Design, synthesis, biological evaluation of novel piperidine-based derivatives as potent poly(ADP-ribose) polymerase-1 (PARP-1) inhibitors.

Poly(ADP-ribose) polymerase-1 (PARP-1) is a crucial member of DNA repair enzymes responsible for repairing DNA single-strand breaks. Developing PARP inhibitors based on synthetic lethality strategies is an effective approach for treating breast cancer and other diseases. In this study, a series of novel piperidine-based benzamide derivatives were designed and synthesized using structure-based drug design principles. The anticancer activities of these compounds were evaluated against five human cancer cell lines (MDA-MB-436, CAPAN-1, SW-620, HepG2, SKOV3, and PC3) and the preliminary structure-activity relationships were delineated. Among the compounds, 6a and 15d demonstrated potent antiproliferative effects against MDA-MB-436 cells with IC50 values of 8.56 ± 1.07 µM and 6.99 ± 2.62 µM, respectively. Furthermore, both compounds exhibited excellent inhibitory activity against PARP-1, with IC50 values of 8.33 nM and 12.02 nM, respectively. Mechanistic investigations revealed that 6a and 15d effectively inhibited colony formation and cell migration of HCT116 cells. Moreover, they induced apoptosis by upregulating the expression of Bax and cleaved Caspase-3, while downregulating the expression of Caspase-3 and Bcl-2 in HCT116 cells. Based on its impressive pharmacodynamic data in vitro, we conducted a study to evaluate the efficacy of 15d in a xenograft tumor model in mice when used in combination with cytotoxic agents. Collectively, these findings suggest that 15d could be promising drug candidates worthy of further investigation.

How changes in landscape patterns affect the carbon emission: a case study in the Chengdu-Chongqing Economic Circle, China.

The construction of low-carbon cities is an optimal means to balance the competing interests of economic growth and carbon emission reduction. This study focuses on the optimization of land use patterns with a low carbon orientation, taking the Chengdu-Chongqing Economic Circle (CCEC), the fourth-largest economic growth pole in China, as an example. The panel data regression analysis is carried out to identify the dynamic correlations between the landscape changes and the carbon emission induced by land use and land cover change (LICE) of each city, each year, for the last 20 years. The results show that the CCEC has witnessed a 142.85% increase in carbon emissions during the period studied, with the growth of built-up land contributing 94% of total carbon emissions from 2000 to 2020. By constructing the panel regression model, this study finds that the intensity of carbon emissions increases significantly as the urban built-up land area and the agglomeration of artificial structures increase. The conversion of cropland, which dominates the landscape pattern, to built-up land has led to further fragmentation of the landscape pattern and a reduction in LPI, thus increasing carbon emissions. And a more complex regional landscape pattern will have a positive impact on carbon emission reduction. Based on the above findings, suggestions are articulated for carbon emission reduction.

IBGJO: Improved Binary Golden Jackal Optimization with Chaotic Tent Map and Cosine Similarity for Feature Selection.

Feature selection is a crucial process in machine learning and data mining that identifies the most pertinent and valuable features in a dataset. It enhances the efficacy and precision of predictive models by efficiently reducing the number of features. This reduction improves classification accuracy, lessens the computational burden, and enhances overall performance. This study proposes the improved binary golden jackal optimization (IBGJO) algorithm, an extension of the conventional golden jackal optimization (GJO) algorithm. IBGJO serves as a search strategy for wrapper-based feature selection. It comprises three key factors: a population initialization process with a chaotic tent map (CTM) mechanism that enhances exploitation abilities and guarantees population diversity, an adaptive position update mechanism using cosine similarity to prevent premature convergence, and a binary mechanism well-suited for binary feature selection problems. We evaluated IBGJO on 28 classical datasets from the UC Irvine Machine Learning Repository. The results show that the CTM mechanism and the position update strategy based on cosine similarity proposed in IBGJO can significantly improve the Rate of convergence of the conventional GJO algorithm, and the accuracy is also significantly better than other algorithms. Additionally, we evaluate the effectiveness and performance of the enhanced factors. Our empirical results show that the proposed CTM mechanism and the position update strategy based on cosine similarity can help the conventional GJO algorithm converge faster.

The General Trends of Genetic Diversity Change in Alien Plants' Invasion.

Genetic diversity is associated with invasion dynamics during establishment and expansion stages by affecting the viability and adaptive potential of exotics. There have been many reports on the comparison between the genetic diversity of invasive alien species (IAS) in and out of their native habitats, but the conclusions were usually inconsistent. In this work, a standard meta-analysis of the genetic diversity of 19 invasive plants based on 26 previous studies was carried out to investigate the general trend for the change of IASs' genetic diversity during their invasion process and its real correlation with the invasion fate. Those 26 studies were screened from a total of 3557 peer-reviewed publications from the ISI Web of Science database during the period of January 2000 to May 2022. Based on the selected studies in this work, a general reduction of IASs' genetic diversity was found in non-native populations compared to that in native ones, while the difference was not significant. This finding suggested that regardless of the change in genetic diversity, it had no substantial effect on the outcome of the invasion process. Therefore, genetic diversity might not serve as a reliable indicator for risk assessment and prediction of invasion dynamic prediction in the case of IASs.

Activated malate circulation contributes to the manifestation of light-dependent mosaic symptoms.

Mosaic symptoms are commonly observed in virus-infected plants. However, the underlying mechanism by which viruses cause mosaic symptoms as well as the key regulator(s) involved in this process remain unclear. Here, we investigate maize dwarf mosaic disease caused by sugarcane mosaic virus (SCMV). We find that the manifestation of mosaic symptoms in SCMV-infected maize plants requires light illumination and is correlated with mitochondrial reactive oxidative species (mROS) accumulation. The transcriptomic and metabolomic analyses results together with the genetic and cytopathological evidence indicate that malate and malate circulation pathways play essential roles in promoting mosaic symptom development. Specifically, at the pre-symptomatic infection stage or infection front, SCMV infection elevates the enzymatic activity of pyruvate orthophosphate dikinase by decreasing the phosphorylation of threonine527 under light, resulting in malate overproduction and subsequent mROS accumulation. Our findings indicate that activated malate circulation contributes to the manifestation of light-dependent mosaic symptoms via mROS.

Dissolved organic matter defines microbial communities during initial soil formation after deglaciation.

Ecosystem succession and pedogenesis reshuffle the composition and turnover of dissolved organic matter (DOM) and its interactions with soil microbiome. The changes of these connections are especially intensive during initial pedogenesis, e.g. in young post-glacial areas. The temporal succession and vertical development of DOM effects on microbial community structure remains elusive. Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS), high-throughput sequencing, and molecular ecological networks, we characterized the molecular diversity of water-extractable DOM and identified its links to microbial communities in soil profiles along deglaciation chronosequence (12, 30, 40, 52, 80, and 120 years) in the southeastern Tibetan Plateau. Low-molecular-weight compound content decreased, whereas the mid- and high-molecular-weight compounds increased with succession age and soil depth. This was confirmed by the increase in double bond equivalents and averaged oxygen-to­carbon ratios (O/C), and decrease in hydrogen-to­carbon ratios (H/C), which reflect DOM accumulation and stabilization. Microbial community succession shifted towards the dominance of oligotrophic Acidobacteria and saprophytic Mortierellomycota, reflecting the increase of stable DOM components (H/C < 1.5 and wider O/C). Less DOM-bacterial positive networks during the succession reduced specialization of labile DOM production (such as lipid- and protein-like compounds), whereas more DOM-fungal negative networks increased specialization of stable DOM decomposition (such as tannin- and condensed aromatic-like compounds). Consequently, DOM stability is not intrinsic during initial pedogenesis: stable DOM compounds remain after fast bacterial utilization of labile DOM compounds, whereas fungi decompose slowly the remaining DOM pools.

Targeting BET proteins inhibited the growth of non-small cell lung carcinoma through downregulation of Met expression.

Hepatocyte growth factor receptor (HGFR or Met) upregulation has been proven to play important roles in non-small cell lung carcinoma (NSCLC). Interestingly, chemoresistance against epidermal growth factor receptor (EGFR) inhibitors including erlotinib and gefitinib was also related to Met. Targeting bromodomain and extra terminal domain (BET) proteins, especially BRD4, has shown inhibitory effects on lung cancer, but the mechanism is unclear. Herein, we found that JQ1 (BET inhibitor) suppressed NSCLC cell growth, reduced the Met expression, and contributed to inactivation of PI3K/Akt and MAPK/ERK pathways. Moreover, another BET protein inhibitor I-BET151, or BRD4 depletion, also inhibited NSCLC cell growth and downregulated Met. JQ1 inhibited HGF-induced cell growth and Met/PI3K/Akt activation, also inhibited A549 tumor growth in xenograft mouse models, in parallel with Met downregulation. Moreover, JQ1 inhibited the growth of paired erlotinib-sensitive and resistant HCC827 cells in parallel with Met downregulation and PI3K/Akt signaling inactivation. JQ1 also exerted inhibitory influences on the growth of erlotinib-sensitive and resistant HCC827 tumors in xenograft mouse models. These results suggested that targeting BET proteins inhibited NSCLC via downregulating Met and inactivating PI3K/AKT pathway. Our findings reveal a novel mechanism of BET proteins implicated in NSCLC progression with Met taken into consideration.

Spin Effect to Promote Reaction Kinetics and Overall Performance of Lithium-Sulfur Batteries under External Magnetic Field.

Lithium-sulfur batteries (LSBs) are still limited by the shuttle of lithium polysulfides (LiPS) and the slow Li-S reaction. Herein, we demonstrate that when using cobalt sulfide as a catalytic additive, an external magnetic field generated by a permanent magnet can significantly improve the LiPS adsorption ability and the Li-S reaction kinetics. More specifically, the results show both experimentally and theoretically how an electron spin polarization of Co ions reduces electron repulsion and enhances the degree of orbital hybridization, thus resulting in LSBs with unprecedented performance and stability. Under an external magnetic field, LSBs with 0.0084 % per cycle decay rate at 2 C during 8150 cycles are produced. Overall, this work not only demonstrates an effective strategy to promote LiPS adsorption and electrochemical conversion in LSBs at no additional energy cost but also enriches the application of the spin effect in the electrocatalysis fields.

Chiral DNA Nanotubes Self-Assembled from Building Blocks with Tailorable Curvature and Twist.

DNA nanotubes with prescribed geometry could allow for nanomaterial organization with designed optical or electrical function. As one of the dominating driving forces for DNA nanotube assembly, intrinsic curvature and twist of building blocks can be induced by bending deformation and twisting deformation. However, it is still unknown that how bending and twisting design on nanoscale building blocks affects the geometry of DNA tubes with micrometer length. Here, through targeted base pair deletion or insertion, the amount of bending deformation in building blocks is modulated by length gradient and the amount of twisting deformation is modulated by average twist density. This work systematically explores the independent effect and synergistic effect of two types of deformation on tube geometry, including diameter, chirality, and helical angles, via a streptavidin-labeling technique. The design rules enable the construction of DNA nanotubes with prescribed chirality and tailored diameters.

Metal Ion Cutting-Assisted Synthesis of Defect-Rich MoS2 Nanosheets for High-Rate and Ultrastable Li2S Catalytic Deposition.

Active metal ions often show a strong cutting effect on the chemical bonds during high-temperature thermal processes. Herein, a one-pot metal ion cutting-assisted method was adopted to design defect-rich MoS2-x nanosheet (NS)/ZnS nanoparticle (NP) heterojunction composites on carbon nanofiber skeletons (CNF@MoS2-x/ZnS) via a simple Ar-ambience annealing. Results show that Zn2+ ions capture S2- ions from MoS2 and form into ZnS NPs, and the MoS2 NSs lose S2- ions and become MoS2-x ones. As sulfur hosts for lithium-sulfur batteries (LSBs), the CNF@MoS2-x/ZnS-S cathodes deliver a high reversible capacity of 1233 mA h g-1 at 0.1 C and keep 944 mA h g-1 at 3 C. Moreover, the cathodes also show an extremely low decay rate of 0.012% for 900 cycles at 2 C. Series of analysis indicate that the MoS2-x NSs significantly improve the chemisorption and catalyze the kinetic process of redox reactions of lithium polysulfides, and the heterojunctions between MoS2-x NSs and ZnS NPs further accelerate the transport of electrons and the diffusion of Li+ ions. Besides, the CNF@MoS2-x/ZnS-S LSBs also show an ultralow self-discharge rate of 1.1% in voltage. This research would give some new insights for the design of defect-rich electrode materials for high-performance energy storage devices.

Photosynthetic regulation in fluctuating light under combined stresses of high temperature and dehydration in three contrasting mosses.

Photosynthesis regulation is fundamental for the response to environmental dynamics, especially for bryophytes during their adaptation to terrestrial life. Alternative electron flow mediated by flavodiiron proteins (FLV) and cyclic electron flow (CEF) around photosystem I (PSI) play seminal roles in the response to abiotic stresses in mosses; nevertheless, their correlation and relative contribution to photoprotection of mosses exposed to combined stresses remain unclear. In the present study, the photosynthetic performance and recovery capacity of three moss species from different growth habitats were examined during heat and dehydration with fluctuating light. Our results showed that dehydration at 22 °C for 24 h caused little photodamage, and most of the parameters recovered to their original values after rehydration. In contrast, dehydration at 38 °C caused drastic injuries, especially to PSII, which was mainly caused by the inactivation of non-photochemical quenching (NPQ). Dehydration also induced a high accumulation of O2- and H2O2. A consistently higher CEF as well as a positive correlation between CEF and FLV was observed in resistant R. japonicum, implying CEF played a more important protective role for R. japonicum. In H. plumaeforme and P. cuspidatum, the positive relationship under mild stress switched to negative when stress became severe. Therefore, FLV pathway was sensitive to environmental fluctuations and maybe less efficient than CEF thus, readily to be lost during land colonization and evolution in angiosperms. Our work provides insights into the coordination of various pathways to fine-tune photosynthetic protection and can be used as a basis for species screening and development of breeding strategies for degraded ecosystem restoration with pioneering mosses.

Effects of long-term organic matter application on soil carbon accumulation and nitrogen use efficiency in a double-cropping rice field.

Increasing soil carbon (C) sequestration in paddy field and improving rice nitrogen use efficiency (NUE) are vital for sustainable agriculture and environmental protection. It was a benefit practice for achieving these goals by taken rice straw and organic manure managements. However, there is still need to further investigate the effects of different long-term fertilizer managements on soil C sequestration and NUE under the double-cropping rice system in southern of China. Therefore, the effects of different long-term (36-years) fertilizer practices on soil C sequestration and NUE under the double-cropping rice system in southern of China were investigated in the present paper. The field experiment was included four different fertilizer treatments: chemical fertilizer alone (MF), rice straw residue and chemical fertilizer (RF), 30% organic manure and 70% chemical fertilizer (OM), and without fertilizer input as a control (CK). This result indicated that soil C content at plough layer in paddy field with RF and OM treatments were increased, compared with MF and CK treatments. Besides input C directly into paddy field, soil original organic C accumulation with RF and OM treatments were increased by 1.54% and 3.01%, compared with MF treatment. This result indicated that soil TOC content increase rate and annual topsoil organic C sequestration rate in paddy field with RF and OM treatments increased by 55.56%, 88.89% and 48.05%, 76.62%, compared with MF treatment, respectively. Compared with MF treatment, NUE with RF and OM treatments increased by 10.43% and 22.61%, respectively, mainly due to increasing soil organic C. Grain yield of double-cropping rice with RF and OM treatments increased by 1009.5 and 1166.5 kg ha-1, compared with MF treatment, respectively. This result indicated that there was significantly correlation between NUE/NUENPK and TOC content with RF and OM treatments, at early rice and late rice growth seasons. Therefore, it was benefit practice for increasing soil carbon sequestration and improving rice NUE in the double-cropping rice system with long-term application of rice straw and organic manure managements.

The exacerbation of soil acidification correlates with structural and functional succession of the soil microbiome upon agricultural intensification.

Agricultural intensification driven by land-use changes has caused continuous and cumulative soil acidification (SA) throughout the global agroecosystem. Microorganisms mediate acid-generating reactions; however, the microbial mechanisms responsible for exacerbating SA feedback remain largely unknown. To determine the microbial community composition and putative function associated with SA, we conducted a metagenomic analysis of soils across a chronosequence that has elapsed since the conversion of rice-wheat (RW) to rice-vegetable (RV) rotations. Compared to RW rotations, soil pH decreased by 0.50 and 1.56 units (p < 0.05) in response to 10-year and 20-year RV rotations, respectively. Additionally, acid saturation ratios were increased by 7.3% and 36.2% (p < 0.05), respectively. The loss of microbial beta-diversity was a key element that contributed to the exacerbation of SA in the RV. Notably, the 20-year RV-enriched microbial taxa were more hydrogen (H+)-, aluminium (Al3+)-, and nitrate nitrogen (NO3--N) -dependent and contained more genera exhibiting dehydrogenation functions than did RW-enriched taxa. "M00115, M00151, M00417, and M00004" and "M00531 and M00135" that are the "proton-pumping" and "proton-consuming" gene modules, respectively, were linked to the massive recruitment of acid-dependent biomarkers in 20-year RV soils, particularly Rhodanobacter, Gemmatirosa, Sphingomonas, and Streptomyces. Collectively, soils in long-term RV rotations were highly acidified and acid-sensitive, as the enrichment of microbial dehydrogenation genes allowing for soil buffering capacity is more vulnerable to H+ loading and consequently promotes the colonization of more acid-tolerant and acidogenic microbes, and ultimately provide new clues for researchers to elucidate the interaction between SA and the soil microbiome.

Farmers' Strategies to Climate Change and Urbanization: Potential of Ecosystem-Based Adaptation in Rural Chengdu, Southwest China.

Ecosystem-based adaptation (EbA) is emerging as a cost-effective approach for helping people adapt to climate and non-climate changes. Nowadays, climate change and urbanization have affected agricultural systems, but it is not clear how rural communities have responded or adapted to those changes. Here, we chose two typical villages in the Chengdu Plain, southwest China, through sociological surveys on 90 local farmers with a semi-structured questionnaire, participatory observation, geospatial analysis of land use and land cover, and a literature review, to explore the local people's perception of changes or disturbances and their adaptation strategies from the perspective of EbA. The results showed that climate change and urbanization had impacted agricultural systems dramatically in the last 40 years. In two case-study sites, climate change and urbanization were perceived by most local farmers as the main drivers impacting on agricultural production, but various resource-use models containing abundant traditional knowledge or practices as well as modern tools, such as information communication technology (ICT), were applied to adapt to these changes. Moreover, culture service through the adaptive decoration of rural landscapes is becoming a new perspective for implementing an EbA strategy. Finally, our findings highlighted the potential value of an EbA strategy for sustaining urban-rural integrated development and enhancing the resilience of agricultural systems.

Construction of all-carbon micro/nanoscale interconnected sulfur host for high-rate and ultra-stable lithium-sulfur batteries: Role of oxygen-containing functional groups.

Carbon nanotubes (CNTs) are often used to settle down the sluggish reaction kinetics in lithium-sulfur batteries (LSBs). However, the self-aggregation of CNTs often makes them fail to effectively inhibit the shuttling effect of soluble lithium polysulfide (LiPS) intermediates. Herein, a type of ultra-stable carbon micro/nano-scale interconnected "carbon cages" has been designed by incorporating polar acid-treated carbon fibers (ACF) into three-dimensional (3D) CNT frameworks during vacuum filtration processes. Results show that the ACF-CNT composite frameworks possess a reinforced-concrete-like structure, in which the ACFs can well work as the main mechanical supporting frames for the composite electrodes, and the oxygen-containing functional groups (OFGs) formed on them as cross linker between ACFs and CNTs. Benefitted from this design, the ACF-CNT/S cathodes deliver an excellent rate capability (retain 72.6% at 4C). More impressively, the ACF-CNT/S cathodes also show an ultrahigh cycling stability (capacity decay rate of 0.001% per cycle over 350 cycles at 2C). And further optimization suggests that the suitable treatment on CFs could balance the chemical adsorption (OFGs) and physical confinement (carbon cages), leading to fast and durable electrochemical reaction dynamics. In addition, the assembled soft-pack LSBs further show a high dynamic bending stability.

Sugarcane mosaic virus orchestrates the lactate fermentation pathway to support its successful infection.

Viruses often establish their own infection by altering host metabolism. How viruses co-opt plant metabolism to support their successful infection remains an open question. Here, we used untargeted metabolomics to reveal that lactate accumulates immediately before and after robust sugarcane mosaic virus (SCMV) infection. Induction of lactate-involved anaerobic glycolysis is beneficial to SCMV infection. The enzyme activity and transcriptional levels of lactate dehydrogenase (LDH) were up-regulated by SCMV infection, and LDH is essential for robust SCMV infection. Moreover, LDH relocates in viral replicase complexes (VRCs) by interacting with SCMV-encoded 6K2 protein, a key protein responsible for inducing VRCs. Additionally, lactate could promote SCMV infection by suppressing plant defense responses. Taken together, we have revealed a viral strategy to manipulate host metabolism to support replication compartment but also depress the defense response during the process of infection.

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To clarify the impacts of long-term different fertilization modes on the soil acid hydrolysable organic nitrogen and its components in the double-cropping rice field of southern China, a long-term (36-year) location field experiment was used as a platform to systematically analyze the variations of soil acid hydrolysable organic nitrogen and its components (amino acid nitrogen, amino sugar nitrogen, ammonium nitrogen, unidentified hydrolysable nitrogen) at 0-10 cm and 10-20 cm soil layers under four fertilization treatments, including chemical fertilizer alone (CF), rice straw and chemical fertilizer (RF), 30% organic manure and 70% chemical fertilizer (OM), and control (CK). The relationships of soil acid hydrolysable organic nitrogen content and soil total nitrogen, soil organic carbon content were also analyzed. The results showed that compared with CK, OM and RF treatments significantly increased the contents of total nitrogen, available nitrogen, and organic carbon at both soil layers. The contents of soil acid hydrolysable organic nitrogen at 0-10 cm and 10-20 cm layers of OM, RF and CF treatments were 10.7%-42.6% and 12.2% -51.5% higher than that of CK, respectively. Compared with CF and CK treatments, OM and RF treatments significantly increased the contents of amino acid nitrogen, ammonium nitrogen, unidentified hydrolysable nitrogen and amino sugar nitrogen contents atboth soil layers. The soil acid hydrolysable organic nitrogen and non-hydrolysable nitrogen contents at 0-10 cm and 10-20 cm paddy soils under different fertilization treatments decreased in an order of OM>RF>CF>CK. The contents of soil amino acid nitrogen, ammonium nitrogen, amino sugar nitrogen and non-hydrolysable nitrogen at 0-10 cm soil layer of each fertilization treatment were higher than those at 10-20 cm soil layer. In addition, the contents of soil acid hydrolyzed organic nitrogen were positively correated with the contents of soil total nitrogen and soil organic carbon. In conclusion, RF and OM treatments were beneficial to increase organic nitrogen content at 0-10 and 10-20 cm soil layers of double cropping paddy fields, with postive consequences on nitrogen supply capacity and soil fertility.

Active Site Fluxional Restructuring as a New Paradigm in Triggering Reaction Activity for Nanocluster Catalysis.

The rationale of the catalytic activity observed in experiments is a crucial task in fundamental catalysis studies. Efficient catalyst design relies on an accurate understanding of the origin of the activity at the atomic level. Theoretical studies have been widely developed to reach such a fundamental atomic scale understanding of catalytic activity. Current theories ascribe the catalytic activity to the geometric and electronic structure of the active site, in which the geometrical and electronic structure effects are derived from the equilibrium geometry of active sites characterizing the static property of the catalyst; however catalysts, especially in the form of nanoclusters, may present fluxional and dynamic structure under reaction conditions, and the effect of this fluxional behavior is not yet widely recognized. Therefore, this Account will focus on the fluxionality of the active sites, which is driven by thermal fluctuations under finite temperature.Under reaction conditions, nanocluster catalysts can readily restructure, either being promoted to another metastable isomer (named as plastic fluxionality) or presenting ample deformations around their equilibrium geometry (named as elastic fluxionality). This Account summarizes our recent studies on the fluxionality of the nanoclusters and how plastic and elastic fluxionalities play roles in highly efficient reaction pathways. Our results show that the low energy metastable isomers formed by plastic fluxionality can manifest high reactivity despite their minor occurrence probability in the mixture of catalyst isomers. In the end, the highly active metastable isomer may dominate the total observed reactivity. In addition, the isomerization between the global minimum structure and the highly active metastable isomer can be a central step in catalytic transformations in order to circumvent some difficult reaction steps and may govern the overall mechanism. In addition, the thermal fluctuation driven elastic fluxionality is also found to play a key role, complementary to plastic fluxionality. The elastic fluxionality creates substantial structural deformations of the active site, and these deformed geometries enable low activation energies and high catalytic activity, which cannot be found from the static equilibrium geometry of the catalyst. A dedicated global activity search algorithm is proposed to search for the optimal reaction pathway on fluxional nanoclusters. In summary, our studies demonstrate that thermal-driven fluxionality provides a different paradigm for understanding the high activity of nanoclusters under reaction conditions beyond the static description of geometric and electronic structure. We first summarize our previous results and then provide a perspective for further studies on how to investigate and take the advantage of the fluxional geometry of nanoclusters. We will defend in this Account that the static picture for the active site is not complete and might miss critical reaction pathways that are highly efficient and only open after thermally induced restructuring of the active site.

Photosynthetic regulation in response to fluctuating light conditions under temperature stress in three mosses with different light requirements.

Under natural field conditions, mosses experience fluctuating light intensities combined with temperature stress. Alternative electron flow mediated by flavodiiron proteins (FLVs) and cyclic electron flow (CEF) around photosystem I (PSI) allow mosses to growth under fluctuating light conditions. However, little is known about the roles of FLVs and CEF in the regulation of photosynthesis under temperature stress combined with fluctuating light. Here, we measured chlorophyll fluorescence and P700 redox state under fluctuating light conditions at 4 °C, 20 °C, and 35 °C in three mosses with different light requirements. Upon a sudden increase in light intensity, electron flow from photosystem II initially increased and then gradually decreased at 20 °C and 35 °C, indicating that the operation of FLV-dependent flow lasted much longer than previously thought. Furthermore, the absolute rates of FLV-dependent flow and CEF were enhanced under fluctuating light at 35 °C, pointing to their important roles in photoprotection when exposed to fluctuating light at moderate high temperature. Furthermore, the downregulation of FLV activity at 4 °C was partially compensated for by enhanced CEF activity. These results suggested the subtle coordination between FLV activity and CEF under fluctuating light and temperature stress. Racomitrium japonicum and Hypnum plumaeforme, which usually grow under relatively high light levels, exhibited higher FLV activity and CEF than the shade-grown moss Plagiomnium ellipticum. Based on our results, we conclude that photosynthetic acclimation to fluctuating light and temperature stress in different mosses is largely linked to the adjustment of FLV activity and CEF.