC-185, Q+= tetrabutylammonium, tetrapropylammonium, 1-butyl-3-methylimidazole; HBD = phenol, p-chlorophenol, p-fluorophenol; HL = benzoic acid, 1-naphthoic acid, 1-pyrenecarboxylic acid, anthracene-9-carboxylic acid). Structural studies reveal that the phenol-coordinated Al molecular ring and the quaternary ammonium ion pair form the cocrystal compounds. The halogen anions in the DES component are confined in the center of the molecular ring, and the quaternary ammonium cations are located in the organic shell. Such an adaptive cocrystal binding pattern is particularly evident in the structures coordinated with low-symmetry ligands such as naphthoic acid and pyrene acid. Finally, the optical behavior of these cocrystal compounds is understood from the analysis of crystal structure and theoretical calculation.

Two-dimensional (2D) metal halide perovskites, such as BA2SnI4(BA═CH3(CH2)3NH3), exhibit an enhanced charge carrier lifetime in experiments under strain. Experiments suggest that significant compression of the BA molecule, rather than of the inorganic lattice, contributes to this enhancement. To elucidate the underlying physical mechanism, we apply a moderate compressive strain to the entire system and subsequently introduce significant compression to the BA molecules. We then perform ab initio nonadiabatic molecular dynamics simulations of nonradiative electron–hole recombination. We observe that the overall lattice compression reduces atomic motions and decreases nonadiabatic coupling, thereby delaying electron–hole recombination. Additionally, compression of the BA molecules enhances hydrogen bonding between the BA molecules and iodine atoms, which lengthens the Sn–I bonds, distorts the [SnI6]4–octahedra, and suppresses atomic motions further, thus reducing nonadiabatic coupling. Also, the elongated Sn–I bonds and weakened antibonding interactions increase the band gap. Altogether, the compression delays the nonradiative electron–hole recombination by more than a factor of 3. Our simulations provide new and valuable physical insights into how compressive strain, accommodated primarily by the organic ligands, positively influences the optoelectronic properties of 2D layered halide perovskites, offering a promising pathway for further performance improvements.

Herein, we have used the “on-the-fly” ring-polymer surface-hopping simulation method with the centroid approximation (RPSH-CA), in combination with the multireference OM2/MRCI electronic structure calculations to study the photoinduced dynamics of a green fluorescent protein (GFP) chromophore analogue in the gas phase, i.e., o-HBI, at 50, 100, and 300 K with 1, 5, 10, and 15 beads (3600 1 ps trajectories). The electronic structure calculations identified five new minimum-energy conical intersection (MECI) structures, which, together with the previous one, play crucial roles in the excited-state decay dynamics of o-HBI. It is also found that the excited-state intramolecular proton transfer (ESIPT) occurs in an ultrafast manner and is completed within 20 fs in all the simulation conditions because there is no barrier associated with this ESIPT process in the S1state. However, the other excited-state dynamical results are strongly related to the number of beads. At 50 and 100 K, the nuclear quantum effects (NQEs) are very important; therefore, the excited-state dynamical results change significantly with the bead number. For example, the S1decay time deduced from time-dependent state populations becomes longer as the bead number increases. Nevertheless, an essentially convergent trend is observed when the bead number is close to 10. In contrast, at 300 K, the NQEs become weaker and the above dynamical results converge very quickly even with 1 bead. Most importantly, the NQEs seriously affect the excited-state decay mechanism of o-HBI. At 50 and 100 K, most trajectories decay to the S0state via perpendicular keto MECIs, whereas, at 300 K, only twisted keto MECIs are responsible for the excited-state decay. The present work not only comprehensively explores the temperature-dependent photoinduced dynamics of o-HBI, but also demonstrates the importance and necessity of NQEs in nonadiabatic dynamics simulations, especially at relatively low temperatures.

Simulation of surface processes is a key part of computational chemistry that offers atomic-scale insights into mechanisms of heterogeneous catalysis, diffusion dynamics, and quantum tunneling phenomena. The most common theoretical approaches involve optimization of reaction pathways, including semiclassical tunneling pathways (called instantons). The computational effort can be demanding, especially for instanton optimizations with an ab initio electronic structure. Recently, machine learning has been applied to accelerate reaction-pathway optimization, showing great potential for a wide range of applications. However, previous methods still suffer from numerical and efficiency issues and were not designed for condensed-phase reactions. We propose an improved framework based on Gaussian process regression for general transformed coordinates, which has improved efficiency and numerical stability, and we propose a descriptor that combines internal and Cartesian coordinates suitable for modeling surface processes. We demonstrate with 11 instanton optimizations in three representative systems that the improved approach makes ab initio instanton optimization significantly cheaper, such that it becomes not much more expensive than a classical transition-state theory rate calculation.

Recent years have witnessed the development of cluster materials as they are atomically precise molecules with uniform size and solution-processability, which are unattainable with traditional nanoparticles or framework materials. The motivation for studying Al(III) chemistry is not only to understand the aggregation process of aluminum in the environment but also to develop novel low-cost materials given its natural abundance. However, the Al-related clusters are underdeveloped compared to the coinage metals, lanthanides, and transition metals. The challenge in isolating crystalline compounds is the lack of an effective method to realize the controllable hydrolysis of Al(III) ions. Compared with the traditional hydrolysis of inorganic Al(III) salts in highly alkaline solutions and hydrolysis of aluminum trialkyl compounds conducted carefully in an inert operating environment, we herein developed an effective way to control the hydrolysis of aluminum isopropanol through an alcoxalation reaction. By solvothermal/low melting point solid melting synthesis and using “ligand aggregation, solvent regulation, and supracluster assembly” strategies, our laboratory has established an organic-inorganic hybrid system of aluminum oxo clusters (AlOCs). The employment of organic ligands promotes the aggregation and slows the hydrolysis of Al(III) ions, which in turn improves the crystallization process. The regulation of the structure types can be achieved through the selection of ligands and the supporting solvents. Compared with the traditional condensed polyoxoaluminates, we successfully isolated a broad range of porous AlOCs, including aluminum molecular rings and Archimedes aluminum oxo cages. By studying ring expansion, structural transformation, and intermolecular supramolecular assembly, we demonstrate unique and unprecedented structural controllability and assembly behavior in cluster science. The advancement of this universal synthetic method is to realize materials customization through modularly oriented supracluster assembly. In this Account, we will provide a clear-cut definition and terminology of “ligand aggregation, solvent regulation, and supracluster assembly”. Then we will discuss the discovery in this area by using a strategy, such as aluminum molecular ring, ring size expansion, ring supracluster assembly, etc. Furthermore, given the internal and external pore structures, as well as the solubility and modifiability of the AlOCs, we will demonstrate their potential applications in both the solid and liquid phases, such as iodine capture, the optical limiting responses, and dopant in polymer dielectrics. The strategy herein can be applied to extensive cluster science and promote the research of main group element chemistry. The new synthetic method, fascinating clusters, and unprecedented assembly behaviors we have discovered will advance Al(III) chemistry and will also lay the foundation for functional applications.

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

A significant decline in both incidence and prevalence of cervical cancers after widespread-introducing cervical screening strategy by Papanicolau test (Pap test) has been found in the world, but cervical cancer is still one of the most common female cancers, reporting the fourth prevalence and also one of the leading causes to result in main women-associated morbidity and mortality, particularly for those women living in low- and middle-income countries. Cervical cancer is one of the most important health concerns directly destroying the global health-care system, partly because of not only increasing the disability either secondary to diseases themselves of victims or mediated by treatment-related adverse events to the survivors but also acting as a leading cause of death of diseased patients worldwide, alarming the urgent need to do something to minimize the catastrophic diseases-related heavy socioeconomic burden. It is fortunate that cervical cancer is a preventable disease, based on its strong association with human papillomavirus (HPV) infection (more than 95%), particularly for those high-risk HPV (HR-HPV) and its high possibility by detecting HPV infection before the development of cervical cancer as well as an effective prevention by HPV vaccination. That is why WHO (World Health Organization) considers cervical cancer as a public problem and attempts to accelerate the elimination of cervical cancer program by three-pillar approach (90:70:90% targets), including (1) 90% of girls are fully vaccinated with HPV vaccine by 15 years of age; (2) 70% of women are screened with a high-performance test by 35 and 45 years of age and precancerous lesions are treated early; and (3) 90% of women identified with cervical diseases receive appropriate and adequate treatment. Herein, this review focuses on the HPV vaccination as Part I, including global recommendations and Taiwan government's policy for HPV vaccination.

Epigenetic modifications of chromatin, including histone acetylation, and tumor angiogenesis play pivotal roles in creating an immunosuppressive tumor microenvironment. In the randomized phase 2 CAPability-01 trial, we investigated the potential efficacy of combining the programmed cell death protein-1 (PD-1) monoclonal antibody sintilimab with the histone deacetylase inhibitor (HDACi) chidamide with or without the anti-vascular endothelial growth factor (VEGF) monoclonal antibody bevacizumab in patients with unresectable chemotherapy-refractory locally advanced or metastatic microsatellite stable/proficient mismatch repair (MSS/pMMR) colorectal cancer. Forty-eight patients were randomly assigned to either the doublet arm (sintilimab and chidamide, n= 23) or the triplet arm (sintilimab, chidamide and bevacizumab, n= 25). The primary endpoint of progression-free survival (PFS) rate at 18 weeks (18wPFS rate) was met with a rate of 43.8% (21 of 48) for the entire study population. Secondary endpoint results include a median PFS of 3.7 months, an overall response rate of 29.2% (14 of 48), a disease control rate of 56.3% (27 of 48) and a median duration of response of 12.0 months. The secondary endpoint of median overall survival time was not mature. The triplet arm exhibited significantly improved outcomes compared to the doublet arm, with a greater 18wPFS rate (64.0% versus 21.7%, P= 0.003), higher overall response rate (44.0% versus 13.0%, P= 0.027) and longer median PFS rate (7.3 months versus 1.5 months, P= 0.006). The most common treatment-emergent adverse events observed in both the triplet and doublet arms included proteinuria, thrombocytopenia, neutropenia, anemia, leukopenia and diarrhea. There were two treatment-related fatalities (hepatic failure and pneumonitis). Analysis of bulk RNA sequencing data from the patients suggested that the triplet combination enhanced CD8+T cell infiltration, resulting in a more immunologically active tumor microenvironment. Our study suggests that the combination of a PD-1 antibody, an HDACi, and a VEGF antibody could be a promising treatment regimen for patients with MSS/pMMR advanced colorectal cancer. ClinicalTrials.gov registration: NCT04724239.

The trend of research using mixed metal oxide as a selective adsorbent for H2S gas is increasing. Inline with that, this paper evaluated the performance of Zn-Fe/Al2O3adsorbent in adsorbing H2S as one of the steps in biogas purification process. The Zn-Fe/Al2O3was successfully synthesized by microwave-assisted wet impregnation technique. The results showed that some operation parameters such as biogas space velocity, H2S inlet concentration, and biogas humidity had obvious influence on the performance of the gas adsorber. At low gas hourly space velocity (GHSV) of 1750 h−1, low H2S inlet concentrations (100 ppm), and no moisture in biogas, the highest breakthrough capacity was achieved with 3.23 mg H2S per gram adsorbent. Fresh and spent adsorbents were characterized by SEM–EDX to investigate the impact of H2S adsorption on the physical properties of the adsorbent. According to the good performance in removing H2S under ambient conditions, the Zn-Fe/Al2O3is expected to be a promising adsorbent for H2S adsorption in biogas purification process.

The spatially resolved identification of active sites on the heterogeneous catalyst surface is an essential step toward directly visualizing a catalytic reaction with atomic scale. To date, ferrous centers on platinum group metals have shown promising potential for low-temperature CO catalytic oxidation, but the temporal and spatial distribution of active sites during the reaction and how molecular-scale structures develop at the interface are not fully understood. Here, we studied the catalytic CO oxidation and the effect of co-adsorbed hydrogen on the FeO2–x/Ir(111) surface. Combining scanning tunneling microscopy (STM), isotope-labeled pulse reaction measurements, and DFT calculations, we identified both FeO2/Ir and FeO2/FeO sites as active sites with different reactivity. The trilayer O–Fe–O structure with its Moiré pattern can be fully recovered after O2exposure, where molecular O2dissociates at the FeO/Ir interface. Additionally, as a competitor, dissociated hydrogen migrates onto the oxide film with the formation of surface hydroxyl and water clusters down to 150 K.

The properties of layered intercalation hybrids are closely related to interlayer molecular packing. To develop functional intercalation hybrids, it is essential to gain deep insights into interlayer molecular packing. This work reports a new comprehensive insight into the controllable multiphase interlayer molecular packing in 4-(phenylazo)benzoate anion-intercalated layered zinc hydroxide (LZH-4-PAB intercalation hybrids). The new insight breaks up the general understanding that the interlayer molecular packing of anions is usually single-phase, lacking diversity and controllability. Furthermore, it uncovers an interesting stepwise rather than the generally expected continuous phase transition of the interlayer molecular packing. The intercalated 4-PAB anions initially organize into the horizontal monolayer packing (θ = 0°, Phase I), which stepwise transforms to the tilted interdigitated antiparallel bilayer packing (θ ≈ 50°, Phase II) along with an increased intercalation loading and eventually to the vertical interdigitated antiparallel bilayer packing (θ = 90°, Phase III). The LZH-4-PAB hybrids exhibited a greatly enhanced interlayer molecular packing-dependent UV–vis absorption. This study provides helpful guidance for developing property-tailored intercalation hybrids. It may attract new interest in more layered intercalation hybrids. New and rich intercalation chemistry might be discovered in more functional intercalation hybrids beyond the 4-PAB anion-intercalated layered zinc hydroxide.

A small chemical modification of the nucleobase structure can significantly enhance the photoactivity of DNA, which may incur DNA damage, thus holding promising applications in photochemotherapy treatment of cancers or pathogens. However, single substitution confers only limited phototoxicity to DNA. Herein, we combine femtosecond and nanosecond time-resolved spectroscopy with high-level ab initiocalculations to disentangle the excited-state dynamics of 6-methylthioguanine (me6-TG) under variable wavelength UVA excitation (310–330 nm). We find that double substitution of nucleobases (thionation and methylation) boosts the photoactivity by introducing more reactive channels. Intriguingly, 1nNπ*, rather than 1nSπ*, acts as the doorway state engendering the formation of the long-lived reactive triplet state in me6-TG. The 1nNπ* induces a low spin–orbit coupling of 8.3 cm–1, which increases the intersystem crossing (ISC) time (2.91 ± 0.14 ns). Despite the slowed ISC, the triplet quantum yield (ΦT) still accounts for a large fraction (0.6 ± 0.1), consistent with the potential energy surface that favors excited-state bifurcation to 1nNπ*min(3.36 ± 0.15 ps) rather than 1ππ*min(5.05 ± 0.26 ps), such that the subsequent ISC to triplet via 1nNπ*minconstitutes the main relaxation pathway in me6-TG. Although this ΦTis inferior to its single-substituted predecessor 6-thioguanine (6-TG, 0.8 ± 0.2), the effect of thionation in synergy with methylation opens a unique C–S bond cleavage pathway through crossing to a repulsive 1πσ* state, generating thiyl radicals as highly reactive intermediates that may invoke biological damage. This photodissociation channel is extremely difficult for conventional nucleobases. These findings demonstrate the synergistic effects of double functionality substitution in modulating excited-state dynamics and enhancing the photolabile character of DNA nucleobases, providing inspirations for the rational design of advanced photodynamic and photochemotherapy approaches.

The synthesis of 1-aminonorbornane (1-aminoNB), a potential aniline bioisostere, through photochemistry or photoredox catalysis signifies a remarkable breakthrough with implications in organic chemistry, pharmaceutical chemistry, and sustainable chemistry. However, an understanding of the underlying mechanisms involved in these reactions remains limited and ambiguous. Herein, we employ high-precision CASPT2//CASSCF calculations to elucidate the intricate mechanisms regulating the intramolecular photo-(3 + 2)-cycloaddition reactions for the synthesis of 1-aminoNB in the presence or absence of the Ir-complex-based photocatalyst. Our investigations delve into radical cascades, stereoselectivity, particularly single-electron-transfer (SET) events, etc. Furthermore, we innovatively introduce and compare two SET models integrating Marcus electron-transfer theory and transition-state theory. These models combined with kinetic data contribute to recognizing the critical control factors in diverse photocatalysis, thereby guiding the design and manipulation of photoredox catalysis as well as the improvement and modification of photocatalysts.

The article focuses on the ancient Chinese political ideal "Tian Xia Wei Gong," meaning "pursuing common good for all under heaven," tracing its origins from Confucius to earlier periods, emphasizing its influence on Chinese politics and its contemporary application. Topics include the historical context, Confucius's vision of a harmonious society, the development of the concept in pre-Qin China, and its relevance to modern Chinese governance.

Alloying Pt with 3d transition metals has proven to be the most attractive oxygen reduction reaction electrocatalysts for proton exchange membrane fuel cells with improved catalytic activity and stability; thus, their large-scale and cost-effective production is in high demand. Herein, we present a strategy for the batch preparation of PtCo/C with a highly uniform morphology and tiny PtCo dispersions of 2.48 nm using a continuous-flow microwave pipeline reactor. Due to its unique structure, which greatly facilitated the catalytic kinetics, the prepared PtCo/C catalyst exhibited an initial mass activity of 485.6 mA·mg–1ptat 0.9 V, which was 3.6 times higher than that of the commercial Pt/C catalysts. The as-obtained PtCo/C was able to maintain 74.6% of the initial activity after 30,000 accelerated cycle tests. Furthermore, a maximum power density of 1.76 W·cm–2was attained in a single-cell test under 0.2 mg·cm–2Pt loading conditions, far exceeding those of commercial Pt/C catalysts.

Heuristic algorithms have been developed to find approximate solutions for high-utility itemset mining (HUIM) problems that compensate for the performance bottlenecks of exact algorithms. However, heuristic algorithms still face the problem of long runtime and insufficient mining quality, especially for large transaction datasets with thousands to tens of thousands of items and up to millions of transactions. To solve these problems, a novel GPU-based efficient parallel heuristic algorithm for HUIM (PHA-HUIM) is proposed in this paper. The iterative process of PHA-HUIM consists of three main steps: the search strategy, fitness evaluation, and ring topology communication. The search strategy and ring topology communication are designed to run in constant time on GPU. The parallelism of fitness evolution helps to substantially accelerate the algorithm. A new data structure with a sort-mapping strategy is proposed to enhance the search ability and reduce memory usage. To improve the mining quality, a multi-start strategy with an unbalanced allocation strategy is employed in the search process. Ring topology communication is adopted to maintain population diversity. A load balancing strategy is introduced to reduce the thread divergence to improve the parallel efficiency. The experimental results on nine large datasets show that PHA-HUIM outperforms state-of-the-art HUIM algorithms in terms of speedup performance, runtime, and mining quality.

Nuclear receptor receptor-related orphan receptor γ (RORγ) is a ligand-dependent transcription factor and has been established as a key player in castration-resistant prostate cancers (CRPC) by driving androgen receptor (AR) overexpression, representing a potential therapeutical target for advanced prostate cancers. Here, we report the identification of the first-in-class RORγ covalent inhibitor 29via the structure-based drug design approach following structure–activity relationship (SAR) exploration. Mass spectrometry assay validated its covalent inhibition mechanism. Compound 29significantly inhibited RORγ transcriptional activity and remarkably suppressed the expression levels of AR and AR-targeted genes. Compound 29also exhibited much superior activity in inhibiting the proliferation and colony formation and inducing apoptosis of the CRPC cell lines relative to the positive control 2and noncovalent control 33. Importantly, it markedly suppressed the tumor growth in a 22Rv1 mouse tumor xenograft model with good safety. These results clearly demonstrate that 29is a highly potent and selective RORγ covalent inhibitor.

The presence of many degenerate d/f orbitals makes polynuclear transition-metal compounds, such as iron–sulfur clusters in nitrogenase, challenging for state-of-the-art quantum chemistry methods. To address this challenge, we present the first distributed multi-graphics processing unit (GPU) ab initiodensity matrix renormalization group (DMRG) algorithm suitable for modern high-performance computing (HPC) infrastructures. The central idea is to parallelize the most computationally intensive part─the multiplication of O(K2) operators with a trial wave function, where Kis the number of spatial orbitals, by combining operator parallelism for distributing the workload with a batched algorithm for performing contractions on GPU. With this new implementation, we are able to reach an unprecedentedly large bond dimension D= 14,000 on 48 GPUs (NVIDIA A100 80 GB SXM) for an active space model (114 electrons in 73 active orbitals) of the P-cluster, which is nearly 3 times larger than the bond dimensions reported in previous DMRG calculations for the same system using only central processing units (CPUs).

Introduction The identification and treatment of traumatic pneumothorax (PTX) has long been a focus of bedside imaging in the trauma patient. While the emergence of bedside ultrasound (BUS) provides an opportunity for earlier detection, the need for tube thoracostomy (TT) based on bedside imaging, including BUS and supine AP chest X-ray (CXR) is less established in the medical literature.Methods Retrospective data from 2017 to 2020 were collected of all adult trauma activations at a level 1 rural trauma facility. Every adult patient included in this study received a CXR and BUS (eFast) upon arrival. The need for TT was determined by the emergency medicine attending or the trauma surgery attending evaluating the patient. McNemar’s chi-squared test and conditional logistic regression analysis were performed comparing BUS, CXR, and the combination of BUS and CXR findings for the need for TT. Subgroup analyses were performed comparing BUS, CXR, and the combination of BUS and CXR for the detection of PTX compared to CT scan.Results Of the 12,244 patients who underwent trauma activation during this timeframe, 602 were included in the study. 74.9% were males with an age range of 36-63 years. Of the 602 patients, 210 received TT. Positive PTX was recorded with BUS in 128 (21%) patients with 16 false negatives (FNs) and 98 false positives (FPs), 100 (17%) PTX were identified with CXR with 114 FNs and 4 FPs, and 72 (11.9%) were noted on both CXR and BUS with 140 FNs and 2 FPs. The odds ratio of TT placement was 22 times with positive BUS alone (P< .0001, 95% CI: 10.9-43.47), 47 times with positive CXR alone (P< .0001, 95% CI: 16.99-127.5), and 70 times with both positive CXR and BUS (P< .0001, 95% CI: 17.08-288.4).Conclusion A positive finding of PTX on BUS combined with CXR is more indicative of the need for TT in the trauma patient when compared with BUS or CXR alone.

The GRACE satellite mission provides a new approach for monitoring, tracking, and assessing drought conditions by detecting changes in Earth’s gravitational fields and inversing signals of terrestrial water storage anomalies. Existing studies of terrestrial water storage anomalies related droughts paid rare attention to the behind atmospheric physical mechanisms, nor quantified the risk propagation patterns between terrestrial water storage deficits and hydrological or agricultural droughts. In this study, we first extract terrestrial water storage (TWS) droughts, hydrological droughts, and agricultural droughts by using multiple variables including TWS from the GRACE/GRACE-FO satellites, runoff and soil moisture from the ERA5-Land reanalysis dataset. We then identify key atmospheric and oceanic oscillation indices affecting water deficits by employing machine learning technologies. We characterize the joint distributions between drought duration and severity by using the Copula function and quantify the risk propagation of hydrological and agricultural droughts to TWS droughts. The results show that: (1) From 2002 to 2021, there is a significant decrasing trend of TWS in China; the WPIO group atmospheric circulation indices (sea surface temperature index within the Western Pacific and Indian Ocean) contributes the most to TWS. Specifically, the sea surface temperature anomalies within the NINO 3.4 region as well as the Western Pacific Warm Pool area index show significantly positive correlation relationships with TWS in southern China; (2) The northwestern China, the Yangtze River basin, and the downstream of the Pearl River basin are the hotspots of TWS droughts. Besides, the hotspots of hydrological droughts locate in northwestern China and the hotspots of agricultural droughts locate in South China and eastern Tibetan Plateau; (3) The elastic coefficients of hydrological droughts propagating to TWS droughts are higher than those of agricultural droughts, indicating that the TWS droughts are more sensitive to hydrological droughts than to agricultural droughts.

Cyclic codes are an important class of linear codes. Bounding the minimum distance of cyclic codes is a long-standing research topic in coding theory, and several well-known and basic results have been developed on this topic. Recently, locally repairable codes (LRCs) have attracted much attention due to their repair efficiency in large-scale distributed storage systems. In this paper, by employing the singleton procedure technique, we first provide a sufficient condition for bounding the minimum distance of cyclic codes with typical defining sets. Secondly, by considering a specific case, we establish a connection between bounds for the minimum distance of cyclic codes and solutions to a system of inequalities. This connection leads to the derivation of new bounds, including some with general patterns. In particular, we provide three new bounds with general patterns, one of which serves as a generalization of the Betti-Sala bound. Finally, we present a generalized lower bound for a special case and construct several families of $(2, \delta)$ -LRCs with unbounded length and minimum distance $2\delta $ . It turns out that these LRCs are distance-optimal, and their parameters are new. To the best of our knowledge, this work represents the first construction of distance-optimal $(r, \delta)$ -LRCs with unbounded length and minimum distance exceeding $r+\delta -1$ .

Renewable power plants require voltage source converters (VSCs) to convert power for further utilization. The converted power needs to be transmitted to load centers that are far from the power plants. Series compensation is widely used in transmission lines to regulate system voltage and realize large amounts of power transmission. However, it has been pointed out that VSCs tend to lose transient synchronization stability when large series compensation is implemented. Although various methods have been proposed to solve the transient instability, most of them require extensive mathematical computations and have insufficient robustness, which makes them difficult for practical applications. This article proposes a hybrid fuzzy optimization controller to improve the transient synchronization stability of series-compensated system. The proposed control strategy does not rely on specific system parameters and has good robustness and adaptability. First, the synchronization instability caused by series compensation is analyzed based on the Lyapunov direct method. Then, a hybrid fuzzy controller is investigated by combining a traditional proportional-integral (PI) controller with a fuzzy PI controller. The fuzzy C-means clustering (FCM) method is proposed to help design the membership function. Finally, simulation and experiment are performed to verify the effectiveness of the proposed method.

IMPORTANCE: The number of syphilis cases continues to increase in the US every year since 2001 with a 74% increase observed since 2017. In addition, there remains a national shortage of injectable penicillin G. Despite the increase in reported cases, to the authors’ knowledge, there has been no recent nationwide study investigating the trends in incidence of syphilitic uveitis. OBJECTIVE: To evaluate the national and regional incidence of syphilitic uveitis–related hospitalizations in the US. DESIGN, SETTING, AND PARTICIPANTS: This was a retrospective, cross-sectional study. The Nationwide Inpatient Sample was queried to identify all inpatient admissions with a diagnosis of syphilitic uveitis in the US between the years 2010 and 2019. Analyses were performed to determine baseline sociodemographic characteristics and identify national and regional trends in incidence. All patients hospitalized with a diagnosis of syphilis, uveitis, and/or syphilitic uveitis were eligible for inclusion. Statistical analysis of study data took place in June 2023. EXPOSURE: Diagnosis of syphilis, uveitis, and/or syphilitic uveitis on inpatient admissions during the years 2010 to 2019 in the Nationwide Inpatient Sample. MAIN OUTCOME MEASURES: The primary outcome was to determine trends in the national and regional incidence of syphilitic uveitis–related hospitalizations in the US. Secondary outcome measures included sociodemographic characteristics of patients with syphilitic uveitis, incidence stratified by sex and race and ethnicity, and median charge per syphilitic uveitis hospital admission. RESULTS: From the Nationwide Inpatient Sample, inpatient data from 444 674 patients (median [IQR] age, 53 [37-67] years; 54.8% male) were analyzed. There were an estimated 5581 syphilitic uveitis–related hospitalizations during the 10-year study period. The median (IQR) age of individuals with syphilitic uveitis was 45 (35-55) years, and 4395 patients (78.9%) were male. Syphilitic uveitis disproportionately affected African American individuals (1787 patients [32%], although they compose 13.6% of the population) and those belonging to the lowest median household income quartile (2163 [38.8%]). The national incidence was 0.15 per 100 000 population and showed an increasing trend over the years, with the lowest incidence in 2011 (0.08 per 100 000 population) and the highest incidence in 2019 (0.23 per 100 000 population; P = .04). Regional analysis showed an increase in incidence across all 4 US geographical regions. A total of 1293 patients (23.2%) had comorbid AIDS. CONCLUSION AND RELEVANCE: Although this cross-sectional study only captured inpatient diagnosis, an increasing incidence of syphilitic uveitis–related hospitalizations was observed in the US between 2010 and 2019. Given the concomitant national shortage of injectable penicillin G, results suggest that clinicians should maintain a high index of suspicion for syphilis when evaluating patients with intraocular inflammation.

Steels are widely used as structural materials, making them essential for supporting our lives and industries. However, further improving the comprehensive properties of steel through traditional trial-and-error methods becomes challenging due to the continuous development and numerous processing parameters involved in steel production. To address this challenge, the application of machine learning methods becomes crucial in establishing complex relationships between manufacturing processes and steel performance. This review begins with a general overview of machine learning methods and subsequently introduces various performance predictions in steel materials. The classification of performance prediction was used to assess the current application of machine learning model-assisted design. Several important issues, such as data source and characteristics, intermediate features, algorithm optimization, key feature analysis, and the role of environmental factors, were summarized and analyzed. These insights will be beneficial and enlightening to future research endeavors in this field.

CO2capture from biogas is an effective route to facilitate the utilization of biogas by improving its CH4purity. In this work, choline chloride-monoethanolamine deep eutectic solvent (ChCl-MEA DES), was employed as a promising absorbent for CO2capture. The effects of absorption pressure and temperature, and water content in DES, on CO2absorption capacity, rates, and selectivity were experimentally evaluated. The experimental data were analyzed by analysis of variance (ANOVA) and response surface method (RSM). The absorption behavior of CO2by DES mainly conformed to the laws of physical absorption. The highest CO2absorption capacity of ChCl-MEA DES was 0.608 mol-CO2/mol-DES, and the best CO2/CH4selectivity factor was 25. Regression equations of CO2absorption capacity and rate were established to evaluate the results under different operating conditions.

The task of Open-World Compositional Zero-Shot Learning (OW-CZSL) is to recognize novel state-object compositions in images from all possible compositions, where the novel compositions are absent during the training stage. The performance of conventional methods degrades significantly due to the large cardinality of possible compositions. Some recent works consider simple primitives (i.e., states and objects) independent and separately predict them to reduce cardinality. However, it ignores the heavy dependence between states, objects, and compositions. In this paper, we model the dependence via feasibility and contextuality. Feasibility-dependence refers to the unequal feasibility of compositions, e.g., hairy is more feasible with cat than with building in the real world. Contextuality-dependence represents the contextual variance in images, e.g., cat shows diverse appearances when it is dry or wet. We design Semantic Attention (SA) to capture the feasibility semantics to alleviate impossible predictions, driven by the visual similarity between simple primitives. We also propose a generative Knowledge Disentanglement (KD) to disentangle images into unbiased representations, easing the contextual bias. Moreover, we complement the independent compositional probability model with the learned feasibility and contextuality compatibly. In the experiments, we demonstrate our superior or competitive performance, SA-and-kD-guided Simple Primitives (SAD-SP), on three benchmark datasets.

Nonadiabatic dynamics (NAMD) simulations have become powerful tools for elucidating complicated photoinduced processes in various systems from molecules to semiconductor materials. In this review, we present an overview of our recent research on photophysics of molecular systems and periodic semiconductor materials with the aid of ab initio NAMD simulation methods implemented in the generalized trajectory surface-hopping (GTSH) package. Both theoretical backgrounds and applications of the developed NAMD methods are presented in detail. For molecular systems, the linear-response time-dependent density functional theory (LR-TDDFT) method is primarily used to model electronic structures in NAMD simulations owing to its balanced efficiency and accuracy. Moreover, the efficient algorithms for calculating nonadiabatic coupling terms (NACTs) and spin–orbit couplings (SOCs) have been coded into the package to increase the simulation efficiency. In combination with various analysis techniques, we can explore the mechanistic details of the photoinduced dynamics of a range of molecular systems, including charge separation and energy transfer processes in organic donor–acceptor structures, ultrafast intersystem crossing (ISC) processes in transition metal complexes (TMCs), and exciton dynamics in molecular aggregates. For semiconductor materials, we developed the NAMD methods for simulating the photoinduced carrier dynamics within the framework of the Kohn–Sham density functional theory (KS-DFT), in which SOC effects are explicitly accounted for using the two-component, noncollinear DFT method. Using this method, we have investigated the photoinduced carrier dynamics at the interface of a variety of van der Waals (vdW) heterojunctions, such as two-dimensional transition metal dichalcogenides (TMDs), carbon nanotubes (CNTs), and perovskites-related systems. Recently, we extended the LR-TDDFT-based NAMD method for semiconductor materials, allowing us to study the excitonic effects in the photoinduced energy transfer process. These results demonstrate that the NAMD simulations are powerful tools for exploring the photodynamics of molecular systems and semiconductor materials. In future studies, the NAMD simulation methods can be employed to elucidate experimental phenomena and reveal microscopic details as well as rationally design novel photofunctional materials with desired properties.

Ultrafast charge and spin dynamics have immense effects on the applications of topological insulators (TIs). By performing spin-adiabatic nonadiabatic molecular dynamics simulations in the presence of electron–phonon (e-ph) and spin–phonon couplings, we investigate temperature-dependent intra- and interband charge and spin relaxation dynamics via the bulk and surface paths in the three-dimensional TI Bi2Te3. The e-phcoupling dominates charge relaxation in the bulk path, and the relaxation rate is positively correlated with temperature due to the large energy gaps and weak spin polarization. Conversely, the relaxation dynamics exhibits an opposite temperature dependence in the surface path because of electron re-excitation and spin mismatching induced by spin–phonon coupling, which arises from small energy gaps and strong spin polarization. The two mechanisms rationalize the charge carriers being long-lived in the bulk and surface phases at low and room temperature, respectively. Additionally, strong thermal fluctuations of the topological states’ magnetic moments destroy the spin-momentum locking and trigger backscattering at room temperature.