bluuebunny/crossref_metadata_2025_split huggingface dataset:
Engineering Peptide‐Oligonucleotide Nano‐Conjugates via Click Reaction as Self‐Delivery System for Gene Therapy of Inflammatory Arthritis
Authors: Wang Qing , Wang Wei , Peng Xiaole , Ge Gaoran , Li Wenhao , Zhu Chen , Chen Xu , Guo Shun , Li Ning , Yang Huilin , Xu Yaozeng , Bai Jiaxiang , Pan Guoqing , Geng Dechun 
Published: August 2024

AbstractIntracellular oligonucleotide delivery possesses unparalleled potential for precise regulation of pathogenic gene expression and alteration of cell destiny. However, limited by its feeble resistance against humoral environment, hindered intracellular transportation, and lysosomal phagocytosis, oligonucleotide therapy remains a formidable challenge. The discovery of cationic peptides has provided innovative insights for the effective delivery of oligonucleotides, yet the stable, efficient, and convenient assembly of peptides and oligonucleotides remains an elusive goal, referred to as the “Holy Grail” challenge in the field. Addressing this challenge, it has pioneered the development of a straightforward and highly efficient engineering carrier‐free covalent peptide‐oligonucleotide nano‐conjugates (PONs) through a mild click reaction. Notably, this PONs can realize self‐assemble into nanoparticles under amphiphilic electrostatic interactions, which exhibits significant RNase resistance and surprisingly effective intracellular oligonucleotide delivery as well as lysosomal escape. Based on this strategy, a PONs named CPP‐(DOPA)6‐miRNA‐223 is synthesized, which demonstrates rapid and effective cellular uptake, swift lysosomal escape in macrophage, remarkable accumulation in inflammatory regions and excellent therapeutic effect in an inflammatory arthritis model. Therefore, this work may provide a breakthrough for the clinical application of all oligonucleotide delivery therapies and expanding the applications in gene therapy.
In Situ Controllably Self‐Assembled CoFe‐TDPAT Metal–Organic Framework Nanosheet Arrays on Iron Foam as Highly Efficient Bifunctional Catalytic Electrodes for Overall Water Splitting at Large Current Density
Authors: Hu Weiguang , Yan Qing , Wang Xiaoyan , Lu Jianguo , He Qinggang , Zhang Qinghua , Yuan Weiyong 
Published: August 2024

AbstractFor the first time, a Co and Fe bimetallic metal‐organic framework (BMOF) nanosheet array (NSA) employing 5,5′,5′'‐(1,3,5‐triazine‐2,4,6‐triyl)tris(azanediyl)triisophthalic acid (H6TDPAT) as the organic ligand is in situ controllably self‐assembled on iron foam (IF). The obtained IF@CoFe‐TDPAT NSA exhibits an oxygen evolution reaction (OER) activity much superior to most reported catalysts and even Ru and Ir‐based ones and hydrogen evolution reaction (HER) activity higher than most metal‐organic framework (MOF)‐based catalysts. The excellent bifunctional activities are ascribed to the superhydrophilic (3D) vertically aligned, interconnected NSA of CoFe‐TDPAT MOF with in situ activated coordinatively unsaturated metal sites remarkably enhancing OH− and H2O adsorption, accelerating electron transfer and transport, and facilitating O2/H2 diffusion. When adopted as a bifunctional electrode for overall water splitting, it achieves 300 mA cm−2 at 1.753 V and exhibits negligible current decay after 100 h. This performance is the highest of recently reported noble‐metal‐free water electrolyzers, and even much higher than those using commercial noble metal‐based catalysts. This work offers an economical, facile, and controllable strategy to fabricate low‐cost, highly efficient, and bifunctional BMOF nanostructured array electrodes for large‐current‐density water splitting, and also sheds light on the mechanisms for in situ self‐assembly and outstanding OER and HER performance of 3D free‐standing complex‐organic‐ligand‐based BMOF nanoarchitectures.
Achieving Super‐Metallophobicity on Silicon‐based Ceramics at High Temperature
Authors: Cao Xinpeng , Deng Shuxiang , He Zengyi , Yang Zengchao , Dai Haoyu , Li Jiangtao , Jiang Lei 
Published: August 2024

AbstractAs a critical concept in physical chemistry, superwettability is widely concerned in both fundamental science and practical engineering in past few decades. Despite this, investigation on high temperature superwettability is still a void, which is significant both in scientific and industrial fields. Herein, a ceramic with specific high temperature non‐wetting property, Si2N2O is proposed. Compared with other materials, Si2N2O is elucidated with better practical non‐wetting property against various non‐ferrous metals. Combining with micro‐nanostructures, the metallophobicity is further improved (contact angle >150° and contact angle hysteresis ≈0°). The extraordinary metal repellency is defined as “super‐metallophobicity”, which is proved to be induced by distinctive thermodynamic and dynamic wetting behavior on the rough surface. The research of super‐metallophobicity not only sheds light on superwettability at high temperature, but also offers worthy insights for future potential material design in a wide range of applications, such as metallurgy, 3D printing and semiconductor industry.
Stable CoO2 Nanoscrolls with Outstanding Electrical Properties
Authors: Hettler Simon , Roy Kankona Singha , Arenal Raul , Panchakarla Leela S. 
Published: August 2024

AbstractLayered CoO2 is of great interest for its promising properties but is meta‐stable in its bulk form. CoO2 is synthesized by converting the quasi‐1D crystal structure of bulk Ca3Co2O6 via a hydrothermal treatment. The resulting nanostructures are predominantly nanoscrolls with very thin walls, which exhibit long‐term stability. A detailed structural investigation reveals that the CoO2 is found to crystallize in monoclinic form, similar to the related CaCoO2‐CoO2 misfit structure. Individual nanoscrolls are characterized electrically and show a p‐type semiconducting nature with a high current‐carrying capacity of 4·105 A cm−2 and an extremely high breakdown voltage of up to 270 kV cm−1. The results demonstrate the possibility to stabilize meta‐stable materials in low‐dimensional forms and a promising application of the nanoscrolls as interconnect in high‐voltage electronic circuitry.
A Robust, Uniform, and Stable Glycerol Liquid Film Substrate for In Situ SERS Quantitative Investigation of Contaminant Distribution on Rough Surfaces
Authors: Peng Dandan , He Xinyue , Hu Zhangmei , de Menezes Jacson Weber , Valsecchi Chiara , Fan Meikun 
Published: August 2024

AbstractRapid, in situ, and real‐time molecule mapping on rough surfaces with high accuracy has long been one of the paramount challenges in many fields. Here, an effortless Ag NPs doped glycerol liquid film SERS substrate (g‐LFS) is developed to investigate the distribution of contaminants on different types of rough surfaces. After substrate optimization, the g‐LFS is characterized in terms of uniformity, reproducibility, and stability with time. The substrate showed an excellent signal stability, even after 96.5 h of usage or 19 days of storage, together with great uniformity (7.4% RSD) and reproducibility (7.1% RSD). As a proof of concept, the distribution of Rhodamine 6G(R6G) dye on rough fabric and the R6G migration in different plant types and tissues have been explored. The g‐LFS substrate demonstrated great accuracy, detecting R6G even in deep fabric grooves, recovering 82.4% of the initial concentration. Moreover, the g‐LFS SERS substrate detected significantly different concentrations in root, stem and leave tissues of bean sprouts, as well as between xylem and phloem in vascular plant branches. Overall, the g‐LFS substrate is proven to be well‐suited for in situ detection on rough surfaces with great versatility and robustness, aggregating new opportunities for contaminant investigation on food and plants using SERS.
Amphiphilic Cationic Carbon Dots for Efficient Delivery of Light‐Dependent Herbicide
Authors: Tang Gang , Wang Jialu , Xiao Jianhua , Liu Yulu , Huang Yuqi , Zhou Zhiyuan , Zhang Xiaohong , Hu Gaohua , Yan Weiyao , Cao Yongsong 
Published: August 2024

AbstractThe inefficient delivery of herbicides causes unpleasant side effects on the ecological environment. Protoporphyrinogen oxidase (PPO)‐inhibiting herbicides rely on the presence of external light to exert the activities and thus their performance in the field is extremely susceptible to the light environment. Here, taking acifluorfen (ACI) as a model PPO‐inhibiting herbicide to enhance efficacy by boosting the utilization rate of sunlight, amphiphilic cationic CDs (CPC‐CDs) from cetylpyridinium chloride (CPC) as a precursor, is first prepared as a supplementary light source generator, and subsequently co‐assembled with ACI through non‐covalent bond interactions to obtain the stable fluorescent nanoparticles (ACI@CPC‐CDs). ACI@CPC‐CDs with fascinating physicochemical properties can penetrate the leaves of weeds through the stomata and undergo a long‐distance transport in the cell intervals. Under low light intensity, CPC‐CDs can be applied as the internal light source to promote the formation of more singlet oxygen to damage the leaf cell membrane, consequently improving the herbicidal activity of ACI. Moreover, the safety evaluation of ACI@CPC‐CDs demonstrates no risk to non‐target organisms and the environment. Therefore, this work offers a promising strategy for the efficient delivery of light‐dependent PPO‐inhibiting herbicides and opens new insights into the application of CDs in the development of sustainable agriculture.
Spiking Reservoir Computing Based on Stochastic Diffusive Memristors
Authors: Ma Zelin , Ge Jun , Pan Shusheng 
Published: August 2024

AbstractReservoir computing (RC), a type of recurrent neural network, is particularly well‐suited for hardware implementation in edge computing. It is shown that RC hardware based on dynamic memristors potentially offers much lower power consumption and reduced computation times than digital electronics. However, challenges such as stochasticity and read noise in these devices can impair its performance. Furthermore, the external analog‐to‐digital (ADC) readout circuits may require substantial area and energy. In this work, it is experimentally demonstrated that a population of stochastic diffusive Ag:SiOx memristors can effectively construct a spiking reservoir computing system. This system demonstrates remarkable resilience to read noise and delivers exceptional performance across a range of computational tasks, achieving a 98% accuracy in waveform classification and a normalized root mean square error (NRMSE) of 0.154 in time‐series prediction. Further simulations reveal that a certain degree of device stochasticity actually enhances system performance. Without using ADC converters, a hybrid memristor‐CMOS spiking RC system is designed that demonstrates significantly lower power consumption compared to fully digital systems.
Wheat seed delivery pathways and varietal turnover in eastern India
Authors: Khed Vijayalaxmi D. , Jaleta Moti , Krishna Vijesh V. 
Published: August 2024

AbstractWhy do certain new crop varieties fail to gain popularity among farmers despite their proven superiority in scientific field trials and on‐farm demonstrations? Empirical microlevel studies in agricultural economics usually address this question from a household or farmer perspective, neglecting the broader socio‐institutional and economic context against which varietal dissemination takes place. In the present study, we explore the relationship between wheat seed delivery networks and varietal turnover, using data from farmers' fields in eastern India. An extensive survey encompassing 7648 wheat farmers was conducted to capture wheat production practices across 31 districts of Bihar and 9 districts of eastern Uttar Pradesh. Additional qualitative interviews led to the initial impression that farmers' selection of varieties often precedes their choice of seed source, challenging the prevailing assumptions about the causal direction of this relationship. To address the challenge of reverse causality between varietal selection and seed source preference, we employed an instrumental variable regression framework. Although new wheat varieties are available in the market, a substantial majority of farmers opt for old ones. Farmers' decisions regarding the selection of wheat varieties and seed sources are not straightforward, and their preference for wheat varieties significantly impacts their seed source selection, indicating a hitherto unexplored bidirectional relationship. Understanding this complex relationship has significant strategic implications for stakeholders in the seed supply system, offering policy recommendations for enhancing varietal turnover rates and encouraging the widespread adoption of new, improved varieties among smallholders. Such initiatives hold the promise of enhancing system resilience and food security in developing countries. [EconLit Citations: O3, Q1, Q16, Q18].
Disrupted mitochondrial response to nutrients is a presymptomatic event in the cortex of the APPSAA knock‐in mouse model of Alzheimer's disease
Authors: Norambuena Andrés , Sagar Vijay Kumar , Wang Zhuoying , Raut Prakash , Feng Ziang , Wallrabe Horst , Pardo Evelyn , Kim Taylor , Alam Shagufta Rehman , Hu Song , Periasamy Ammasi , Bloom George S. 
Published: August 2024

AbstractINTRODUCTIONReduced brain energy metabolism, mammalian target of rapamycin (mTOR) dysregulation, and extracellular amyloid beta (Aβ) oligomer (xcAβO) buildup are some well‐known Alzheimer's disease (AD) features; how they promote neurodegeneration is poorly understood. We previously reported that xcAβOs inhibit nutrient‐induced mitochondrial activity (NiMA) in cultured neurons. We now report NiMA disruption in vivo.METHODSBrain energy metabolism and oxygen consumption were recorded in heterozygous amyloid precursor protein knock‐in (APPSAA) mice using two‐photon fluorescence lifetime imaging and multiparametric photoacoustic microscopy.RESULTSNiMA is inhibited in APPSAA mice before other defects are detected in these Aβ‐producing animals that do not overexpress APP or contain foreign DNA inserts into genomic DNA. Glycogen synthase kinase 3 (GSK3β) signals through mTORC1 to regulate NiMA independently of mitochondrial biogenesis. Inhibition of GSK3β with TWS119 stimulates NiMA in cultured human neurons, and mitochondrial activity and oxygen consumption in APPSAA mice.DISCUSSIONNiMA disruption in vivo occurs before plaques, neuroinflammation, and cognitive decline in APPSAA mice, and may represent an early stage in human AD.Highlights
Amyloid beta blocks communication between lysosomes and mitochondria in vivo.
Nutrient‐induced mitochondrial activity (NiMA) is disrupted long before the appearance of Alzheimer's disease (AD) histopathology in heterozygous amyloid precursor protein knock‐in (APPSAA/+) mice.
NiMA is disrupted long before learning and memory deficits in APPSAA/+ mice.
Pharmacological interventions can rescue AD‐related NiMA disruption in vivo.
Lewis Acid‐Catalyzed Unusual (4+3) Annulation of para‐Quinone Methides with Bicyclobutanes: Access to Oxabicyclo[4.1.1]Octanes
Authors: Deswal Shiksha , Guin Avishek , Biju Akkattu T. 
Published: August 2024

AbstractOver the past few years, there has been a surge of interest in the chemistry of bicyclobutanes (BCBs). Although BCBs have been used to synthesize bicyclo[2.1.1]hexanes and bicyclo[3.1.1]heptanes, the synthesis of bicyclo[4.1.1]octanes has remained elusive. Herein, we report the first Lewis acid‐catalyzed unexpected (4+3) annulation of para‐quinonemethides (p‐QMs) with BCBs allowing the synthesis of oxabicyclo[4.1.1]octanes proceeding under mild conditions. With 5 mol % of Bi(OTf)3, the reaction afforded the (4+3) annulated product in high regioselectivity and good functional group compatibility via a simultaneous Lewis acid activation of BCBs and p‐QMs. The reaction is likely initiated by the 1,6‐addition of Lewis acid activated BCBs to p‐QMs followed by the C2‐selective intramolecular addition of the phenol moiety to the generated cyclobutyl cation intermediate. Moreover, detailed mechanistic studies provided insight into the mechanism of the reaction.
Engineering the Substrate Specificity of UDP‐Glycosyltransferases for Synthesizing Triterpenoid Glycosides with a Linear Trisaccharide as Aided by Ancestral Sequence Reconstruction
Authors: Jian Xing , Sun Qiuyan , Xu Wentao , Qu Haobo , Feng Xudong , Li Chun 
Published: August 2024

AbstractTriterpenoids have wide applications in the pharmaceutical and agricultural industries. The glycosylation of triterpenoids catalyzed by UDP‐glycosyltransferases (UGTs) is a crucial method for producing valuable derivatives with enhanced functions. However, only a few UDP‐glucosyltransferases have been reported to synthesize the rare triterpenoids with linear‐chain trisaccharide at C3−OH. This study revealed that the UGT91H subfamily primarily contributed to the 2“‐O‐glycosylation of triterpenoids with high regioselectivity, then the substrate scope was further expanded by ancestral sequence reconstruction (ASR). With ancestral enzyme UGT91H_A1 as a model, the sequence‐structure‐function relationship was explored. A RTAS loop (R212/T213/A214/S215) was identified to affect the substrate specificity of UGT91H_A1. Transferring this RTAS loop to the corresponding position of UGT91H enzymes successfully expanded their substrate spectra. The functional role of RTAS loop was further elucidated by molecular dynamics simulation and quantum mechanical computation. UGT91H_A1 was applied to the low‐cost synthesis of terpenoid rhamnosides with a linear trisaccharide in combining with a self‐sufficient UDP‐rhamnose regeneration system. Finally, we developed a phylogeny‐based platform to efficiently mining new UGT91Hs from plant genomic data. This study provided robust biocatalysts for synthesizing various triterpenoid glycosides with a linear trisaccharide and demonstrated ASR as an efficient tool in engineering the function of UDP‐glycosyltransferases.
Synthesis, Structural Analysis, and Polymerization Activity of Noncyclopentadienyl Constrained Geometry Complex [Me2Si(Ph2C)(tBuN)]ZrCl2(thf)
Authors: Toda Tomoyuki , Miura Itaru , Ohta Shun , Takenaka Katsuhiko 
Published: August 2024

ABSTRACTConstrained geometry complexes (CGCs) are homogeneous olefin polymerization catalysts that have been improved because of their considerably high activity and their copolymerization abilities for ethylene with α‐olefins. The ancillary ligands in CGCs comprise bridged 6π‐electron moieties (e.g., cyclopentadienyl (Cp) and fluorenyl) and amide donors. In this study, we investigated the effect of changing the 6π‐electron moieties to a diphenylmethyl moiety (Ph2C) on the polymerization activity of [Me2Si(Ph2C)(tBuN)]ZrCl2(thf) (thf = tetrahydrofuran). We synthesized [Me2Si(Ph2C)(tBuN)]ZrCl2(thf) and characterized it via 1H nuclear magnetic resonance analysis and single‐crystal X‐ray crystallography. Ethylene polymerization at 2 MPa using a catalyst of the [Me2Si(Ph2C)(tBuN)]ZrCl2(thf) and modified methylaluminoxane (MMAO) as a cocatalyst yielded a linear polyethylene (PE) with a high melting point (124°C–134°C); moreover, the polymerization activity of the catalyst was found to be up to 445 g (PE) mmol (Zr)−1 h−1. The polymerization of styrene using the zirconium complex and MAOs did not proceed, but the polymerization of 1,3‐butadiene produced a small amount of polybutadiene with ~60% cis‐1,4‐structure. These results indicate that non‐Cp‐type CGCs, which can be defined as metal complexes bearing an ancillary ligand in which non‐Cp moieties (benzyl moiety in this study) and an amido group are bridged by an organic linker, can become a new family of homogeneous olefin polymerization catalysts.
Chitin synthase genes of Aedes albopictus and their effects on development of pupae
Authors: Ruiling Zhang , Sha An , Zhong Zhang 
Published: August 2024

AbstractThe invasive species Aedes albopictus is a major vector of several arboviruses. The global spread of this species seriously threatens human health. Insecticide resistance is an increasing problem worldwide that limits the efficacy of mosquito control. As the major structural component of cuticles, chitin is indispensable to insects. Chitin synthase (CHS) is the enzyme that catalyzes the biosynthesis of chitin at the final step. In this study, two CHS genes of Aedes albopictus (AaCHS1 and AaCHS2) were identified and their basic characteristics were evaluated via bioinformatics analysis. The highest abundance of AaCHS1 transcripts was detected in pupae, whereas that of AaCHS2 transcripts was detected in females; the highest expression levels of AaCHS1 and AaCHS2 were found in the epidermis and the midgut of pupae, respectively. The survival and emergence rates of pupae were significantly reduced after the injection of double‐stranded RNA of AaCHS1 or AaCHS2, indicating that both AaCHS1 and AaCHS2 play crucial roles in the pupal development. In addition, the chitin content of pupae was obviously decreased after the suppression of AaCHS1 expression by RNA interference (RNAi) treatment. This influence of the RNAi treatment was further supported by the reduced chitin thickness and weakened chitin fluorescence signal in the new cuticle. The midgut of pupae presented a reduced intensity of the chitin fluorescence signal along with RNAi treatment specific to AaCHS2 expression. The results of this study indicate that CHS genes may be suitable as molecular targets used for controlling mosquitoes.
Facilitating secretory expression of apple seed β‐glucosidase in Komagataella phaffii for the efficient preparation of salidroside
Authors: Lu Xin‐Yi , Lai Ming‐Yuan , Qin Peng , Zheng Yu‐Cong , Liao Jia‐Yi , Zhang Zhi‐Jun , Xu Jian‐He , Yu Hui‐Lei 
Published: August 2024

AbstractPlant‐derived β‐glucosidases hold promise for glycoside biosynthesis via reverse hydrolysis because of their excellent glucose tolerance and robust stability. However, their poor heterologous expression hinders the development of large‐scale production and applications. In this study, we overexpressed apple seed β‐glucosidase (ASG II) in Komagataella phaffii and enhanced its production from 289 to 4322 U L−1 through expression cassette engineering and protein engineering. Upon scaling up to a 5‐L high cell‐density fermentation, the resultant mutant ASG IIV80A achieved a maximum protein concentration and activity in the secreted supernatant of 2.3 g L−1 and 41.4 kU L−1, respectively. The preparative biosynthesis of salidroside by ASG IIV80A exhibited a high space‐time yield of 33.1 g L−1 d−1, which is so far the highest level by plant‐derived β‐glucosidase. Our work addresses the long‐standing challenge of the heterologous expression of plant‐derived β‐glucosidase in microorganisms and presents new avenues for the efficient production of salidroside and other natural glycosides.