Super-Ionic Conductor Soft Filler Promotes Li+ Transport in Integrated Cathode-Electrolyte for Solid-State Battery at Room Temperature.

Composite polymer solid electrolytes (CPEs), possessing good rigid flexible, are expected to be used in solid-state lithium-metal batteries. The integration of fillers into polymer matrices emerges as a dominant strategy to improve Li+ transport and form a Li+-conducting electrode-electrolyte interface. However, challenges arise as traditional fillers: 1) inorganic fillers, characterized by high interfacial energy, induce agglomeration; 2) organic fillers, with elevated crystallinity, impede intrinsic ionic conductivity, both severely hindering Li+ migration. Here, a concept of super-ionic conductor soft filler, utilizing a Li+ conductivity nanocellulose (Li-NC) as a model, is introduced which exhibits super-ionic conductivity. Li-NC anchors anions, and enhances Li+ transport speed, and assists in the integration of cathode-electrolyte electrodes for room temperature solid-state batteries. The tough dual-channel Li+ transport electrolyte (TDCT) with Li-NC and polyvinylidene fluoride (PVDF) demonstrates a high Li+ transfer number (0.79) due to the synergistic coordination mechanism in Li+ transport. Integrated electrodes' design enables stable performance in LiNi0.5Co0.2Mn0.3O2|Li cells, with 720 cycles at 0.5 C, and 88.8% capacity retention. Furthermore, the lifespan of Li|TDCT|Li cells over 4000 h and Li-rich Li1.2Ni0.13Co0.13Mn0.54O2|Li cells exhibits excellent performance, proving the practical application potential of soft filler for high energy density solid-state lithium-metal batteries at room temperature.

Completing the loop of the Late Jurassic-Early Cretaceous true polar wander event.

The reorientation of Earth through rotation of its solid shell relative to its spin axis is known as True polar wander (TPW). It is well-documented at present, but the occurrence of TPW in the geologic past remains controversial. This is especially so for Late Jurassic TPW, where the veracity and dynamics of a particularly large shift remain debated. Here, we report three palaeomagnetic poles at 153, 147, and 141 million years (Myr) ago from the North China craton that document an ~ 12° southward shift in palaeolatitude from 155-147 Myr ago (~1.5° Myr-1), immediately followed by an ~ 10° northward displacement between 147-141 Myr ago (~1.6° Myr-1). Our data support a large round-trip TPW oscillation in the past 200 Myr and we suggest that the shifting back-and-forth of the continents may contribute to the biota evolution in East Asia and the global Jurassic-Cretaceous extinction and endemism.

Earliest Prepared core technology in Eurasia from Nihewan (China): Implications for early human abilities and dispersals in East Asia.

Organized flaking techniques to obtain predetermined stone tools have been traced back to the early Acheulean (also known as mode 2) in Africa and are seen as indicative of the emergence of advanced technical abilities and in-depth planning skills among early humans. Here, we report one of the earliest known examples of prepared core technology in the archaeological record, at the Cenjiawan (CJW) site in the Nihewan basin of China, dated 1.1 Mya. The operational schemes reconstructed from the CJW refit sets, together with shaping patterns observed in the retouched tools, suggest that Nihewan basin toolmakers had the technical abilities of mode 2 hominins, and developed different survival strategies to adapt to local raw materials and environments. This finding predates the previously earliest known prepared core technology from Eurasia by 0.3 My, and the earliest known mode 2 sites in East Asia by a similar amount of time, thus suggesting that hominins with advanced technologies may have migrated into high latitude East Asia as early as 1.1 Mya.

Bipolar Polymeric Protective Layer for Dendrite-Free and Corrosion-Resistant Lithium Metal Anode in Ethylene Carbonate Electrolyte.

The unstable interface between Li metal and ethylene carbonate (EC)-based electrolytes triggers continuous side reactions and uncontrolled dendrite growth, significantly impacting the lifespan of Li metal batteries (LMBs). Herein, a bipolar polymeric protective layer (BPPL) is developed using cyanoethyl (-CH2CH2C≡N) and hydroxyl (-OH) polar groups, aiming to prevent EC-induced corrosion and facilitating rapid, uniform Li+ ion transport. Hydrogen-bonding interactions between -OH and EC facilitates the Li+ desolvation process and effectively traps free EC molecules, thereby eliminating parasitic reactions. Meanwhile, the -CH2CH2C≡N group anchors TFSI- anions through ion-dipole interactions, enhancing Li+ transport and eliminating concentration polarization, ultimately suppressing the growth of Li dendrite. This BPPL enabling Li|Li cell stable cycling over 750 cycles at 10 mA cm-2 for 2 mAh cm-2. The Li|LiNi0.8Mn0.1Co0.1O2 and Li|LiFePO4 full cells display superior electrochemical performance. The BPPL provides a practical strategy to enhanced stability and performance in LMBs application.

Initial Upper Palaeolithic material culture by 45,000 years ago at Shiyu in northern China.

The geographic expansion of Homo sapiens populations into southeastern Europe occurred by ∼47,000 years ago (∼47 ka), marked by Initial Upper Palaeolithic (IUP) technology. H. sapiens was present in western Siberia by ∼45 ka, and IUP industries indicate early entries by ∼50 ka in the Russian Altai and 46-45 ka in northern Mongolia. H. sapiens was in northeastern Asia by ∼40 ka, with a single IUP site in China dating to 43-41 ka. Here we describe an IUP assemblage from Shiyu in northern China, dating to ∼45 ka. Shiyu contains a stone tool assemblage produced by Levallois and Volumetric Blade Reduction methods, the long-distance transfer of obsidian from sources in China and the Russian Far East (800-1,000 km away), increased hunting skills denoted by the selective culling of adult equids and the recovery of tanged and hafted projectile points with evidence of impact fractures, and the presence of a worked bone tool and a shaped graphite disc. Shiyu exhibits a set of advanced cultural behaviours, and together with the recovery of a now-lost human cranial bone, the record supports an expansion of H. sapiens into eastern Asia by about 45 ka.

Application scenario-oriented molecule generation platform developed for drug discovery.

Design of molecules for candidate compound selection is one of the central challenges in drug discovery due to the complexity of chemical space and requirement of multi-parameter optimization. Here we present an application scenario-oriented platform (ID4Idea) for molecule generation in different scenarios of drug discovery. This platform utilizes both library or rule based and generative based algorithms (VAE, RNN, GAN, etc.), in combination with various AI learning types (pre-training, transfer learning, reinforcement learning, active learning, etc.) and input representations (1D SMILES, 2D graph, 3D shape, binding site, pharmacophore, etc.), to enable customized solutions for a given molecular design scenario. Besides the usual generation followed screening protocol, goal-directed molecule generation can also be conducted towards predefined goals, enhancing the efficiency of hit identification, lead finding, and lead optimization. We demonstrate the effectiveness of ID4Idea platform through case studies, showcasing customized solutions for different design tasks using various input information, such as binding pockets, pharmacophores, and compound representations. In addition, remaining challenges are discussed to unlock the full potential of AI models in drug discovery and pave the way for the development of novel therapeutics.

LiPF6 Induces Phosphorization of Garnet-Type Solid-State Electrolyte for Stable Lithium Metal Batteries.

Garnet solid electrolyte Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) is an excellent inorganic ceramic-type solid electrolyte; however, the presence of Li2 CO3 impurities on its surface hinders Li-ion transport and increases the interface impedance. In contrast to traditional methods of mechanical polishing, acid corrosion, and high-temperature reduction for removing Li2 CO3 , herein, a straightforward "waste-to-treasure" strategy is proposed to transform Li2 CO3 into Li3 PO4 and LiF in LiPF6 solution under 60 °C. It is found that the formation of Li3 PO4 during LLZTO pretreatment facilitates rapid Li-ion transport and enhances ionic conductivity, and the LLZTO/PAN composite polymer electrolyte shows the highest Li-ion transference number of 0.63. Additionally, the dense LiF layer serves to safeguard the internal garnet solid electrolyte against solvent decomposition-induced chemical adsorption. Symmetric Li/Li cells assembled with treated LLZTO/PAN composite electrolyte exhibit a critical current density of 1.1 mA cm-2 and a long lifespan of up to 700 h at a current density of 0.2 mA cm-2 . The Li/LiFePO4 solid-state cells demonstrate stable cycling performances for 141 mAh g-1 at 0.5 C, with capacity retention of 93.6% after 190 cycles. This work presents a novel approach to converting waste into valuable resources, offering the advantages of simple processes, and minimal side reactions.

Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters.

Accurate identifying and in-depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect-activity relationships. Yet, atomically precise coinage-metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed-ligand strategy to synthesizing an intrinsically chiral and metal-deficient copper hydride-rich NC [Cu57 H20 (PET)36 (TPP)4 ]+ (Cu57 H20 ). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu57 H20 features a cube-like Cu8 kernel embedded in a corner-missing metal-ligand shell of Cu49 (PET)36 (TPP)4 . Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono-lacunary polyoxometalates. Theoretical calculations demonstrate that the above-mentioned point vacancy causes one surface hydride exposed as an interfacial capping µ3 -H- , which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu57 H20 shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well-defined chiral metal-deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis.

Dynamic link between Neo-Tethyan subduction and atmospheric CO2 changes: insights from seismic tomography reconstruction.

Volcanic arc degassing contributes significantly to atmospheric CO2 levels and therefore has a pivotal impact on paleoclimate changes. The Neo-Tethyan decarbonation subduction is thought to have played a major role in Cenozoic climate changes, although there are still no quantifiable restrictions. Here we build past subduction scenarios using an improved seismic tomography reconstruction method and calculate the subducted slab flux in the India-Eurasia collision region. We find remarkable synchronicity between calculated slab flux and paleoclimate parameters in the Cenozoic, indicating a causal link between these processes. The closure of the Neo-Tethyan intra-oceanic subduction resulted in more carbon-rich sediments subducting along the Eurasia margin, as well as continental arc volcanoes, which further triggered global warming up to the Early Eocene Climatic Optimum. The abrupt termination of the Neo-Tethyan subduction due to the India-Eurasia collision could be the primary tectonic cause of the âˆ¼50-40 Ma CO2 drop. The gradual decrease in atmospheric CO2 concentration after 40 Ma may be attributed to enhance continental weathering due to the growth of the Tibetan Plateau. Our results contribute to a better understanding of the dynamic implications of Neo-Tethyan Ocean evolution and may provide new constraints for future carbon cycle models.

Plio-Pleistocene deep-sea ventilation in the eastern Pacific and potential linkages with Northern Hemisphere glaciation.

Antarctic bottom water (AABW) production is a key factor governing global ocean circulation, and the present disintegration of the Antarctic Ice Sheet slows it. However, its long-term variability has not been well documented. On the basis of high-resolution chemical scanning of a well-dated marine ferromanganese nodule from the eastern Pacific, we derive a record of abyssal ventilation spanning the past 4.7 million years and evaluate its linkage to AABW formation over this period. We find that abyssal ventilation was relatively weak in the early Pliocene and persistently intensified from 3.4 million years ago onward. Seven episodes of markedly reduced ocean ventilation indicative of AABW formation collapse are identified since the late Pliocene, which were accompanied by key stages of Northern Hemisphere glaciation. We suggest that the interpolar climate synchronization within these inferred seven collapse events may have intensified global glaciation by inducing poleward moisture transport in the Northern Hemisphere.

Multi-channel GCN ensembled machine learning model for molecular aqueous solubility prediction on a clean dataset.

This study constructed a new aqueous solubility dataset and a solubility regression model which was ensembled by GCN and machine learning models. Aqueous solubility is a key physiochemical property of small molecules in drug discovery. In the past few decades, there have been many studies about solubility prediction. However, many of these studies have high root mean squared error (RMSE). Meanwhile, their dataset always contains salt compounds and solubility data obtained from different experimental conditions. In this paper, we constructed a clean dataset with 2609 compounds, which was small but contains only solubility records without salts at the same temperatures (25 °C). Here, we applied graph convolutional neural network (GCN) to construct an aqueous solubility prediction model. To enhance the performance of the model, the molecular MACCS key fingerprints and physiochemical descriptors were also combined with the GCN model to build a multi-channel model. Additionally, the authors also built two machine learning models (support vector regression and gradient boost decision tree) and assembled them to the GCN model to improve the root mean squared error (RMSE = 0.665). Finally, comparative experiments have shown that our framework achieved the best performance on ESOL dataset (RMSEval = 0.56, RMSEtest = 0.44) and surpassed four established software on aqueous solubility prediction of new compounds.

Low dinosaur biodiversity in central China 2 million years prior to the end-Cretaceous mass extinction.

Whether or not nonavian dinosaur biodiversity declined prior to the end-Cretaceous mass extinction remains controversial as the result of sampling biases in the fossil record, differences in the analytical approaches used, and the rarity of high-precision geochronological dating of dinosaur fossils. Using magnetostratigraphy, cyclostratigraphy, and biostratigraphy, we establish a high-resolution geochronological framework for the fossil-rich Late Cretaceous sedimentary sequence in the Shanyang Basin of central China. We have found only three dinosaurian eggshell taxa (Macroolithus yaotunensis, Elongatoolithus elongatus, and Stromatoolithus pinglingensis) representing two clades (Oviraptoridae and Hadrosauridae) in sediments deposited between ∼68.2 and ∼66.4 million y ago, indicating sustained low dinosaur biodiversity, and that assessment is consistent with the known skeletal remains in the Shanyang and surrounding basins of central China. Along with the dinosaur eggshell records from eastern and southern China, we find a decline in dinosaur biodiversity from the Campanian to the Maastrichtian. Our results support a long-term decline in global dinosaur biodiversity prior to 66 million y ago, which likely set the stage for the end-Cretaceous nonavian dinosaur mass extinction.

A combination of eye-gaze and head-gaze interactions improves efficiency and user experience in an object positioning task in virtual environments.

Eye-gaze and head-gaze are two hands-free interaction modes in virtual reality, each of which has demonstrated different strengths. Selecting suitable interaction modes in different scenarios is important to achieve efficient interaction in virtual scenes. This study compared the movement time in an object positioning task by examining eye-gaze interaction and head-gaze interaction in various conditions. In turn, it identified the superior zones for each mode, respectively. Based on this information, we designed a combination mode - utilizing eye-gaze interaction at the acceleration phase and deceleration phase and head-gaze interaction at the correction phase - to achieve the optimal interaction mode, which has allowed us to obtain higher efficiency and subjective satisfaction. This study provides a comprehensive analysis of the characteristics of the eye-gaze and head-gaze interaction modes and provides valuable insights into selecting the appropriate interaction modes for virtual reality applications.

Accurate calculation of absolute free energy of binding for SHP2 allosteric inhibitors using free energy perturbation.

Accurate prediction of binding affinity is a primary objective in structure-based drug discovery. A free energy perturbation (FEP) method based on molecular dynamics simulation shows great promise for protein-ligand binding affinity predictions. However, accurate calculation of binding affinity for allosteric inhibitors remains unknown and elusive, which hampers the discovery of allosteric inhibitors. Allosteric inhibitors exhibit several significant advantages over orthosteric inhibitors including higher specificity and lower side effects. Allosteric inhibitors against SHP2 are thought to be beneficial not only for diseases related to metabolism, but also for cancer, which make SHP2 a potential drug target. However, high structural sensitivity makes structural optimization of SHP2 allosteric inhibitors face challenges. Herein, we calculated the absolute binding free energy of SHP2 allosteric inhibitors using the FEP method by employing different λ-windows/simulation time sampling strategies. A simulation run with 32 λ-windows/64 ps sampling strategy delivered an excellent correlation (r = 0.96) and an unprecedented low mean absolute error of 0.5 kcal mol-1 between predicted binding free energies and experimental ones, outperforming the MM/PBSA method. Our study demonstrates the possibility to accurately calculate the absolute binding free energy of allosteric inhibitors using FEP, which offers exciting prospects for the discovery of more effective allosteric inhibitors.

Effective Reaction-Based De Novo Strategy for Kinase Targets: A Case Study on MERTK Inhibitors.

Reaction-based de novo design is the computational generation of novel molecular structures by linking building blocks using reaction vectors derived from chemistry knowledge. In this work, we first adopted a recurrent neural network (RNN) model to generate three groups of building blocks with different functional groups and then constructed an in silico target-focused combinatorial library based on chemical reaction rules. Mer tyrosine kinase (MERTK) was used as a study case. Combined with a scaffold enrichment analysis, 15 novel MERTK inhibitors covering four scaffolds were achieved. Among them, compound 5a obtained an IC50 value of 53.4 nM against MERTK without any further optimization. The efficiency of hit identification could be significantly improved by shrinking the compound library with the fragment iterative optimization strategy and enriching the dominant scaffold in the hinge region. We hope that this strategy can provide new insights for accelerating the drug discovery process.

Innovative ochre processing and tool use in China 40,000 years ago.

Homo sapiens was present in northern Asia by around 40,000 years ago, having replaced archaic populations across Eurasia after episodes of earlier population expansions and interbreeding1-4. Cultural adaptations of the last Neanderthals, the Denisovans and the incoming populations of H. sapiens into Asia remain unknown1,5-7. Here we describe Xiamabei, a well-preserved, approximately 40,000-year-old archaeological site in northern China, which includes the earliest known ochre-processing feature in east Asia, a distinctive miniaturized lithic assemblage with bladelet-like tools bearing traces of hafting, and a bone tool. The cultural assembly of traits at Xiamabei is unique for Eastern Asia and does not correspond with those found at other archaeological site assemblages inhabited by archaic populations or those generally associated with the expansion of H. sapiens, such as the Initial Upper Palaeolithic8-10. The record of northern Asia supports a process of technological innovations and cultural diversification emerging in a period of hominin hybridization and admixture2,3,6,11.

Controllable spontaneous resolution in ultrasmall Cu-Ag bimetallic cluster ion pairs from achiral components.

Bimetallic cluster ion pairs containing a quaternary phosphonium and an ultrasmall Cu2Ag3 anionic cluster protected by thiolates: (PPh3R'')[Cu2Ag3(SR')6] (R'SH = cyclohexylthiol (CySH), R'' = Ph, 1; Me, 2; Et, 3; Pr, 4; R'SH = tert-butylthiol (tBuSH) and R'' = Ph, 5) were reported. Without any chiral source, 1 crystallizes as conglomerate crystals with homochiral packings and spontaneous resolution occurs, while four other clusters 2-5 crystallize as racemic crystals with heterochiral packings. These results indicate that racemic and homochiral crystallization in the cluster system could be controlled through fine-tuning internal achiral structural components.

Technological innovations at the onset of the Mid-Pleistocene Climate Transition in high-latitude East Asia.

The interplay between Pleistocene climatic variability and hominin adaptations to diverse terrestrial ecosystems is a key topic in human evolutionary studies. Early and Middle Pleistocene environmental change and its relation to hominin behavioural responses has been a subject of great interest in Africa and Europe, though little information is available for other key regions of the Old World, particularly from Eastern Asia. Here we examine key Early Pleistocene sites of the Nihewan Basin, in high-latitude northern China, dating between ∼1.4 and 1.0 million years ago (Ma). We compare stone-tool assemblages from three Early Pleistocene sites in the Nihewan Basin, including detailed assessment of stone-tool refitting sequences at the ∼1.1-Ma-old site of Cenjiawan. Increased toolmaking skills and technological innovations are evident in the Nihewan Basin at the onset of the Mid-Pleistocene Climate Transition (MPT). Examination of the lithic technology of the Nihewan sites, together with an assessment of other key Palaeolithic sites of China, indicates that toolkits show increasing diversity at the outset of the MPT and in its aftermath. The overall evidence indicates the adaptive flexibility of early hominins to ecosystem changes since the MPT, though regional abandonments are also apparent in high latitudes, likely owing to cold and oscillating environmental conditions. The view presented here sharply contrasts with traditional arguments that stone-tool technologies of China are homogeneous and continuous over the course of the Early Pleistocene.

Rapid drift of the Tethyan Himalaya terrane before two-stage India-Asia collision.

The India-Asia collision is an outstanding smoking gun in the study of continental collision dynamics. How and when the continental collision occurred remains a long-standing controversy. Here we present two new paleomagnetic data sets from rocks deposited on the distal part of the Indian passive margin, which indicate that the Tethyan Himalaya terrane was situated at a paleolatitude of ∼19.4°S at ∼75 Ma and moved rapidly northward to reach a paleolatitude of ∼13.7°N at ∼61 Ma. This implies that the Tethyan Himalaya terrane rifted from India after ∼75 Ma, generating the North India Sea. We document a new two-stage continental collision, first at ∼61 Ma between the Lhasa and Tethyan Himalaya terranes, and subsequently at ∼53-48 Ma between the Tethyan Himalaya terrane and India, diachronously closing the North India Sea from west to east. Our scenario matches the history of India-Asia convergence rates and reconciles multiple lines of geologic evidence for the collision.

Enhancing Interfacial Contact in Solid-State Batteries with a Gradient Composite Solid Electrolyte.

Solid-state batteries promise to meet the challenges of high energy density and high safety for future energy storage. However, poor interfacial contact and complex manufacturing processes limit their practical applications. Herein, a simple strategy is proposed to enhance interfacial contact by introducing a gradient composite polymer solid electrolyte (GCPE), which is prepared by a facile UV-curing polymerization technique. The high-Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO)-content side of the electrolyte exhibits high oxidation resistance (5.4 V versus Li+ /Li), making it compatible with a high-voltage cathode material, whereas the LLZTO-deficient side achieves excellent interfacial contact with the Li metal anode, facilitating uniform Li deposition. Benefiting from the elaborate composition and structure of GCPE films, the symmetric Li//Li cell exhibits a low-voltage hysteresis potential of 42 mV and a long cycle life of >1900 h without short-circuiting. The Li//LiFePO4 solid-state batteries deliver a capacity of 161.0 mA h g-1 at 60 °C and 0.1 C (82.4% capacity is retained after 200 cycles). Even at 80 °C, the cell still shows an outstanding capacity of 132.9 mAh g-1 at 0.2 C after 100 cycles. The design principle of gradient electrolytes provides a new path for achieving enhanced interfacial contact in high-performance solid-state batteries.