Search

Soil setup has a significant contribution to the performance of jacked piles in natural clays with structure characteristics. In this paper, a series of model pile tests are conducted to investigate the pile setup in structured clays, focusing on the influence of soil structure on time-dependent pile response. Three artificially structured clays are prepared as model soils to avoid the sampling challenge of undisturbed clays. The model tests are capable of modeling pile response through installation, equalization, and loading, and hence the initial structure and stress-induced structure degradation of clays, as well as the following thixotropic effect and reconsolidation of disturbed clays, can be adequately incorporated. Meanwhile, the behaviors of the piles and pile–soil interface are constantly monitored by the measurement system during and after pile installation. The results demonstrate that by increasing the cement content of structured clays from 0 to 4%, the penetration resistance is almost doubled, and the pore water pressure (PWP) and radial stress of the pile–soil interface located 20 cm from the pile toe increase by 1.27 and 1.38 times, respectively. A higher cement content in model soils leads to a quicker dissipation of excess pore water pressure (EPWP) due to the presence of a larger void structure and a smaller zone of damage caused by pile driving in structured clays. The growth rate of the ultimate bearing capacity of piles increases sharply with the cement content. The normal stress of the interface first decreases slightly and then grows dramatically with the mobilized shear stress during static loading tests. [ABSTRACT FROM AUTHOR]

Blastic plasmacytoid dendritic cell neoplasm (BPDCN) is a rare and aggressive myeloid malignancy which characteristically expresses an atypical phenotype including CD123+, CD56+, and CD4+. We are aimed to investigate the clinical and prognostic characteristics of AML patients exhibiting BPDCN-like immunophenotype and provide additional insights for risk stratification of AML. A total of 241 newly diagnosed AML patients were enrolled in this retrospective study and categorized into BPDCN-like positive (n = 125)/negative (n = 116) groups, determined by the present with CD123+ along with either CD56+ or CD4+, or both. Subsequently, an analysis was conducted to examine the general clinical characteristics, genetic profiles, and prognosis of the two respective groups. Patients with BPDCN-like immunophenotype manifested higher frequencies of acute myelomonocytic leukemia and acute monoblastic leukemia. Surprisingly, the presence of the BPDCN-like immunophenotype exhibited an inverse relationship with CEBPA bZIP mutation. Notably, patients with BPDCN-like phenotype had both worse OS and EFS compared to those without BPDCN-like phenotype. In the CN-AML subgroups, the BPDCN-like phenotype was associated with worse EFS. Similarly, a statistically significant disparity was observed in both OS and EFS within the favorable-risk subgroup, while only OS was significant within the adverse-risk subgrouMoreover, patients possessing favorable-risk genetics without BPDCN-like phenotype had the longest survival, whereas those who had both adverse-risk genetics and BPDCN-like phenotype exhibited the worst survival. Our study indicated that BPDCN-like phenotype negatively associated with CEBPA bZIP mutation and revealed a significantly poor prognosis in AML. Moreover, the 2022 ELN classification, in combination with the BPDCN-like phenotype, may better distinguish between different risk groups. [ABSTRACT FROM AUTHOR]

Context: The reaction between Na and HF is a typical harpooning reaction which is of great interest due to its significance in understanding the elementary chemical reaction kinetics. This work aims to investigate the detailed reaction mechanisms of sodium with hydrogen fluoride and the adsorption of HF on the resultant NaF as well as the (NaF)4 tetramer. The results suggest that the reaction between Na and HF leads to the formation of sodium fluoride salt NaF and hydrogen gas. Na interacts with HF to form a complex HF···Na, and then the approaching of F atom of HF to Na results in a transition state H···F···Na. Accompanied by the broken of H-F bond, the bond forms between F and Na atoms as NaF, then the product NaF is yielded due to the removal of H atom. The resultant NaF can further form (NaF)4 tetramer. The interaction of NaF with HF leads to the complex NaF···HF; the form I as well as II of (NaF)4 can interact with HF to produce two complexes (i.e., (NaF)4(I-1)···HF, (NaF)4(I-2)···HF, (NaF)4(II-1)···HF and (NaF)4(II-2)···HF), but the form III of (NaF)4 can interact with HF to produce only one complex (NaF)4(III)···HF. These complexes were explored in terms of noncovalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analyses. NCI analyses confirm the existences of attractive interactions in the complexes HF···Na, NaF···HF, (NaF)4(I-1)···HF, (NaF)4(I-2)···HF, (NaF)4(II-1)···HF and (NaF)4(II-2)···HF, and (NaF)4(III)···HF. QTAIM analyses suggest that the F···Na interaction forms in the HF···Na complex while the F···H hydrogen bonds form in NaF···HF, (NaF)4(I-1)···HF, (NaF)4(I-2)···HF, (NaF)4(II-1)···HF and (NaF)4(II-2)···HF, and (NaF)4(III)···HF complexes. Natural bond orbital (NBO) analyses were also applied to analyze the intermolecular donor-acceptor orbital interactions in these complexes. These results would provide valuable insight into the chemical reaction of Na and HF and the adsorption interaction between sodium fluoride salt and HF. Methods: The calculations were carried out at the M06-L/6-311++G(2d,2p) level of theory which were performed using the Gaussian16 program. Intrinsic reaction coordinate (IRC) calculations were carried out at the same level of theory to confirm that the obtained transition state was true. The molecular surface electrostatic potential (MSEP) was employed to understand how the complex forms. Quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) analysis was used to know the topology parameters at bond critical points (BCPs) and intermolecular interactions in the complex and intermediate. The topology parameters and the BCP plots were obtained by the Multiwfn software. [ABSTRACT FROM AUTHOR]

Copyright of Rare Metals is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Microbiota have an important function in shaping and priming neonatal immunity, although the cellular and molecular mechanisms underlying these effects remain obscure. Here we report that prenatal antibiotic exposure causes significant elevation of group 2 innate lymphoid cells (ILC2s) in neonatal lungs, in both cell numbers and functionality. Downregulation of type 1 interferon signaling in ILC2s due to diminished production of microbiota-derived butyrate represents the underlying mechanism. Mice lacking butyrate receptor GPR41 (Gpr41-/-) or type 1 interferon receptor IFNAR1 (Ifnar1-/-) recapitulate the phenotype of neonatal ILC2s upon maternal antibiotic exposure. Furthermore, prenatal antibiotic exposure induces epigenetic changes in ILC2s and has a long-lasting deteriorative effect on allergic airway inflammation in adult offspring. Prenatal supplementation of butyrate ameliorates airway inflammation in adult mice born to antibiotic-exposed dams. These observations demonstrate an essential role for the microbiota in the control of type 2 innate immunity at the neonatal stage, which suggests a therapeutic window for treating asthma in early life. Treatment of pregnant animals with antibiotics can have unexpected effects on offspring. Here the authors use mouse models to show that antibiotic treatment of mothers leads to changes in ILC2 phenotype in neonatal lungs accompanied by changes in the microbiota and microbiota derived butyrate. [ABSTRACT FROM AUTHOR]

Aims: Coastal salt marshes are productive ecosystems that are highly efficient carbon sinks, but there is uncertainty regarding the interactions among climate warming, plant species, and tidal restriction on C cycling. Methods: Open-top chambers (OTCs) were deployed at two coastal wetlands in Yancheng, China, where native Phragmites australis (Phragmites) and invasive Spartina alterniflora (Spartina) were dominant, respectively. Two study locations were set up in each area based on difference in tidal action. The OTCs achieved an increase of average daytime air temperature of ~ 1.11–1.55 °C. Net ecosystem CO2 exchange (NEE), ecosystem respiration (Reco), CH4 fluxes, aboveground biomass and other abiotic factors were monitored over three years. Results: Warming reduced the magnitude of the radiative balance of native Phragmites, which was determined to still be a consistent C sink. In contrast, warming or tidal flooding presumably transform the Spartina into a weak C source, because either warming-induced high salinity reduced the magnitude of NEE by 19% or flooding increased CH4 emissions by 789%. Remarkably, native Phragmites affected by tidal restrictions appeared to be a consistent C source with the radiative balance of 7.11–9.64 kg CO2-eq m–2 yr–1 because of a reduction in the magnitude of NEE and increase of CH4 fluxes. Conclusions: Tidal restrictions that disconnect the tidal hydrologic connection between the ocean and land may transform coastal wetlands from C sinks to C sources. This transformation may potentially be an even greater threat to coastal carbon sequestration than climate warming or invasive plant species in isolation. [ABSTRACT FROM AUTHOR]

The activation of ethers by weak interactions is a long-standing objective in supramolecular catalysis, but yet it remains an underdeveloped topic. The obstacles towards solving this problem are prominent since it is difficult for a weak interaction to cleave a relatively strong C-O σ-bond and moreover, the ionic intermediate composing of an alkoxide ion and an electrophilic carbocation would deactivate weak interaction donors. Herein, we describe a distinctive activation mode, dual Se···π and Se···O bonding, that could activate benzylic as well as allylic ether C-O σ-bonds to achieve cyclization, coupling and elimination reactions. This dual Se···π and Se···O bonding catalysis approach could tolerate various alkoxide leaving groups, while the other representative weak interaction donors showed no catalytic activity. The activation of ethers by weak interactions in supramolecular catalysis remains challenging. Here, the authors describe an activation mode based on dual Se···π and Se···O bonding, that can activate benzylic as well as allylic ether C-O σ-bonds to achieve cyclization, coupling and elimination reactions. [ABSTRACT FROM AUTHOR]

In this article, we are concerned with a diffusive SVEIR epidemic model with nonlinear incidences. We first obtain the well-posedness of solutions for the model. Then, the basic reproduction number R 0 and the local basic reproduction number R ¯ 0 (x) are calculated, which are defined as the spectral radii of the next-generation operators. The relationship between R 0 and R ¯ 0 (x) as well as the asymptotic properties of R 0 when the diffusive rates tend to infinity or zero is investigated by introducing two compact linear operators L 1 and L 2 . Using the theory of monotone dynamical systems and the persistence theory of dynamical systems, we show that the disease-free equilibrium is globally asymptotically stable when R 0 < 1 , while the disease is uniformly persistent when R 0 > 1 . Furthermore, in the spatially homogeneous case, by using the Lyapunov functions method and LaSalle's invariance principle, we completely obtain that the disease-free equilibrium is globally asymptotically stable if R 0 ≤ 1 , and the endemic equilibrium is globally asymptotically stable if R 0 > 1 and an additional condition is satisfied. [ABSTRACT FROM AUTHOR]

Let C be a Krull–Schmidt n-exangulated category and A be an n-extension closed subcategory of C . Then A inherits the n-exangulated structure from the given n-exangulated category in a natural way. This construction gives n-exangulated categories which are neither n-exact categories in the sense of Jasso nor (n + 2)-angulated categories in the sense of Geiss–Keller–Oppermann in general. Furthermore, we also give a sufficient condition on when an n-exangulated category A is an n-exact category. These results generalize work by Klapproth and Zhou. [ABSTRACT FROM AUTHOR]

Growing market demand from portable electronics to electric automobiles boosts the development of lithium-ion batteries (LIBs) with high energy density and rate performance. However, strong solvation effect between lithium ions (Li+) and solvent molecules in common electrolytes limits the mobility of Li+ ions in electrolytes. Consequently, anions dominate the charge conduction in electrolytes, and in most cases, the value of Li+ transference number (T+) is between 0.2 and 0.4. A low T+ will aggravate concentration polarization in the process of charging and discharging, especially at high rate, which not only increases the overpotential but also intensifies side reactions, along with uneven deposition of lithium (Li) and the growth of lithium dendrites when lithium metal is used as anode. In this review, promising strategies to improve T+ in liquid electrolytes would be summarized. The migration of Li+ ions is affected directly by the types and concentration of lithium salts, solvents, and additives in bulk electrolytes. Besides, Li+ ions will pass through the separator and solid electrolyte interphase (SEI) when transferring between anodes and cathodes. With this in mind, we will classify and summarize threads of enhancing T+ from five aspects: lithium salts, solvents, additives, separators, and SEI based on different mechanisms, including covalently bonding, desolvation effect, Lewis acid-base interaction, electrostatic interaction, pore sieving, and supramolecular interaction. We believe this review will present a systematic understanding and summary on T+ and point out some feasible threads to enhance battery performance by enhancing T+. [ABSTRACT FROM AUTHOR]

With the increasing scale of energy storage, it is urgently demanding for further advancements on battery technologies in terms of energy density, cost, cycle life and safety. The development of lithium-ion batteries (LIBs) not only relies on electrodes, but also the functional electrolyte systems to achieve controllable formation of solid electrolyte interphase and high ionic conductivity. In order to satisfy the needs of higher energy density, high-voltage (> 4.3 V) cathodes such as Li-rich layered compounds, olivine LiNiPO4, spinel LiNi0.5Mn1.5O4 have been extensively studied. However, high-voltage cathode-based LIBs fade rapidly mainly owing to the anodic decomposition of electrolytes, gradually thickening of interfacial passivation layer and vast irreversible capacity loss, hence encountering huge obstacle toward practical applications. To tackle this roadblock, substantial progress has been made toward oxidation-resistant electrolytes to block its side reaction with high-voltage cathodes. In this review, we discuss degradation mechanisms of electrolytes at electrolyte/cathode interface and ideal requirements of electrolytes for high-voltage cathode, as well as summarize recent advances of oxidation-resistant electrolyte optimization mainly from solvents and additives. With these insights, it is anticipated that development of liquid electrolyte tolerable to high-voltage cathode will boost the large-scale practical applications of high-voltage cathode-based LIBs. [ABSTRACT FROM AUTHOR]

Humic acid (HA) in makeup water is one of the important safety issues of high-parameter power plants. Herein, the Zr-based metal-organic frameworks (NH2-UiO-66) was applied to remove humic acid in water. The mesoporous of NH2-UiO-66 was controlled by surfactants sodium dodecyl benzene sulfonate (SDBS) to increase the adsorption of HA. The adsorption of HA at 25°C and pH 7 increased fast at the first 0.5 h and then gradually reached equilibrium after 10 h. The maximum adsorption capacity was 108.93 mg g−1, which removal efficiency was high as 95.0%. The morphology and adsorption properties of NH2-UiO-66 were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), surface charge, Fourier transform infrared (FT-IR), N2 adsorption–desorption, and adsorption test. The adsorption process of HA accorded with the pseudo-second-order kinetics, while the adsorption isotherm conformed to be the Langmuir model and the adsorption was proved to be monolayer adsorption. Adsorption was the spontaneous and endothermic process (ΔG°<0, ΔH°>0). The accessible surface area provided by mesopores on the 5 different Zr-MOFs was the reason for the enhanced HA adsorption capacity. These results provided useful information for effective HA removing and enhanced our understanding of the adsorption mechanism of HA on NH2-UiO-66. [ABSTRACT FROM AUTHOR]

This document is a correction notice for an article titled "Instant3D: Instant Text-to-3D Generation" published in the International Journal of Computer Vision. The correction addresses an error in the authors' affiliations. The original version incorrectly listed the authors' affiliation as the "School of Computing and Information Systems, Singapore Management University," when they were actually affiliated with the "Sea AI Lab, Singapore." The correction provides the correct affiliations for the authors. The publisher, Springer Nature, remains neutral regarding jurisdictional claims and institutional affiliations. The original article can be found online at the provided link. [Extracted from the article]

Copyright of Rare Metals is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The activation of aziridines typically involves the use of strong Lewis acids or transition metals, and methods relying on weak interactions are rare. Herein, we report that cooperative chalcogen bonding interactions in confined sites can activate sulfonyl-protected aziridines. Among the several possible distinct bonding modes, our experiments and computational studies suggest that an activation mode involving the cooperative Se···O and Se···N interactions is in operation. The catalytic reactions between weakly bonded supramolecular species and nonactivated alkenes are considered as unfavorable approaches. However, here we show that the activation of aziridines by cooperative Se···O and Se···N interactions enables the cycloaddition of weakly bonded aziridine-selenide complex with nonactivated alkenes in a catalytic manner. Thus, weak interactions can indeed enable these transformations and are an alternative to methods relying on strong Lewis acids. The activation of aziridines is typically achieved via reaction with strong Lewis acids or transition metals. Here, the authors report that cooperative Se ∙ ∙∙O and Se ∙ ∙∙N noncovalent interactions can activate sulfonyl-protected aziridines, which enables their use in cycloaddition reactions with nonactivated alkenes. [ABSTRACT FROM AUTHOR]

In electrochemical devices, such as batteries, traditional electric double layer (EDL) theory holds that cations in the cathode/electrolyte interface will be repelled during charging, leaving a large amount of free solvents. This promotes the continuous anodic decomposition of the electrolyte, leading to a limited operation voltage and cycle life of the devices. In this work, we design a new EDL structure with adaptive and passivating properties. It is enabled by adding functional anionic additives in the electrolyte, which can selectively bind with cations and free solvents, forming unique cation-rich and branch-chain like supramolecular polymer structures with high electrochemical stability in the EDL inner layer. Due to this design, the anodic decomposition of ether-based electrolytes is significantly suppressed in the high voltage cathodes and the battery shows outstanding performances such as super-fast charging/discharging and ultra-low temperature applications, which is extremely hard in conventional electrolyte design principle. This unconventional EDL structure breaks the inherent perception of the classical EDL rearrangement mechanism and greatly improve electrochemical performances of the device. Developing an electrolyte that is compatible with both high-voltage cathodes and Li metal anodes has always been challenging. Here, the authors created a new strategy by engineering a passivating electric double layer to achieve a fast-charging and lowtemperature high voltage lithium metal batteries. [ABSTRACT FROM AUTHOR]

Experimental studies on the Kolbe–Schmitt reaction and its side reactions have made great progresses; however, the relative theoretical studies fall behind. In order to study the mechanism of the Kolbe–Schmitt reaction with 2,6-di-tert-butylphenol and 2,4-di-tert-butylphenol as reactants, we carried out theoretical calculation studies at the M06-2X/Def2-SVP/SMD level of theory using the Gaussian 09 D.01 software package. For the reactant 2,6-di-tert-butylphenol, there is a dynamic equilibrium between the main product and side product, which can rapidly transform into each other at 160 °C by crossing the Gibbs free energy barrier of 14.1 kcal/mol. Moreover, the relative Gibbs free energy of the main product and side product is close; both of them may be observed in the experimental system. However, for 2,4-di-tert-butylphenol, the main product is thermodynamically favorable due to its lower Gibbs free energy, while the side product is kinetically favorable due to the lower activation energy barrier; the main product and the side product compete with each other. We hope the study can shed light on the Kolbe–Schmitt reaction. [ABSTRACT FROM AUTHOR]

Text-to-3D generation has attracted much attention from the computer vision community. Existing methods mainly optimize a neural field from scratch for each text prompt, relying on heavy and repetitive training cost which impedes their practical deployment. In this paper, we propose a novel framework for fast text-to-3D generation, dubbed Instant3D. Once trained, Instant3D is able to create a 3D object for an unseen text prompt in less than one second with a single run of a feedforward network. We achieve this remarkable speed by devising a new network that directly constructs a 3D triplane from a text prompt. The core innovation of our Instant3D lies in our exploration of strategies to effectively inject text conditions into the network. In particular, we propose to combine three key mechanisms: cross-attention, style injection, and token-to-plane transformation, which collectively ensure precise alignment of the output with the input text. Furthermore, we propose a simple yet effective activation function, the scaled-sigmoid, to replace the original sigmoid function, which speeds up the training convergence by more than ten times. Finally, to address the Janus (multi-head) problem in 3D generation, we propose an adaptive Perp-Neg algorithm that can dynamically adjust its concept negation scales according to the severity of the Janus problem during training, effectively reducing the multi-head effect. Extensive experiments on a wide variety of benchmark datasets demonstrate that the proposed algorithm performs favorably against the state-of-the-art methods both qualitatively and quantitatively, while achieving significantly better efficiency. The code, data, and models are available at https://ming1993li.github.io/Instant3DProj/. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) exhibit attractive properties such as highly accessible surface area, large porosity, tunable pore size, and built-in redox-active metal sites. They may serve as excellent candidates to construct implantable flexible devices for biochemical sensing due to their high thermal and solution stability. However, MOFs-based sensors have only been mostly reported for in-vitro chemical sensing, their use in implantable chemical sensing and combination with flexible electronics to achieve excellent mechanical compatibility with tissues and organs has rarely been summarized. This paper systematically reviews the biochemical sensors based on MOFs and discusses the feasibility to achieve implantable biochemical sensing through MOFs-based flexible electronics. The properties of MOFs and underlying mechanisms have been introduced, followed by a summarization of different biochemical sensing applications. Strategies to integrate MOFs with flexible devices have been supplied from the standpoints of matching mechanics and compatible fabrication processes. Issues that should be addressed in developing flexible MOFs sensors and potential solutions have also been provided, followed by the perspective for future applications of flexible MOFs sensors. This paper may serve as a reference to offer potential guidelines for the development of flexible MOFs-based biochemical sensors that may benefit future applications in personal healthcare, disease diagnosis and treatment, and fundamental study of various biological processes. [ABSTRACT FROM AUTHOR]

The anaerobic digestion performance correlates with the functional microbial community. Mesophilic and thermophilic digestions of vegetable waste were conducted, and dynamics of the microbial community were investigated. The mesophilic and thermophilic collapsed stages occurred at organic loading rates of 1.5 and 2.0 g VS/(L d) due to the accumulation of volatile fatty acids with final concentrations of 2276 and 6476 mg/L, respectively. A high concentration of volatile fatty acids caused the severe inhibition of methanogens, which finally led to the imbalance between acetogenesis and methanogenesis. The mesophilic digestion exhibited a higher microbial diversity and richness than the thermophilic digestion. Syntrophic acetate-oxidizing coupled with hydrogenotrophic methanogenesis was the dominant pathway in the thermophilic stable system, and acetoclastic methanogenesis in the mesophilic stable system. The dominant acidogens, syntrophus, and methanogens were unclassified_f__Anaerolineaceae (8.68%), Candidatus_Cloacamonas (19.70%), Methanosaeta (6.10%), and Methanosarcina (4.08%) in the mesophilic stable stage, and Anaerobaculum (12.59%), Syntrophaceticus (4.84%), Methanosarcina (30.58%), and Methanothermobacter (3.17%) in thermophilic stable stage. Spirochaetae and Thermotogae phyla were the characteristic microorganisms in the mesophilic and thermophilic collapsed stages, respectively. These findings provided valuable information for the deep understanding of the difference of the microbial community and methane-producing mechanism between mesophilic and thermophilic digestion of vegetable waste. [ABSTRACT FROM AUTHOR]

This paper presents a new method for assessing the stability of an underground cavern with anchor reinforcement under the seepage field. Firstly, the reinforcement effect of the anchor is considered as a set of clamping forces acting on both sides of the anchored rock mass, besides, whose strength parameters are also considered to be improved. Secondly, a mechanics model for a deep-buried circular cavern with anchor reinforcement under the seepage field is established, and the analytical solution incorporating the characteristics of dilatancy and strain softening of the surrounding rock are derived based on the unified strength theory. Finally, the validity and accuracy of the present solution are examined via comparison with published researches and field monitoring data. Subsequently, extensive parameter investigation is performed to systematically discuss the influence of the intermediate principal stress, dilatancy, strain softening, and seepage force on the cavern deformation and study the variation of the axial force of anchors. The results show that the surrounding rock stresses increase significantly but its radical displacement and the anchor axial force decreased as the intermediate principal stress coefficient increases. With the increase in dilatancy angle, the surrounding rock radial displacement and the anchor axial force increase sharply, but the plastic zone radius and the stresses are almost constant. Moreover, considering the seepage field, the peak value of maximum tangential stress and the stresses in the elastic zone increases but the radial stress in the plastic zone decreases, and the radial and tangential stress distributions are no longer asymptotic with the initial ground stress. [ABSTRACT FROM AUTHOR]

The flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under a dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds under mild conditions (visible light, ambient temperature, no strong base) to access the versatile benzylic boronic esters with good functional group tolerance and excellent enantioselectivities. Metallaphototoredox catalysis has been rarely applied to reductive cross-couplings, in contrast to typical redox-neutral methods. Here, the authors report a mild Ni/photoredox-catalyzed reductive cross-coupling of aryl iodides and α-chloroboranes, further enriching the metallaphotoredox chemistry. [ABSTRACT FROM AUTHOR]

Anaerobic digestion is an effective process for the treatment of organic solid waste and wastewater and the production of biogas, which is a clean energy source. The carbon dioxide in the biogas can be converted into methane using hydrogen generated from water electrolysis through an approach referred to as power-to-gas. Recently, hydrogen has been added to digesters as an in-situ or ex-situ biogas upgrade to reduce the levels of carbon dioxide. Biogas production systems consist of microbial complexes with highly organized microorganisms in different niches, which can either produce or consume hydrogen. However, the produced endogenous hydrogen should be constantly consumed to maintain a low hydrogen partial pressure. This review addresses the biochemical processes of anaerobic digestion and hydrogen-related microorganisms, including fermentative acid-producing bacteria, syntrophic organic acid degrading bacteria, syntrophic acetate-oxidizing bacteria, homoacetogens, hydrogenotrophic methanogens, and newly reported hydrogen-dependent methylotrophic methanogens. This study also investigates (1) the role of endogenous hydrogen as an intermediate metabolite and of interspecies electron transfer in anaerobic digestion, (2) effects of exogenous hydrogen addition on microbial community structure and metabolic processes, and (3) recent developments regarding in-situ and ex-situ biogas upgrading systems via hydrogen addition. [ABSTRACT FROM AUTHOR]

With the rapid growth of user equipment (UE), the amount of data transmitted over networks has become enormous, exerting immense pressure on backbone networks and central cloud infrastructures. Simultaneously, corresponding applications requiring high energy consumption and low latency have multiplied the requirements for UE. Mobile edge computing (MEC) has been proposed to support the offloading of UE tasks to edge clouds for execution. The implementation of MEC requires fast data transmission between UE and edge servers, and the emerging 5G network appears to render this technology possible. In this paper, considering a large number of UE, a fixed MEC server, and an advanced intelligent network, we suggest an intelligent overclocking mechanism for the MEC server that operates for an intelligently calculated period to allow it to leverage more computing power without introducing additional hardware resources for a certain period of time. We jointly manage task offloading, server resource allocation, and overclocking to minimize the system-wide computation overhead and other risks. The proposed optimization problem is a mixed-integer nonlinear programming problem that is divided into three subproblems: offloading decision, resource allocation, and overclocking decision. We solve these subproblems using non-convex techniques and provide an iterative algorithm to obtain a heuristic solution for the original problem. Finally, simulation results show that the overclocked MEC server has lower system-wide computation overhead, faster task processing, and more offloaded UE as compared with the case without overclocking. [ABSTRACT FROM AUTHOR]

Physisorption of bromopentafluorobenzene (C6F5Br) on graphene can occur due to the unique σ-hole and π-hole characters of C6F5Br and the rich π-electrons region of graphene, leading to the formation of three types of π-hole···π and σ-hole···π interactions. The π-hole···π interactions are even stronger than the σ-hole···π interactions. The property of graphene was significantly affected by such physisorption. [ABSTRACT FROM AUTHOR]

Explicit congestion notification (ECN) has been widely adopted by recent proposals to build up high-throughput and low-latency datacenter network transport. In these ECN-based proposals, when the queue length of a switch exceeds a pre-defined threshold, the switch would mark all arriving packets with ECN to explicitly notify their senders to slow down the rates. Such a design enables the network to eliminate congestions quickly. However, it marks packets without considering the flow state, which may overkill flows, especially those only send a few packets, thus resulting in significant throughput loss and long flow completion times. In this paper, we propose a novel flow-aware ECN marking approach (FECN), which can improve the throughput and flow completion time by taking flow states into consideration. By selectively marking packets respecting to their flow rates, FECN enables the network to precisely slow down the high-speed flows to avoid congestions without killing low-speed short flows. Moreover, FECN does not require switches to maintain per-flow state, which yields low overhead and thus makes FECN to be easily implemented and deployed in commodity switches. Simulations show that FECN can shorten the flow completion time by up to 44.7% and reduce the throughput loss by up to 40.3%, compared with prior flow-agnostic ECN marking approach. [ABSTRACT FROM AUTHOR]

Background: Aberrant expression of retinoic acid receptor α (RARα) was correlated with diverse carcinomas such as acute promyelocytic leukemia and colorectal carcinoma. Nevertheless, the function and mechanism of RARα in esophageal carcinoma (EC) remain unclear.Aim: To investigate the expression of RARα in EC and its effect in the tumorigenesis of EC.Methods and Results: In immunohistochemistry study, RARα was overexpressed in human EC tissues, and its overexpression was closely related to the pathological differentiation, lymph node metastasis, and clinical stages in EC patients. Functionally, RARα knockdown suppressed the proliferation and metastasis of EC cells through downregulating the expression of PCNA, Ki67, MMP7, and MMP9, as well as enhanced drug susceptibility of EC cells to 5-fluorouracil and cisplatin. Mechanistically, RARα knockdown inhibited the activity of Wnt/β-catenin pathway through reducing the phosphorylation level of GSK3β at Ser-9 and inducing phosphorylation level at Tyr-216, which resulted in downregulation of its downstream targets such as MMP7, MMP9, and P-gP.Conclusions: Our results demonstrated that RARα knockdown suppressed the tumorigenicity of EC via Wnt/β-catenin pathway. RARα might be a potential molecular target for EC clinical therapy. [ABSTRACT FROM AUTHOR]

To uncover the correlation between the bond length change and the corresponding stretching frequency shift of the proton donor D-H upon hydrogen bond formation, a series of hydrogen-bonded complexes involving HF and HCl which exhibit the characteristics of red-shifted hydrogen bond were investigated at the MP2/aug-cc-pVTZ, M062X/aug-cc-pVTZ, and B3LYP/aug-cc-pVTZ(GD3) levels of theory with CP optimizations. A statistical analysis of these complexes leads to the quantitative illustrations of the relations between bond length and stretching vibrational frequency, between bond length and bond force constant, between stretching vibrational frequency and bond force constant, between bond length and bond order for hydrohalides in a mathematical way, which would provide valuable insights into the explanation of the geometrical and spectroscopic behaviors during hydrogen bond formation. [ABSTRACT FROM AUTHOR]

Neuronal cell death following spinal cord injury (SCI) is an important contributor to neurological deficits. The purpose of our work was to delineate the function of mammalian sterile 20-like kinase 1 (Mst1), a pro-apoptotic kinase and key mediator of apoptotic signaling, in the pathogenesis of an experimental mouse model of SCI. Male mice received a mid-thoracic spinal contusion injury, and it was found that phosphorylation of Mst1 at the injured site was enhanced significantly following SCI. Furthermore, when compared to the wild-type controls, Mst1-deficient mice displayed improved locomotor function by increased Basso mouse scale score. Deletion of Mst1 in mice attenuated loss of motor neurons and suppressed microglial and glial activation following SCI. Deletion of Mst1 in mice reduced apoptosis via suppressing cytochrome c release and caspase-3 activation following SCI. Deletion of Mst1 attenuated mitochondrial dysfunction and increased ATP formation following SCI. Deletion of Mst1 in mice inhibited local inflammation following SCI, evidenced by reduced activities of myeloperoxidase and protein levels of TNF-α, IL-1β, and IL-6. In conclusion, the present study demonstrated that deletion of Mst1 attenuated neuronal loss and improved locomotor function in a mouse model of SCI, via preserving mitochondrial function, attenuating mitochondria-mediated apoptotic pathway, and suppressing inflammation, at least in part. [ABSTRACT FROM AUTHOR]

Intermolecular interactions between phenol and benzene molecules with the T-shaped geometries could be diverse. They can be pursued via two structural series: one with benzene standing above phenol using one or two C–H bonds as the anchoring point and the other with phenol standing on top of benzene with either C–H or O–H bond as the leg. In this work, structure and interaction properties of these species are investigated at the DFT M06-2X/6-311++G(2d,2p) level of theory without and with the counterpoise correction. A total of twelve distinct isomers have been identified, eight of which were unveiled for the first time. It is found that π–π interactions play essential roles in stabilizing these conformations, while C–H/π, C–H···O van der Waals interactions, and C–H···O and O–H/π hydrogen bonds are also involved and positively contribute to the stability of these species. Our energy decomposition analysis shows that the driving force for the formation of these complexes arises from attractive electrostatic, exchange, polarization, and dispersion terms, balanced by the repulsion term. The dispersion effect plays a dominant role, but the electrostatic and exchange terms are also markedly significant. Their close relationships between one another have also been disclosed. [ABSTRACT FROM AUTHOR]

HNbO nanosheet aggregates ( e-HNbO) were prepared by exfoliation and aggregation of layered HNbO, which was obtained by protonation of KNbO. Especially, in this research, KNbO was synthesized through a novel polymerized complex method (PC) from niobium oxalate. The as-prepared samples were characterized by SEM, HRTEM, XRD, LRS, NH-TPD, and FT-IR methods. The toluene nitration was used to evaluate the acid catalytic performance of HNbO and e-HNbO samples. The catalytic activity in toluene nitration was related to the structure and acidity of the as-prepared samples. The results show that e-HNbO has a higher specific surface area, stronger acidity and better para-selectivity than the precursor HNbO. [ABSTRACT FROM AUTHOR]

We report on a method for the determination of the herbicide atrazine in tap water samples using melamine-modified gold nanoparticles (Mel-AuNPs). If a solution containing atrazine is added to a solution of such NPs, a color change occurs from wine-red to blue. This is due to a transition from monodisperse to aggregated Mel-AuNPs and caused by strong hydrogen bonding between atrazine and melamine. The color change can be monitored by a UV-vis spectrophotometer or with bare eyes. The ratio of the absorbances at 640 and 523 nm is linearly related to the logarithm of the atrazine concentration in the 0.165 to 16.5 μM range, and (with different slope) in the 16.5 μM to 330 μM range. The detection limit of atrazine is as low as 16.5 nM (S/N = 3). The method was successfully applied to the determination of atrazine in spiked tap water and gave recoveries that ranged from 72.5 % to 102.3 %. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Synthesis and anionic polymerization of the fluorine-substituted phenyl methacrylates are herein reported. A series of mono-, di-, and multi-substituted fluorophenyl methacrylates HC=C(CH)C(O)OCHF-4 ( M), HC=C(CH)C(O)OCHF-3 ( M), HC=C(CH)C(O)OCHF-2,4 ( M), HC=C(CH)C(O)OCHF-2,3,4 ( M), HC=C(CH)C(O)OCHF-2,3,5,6 ( M), and HC=C(CH)C(O)OCF ( M) were synthesized and characterized. Initially, the polymerization was carried out on the monomer M by using nBuLi, tBuLi, and KH as the respective catalysts; this approach produced the polymers in yields of 12%-50%, but with lower molecular weights. Similar results were obtained by using tBuLi for catalytically polymerizing the other five monomers. By introducing a co-catalyst MeAl(BHT), the catalysts NaH, LiH, and tBuOLi each were tested to polymerize M1a, which gave the polymers in very low yields (3%-7%). Polymer yields of 13%-27% were obtained by each of the catalysts LiAlH, nBuLi, PhLi, and tBuLi in connection with MeAl(BHT), but a better yield (61%) was achieved with KH/MeAl(BHT). The KH/MeAl(BHT) catalyst system was further employed to polymerize M and M, which afforded respective polymer yields of 12%-63% and 10%-53%, depending on the molar ratios of KH:MeAl(BHT) as well as on the monomer concentrations. All of the polymers produced were syndiotactically rich in structure, as indicated by either H or F NMR data. The polymerization mechanism by the combined catalyst system is proposed. [ABSTRACT FROM AUTHOR]

The equilibrium geometries, growth patterns, stabilities, and electronic properties of bimetallic BeSi ( n = 1-11) clusters are systematically investigated at the B3LYP/6-311G(d) level of theory. Harmonic vibrational analysis has been performed to assure that the optimized geometries are stable. The optimized results suggest that the three-dimensional structures are observed for the most stable isomers of BeSi clusters when n > 2. The calculated vertical ionization potential for the lowest-energy isomers are comparable to the experimental values of Si. According to the averaged binding energy, fragmentation energy, second-order energy difference and HOMO-LUMO gaps calculations, we identify that the BeSi and BeSi clusters are more stable, and Be atoms doping enhance the chemical reactivity of the Si host. The natural population and natural electron configuration analyses indicate that the Be atoms possess positive charge at n = 1-5 but negative charge at n = 6-11. The chemical hardness of BeSi clusters show three local maxima at n = 2, 5, and 9, whereas three local minima are found for the corresponding chemical potential, meaning these clusters are more stable than their neighboring cluster sizes. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Micro- and nano-sized SiC/fluoroelastomer (FKM) composites were prepared by a mechanical mixing method. These composites were first characterized by a rotorless rheometer. Then the effects of micro- and nano-sized SiC on hardness, static and dynamic mechanical properties of the composites were investigated. The increasing amount of the SiC filler increased the curing efficiency of the biphenyl curing system, which was evident from the rheometric properties of the resulting composites. The tensile properties of composite increased with the increasing of micro- and nano-sized SiC content. When the micro- and nano-sized SiC content was higher than 20 phr, the composites showed almost unchanged tensile properties. The increasing of the tensile property was mainly attributed to the well dispersed micro- and nano-sized SiC particles characterized by SEM images. Compared to pure FKM, the composites exhibited a higher glass transition temperature and lower tan δ peak value. [ABSTRACT FROM AUTHOR]

A simple model for describing the non-quasi-equivalent icosahedral virus capsid composed of 72 pentameric capsomeres is developed. By means of six-step operations, a new 4-gons polyhedron P is obtained which contains 72 pentagons, 80 trigons and 210 quadrilaterals. More importantly, it bears icosahedral symmetry. The rationality of the existence of the 4-gons polyhedron P is further discussed. The results show that this model can be used to represent the capsids of papovaviruses. [ABSTRACT FROM AUTHOR]

Objective: Acute pulmonary thromboembolism (PTE) is a serious high mortality pulmonary vascular disease whose effective treatment decreases morbidity and mortality. To determine if low-molecular-weight-heparin (LMWH) is clinically as efficient and safe as unfractionated heparin (UH) in patients with diagnosis of acute non-massive PTE, our study compares the efficacy, adverse effects and costs of LMWH and UH. Methods: One hundred and fourteen patients with non-massive acute PTE were randomly divided into LMWH (nadroparin calcium) and UH groups. Oxygenation index, D-dimer, fibrinogen (FG), lung ventilation/perfusion (V/Q) scan and computed tomography pulmonary angiography (CTPA) were observed before anticoagulation and on day 14 after anticoagulation. Results: In both groups, the ABG (arterial blood gas) analysis showed PaO2 and PaCO2 were elevated, P(A-a)O2 was decreased and oxygenation index (PaO2/FIO2) was elevated, D-dimer and fibrinogen were decreased, lung V/Q and CTPA showed embolized segments reduced ( P<0.05). Hemorrhage and thrombocytopenia occurred in 3.5% of the LMWH group. Hemorrhage occurred in 5.3% and thrombocytopenia occurred in 7.0% of the UH group. The average cost in the LMWH group was RMB 1218.60 Yuan and RMB 1541.40 Yuan in the UH group. Conclusion: LMWH and UH are equally effective for treatment of non-massive acute PTE, but LMWH may have a lower prevalence of complications and is less expensive. [ABSTRACT FROM AUTHOR]

Styrene-butadiene rubber (SBR) modified asphalt (SBRMA) can exhibit a good low-temperature performance. However, exposure to high-temperature and oxygen-containing environment can easily lead to decomposition of SBR modifier during the pavement construction process, which seriously compromises the modifying effects endowed by SBR modifier. To mitigate the negative influence of short-term aging on the performance of SBRMA, the warm-mix additive Sasobit was added into SBRMA due to its role in reducing mixing temperatures of asphalt mixture. In this paper, the mixing temperature of asphalt mixture was determined based on equal viscosity principle and set as short-term aging temperature of corresponding asphalt binder. The effect of Sasobit on the short-term aging temperature of the asphalt binder was further evaluated. In addition, the effects of Sasobit on un-aged and short-term aged SBRMA were investigated by physical, rheological, infrared spectrum, fluorescence microscopy and gel permeation chromatography tests. The results indicated the addition of Sasobit can effectively reduce the short-term temperature of SBRMA by 14 ºC through its effect of reducing viscosity. And the addition of Sasobit can improve the high-temperature stability of SBRMA but decrease its low-temperature ductility. The reduced short-term temperature due to adding Sasobit can mitigate the negative influence of short-term aging on SBRMA and SBR modifiers through physical and rheological aging indexes, chemical functional group, fluorescent images and polymer molecular weight evaluation. [ABSTRACT FROM AUTHOR]

Disruption of circadian rhythm during pregnancy produces adverse health outcomes in offspring; however, the role of maternal circadian rhythms in the immune system of infants and their susceptibility to inflammation remains poorly understood. Here we show that disruption of circadian rhythms in pregnant mice profoundly aggravates the severity of neonatal inflammatory disorders in both male and female offspring, such as necrotizing enterocolitis and sepsis. The diminished maternal production of docosahexaenoic acid (DHA) and the impaired immunosuppressive function of neonatal myeloid-derived suppressor cells (MDSCs) contribute to this phenomenon. Mechanistically, DHA enhances the immunosuppressive function of MDSCs via PPARγ-mediated mitochondrial oxidative phosphorylation. Transfer of MDSCs or perinatal supplementation of DHA relieves neonatal inflammation induced by maternal rhythm disruption. These observations collectively demonstrate a previously unrecognized role of maternal circadian rhythms in the control of neonatal inflammation via metabolic reprograming of myeloid cells., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)