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An analytical equation of state (EOS) for a hard sphere fluid confined in random porous media is derived by extending the scaled particle theory to such complex systems with quenched disorders. A simple empirical correction allows us to obtain a highly accurate EOS with errors within the simulation ones. These are the first analytical results for non trivial off-lattice quench-annealed systems. [ABSTRACT FROM AUTHOR]

Positron annihilation lifetime spectroscopy (PALS) has potential as a novel rapid characterization method for self-assembly amphiphile systems; however, a lack of systematic correlation of PALS parameters with structural attributes has limited its more widespread application. In this study, using the well-characterized phytantriol/water and the phytantriol/vitamin E acetate/water self-assembly amphiphile systems, the impact of systematic structural changes controlled by changes in composition and temperature on PALS parameters has been studied. The PALS parameters (orthopositronium (oPs) lifetime and intensity signatures) were shown to be sensitive to the molecular packing and mobility of the self-assembled lipid molecules in various lyotropic liquid crystalline phases, enabling differentiation between liquid crystalline structures. The oPs lifetime, related to the molecular packing and mobility, is correlated with rheological properties of the individual mesophases. The oPs lifetime links the lipid chain packing and mobility in the various mesophases to resultant macroscopic properties, such as permeability, which is critical for the use of these mesophase structures as diffusion-controlled release matrices for active liposoluble compounds. [ABSTRACT FROM AUTHOR]

The lyotropic liquid-crystalline phase behavior of phytantriol is receiving increasing interest in the literature as a result of similarities with glyceryl monooleate, despite its very different molecular structure. Some differences in the phase-transition temperature for the bicontinuous cubic to reverse hexagonal phase have been reported in the literature. In this study, we have investigated the influence that the commercial source and hence the purity has on the lyotropic phase behavior of phytantriol. Suppression of the phase-transition temperatures (by up to 15 °C for the bicontinuous cubic to reverse hexagonal phase transition) is apparent with lower-purity phytantriol. In addition, the composition boundaries were also found to depend significantly on the source and purity of phytantriol, with the bicontinuous cubic phase + excess water boundary occurring at a water content above that reported previously (i.e., >5% higher). Both the temperature and compositional changes in phase boundaries have significant implications on the use of these materials and highlight the impact that subtle levels of impurities can play in the phase behavior of these types of materials. [ABSTRACT FROM AUTHOR]

Antimicrobial sonodynamic therapy (SDT) holds great promise in clinical practice regarding its noninvasiveness, high safety profile, and absence of resistance concern. However, exploring high-efficiency sonodynamic sensitizers is slow-moving and remains a big challenge. We, herein, employed gold nanoclusters (Au NCs) as a novel class of sonodynamic sensitizers, demonstrating notable antimicrobial efficacy in treating infected wounds. Specifically, l-arginine (Arg) and 6-azido-2-thiothymidine (ATT) cocapped Au NCs featured enhanced structural rigidity, suppressing nonradiative relaxation of excited electrons and achieving a reactive oxygen species (ROS) yield exceeding 45%. Moreover, the modification of ATT-Au NCs by Arg imparted amino acid-like properties to the Au NCs, while the ultrasound (US) up-regulates the expression of OmpF porins in E. coli . This synergy resulted in a burst of ROS production within the bacterial cells, ultimately leading to a four-order-of-magnitude reduction in microbial viability.

Asymmetric transfer hydrogenation (ATH) has been recognized as a highly valuable strategy that allows access to enantioenriched substances and has been widely applied in the industrial production of drug molecules. However, despite the great success in ATH of ketones, highly efficient, regio- and stereoselective ATH on enones remains underdeveloped. Moreover, optically pure acyloins and 1,2-diols are both extremely useful building blocks in organic synthesis, medicinal chemistry, and materials science, but concise asymmetric approaches allowing access to different types of acyloins and 1,2-diols have scarcely been discovered. We report in this paper the first highly efficient ATH of readily accessible β,γ-unsaturated α-diketones. The protocol affords four types of enantioenriched acyloins and four types of optically pure 1,2-diols in highly regio- and stereoselective fashion. The synthetic value of this work has been showcased by the divergent synthesis of four related natural products. Moreover, systematic mechanistic studies and density functional theory (DFT) calculations have illustrated the origin of the reactivity divergence, revealed the different roles of aromatic and aliphatic substituents in the substrates, and provided a range of unique mechanistic rationales that have not been disclosed in ATH-related studies.

The tea plant ( Camellia sinensis ) is a unique beverage crop worldwide, but its yield and quality are adversely affected by Toxoptera aurantii . However, the response mechanisms of tea plants to T. aurantii stress remain poorly known. Herein, we present the life table of T. aurantii on resistant (W016) and susceptible (HJY) tea cultivars, demonstrating that the fitness of T. aurantii on W016 was lower than that on HJY. Integrated metabolic and transcriptomic analyses revealed that T. aurantii feeding activated pathways associated with phenylpropanoid biosynthesis, plant hormone signal transduction, and ATP-binding cassette (ABC) transporters. Notably, T. aurantii feeding significantly upregulated the levels of brassinolide and p -coumaryl alcohol in W016 but not in HJY. Furthermore, in vitro enzymatic assays indicated that C. sinensis cinnamyl alcohol dehydrogenase (CsCAD1) catalyzes the formation of p -coumaryl alcohol participation in lignin synthesis. Our findings highlight the role of brassinolide-mediated lignin biosynthesis of the tea plant in response to T. aurantii feeding.

The conversion of CO 2 into value-added chemicals and fuels using stable, cost-effective, and eco-friendly metal-free catalysts is a promising technology to mitigate the global environmental crisis. In the Calvin cycle of natural photosynthesis, CO 2 reduction (CO 2 R) is achieved using the cofactor NADPH as the reducing agent through 2 e - /1H + or H - transfer. Consequently, inspired by NAD(P)H, a series of organohydrides with adjustable reducibility show remarkable potential for efficient metal-free CO 2 R. In this review, we first summarize the photosensitizers for NAD(P)H regeneration and list the representative photoenzyme CO 2 R system. Then, we introduce the NAD(P)H-inspired organohydrides and their applications in redox reactions. Furthermore, we discuss recent progress and breakthroughs by utilizing organohydrides as metal-free CO 2 R catalysts. Moreover, we delve into the reaction mechanisms and applications of these organohydrides, shedding light on their potential as sustainable alternatives to metal-based CO 2 R catalysts. Finally, we offer insights into the prospects and potential directions for advancing this intriguing avenue of organohydride-based catalysts for CO 2 R.

Classifications of fluids using miniaturized sensors are of substantial importance for various fields of application. Modified with functional nanomaterials, a moisture-enabled electricity generation (MEG) device can execute a dual-purpose operation as both a self-powered framework and a fluid detection platform. In this study, a novel intelligent self-sustained sensing approach was implemented by integrating MEG with deep learning in microfluidics. Following a multilayer design, the MEG device including three individual units for power generation/fluid classification was fabricated in this study by using nonwoven fabrics, hydroxylated carbon nanotubes, poly(vinyl alcohol)-mixed gels, and indium tin bismuth liquid alloy. A composite configuration utilizing hydrophobic microfluidic channels and hydrophilic porous substrates was conducive to self-regulation of the on-chip flow. As a generator, the MEG device was capable of maintaining a continuous and stable power output for at least 6 h. As a sensor, the on-chip units synchronously measured the voltage (V), current (C), and resistance (R) signals as functions of time, whose transitions were completed using relays. These signals can serve as straightforward indicators of a fluid presence, such as the distinctive "fingerprint". After normalization and Fourier transform of raw V/C/R signals, a lightweight deep learning model (wide-kernel deep convolutional neural network, WDCNN) was employed for classifying pure water, kiwifruit, clementine, and lemon juices. In particular, the accuracy of the sample distinction using the WDCNN model was 100% within 15 s. The proposed integration of MEG, microfluidics, and deep learning provides a novel paradigm for the development of sustainable intelligent environmental perception, as well as new prospects for innovations in analytical science and smart instruments.

In this study, we developed ratiometric surface-enhanced Raman scattering (SERS) biosensors using Ag-Au alloy nanoflowers as SERS substrates, molecules having amide bonds and alkyne groups (Tag A) as Raman reporters, and sodium thiocyanate as an internal standard molecule (Tag B) for the sensitive detection of human carboxylesterase-1 (hCE1) in HepG-2 cells. The correlation between HepG-2 cell damage and hCE1 activity levels was investigated. Both Tag A's alkyne group and Tag B's cyanide group produced characteristic SERS signals in the Raman-silent region ( I 2000 cm -1 and I 2115 cm -1 , respectively). The hydrolysis of the amide bond in Tag A via hCE1 and the shedding of the alkyne group led to a reduction in the SERS signal intensity observed at I 2000 cm -1 . Conversely, the SERS signal intensity of Tag B at I 2115 cm -1 exhibited a consistent pattern. As the activity level of hCE1 and the ratiometric peak intensity ( I 2000 cm -1 / I 2115 cm -1 ) correlated negatively, hCE1 could be quantitatively detected within the range of 10 -2 to 2 × 10 2 ng·mL -1 , with a detection limit of 7.3 pg·mL -1 . The ratiometric SERS probe strategy, in which a ratio response is employed, permits sensitive and reproducible SERS detection by facilitating intrinsic calibration to rectify signal fluctuations resulting from temporal and spatial variations in the detection conditions. Concurrently, the implementation of Raman-silent region reporter molecules mitigates the interference from endogenous biomolecules in SERS measurements and offers a novel approach for achieving highly sensitive and interference-free detection of intracellular hCE1.

Clusteroluminescent polymers have the most potential to be used in light conversion agricultural films due to tunable emission wavelength and large-scale production, but they are still limited by shortcomings such as poor stability and sensitivity to melting processes. In this work, we propose a core-shell confined stable clusteroluminescent polymeric nanoparticle strategy with adjustable shell thickness. By the employment of a combination of solvent and heat treatment methods, the structures, rigid-flexible properties, and aggregation states of the core polymer chains have been modified. The presence of cross-linked shells has significantly enhanced the stability of the clusteroluminescent nanoparticles, ensuring that they retain their structure form even after undergoing high temperature and shear. Finally, the stable agricultural light conversion films with tunable clusteroluminescence are obtained via melt blending of the core-shell confined nanoparticles and polyethylene (PE). Due to the shell confinement effect, when melt-blended, the shell can protect the clusteroluminescent polymer within the core from the effects of high temperature and shear. It is anticipated that the completion of this work will provide a significant foundation for the large-scale application of cluster-luminescent polymers in agriculture.

Improving the performance of energy storage, neuromorphic computing, and more applications requires an in-depth understanding of ion transport at interfaces, which are often hindered by facile atomic reconfiguration at working conditions and limited characterization capability. Here, we construct an in situ double-tilt electric manipulator inside an aberration-corrected scanning transmission electron microscope. Coupled with deep learning-based image enhancement, atomic images are enhanced 3-fold compared to traditional methods to observe the potassium ion migration and microstructure evolution at the crystalline-amorphous interface in antimony selenide. Potassium ions form stable anisotropic insertion sites outside the (Sb 4 Se 6 ) chain, with a few potassium ions present within the moieties. Combined experiments and density functional theory calculations reveal a reaction pathway of forming a novel metastable state during potassium ion insertion, followed by recovery and unexpected chirality changes at the interface upon potassium ion extraction. Our unique methodology paves the way for facilitating the improvement and rational design of nanostructured materials.

A photocatalysis-electro-Fenton (PEF) system was constructed via molybdenum disulfide (MoS 2 ) to remove tetracycline (TC) without an external oxidant supply and solution pH adjustment. In the system, original graphite felt (GF) was used as a cathode, from which H 2 O 2 was in situ generated continuously under power. MoS 2 was motivated by visible light to facilitate the cycle of Fe 2+ /Fe 3+ , enhancing the Fenton process to produce • OH. The experimental results showed that the system can increase the degradation rate of pollutants by more than 5 times. Moreover, the quenching and electron paramagnetic resonance (EPR) tests demonstrated that • OH was the dominant active species. X-ray photoelectron spectroscopy (XPS) characterization, Mo concentration, and cycle experiments proved the excellent catalytic activity and chemical stability of MoS 2 . It is worth mentioning that the photocatalytic performances of different morphologies of MoS 2 (flower, flake, and radar) were compared. As a result, flower-like MoS 2 exhibited a much superior photoresponse than flake and radar, which could accelerate the Fe 2+ /Fe 3+ cycle further effectively. These findings highlight the morphology-performance relationship of MoS 2 under a PEF system and the mechanisms of contaminant degradation, which is of great significance for developing photoelectric Fenton technology.

Symmetrical biheteroaryl compounds, such as bypyridines and bipyrazoles, are important ligands in transition-metal catalysis. They also serve as synthetic precursors of photo catalysts/sensitizers, bioactive agents, and energetic materials. To facilitate the concise synthesis of these useful structures, an efficient Pd-catalyzed homocoupling of heteroaryl bromides has been successfully established using the electron-rich and sterically hindered monophosphorus ligand BIDIME. The coupling protocol features a tandem Miyaura borylation/Suzuki coupling sequence and exhibits unprecedented tolerance of a wide range of heteroaryl bromides, providing a series of symmetrical biheteroaryls in moderate to good yields. Notably, the use of the corresponding polymeric ligand, PolyBIDIME, enabled the recycling of a palladium catalyst, demonstrating the potential of the homocoupling in practical applications.

In recent years, with the rapid development of ultrastrong and ultrafast lasers, it has become essential to develop new materials with excellent nonlinear optical (NLO) properties. Porphyrin-based metal-organic frameworks (MOFs) have great potential for application in the field of NLO due to their large conjugated structure and good stability. As a typical porphyrin-based MOF, porphyrin paddle-wheel framework-3 (PPF-3) has been prepared and applied in the fields of catalysis and sensing, yet the investigation of PPF-3 in NLO remains unexplored. In this study, the ZnS/PPF-3 composite was successfully prepared using a solvent thermal method to in situ load ZnS on the surface of PPF-3. Utilizing the Z-scan technique, the NLO properties of ZnS, PPF-3, and ZnS/PPF-3 composite were investigated under different input energy intensities. ZnS/PPF-3 composite material exhibits significantly enhanced NLO properties, with the third-order nonlinear absorption coefficient (β eff ) of up to 7.00 × 10 -10 m/W and a limiting threshold as low as 1.52 J/cm 2 , indicating its promising application potential value in the field of optical limiting. To enhance the practical utility, the ZnS/PPF-3/PVA film was prepared via the drop-casting method, achieving a maximum β eff of 5.00 × 10 -8 m/W. The smaller optical bandgap of ZnS/PPF-3 and electron transfer from PPF-3 to ZnS are the key factors that enable the ZnS/PPF-3 composite to a superior NLO performance.

Simultaneous detection of the dynamic distribution of long-chain fatty acid ethyl esters (LCFAEEs) during Baijiu distillation is crucial for optimizing its flavor and health attributes. In this study, we synthesized a simple, cost-effective Fe 3 O 4 @NH 2 adsorbent to simultaneously extract eight LCFAEEs from Baijiu. Through density functional theory and adsorption experiments, we elucidated 1,6-hexanediamine as a surface modifier, with the -NH 2 groups providing adsorption sites for the LCFAEEs via hydrogen-bonding interactions and van der Waals forces. Additionally, we established the magnetic solid-phase extraction-GC-MS extraction technique combined with stable isotope dilution analysis to analyze LCFAEEs. This method revealed the dynamic distribution patterns of LCFAEEs during strong aroma-type Baijiu (SAB) distillation. We observed that the concentrations of the eight LCFAEEs gradually decreased with prolonged distillation and were significantly correlated with ethanol concentration. To ensure optimal flavor and clarity in SAB, it is recommended to select the heart-stage base Baijiu with an alcohol content of 58%-63%.

Core fucosylation, the attachment of an α-1,6-linked-fucose to the N-glycan core pentasaccharide, is an abundant protein modification that plays critical roles in various biological processes such as cell signaling, B cell development, antibody-dependent cellular cytotoxicity, and oncogenesis. However, the tools currently used to detect core fucosylation suffer from poor specificity, exhibiting cross-reactivity against all types of fucosylation. Herein we report the development of a new chemoenzymatic strategy for the rapid and selective detection of core fucosylated glycans. This approach employs a galactosyltransferase enzyme identified from Caenorhabditis elegans that specifically transfers an azido-appended galactose residue onto core fucose via a β-1,4 glycosidic linkage. We demonstrate that the approach exhibits superior specificity toward core fucose on a variety of complex N-glycans. The method enables detection of core fucosylated glycoproteins from complex cell lysates, as well as on live cell surfaces, and it can be integrated into a diagnostic platform to profile protein-specific core fucosylation levels. This chemoenzymatic labeling approach offers a new strategy for the identification of disease biomarkers and will allow researchers to further characterize the fundamental role of this important glycan in normal and disease physiology.

A robust and fully biobased covalent adaptable network (CAN) that allows recyclability, biocompatibility, and controlled biodegradability is reported. The CAN was fabricated through a simple photo-cross-linking method, wherein low-molecular-weight poly(lactic acid) (∼3 kDa) was modified with end 1,2-dithiolane rings through a one-step Steglich esterification reaction with thioctic acid (TA). These incorporated 1,2-dithiolane rings undergo photoinduced ring-opening polymerization, thus enabling the cross-linking of poly(lactic acid) with abundant dynamic disulfide bonds. The resultant CAN demonstrates excellent transparency, effective UV-blocking capabilities below 320 nm, robust tensile strength (∼39 MPa), and superior dimensional stability at 80 °C, alongside attractive biocompatibility. Moreover, owing to the dynamic exchange and redox-responsiveness of disulfide bonds, the material can be recycled by hot-pressing and a reduction-oxidation process while also being capable of controllably biodegrading at the end of its lifecycle. Furthermore, it exhibits reconfigurable shape memory properties with fast recovery. This study elucidates a straightforward approach to fabricating multifunctional and sustainable polymer materials with potential applications in diverse fields such as packaging, coating, and biomedicine.

The potential threat of cadmium (Cd)-induced acute kidney injury (AKI) is increasing. In this study, our primary goal was to investigate the individual roles played by mTOR complexes, specifically mTORC1 and mTORC2, in Cd-induced apoptosis in mouse kidney cells. We constructed a mouse model with specific deletion of Raptor/Rictor renal cells. Inhibitors and activators of mTORC1 or mTORC2 were also applied. The effects of protein kinase B (AKT) activation and autophagy were studied. Both mTORC1 and mTORC2 were found to mediate the antiapoptotic mechanism of renal cells by regulating the AKT activity. Inhibition of mTORC1 or mTORC2 exacerbated Cd-induced kidney cell apoptosis, suggesting that both proteins exert antiapoptotic effects under Cd exposure. We further found that the AKT activation plays a key role in mTORC1/TORC2-mediated antiapoptosis, protecting Cd-exposed kidney cells from apoptosis. We also found that mTOR activators inhibited excessive autophagy, alleviated apoptosis, and promoted cell survival. These findings provide new insights into the regulatory mechanisms of mTOR in renal diseases and provide a theoretical basis for the development of novel therapeutic strategies to treat renal injury.

Diagnostic and monitoring for drug-induced liver injury (DILI) predominantly rely on serum aminotransferases. However, owing to their widespread expression across multiple organs, a significant challenge emerges from the absence of reliable biomarkers for DILI diagnosis. Herein, we introduce a concept for DILI detection, circumventing the nonspecific elevation and delayed release of aminotransferases and then straightforwardly focusing on the core feature of DILI, abnormal gene expression caused by drug overdose. The developed full-scale platform integrates the properties of spherical nucleic acids with elaborately designed fluorescence in situ hybridization sequences, enabling the sensitive and specific profiling of drug-overdosed miR-122 expression alterations across molecular, cellular, organismal, and clinical scales and effectively bypassing the phenotypic features of disease. Furthermore, the diagnostic efficacies of serum and total RNA extracted from both mouse and human blood samples for DILI diagnosis were analyzed using the receiver operating characteristic curve and principal component analysis. We anticipate that this universal platform holds potential in facilitating DILI diagnosis, therapeutic evaluation, and prognosis.

Acute myeloid leukemia (AML) is a relatively common malignant hematological disease whose development is mostly associated with abnormal activation of the JAK/STAT3 signaling pathway. Our previous study revealed that SAR317461, a novel JAK2/STAT3 inhibitor, can effectively inhibit the activation of the JAK2/STAT3 signaling pathway and has significant damaging and pro-apoptotic effects on AML cell lines. This project aims to build upon our prior research to enhance the application of SAR317461 in AML. The surface modification of liposomes with the CD34 antibody, along with the inclusion of the SAR317461 and cytarabine (a common AML chemotherapeutic agent), is observed. Due to the high expression of CD34 on the surface of AML cells, the nanoliposome could target AML cells specifically, further achieving an effective treatment for AML through the synergistic effect of JAK2/STAT3 inhibitors and chemotherapeutic agents. The implementation of this project will provide more theoretical support and ideas for the clinical application of JAK/STAT3 inhibitors in malignant tumors and for overcoming chemotherapy resistance., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Natural cyclic dinucleotide (CDN) is the secondary messenger involved in bacterial hemostasis, human innate immunity, and bacterial antiphage immunity. Synthetic CDN and its analogues are key molecular probes and potential immunotherapeutic agents. Several CDN analogues are under clinical research for antitumor immunotherapy. A myriad of synthetic methods have been developed and reported for the preparation of CDN and its analogues. However, most of the protocols require multiple steps, and only one CDN or its analogue is prepared at a time. In this study, a strategy based on a macrocyclic ribose phosphate skeleton containing a 1'-alkynyl group was designed and developed to prepare CDN analogues containing triazolyl C-nucleosides by click chemistry. Combinatorial application of click chemistry and the sulfenylation cascade to the macrocyclic skeleton expanded the diversity of the CDN analogues. This macrocyclic skeleton strategy rapidly and efficiently provides CDN analogues to facilitate research on microbiology, immunology, and immunotherapy.

Metal nanoclusters (NCs) hold great promise for expressing multipeak emission based on their well-defined total structure with diverse luminescent centers. Herein, we report the surface motif-dictated triple phosphorescence of Au NCs with dynamic color turning. The deprotonation-triggered isomerization of terminal thiouracils can evolve into a mutual transformation among their hierarchical motifs, thus serving a multipeak-emission expression with good tailoring. More importantly, the underlying electron transfer is thoroughly identified by excluding the radiative and nonradiative energy transfer, where electrons flow from the first phosphorescent state to the last two ones. The findings shed light on finely tailing motifs at the molecular level to motivate studies on customizable luminescence characteristics of metal NCs.

Excessive production of waste polyethylene terephthalate (PET) poses an ecological challenge, which necessitates developing technologies to extract the values from end-of-life PET. Upcycling has proven effective in addressing the low profitability of current recycling strategies, yet existing upcycling technologies operate under energy-intensive conditions. Here we report a cascade strategy to steer the transformation of PET waste into glycolate in an overall yield of 92.6% under ambient conditions. The cascade approach involves setting up a robust hydrolase with 95.6% PET depolymerization into ethylene glycol (EG) monomer within 12 h, followed by an electrochemical process initiated by a CO-tolerant Pd/Ni(OH) 2 catalyst to convert the EG intermediate into glycolate with high Faradaic efficiency of 97.5%. Techno-economic analysis and life cycle assessment indicate that, compared with the widely adopted electrochemical technology that heavily relies on alkaline pretreatment for PET depolymerization, our designed enzymatic-electrochemical approach offers a cost-effective and low-carbon pathway to upgrade PET.

The research focused on the distinctive empty cup aroma, with the aim of identifying the key aroma compounds and the formation mechanism of empty cup aroma in soy sauce aroma type baijiu (SSB). The lasting times of SSB is significantly longer than that of other types of baijiu, with an average duration of 28 days. Key compounds such as 2,3-dimethyl-5-ethylpyrazine, phenylethyl alcohol, p -cresol, sotolon, benzeneacetic acid were identified in empty cup aroma due to their highest flavor dilution factor. Molecular dynamics (MD) simulation was performed to study the mechanism of empty cup aroma on the liquid-gas interface and solid-gas interface. The results revealed the existence of hydrogen bonding and van der Waals forces between sotolon and lactic acid, a representative nonvolatile compound, which are speculated to be an important reason for the empty cup aroma.

Developing a general method that leads to the formation of different classes of chiral bioactive compounds and their stereoisomers is an attractive but challenging research topic in organic synthesis. Furthermore, despite the great value of asymmetric transfer hydrogenation (ATH) in both organic synthesis and the pharmaceutical industry, the monohydrogenation of unsymmetrical 1,2-diketones remains underdeveloped. Here, we report the aryloxy group-assisted highly regio-, diastereo-, and enantioselective ATH of racemic 1,2-diketones. The work produces a myriad of enantioenriched dihydroxy ketones, and further transformations furnish all eight stereoisomers of diaryl triols, polyphenol, emblirol, and glycerol-type natural products. Mechanistic studies and calculations reveal two working modes of the aryloxy group in switching the regioselectivity from a more reactive carbonyl to a less reactive one, and the potential of ATH on 1,2-diketones in solving challenging synthetic issues has been clearly demonstrated.

With increasing battery demand comes a need for diversified Li sources beyond brines. Among all Li-bearing minerals, spodumene is most often used for its high Li content and natural abundance. However, the traditional approach to process spodumene is costly and energy-intensive, requiring the mineral be transformed from its natural α to β phase at >1000 °C. Acid leaching is then applied, followed by neutralization to precipitate Li 2 CO 3 . In this work, we report an alternative method to extract Li directly from α-spodumene, which is performed at lower temperatures and avoids the use of acids. It is shown that Li 2 CO 3 is formed with >90% yield at 750 °C by reacting α-spodumene with Na 2 CO 3 and Al 2 O 3 . The addition of Al 2 O 3 is critical to reduce the amount of Li 2 SiO 3 that forms when only Na 2 CO 3 is used, instead providing increased thermodynamic driving force to form NaAlSiO 4 and Li 2 CO 3 as the sole products. We find that this reaction is most effective at 4 h, after which volatility limits the yield. Following its extraction, Li 2 CO 3 can be isolated by washing the sample using deionized water. This energy-saving and acid-free route to obtain Li 2 CO 3 directly from spodumene can help meet the growing demand for Li.

The pursuit of a straightforward method to recycle organic dyes from effluents and repurpose them into valuable materials represents a highly sought-after yet huge challenge within the realms of chemistry, environment, and materials science. In this context, we employ a host-guest strategy that leverages the recycling of the rhodamine B molecule within the porous structure of a metal-organic framework to facilitate photothermal conversion. This achievement is realized through the electrostatic interaction, which then gives rise to remarkable selectivity and unparalleled uptake capacity for the cationic rhodamine B molecule. Capitalizing on this approach, the application of a columnar device and membrane technology for efficiently trapping rhodamine B molecules becomes feasible. On account of the aggregation effect resulting from the confined pore structure of the host matrix, the fluorescence emission of the encapsulated RhB molecules is significantly reduced, which consequently enhances the photothermal performance of the hybrid material through nonradiative transition. Moreover, the photothermal conversion achieved showcases a myriad of high-performance applications, including bacterial inhibition against Escherichia coli and seawater desalination.

One of the routes for adaptation to extreme environments is via remodeling of cell membrane structure, composition, and biophysical properties rendering a functional membrane. Collective studies suggest some form of membrane feedback in mycobacterial species that harbor complex lipids within the outer and inner cell wall layers. Here, we study the homeostatic membrane landscape of mycobacteria in response to high hydrostatic pressure and temperature triggers using high pressure fluorescence, mass and infrared spectroscopies, NMR, SAXS, and molecular dynamics simulations. Our findings reveal that mycobacterial membrane possesses unique and lipid-specific pressure-induced signatures that attenuate progression to highly ordered phases. Both inner and outer membrane layers exhibit phase coexistence of nearly identical lipid phases keeping residual fluidity over a wide range of temperature and pressure, but with different sensitivities. Lipidomic analysis of bacteria grown under pressure revealed lipidome remodeling in terms of chain length, unsaturation, and specific long-chained characteristic mycobacterial lipids, rendering a fluid bacterial membrane. These findings could help understand how bacteria may adapt to a broad spectrum of harsh environments by modulating their lipidome to select lipids that enable the maintenance of a fluid functional cell envelope.

We present maximally localized Wannier functions and Voronoi tessellation to obtain dipole moment distributions for vibrational spectra in several important ionic liquids calculated by using ab initio molecular dynamics simulations. IR and Raman spectra of various imidazolium-based ionic liquids (ILs) paired with six amino acid anions are shown herein. For IR spectra, two approaches (Wannier and Voronoi) are in agreement with respect to the relative intensities and the overall shapes for the main peaks. Under Raman spectra, the polarizability of the covalent bonds is shown to affect the strength of the Raman scattering signal. The advantage of the Voronoi tessellation method, being that it does not have strong spikes in its time development, is demonstrated by the comparison of two theoretical methods (Wannier and Voronoi) with experimental data. We analyze the errors between theoretical and experimental spectroscopic data, with the Voronoi method shown to accurately reproduce experimental values. In addition, theoretical spectroscopy shows the ability to accurately separate components of a mixture. The combination of theoretical and experimental methods is utilized to understand the spectroscopic properties of amino acid-based imidazolium ILs.

The receptor for advanced glycation end products (RAGE) plays a crucial role in inflammation-related pathways and various chronic diseases. Despite the recognized significance of N-glycosylation in the ligand-binding V domain (VD) of RAGE, a comprehensive understanding of the site-activity and structure-activity relationships is lacking due to the challenges in obtaining homogeneous glycoprotein samples through biological expression. Here, we combined chemical and chemoenzymatic approaches to synthesize RAGE-VD and its congeners with Asn3-glycosylation by incorporating precise N-glycan structures. Evaluation of these samples revealed that, in comparison to other RAGE-VD forms, α2,6-sialylated N-glycosylation at the Asn3 site results in more potent inhibition of HMGB1-induced nuclear factor-κB (NF-κB) expression in RAGE-overexpressing cells. Hydrogen/deuterium exchange-mass spectrum analysis revealed a sialylated RAGE-VD-induced interaction region within HMGB1. Conversely, Asn3 N-glycosylation in VD has negligible effects on RAGE-VD/S100B interactions. This study established an approach for accessing homogeneously glycosylated RAGE-VD and explored the modulatory effects of N-glycosylation on the interactions between RAGE-VD and its ligand proteins.

The interfacial FeSe/TiO 2-δ coupling induces high-temperature superconductivity in monolayer FeSe films. Using cryogenic atomically resolved scanning tunneling microscopy/spectroscopy, we obtained atomic-site dependent surface density of states, work function, and the pairing gap in the monolayer FeSe on the SrTiO 3 (001)-(√13 × √13)-R33.7° surface. Our results disclosed the out-of-plane Se-Fe-Se triple layer gradient variation, switched DOS for Fe sites on and off TiO 5□ , and inequivalent Fe sublattices, which gives global spatial modulation of pairing gap contaminants with the (√13 × √13) pattern. Moreover, the coherent lattice coupling induces strong inversion asymmetry and in-plane anisotropy in the monolayer FeSe, which is demonstrated to correlate with the particle-hole asymmetry in coherence peaks. These results disclose delicate atomic-scale correlations between pairing and lattice-electronic coupling in the Bardeen-Cooper-Schrieffer to Bose-Einstein condensation crossover regime, providing insights into understanding the pairing mechanism of multiorbital superconductivity.

The discovery of high-mobility two-dimensional electron gas and low carrier density superconductivity in multiple SrTiO 3 -based heterostructures has stimulated intense interest in the surface properties of SrTiO 3 . The recent discovery of high- T c superconductivity in the monolayer FeSe/SrTiO 3 led to the upsurge and underscored the atomic precision probe of the surface structure. By performing atomically resolved cryogenic scanning tunneling microscopy/spectroscopy characterization on dual-TiO 2-δ -terminated SrTiO 3 (001) surfaces with (√13 × √13), c(4 × 2), mixed (2 × 1), and (2 × 2) reconstructions, we disclosed universally broken rotational symmetry and contrasting bias- and temperature-dependent electronic states for apical and equatorial oxygen sites. With the sequentially evolved surface reconstructions and simultaneously increasing equatorial oxygen vacancies, the surface anisotropy reduces and the work function lowers. Intriguingly, unidirectional stripe orders appear on the c(4 × 2) surface, whereas local (4 × 4) order emerges and eventually forms long-range unidirectional c(4 × 4) charge order on the (2 × 2) surface. This work reveals robust unidirectional charge orders induced by oxygen vacancies due to strong and delicate electronic-lattice interaction under broken rotational symmetry, providing insights into understanding the complex behaviors in perovskite oxide-based heterostructures.

Inflammation induced by activated macrophages within vulnerable atherosclerotic plaques (VAPs) constitutes a significant risk factor for plaque rupture. Translocator protein (TSPO) is highly expressed in activated macrophages. This study investigated the effectiveness of TSPO radiotracers, 18 F-FDPA, in detecting VAPs and quantifying plaque inflammation in rabbits. 18 New Zealand rabbits were divided into 3 groups: sham group A, VAP model group B, and evolocumab treatment group C. 18 F-FDPA PET/CTA imaging was performed at 12, 16, and 24 weeks in all groups. Optical coherence tomography (OCT) was performed on the abdominal aorta at 24 weeks. The VAP was defined through OCT images, and ex vivo aorta PET imaging was also performed at 24 weeks. The SUV max and SUV mean of 18 F-FDPA were measured on the target organ, and the target-to-background ratio (TBR max ) was calculated as SUV max /SUV blood pool . The arterial sections of the isolated abdominal aorta were analyzed by HE staining, CD68 and TSPO immunofluorescence staining, and TSPO Western blot. The results showed that at 24 weeks, the plaque TBR max of 18 F-FDPA in group B was significantly higher than in groups A and C. Immunofluorescence staining of CD68 and TSPO, as well as Western blot, confirmed the increased expression of macrophages and TSPO in the corresponding regions of group B. HE staining revealed an increased presence of the lipid core, multiple foam cells, and inflammatory cell infiltration in the area with high 18 F-FDPA uptake. This indicates a correlation between 18 F-FDPA uptake, inflammation severity, and VAPs. The TSPO-targeted tracer 18 F-FDPA shows specific uptake in macrophage-rich regions of atherosclerotic plaques, making it a valuable tool for assessing inflammation in VAPs.

Criegee intermediates exert a crucial influence on atmospheric chemistry, functioning as powerful oxidants that facilitate the degradation of pollutants, and understanding their reaction kinetics is essential for accurate atmospheric modeling. In this study, the kinetics of CH 2 OO and syn -CH 3 CHOO reactions with acetaldehyde (CH 3 CHO) were investigated using a flash photolysis reaction tube coupled with the OH laser-induced fluorescence (LIF) method. The experimental results indicate that the reaction of syn -CH 3 CHOO with CH 3 CHO is independent of pressure in the range of 5-50 Torr when using Ar as the bath gas. However, the rate coefficient for the reaction between CH 2 OO and CH 3 CHO at 5.5 Torr was found to be lower compared to the near-constant values observed between 10 and 100 Torr. Furthermore, the reaction of syn -CH 3 CHOO with CH 3 CHO demonstrated positive temperature dependence from 283 to 330 K, with a rate coefficient of (2.11 ± 0.45) × 10 -13 cm 3 molecule -1 s -1 at 298 K. The activation energy and pre-exponential factor derived from the Arrhenius plot for this reaction were determined to be 2.32 ± 0.49 kcal mol -1 and (1.66 ± 0.61) × 10 -11 cm 3 molecule -1 s -1 , respectively. In comparison, the reaction of CH 2 OO with CH 3 CHO exhibited negative temperature dependence, with a rate coefficient of (2.16 ± 0.39) × 10 -12 cm 3 molecule -1 s -1 at 100 Torr and 298 K and an activation energy and a pre-exponential factor of -1.73 ± 0.31 kcal mol -1 and (1.15 ± 0.21) × 10 -13 cm 3 molecule -1 s -1 , respectively, over the temperature range of 280-333 K.

To enable rapid and accurate point-of-care DNA detection, we have developed a single-step, amplification-free nucleic acid detection platform, a DNA substrate-mediated autocatalysis of CRISPR/Cas12a (DSAC). DSAC makes use of the trans-cleavage activity of Cas12a and target template-activated DNA substrate for dual signal amplifications. DSAC employs two distinct DNA substrate types: one that enhances signal amplification and the other that negatively modulates fluorescent signals. The positive inducer utilizes nicked- or loop-based DNA substrates to activate CRISPR/Cas12a, initiating trans-cleavage activity in a positive feedback loop, ultimately amplifying the fluorescent signals. The negative modulator, which involves competitor-based DNA substrates, competes with the probes for trans-cleaving, resulting in a signal decline in the presence of target DNA. These DNA substrate-based DSAC systems were adapted to fluorescence-based and paper-based lateral flow strip detection platforms. Our DSAC system accurately detected African swine fever virus (ASFV) in swine's blood samples at femtomolar sensitivity within 20 min. In contrast to the existing amplification-free CRISPR/Dx platforms, DSAC offers a cost-effective and straightforward detection method, requiring only the addition of a rationally designed DNA oligonucleotide. Notably, a common ASFV sequence-encoded DNA substrate can be directly applied to detect human nucleic acids through a dual crRNA targeting system. Consequently, our single-step DSAC system presents an alternative point-of-care diagnostic tool for the sensitive, accurate, and timely diagnosis of viral infections with potential applicability to human disease detection., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Light management is critical to maximizing the external quantum efficiency of perovskite light-emitting diodes (PeLEDs), but strategies for enhancing light out-coupling are typically complex and expensive. Here, using a facile solvent treatment strategy, we create a layer of lithium fluoride (LiF) nanoislands that serve as a template to reconstruct the light-extracting interfaces for PeLEDs. The nanoisland interface rearranges the near-field light distribution in order to maximize the efficiency of internal light extraction. With the proper adjustment of the nanoisland size and distribution, we have achieved an optimal balance between charge injection and light out-coupling, resulting in bright, pure-red quasi-two-dimensional PeLEDs with a 21.8% peak external quantum efficiency.

We report that constructed Au nanoclusters (NCs) can afford amazing white emission synergistically dictated by the Au(0)-dominated core-state fluorescence and Au(I)-governed surface-state phosphorescence, with record-high absolute quantum yields of 42.1% and 53.6% in the aqueous solution and powder state, respectively. Moreover, the dynamic color tuning is achieved in a wide warm-to-cold white-light range (with the correlated color temperature varied from 3426 to 24 973 K) by elaborately manipulating the ratio of Au(0) to Au(I) species and thus the electron transfer rate from staple motif to metal kernel. This study not only exemplifies the successful integration of multiple luminescent centers into metal NCs to accomplish efficient white-light emission but also inspires a feasible pathway toward customizing the optical properties of metal NCs by regulating electron transfer kinetics.

The spleen emerges as a pivotal target for mRNA delivery, prompting a continual quest for specialized and efficient lipid nanoparticles (LNPs) designed to enhance spleen-selective transfection efficiency. Here we report imidazole-containing ionizable lipids (IMILs) that demonstrate a pronounced preference for mRNA delivery into the spleen with exceptional transfection efficiency. We optimized IMIL structures by constructing and screening a multidimensional IMIL library containing multiple heads, tails, and linkers to perform a structure-activity correlation analysis. Following high-throughput in vivo screening, we identified A3B7C2 as a top-performing IMIL in spleen-specific mRNA delivery via the formulated LNPs, achieving a remarkable 98% proportion of splenic transfection. Moreover, A3B7C2-based LNPs are particularly potent in splenic dendritic cell transfection. Comparative analyses revealed that A3B7C2-based LNPs achieved a notable 2.8-fold and 12.9-fold increase in splenic mRNA transfection compared to SM102 and DLin-MC3-DMA lipid formulations, respectively. Additionally, our approach yielded an 18.3-fold enhancement in splenic mRNA expression compared to the SORT method without introducing additional anionic lipids. Collectively, these IMILs highlight promising avenues for further research in spleen-selective mRNA delivery. This work offers valuable insights for the swift discovery and rational design of ionizable lipid candidates tailored for spleen-selective transfection, thereby facilitating the application of mRNA therapeutics in spleen-related interventions.

Lipid nanoparticles (LNPs) represent the forefront of mRNA delivery platforms, yet achieving precise delivery to specific cells remains a challenge. The current targeting strategies complicate the formulation and impede the regulatory approval process. Here, through a straightforward regulation of helper lipids within LNPs, we introduce an engineered LNP designed for targeted delivery of mRNA into hepatocytes for metabolic dysfunction-associated fatty liver disease (MAFLD) treatment. The optimized LNP, supplied with POPC as the helper lipid, exhibits a 2.49-fold increase in mRNA transfection efficiency in hepatocytes compared to that of FDA-approved LNPs. CTP:phosphocholine cytidylyltransferase α mRNA is selected for delivery to hepatocytes through the optimized LNP system for self-calibration of phosphatidylcholine levels to prevent lipid droplet expansion in MAFLD. This strategy effectively regulates lipid homeostasis, while demonstrating proven biosafety. Our results present a mRNA therapy for MAFLD and open a new avenue for discovering potent lipids enabling mRNA delivery to specific cells.

The ability to control the catalytic activity of enzymes in chemical transformations is essential for the design and development of artificial catalysts. Herein, we report the synthesis and characterization of functional ligands featuring two 1,4,7,10-tetraazacyclododecane units linked by an azobenzene group and their corresponding dinuclear Zn(II) complexes. We show that the configuration switching ( E/Z ) of the azobenzene spacer in the ligands and their dinuclear Zn(II) complexes is reversibly controlled by irradiation with UV and visible light. The Zn(II)-metal complexes are light-responsive catalysts for the hydrolytic cleavage of nerve agent simulants, i.e., p -nitrophenyl diphenyl phosphate and methyl paraoxon. The catalytic activity of the Z -isomers of the dinuclear Zn(II) complexes outperformed that of the E -counterparts. Moreover, combining the less active E -isomers with gold nanoparticles induced an enhancement in the hydrolysis rate of p -nitrophenyl diphenyl phosphate. Kinetic analysis has shown that the catalytic site appears to involve a single metal ion. We explain our results by considering the different desolvation effects occurring in the catalyst's configurations in the solution and the catalytic systems involving gold nanoparticles.

Single-atom catalysts, characterized by transition metal-(N/O) 4 units on nanocarbon (M-(N/O) 4 -C), have emerged as efficient performers in water electrolysis. However, there are few guiding principles for accurately controlling the ligand fields of single atoms to further stimulate the catalyst activities. Herein, using the Ni-(N/O) 4 -C unit as a model, we develop a further modification of the P anion on the outer shells to modulate the morphology of the ligand. The catalyst thus prepared possesses high activity and excellent long-term durability, surpassing commercial Pt/C, RuO 2 , and currently reported single-atom catalysts. Notably, mechanistic studies demonstrated that the pseudocapacitive feature of multiscale anion-hybrid nanocarbon is considerable at accumulating enough positive charge [Q], contributing to the high oxygen evolution reaction (OER) order (β) through the rate formula. DFT calculations also indicate that the catalytic activity is decided by the suitable barrier energy of the intermediates due to charge accumulation. This work reveals the activity origin of single atoms on multihybrid nanocarbon, providing a clear experiential formula for designing the electronic configuration of single-atom catalysts to boost electrocatalytic performance.

Aqueous zinc-bromine batteries (ZBBs) are highly promising because of the advantages of safety and cost. Compared with flow ZBBs, static ones without the assistance of pumping and tank components possess decreased cost and increased energy density and efficiency. Yet, the issues of Zn dendrites and shuttle effect of polybromide ions (Br n - ) are more serious in nonflow ZBBs. Meanwhile, the hydrogen evolution reaction (HER) and the sluggish kinetics of the Br 2 /Br - couple are also in-negligible. Herein, a compressive approach, the cation-exchange membrane (CEM) coating on Zn anodes and N-defect decoration toward carbon felt cathodes, is developed. The CEM with cation-only function can inhibit the formation of Zn dendrites via tuning the Zn 2+ flow at the interface, block the noncationic substances, and hence prevent the shuttle of Br 2 /Br n - and the water decomposition-concerned HER. The optimized nonflow ZBBs can deliver high Coulombic, voltage, and energy efficiencies of 94.1, 92.8, and 87.4%, respectively, which can be well remained in 1000 cycles. Meanwhile, the output voltage is as high as 1.7 V at 10 mA cm -2 with a high areal capacity of 2 mA h cm -2 , and a LED with a rated voltage of 1.6 V can be powered successfully, exhibiting high application value.

An optical sensing approach that balances portability with cost efficiency has been designed for the reliable monitoring of fugitive methane (CH 4 ) emissions. Employing a LiTaO 3 -based pyroelectric detector integrated with micro-electro-mechanical systems and a broad infrared source, the developed gas sensor adeptly measured CH 4 concentrations with a low limit of detection of about 5.6 ppm v and showed rapid response times with t 90 consistently under 3 s. Notably, the novelty of our method lies in its precise control and reduction of CH 4 levels, enhanced by wavelet denoising. This technique, optimized through meticulous grid search, effectively mitigated noise interference noticeable at CH 4 levels below 10 ppm v . Postdenoising, nonlinear regression analyses based on the modified Beer-Lambert equation returned R 2 values of 0.985 and 0.982 for the training and validation sets, respectively. In conclusion, this gas sensor has been shown to be able to meet the requirements for early warning of CH 4 leakage on the surface in various carbon capture, utilization, and storage projects such as enhanced oil or gas recovery projects using CO 2 injection., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

This work aims to enhance the adsorption performance of Laponite @diatomite for organic pollutants by modifying it with cetyltrimethylammonium bromide (CTAB). The microstructure and morphology of the CTAB-modified Laponite @diatomite material were characterized using SEM, XRD, FTIR, BET, and TG. Furthermore, the influences of key parameters, containing pH, adsorbent dosage, reaction time, and reaction temperature, on the adsorption process were investigated. The kinetics, thermodynamics, and isotherm models of the adsorption process were analyzed. Finally, potential adsorption mechanisms were given based on the characterization. The research findings indicate that CTAB-La@D exhibits good adsorption performance toward Congo red (CR) over a broad pH range. The maximum adsorption capacity of CR was 451.1 mg/g under the optimum conditions (dosage = 10 mg, contact time = 240 min, initial CR concentration = 100 mg/L, temperature = 25 °C, and pH = 7). The adsorption process conformed to the pseudo-second-order kinetic model, and the adsorption isotherms indicated that the adsorption process of CR was more in line with the Langmuir model, and it was physical adsorption. Thermodynamic analysis illustrates that the adsorption process is exothermic and spontaneous. Additionally, the mechanisms of electrostatic adsorption and hydrophobic effect adsorption of CR were investigated through XPS and FTIR analysis. This work provides an effective pathway for designing high-performance adsorbents for the removal of organic dye, and the synthesized materials hold great capability for practical utilization in the treatment of wastewater.

Despite light-emitting diodes (LEDs) based on quasi-two-dimensional (Q-2D) perovskites being inexpensive and exhibiting high performance, defects still limit the improvement of electroluminescence efficiency and stability by causing nonradiative recombination. Here, an organic molecule, 1-( o -tolyl) biguanide, is used to simultaneously inhibit and passivate defects of Q-2D perovskites via in situ synchronous crystallization. This molecule not only prevents surface bromine vacancies from forming through hydrogen bonding with the bromine of intermediaries but also passivates surface defects through its interaction with uncoordinated Pb. Via combination of defect inhibition and passivation, the trap density of Q-2D perovskite films can be significantly reduced, and the emission efficiency of the film can be improved. Consequently, the corresponding LED shows an external quantum efficiency of 24.3%, and its operational stability has been increased nearly 15 times.

To boost the enzyme-like activity, biological compatibility, and antiaggregation effect of noble-metal-based nanozymes, folic-acid-strengthened Ag-Ir quantum dots (FA@Ag-Ir QDs) were developed. Not only did FA@Ag-Ir QDs exhibit excellent synergistic-enhancement peroxidase-like activity, high stability, and low toxicity, but they could also promote the lateral root propagation of Arabidopsis thaliana . Especially, ultratrace cysteine or Hg 2+ could exclusively strengthen or deteriorate the inherent fluorescence property with an obvious "turn-on" or "turn-off" effect, and dopamine could alter the peroxidase-like activity with a clear hypochromic effect from blue to colorless. Under optimized conditions, FA@Ag-Ir QDs were successfully applied for the turn-on fluorescence imaging of cysteine or the stress response in cells and plant roots, the turn-off fluorescence monitoring of toxic Hg 2+ , or the visual detection of dopamine in aqueous, beverage, serum, or medical samples with low detection limits and satisfactory recoveries. The selective recognition mechanisms for FA@Ag-Ir QDs toward cysteine, Hg 2+ , and dopamine were illustrated. This work will offer insights into constructing some efficient nanozyme sensors for multichannel environmental analyses, especially for the prediagnosis of cysteine-related diseases or stress responses in organisms.

Collisions between particles or with a surface have been widely applied, in which the restitution coefficients are the important parameter to describe the particle rebound behavior. SiO 2 particles are often used instead of ash particles in theoretical analyses; however, whether this is justifiable has not been confirmed. This paper compares the rebound characteristics of oblique impact for SiO 2 particles and ash particles by experimental and theoretical analyses. Based on the rigid-body theory, the tangential restitution coefficients, rebound angle-particle center, and reflection angle-contact path predicted by SiO 2 particles are basically in agreement with the experimental results for ash particles, especially at large impact angles. However, there is a slight error at 2.2 m/s as the velocity approaches the critical capture velocity., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Four-membered carbocycles are fundamental substructures in bioactive molecules and approved drugs and serve as irreplaceable building blocks in organic synthesis. However, developing efficient protocols furnishing diversified four-membered ring compounds in a highly regio-, diastereo-, and enantioselective fashion remains challenging but very desirable. Here, we report the unprecedented asymmetric transfer hydrogenation of cyclobutenediones. The reaction can selectively afford three types of four-membered products in high yields with high stereoselectivities, and the highly functionalized products enable a series of further transformations to form more diversified four-membered compounds. Asymmetric synthesis of di-, tri-, and tetrasubstituted bioactive molecules has also been achieved. Systematic mechanistic studies and theoretical calculations have revealed the origin of the regioselectivity, the key hydrogenation transition state models, and the sequence of the double and triple hydrogenation processes. The work provides a new choice for the catalytic asymmetric synthesis of cyclobutanes and related structures and demonstrates the robustness of asymmetric transfer hydrogenation in the accurate selectivity control of highly functionalized substrates.