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Valency is a major source of lexical errors in foreign language learning. Accordingly, the research question is how the syntactic and semantic properties of a word can be retrieved from the corpora and represented in a Chinese valency dictionary to facilitate foreign learners' vocabulary acquisition. Within the three aspects of the valency framework - logical-semantic, syntactic and semantic-pragmatic valency - this study examines 60 cases of Chinese lexical misuse extracted from the HSK (Chinese Language Proficiency Test) Dynamic Compositions Corpus. The results suggest that the majority of cases of misuse occur in the dimension of semantic-pragmatic valency and that this semantic-pragmatic misuse can be ascribed to various factors such as semantic collocations, emotive variables, text styles, registers, and other contextual factors. The results are then utilized as syntactic, semantic and pragmatic information to be presented in a Chinese valency dictionary. Specifically, the results obtained from a case study of a misused word by referring to a large-scale native Chinese speaker corpus help retrieve a relatively full list of complementation patterns, based on which the study designs a Chinese valency entry that embodies three basic elements - quantitative valency, qualitative valency and valency patterns.

The Co₄O₄ cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV)₂ state may be captured in a Co(III)₂(IV)₂ cubane. We demonstrate that the Co(III)₂(IV)₂ cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III)₂(IV)₂ cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV)₂ dimer. The exchange coupling in the cofacial Co(IV)₂ site allows for parallels to be drawn between the electronic structure of the Co₄O₄ cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV)₂ center on O–O bond formation.

Patchy particles have directional interactions that enable self-assembly into materials with precisely tailored microstructures. The patches are usually rigid, but a study now shows that flexible patches can fluctuate between an on- and off-state, which dramatically affects the assembly process.

Valence tuning of transition metal oxides is an effective approach to design high‐performance catalysts, particularly for the oxygen evolution reaction (OER) that underpins solar/electric water splitting and metal‐air batteries. Recently, high‐valence oxides (HVOs) are reported to show superior OER performance, in association with the fundamental dynamics of charge transfer and the evolution of the intermediates. Particularly considered are the adsorbate evolution mechanism (AEM) and the lattice oxygen‐mediated mechanism (LOM). High‐valence states enhance the OER performance mainly by optimizing the eg‐orbital filling, promoting the charge transfer between the metal d band and oxygen p band. Moreover, HVOs usually show an elevated O 2p band, which triggers the lattice oxygen as the redox center and enacts the efficient LOM pathway to break the “scaling” limitation of AEM. In addition, oxygen vacancies, induced by the overall charge‐neutrality, also promote the direct oxygen coupling in LOM. However, the synthesis of HVOs suffers from relatively large thermodynamic barrier, which makes their preparation difficult. Hence, the synthesis strategies of the HVOs are discussed to guide further design of the HVO electrocatalysts. Finally, further challenges and perspectives are outlined for potential applications in energy conversion and storage. High valence oxides of transition metals represent an emerging group of valence‐engineered catalysts, capable of offering very high catalytic activity and stability. The mechanisms of such “unconventional” characteristics and their synthesis strategies are discussed here. The case for oxygen evolution reaction is reviewed to guide effective development of the catalytic structures for water‐splitting hydrogen generation and metal‐air batteries.

Bivalent proteolysis-targeting chimeras (PROTACs) drive protein degradation by simultaneously binding a target protein and an E3 ligase and forming a productive ternary complex. We hypothesized that increasing binding valency within a PROTAC could enhance degradation. Here, we designed trivalent PROTACs consisting of a bivalent bromo and extra terminal (BET) inhibitor and an E3 ligand tethered via a branched linker. We identified von Hippel–Lindau (VHL)-based SIM1 as a low picomolar BET degrader with preference for bromodomain containing 2 (BRD2). Compared to bivalent PROTACs, SIM1 showed more sustained and higher degradation efficacy, which led to more potent anticancer activity. Mechanistically, SIM1 simultaneously engages with high avidity both BET bromodomains in a cis intramolecular fashion and forms a 1:1:1 ternary complex with VHL, exhibiting positive cooperativity and high cellular stability with prolonged residence time. Collectively, our data along with favorable in vivo pharmacokinetics demonstrate that augmenting the binding valency of proximity-induced modalities can be an enabling strategy for advancing functional outcomes. Trivalent PROTACs are reported as a strategy to increase protein degradation efficacy and therapeutic window by combining avidity of target engagement with cooperativity to form highly favorable and productive ternary complexes.

One of the key mechanisms used by cells to control the spatiotemporal organization of their many components is the formation and dissolution of biomolecular condensates through liquid–liquid phase separation (LLPS). Using a minimal coarse-grained model that allows us to simulate thousands of interacting multivalent proteins, we investigate the physical parameters dictating the stability and composition of multicomponent biomolecular condensates. We demonstrate that the molecular connectivity of the condensed-liquid network—i.e., the number of weak attractive protein–protein interactions per unit of volume—determines the stability (e.g., in temperature, pH, salt concentration) of multicomponent condensates, where stability is positively correlated with connectivity. While the connectivity of scaffolds (biomolecules essential for LLPS) dominates the phase landscape, introduction of clients (species recruited via scaffold–client interactions) fine-tunes it by transforming the scaffold–scaffold bond network. Whereas low-valency clients that compete for scaffold–scaffold binding sites decrease connectivity and stability, those that bind to alternate scaffold sites not required for LLPS or that have higher-than-scaffold valencies form additional scaffold–client–scaffold bridges increasing stability. Proteins that establish more connections (via increased valencies, promiscuous binding, and topologies that enable multivalent interactions) support the stability of and are enriched within multicomponent condensates. Importantly, proteins that increase the connectivity of multicomponent condensates have higher critical points as pure systems or, if pure LLPS is unfeasible, as binary scaffold–client mixtures. Hence, critical points of accessible systems (i.e., with just a few components) might serve as a unified thermodynamic parameter to predict the composition of multicomponent condensates.

To systematically compare the immunogenicity differences between measles-mumps-rubella combined (MMR) vaccine and measles-rubella combined (MR) vaccine following first dose vaccination in 8–9-month-old infants, with emphasis on evaluating the response levels of measles, rubella and mumps-specific IgG antibody response levels induced by both vaccines, thereby providing evidence for optimized vaccine selection in China’s childhood immunization program. We conducted a randomized controlled trial enrolling 400 healthy infants aged 8–9 months from five counties and districts in Gansu Province, who were randomly allocated at a 1:1 ratio to either the MMR group ( n  = 200) or MR group ( n  = 200). Venous blood samples were collected from subjects before immunization and 4–8 weeks post-vaccination. Enzyme-linked immunosorbent assay (ELISA) was used to quantitatively detect measles-, rubella-, and mumps-specific (MMR group only) IgG antibody levels. Bayesian Generalized Linear Mixed Models (BGLIMM) were employed to analyze between-group differences in geometric mean concentrations (GMCs) of antibodies. Antibody data were fitted using Gamma distribution; fixed effects included age in months, gender, vaccine group (MMR vs. MR), sampling time point (pre- vs. post-immunization) and days post-vaccination while random effects included individual-level effects. Model evaluation metrics included Deviance Information Criterion (DIC) and effective number of parameters, with statistical inference based on 95% credible intervals (CrI) of the posterior distribution. Post-immunization, although the absolute measles IgG antibody GMC in the MR group (1338.36 IU/mL) was lower than that in the MMR group (1506.52 IU/mL), the MR group exhibited a substantially higher vaccine-induced fold-increase from baseline (248-fold vs. 200-fold). BGLIMM indicated that the increase in measles antibodies (GMC) was approximately 34% higher in the MR group compared to the MMR group (β = 0.29, 95% CrI: 0.08 to 0.49, corresponding to a GMC ratio of 1.34). No meaningful difference was observed in rubella IgG antibody GMCs between groups (31.78 vs. 26.67 IU/mL, fold-increase 29-fold vs. 22-fold, β = 0.01, 95% CrI: −0.13 to 0.16). Mumps IgG antibody GMCs in the MMR group was 164.37 U/mL (95% CrI: 145.13 to 186.16). Fixed-effects analysis revealed immunogenicity differences among the three antigens: measles (β = 5.12) > rubella (β = 3.26) > mumps (β = 2.61). Random-effects variance analysis demonstrated that inter-individual response heterogeneity exhibited substantial differences across antigens, with measles antibody showing the greatest inter-individual variability (precision for ID = 1.63, 95% CrI: 1.33–2.00), followed by rubella (precision = 3.56, 95% CrI: 2.83–4.43), and mumps showing the least (precision = 11.02, 95% CrI: 6.52–18.07). Both MMR and MR vaccines induce effective immune responses in 8–9-month-old infants; however, the MR vaccine demonstrates superior measles antibody responses compared to the MMR vaccine, consistent with established evidence that antibody responses tend to decrease as vaccine valency increases. These findings provide high-quality clinical evidence to inform vaccine selection and optimization in China’s childhood immunization program, suggesting that MR vaccine may be considered as an alternative for the first dose when maximizing measles antibody response is prioritized.

NomVallex 2.5 is a valency lexicon of Czech nouns and adjectives that besides valency of particular noun and adjectival lexical units captures several valency-related syntactic phenomena, namely (i) active and passive syntax, (ii) systemic and non-systemic valency behavior, (iii) reflexivity and reciprocity, and (iv) negation. These phenomena, represented in the lexicon mostly by deverbal and deadjectival derivatives, are described here with respect to the derivational category of denominal adjectives. Though being regarded as less typical representatives of valency bearers in the non-verbal domain, denominal adjectives turned out to be involved in all of the studied syntactic phenomena. Their syntactic behavior thus can be viewed as similar to other derivational categories, especially to deverbal adjectives.

Entropy alone can self-assemble hard nanoparticles into colloidal crystals of remarkable complexity whose structures are the same as atomic and molecular crystals, but with larger lattice spacings. Molecular simulation is a powerful tool used extensively to study the self-assembly of ordered phases from disordered fluid phases of atoms, molecules, or nanoparticles. However, it is not yet possible to predict colloidal crystal structures a priori from particle shape as we can for atomic crystals from electronic valency. Here, we present such a first-principles theory. By calculating and minimizing excluded volume within the framework of statistical mechanics, we describe the directional entropic forces that collectively emerge between hard shapes, in familiar terms used to describe chemical bonds. We validate our theory by demonstrating that it predicts thermodynamically preferred structures for four families of hard polyhedra that match, in every instance, previous simulation results. The success of this first-principles approach to entropic colloidal crystal structure prediction furthers fundamental understanding of both entropically driven crystallization and conceptual pictures of bonding in matter.

Insulin binds the insulin receptor (IR) and regulates anabolic processes in target tissues. Impaired IR signalling is associated with multiple diseases, including diabetes, cancer and neurodegenerative disorders. IRs have been reported to form nanoclusters at the cell membrane in several cell types, even in the absence of insulin binding. Here we exploit the nanoscale spatial organization of the IR to achieve controlled multivalent receptor activation. To control insulin nanoscale spatial organization and valency, we developed rod-like insulin–DNA origami nanostructures carrying different numbers of insulin molecules with defined spacings. Increasing the insulin valency per nanostructure markedly extended the residence time of insulin–DNA origami nanostructures at the receptors. Both insulin valency and spacing affected the levels of IR activation in adipocytes. Moreover, the multivalent insulin design associated with the highest levels of IR activation also induced insulin-mediated transcriptional responses more effectively than the corresponding monovalent insulin nanostructures. In an in vivo zebrafish model of diabetes, treatment with multivalent—but not monovalent—insulin nanostructures elicited a reduction in glucose levels. Our results show that the control of insulin multivalency and spatial organization with nanoscale precision modulates the IR responses, independent of the insulin concentration. Therefore, we propose insulin nanoscale organization as a design parameter in developing new insulin therapies. DNA-origami-based insulin assembly into well-defined nanoclusters reveals that insulin valency and spatial organization modulate insulin receptor activation and downstream responses independent of ligand concentration.