bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Novel Electrocatalyst Pd(II)@Ni3(HITP)2 for Ultrasensitive Detection of Chloramphenicol: Experimental and Computational Investigation
Authors: He Yuan , Li Nian‐Heng , Wen Fubin , He Zijian , Wu Yunan , Lin Shi‐Hsin , Jin Tao 
Published: February 2023

AbstractUltrasensitive electrochemical detection on hazardous substances like antibiotics and pesticides is essential but still challenging in rapid test technology. Herein, the first electrode using highly conductive metal–organic frameworks (HCMOFs) for electrochemical detection of chloramphenicol is proposed. The design of electrocatalyst Pd(II)@Ni3(HITP)2 with ultra‐sensitivity in detection of chloramphenicol is demonstrated by loading Pd onto HCMOFs. An ultra‐low limit of detection (LOD) of 0.2 nM (64.6 pg/mL) was observed for these materials, which is 1–2 orders of magnitude lower than the other reported materials for chromatographic detection. Moreover, the proposed HCMOFs showed long‐time stability over 24 h. The superior detection sensitivity can be attributed to the high conductivity of Ni3(HITP)2, and the large Pd loading. The experimental characterizations and computational investigation determined the Pd loading mechanism in Pd(II)@Ni3(HITP)2, revealing PdCl2 adsorption on the abundant adsorption sites of Ni3(HITP)2. The proposed electrochemical sensor design using HCMOFs was demonstrated to be both effective and efficient, showing that the adoption of HCMOFs decorated with other effective electrocatalysts, which combine high conductivity and high catalytic activity, is of great advantage for ultrasensitive detection.
Ferrier/Aza‐Wacker/Epoxidation/Glycosylation (FAWEG) Sequence to Access 1,2‐Trans 3‐Amino‐3‐deoxyglycosides
Authors: Geulin Anselme , Bourne‐Branchu Yann , Ben Ayed Kawther , Lecourt Thomas , Joosten Antoine 
Published: February 2023

Abstract3‐Amino‐3‐deoxyglycosides constitute an essential class of nitrogen‐containing sugars. Among them, many important 3‐amino‐3‐deoxyglycosides possess a 1,2‐trans relationship. In view of their numerous biological applications, the synthesis of 3‐amino‐3‐deoxyglycosyl donors giving rise to a 1,2‐trans glycosidic linkage is thus an important challenge. Even though glycals are highly polyvalent donors, the synthesis and reactivity of 3‐amino‐3‐deoxyglycals have been little studied. In this work, we describe a new sequence, involving a Ferrier rearrangement and subsequent aza‐Wacker cyclization that allows the rapid synthesis of orthogonally protected 3‐amino‐3‐deoxyglycals. Finally a 3‐amino‐3‐deoxygalactal derivative was submitted for the first time to an epoxidation/glycosylation with high yield and great diastereoselectivity, highlighting FAWEG (Ferrier/Aza‐Wacker/Epoxidation/Glycosylation) as a new approach to access 1,2‐trans 3‐amino‐3‐deoxyglycosides.
Construction of a Diverse Range of Boron Heterocycles via Ring Expansion of a Carboranyl‐Substituted 9‐Borafluorene
Authors: Bischof Tobias , Beßler Lukas , Krummenacher Ivo , Erhard Leon , Braunschweig Holger , Finze Maik 
Published: February 2023

AbstractDirect insertion of unsaturated substrates into a five‐membered borole ring is a useful method to obtain valuable heterocycles containing one or more three‐coordinate boron atoms. A highly Lewis acidic 9‐o‐carboranyl‐9‐borafluorene, in which the o‐carboranyl substituent is connected via one of the cluster carbon atoms to the boron atom of the 9‐borafluorene unit, was found to react with a vast array of unsaturated molecules, such as alkynes, aldehydes and various organic azides, to form larger boraheterocyclic products. The ring expansion reactions of the central borole ring proceed rapidly at room temperature, cementing the role of the o‐carboranyl substituent in enhancing the insertion reactivity of 9‐borafluorenes.
Control over Dethreading Kinetics Allows Evaluating the Entropy Stored in an Interlocked Molecular Machine Out‐of‐Equilibrium**
Authors: Di Noja Simone , Garrido Marina , Gualandi Lorenzo , Ragazzon Giulio 
Published: February 2023

AbstractThe operation of nanomachines is fundamentally different from that of their macroscopic counterparts. In particular, the role of solvent is critical yet rarely associated with machine functionality. Here, we study a minimal model of one of the most advanced molecular machines to gain control of its operation by engineering components and the employed solvent. Operation kinetics were changed over more than four orders of magnitude and could be modulated by solvent. Leveraging solvent properties, it was possible to monitor the relaxation of the molecular machine towards equilibrium and measure the heat exchanged in the process. Our work expands the capabilities of acid‐base powered molecular machines, confirming experimentally that such systems have a dominant entropy content.
Thermo‐Induced Bathochromic Emission in Columnar Discotic Liquid Crystals Realized by Intramolecular Planarization
Authors: Mu Bin , Ma Tianshu , Zhang Zhelin , Hao Xiangnan , Wang Liang , Wang Jingxia , Yan Hongxia , Tian Wei 
Published: February 2023

AbstractMost organic thermochromic fluorescent materials exhibit thermo‐induced hypsochromic emission due to the formation of excimers in ordered molecular solids; however, it is still a challenge to endow them with bathochromic emission despite its significance in making up the field of thermochromism. Here, a thermo‐induced bathochromic emission in columnar discotic liquid crystals is reported realized by intramolecular planarization of the mesogenic fluorophores. A three‐armed discotic molecule of dialkylamino‐tricyanotristyrylbenzene was synthesized, which preferred to twist out of the core plane to accommodate ordered molecular stacking in hexagonal columnar mesophases, giving rise to bright green monomer emission. However, intramolecular planarization of the mesogenic fluorophores occurred in isotropic liquid increasing the conjugation length, and as a result led to thermo‐induced bathochromic emission from green to yellow light. This work reports a new concept in the thermochromic field and provides a novel strategy to achieve fluorescence tuning from intramolecular actions.
N, S‐Doped Carbon Dots as Additive for Suppression of Zinc Dendrites in Alkaline Electrolyte†
Authors: Cai Shan , Chang Ge , Hu Jiugang , Wu Jiae , Luo Yuqing , Zou Guoqiang , Hou Hongshuai , Ji Xiaobo 
Published: February 2023

Comprehensive SummaryThe severe dendrite growth on zinc anode in alkaline electrolyte brings great challenge to the development of zinc‐based batteries. It is a simple and effective strategy to inhibit zinc dendrite formation by introducing additives into the electrolyte. In this study, N, S‐doped carbon dots (TU‐CQDs) were synthesized and used as additives to regulate zinc deposition in a typical KOH electrolyte. The experimental and three‐dimensional transient nucleation model disclosed that the special functional groups of carbon dots can change the electrode surface state and the coordination behaviors of zinc species in the electrolyte. Therefore, TU‐CQDs can not only inhibit the hydrogen evolution reaction, but also achieve uniform zinc deposition. The in‐situ synchrotron radiation X‐ray imaging elucidated that TU‐CQDs can effectively inhibit the dendrite growth and improve the reversibility of zinc plating/stripping process. This work provides a feasible route for regulating the reversibility of zinc metal anode in alkaline electrolyte.
DNA Reaction Network Mimicking the Basic Steps of Synaptic Communication
Authors: Hu Minghao , Hu Yuqiang , Yuan Wenqian , Zhang Zhen , Wu Tongbo 
Published: February 2023

Comprehensive SummaryBiological systems use intricate networks of chemical reactions to exchange information. How to simulate complex systems with simple strand‐displacement reactions is crucial to broaden the application scenario of the DNA reaction network. Here, we report the artificial DNA reaction network to mimic the operation and function of biological information transfer via strand‐displacement reaction. DNA is used as simple artificial analogs to schematize structures and transmit information. Using chemical synapses in neural networks as an example, we show that the proposed network enables core functions of biological systems, such as the long‐term potential of synapses, which underpin learning and memory. Also, we performed the simple “silicon mimetic” to link electronic circuits to chemical network‐based biological structures. As such, synaptic communication simulated by the DNA reaction network provides a complete demonstration for designing artificial reaction networks based on the essence of information interaction.
PCA Rerandomization
Authors: Zhang Hengtao , Yin Guosheng , Rubin Donald B. 
Published: February 2023

AbstractMahalanobis distance of covariate means between treatment and control groups is often adopted as a balance criterion when implementing a rerandomization strategy. However, this criterion may not work well for high‐dimensional cases because it balances all orthogonalized covariates equally. We propose using principal component analysis (PCA) to identify proper subspaces in which Mahalanobis distance should be calculated. Not only can PCA effectively reduce the dimensionality for high‐dimensional covariates, but it also provides computational simplicity by focusing on the top orthogonal components. The PCA rerandomization scheme has desirable theoretical properties for balancing covariates and thereby improving the estimation of average treatment effects. This conclusion is supported by numerical studies using both simulated and real examples.
Biotic resistance to fish invasions in southern China: Evidence from biomass, habitat, and fertility limitation
Authors: Gu Dangen , Jia Tao , Wei Hui , Fang Miao , Yu Fandong , Shu Lu , Wang Xuejie , Li Gaojun , Cai Xingwei , Mu Xidong , Xu Meng , Wang Jianwei , Hu Yinchang 
Published: February 2023

AbstractUnderstanding the mechanisms underlying the invasion success or failure of alien species can help to predict future invasions and cope with the invaders. The biotic resistance hypothesis posits that diverse communities are more resistant to invasion. While many studies have examined this hypothesis, the majority of them have focused on the relationship between alien and native species richness in plant communities, and results have often been inconsistent. In southern China, many rivers have been invaded by alien fish species, providing an opportunity to test the resistance of native fish communities to alien fish invasions. Using survey data for 60,155 freshwater fish collected from five main rivers of southern China for 3 years, we assessed the relationships between native fish richness and the richness and biomass of alien fishes at river and reach spatial scales, respectively. Based on two manipulative experiments, we further examined the impact of native fish richness on habitat selection and the reproductive ability of an exotic model species Coptodon zillii. We found no apparent relationship between alien and native fish richness, whereas the biomass of alien fish significantly decreased with increasing native fish richness. In experiments, C. zillii preferred to invade those habitats that had low native fish richness, given evenly distributed food resources; reproduction of C. zillii was strongly depressed by a native carnivorous fish Channa maculata. Together, our results indicate that native fish diversity can continue to provide biotic resistance to alien fish species in terms of limiting their growth, habitat selection, and reproduction when these aliens have successfully invaded southern China. We thus advocate for fish biodiversity conservation, especially for key species, to mitigate against the population development and ecological impact of alien fish species.
Hydrodynamics structure plankton communities and interactions in a freshwater tidal estuary
Authors: Smits Adrianne P. , Loken Luke C. , Van Nieuwenhuyse Erwin E. , Young Matthew J. , Stumpner Paul R. , Lenoch Leah E. K. , Burau Jon R. , Dahlgren Randy A. , Brown Tiffany , Sadro Steven 
Published: February 2023

AbstractDrivers of phytoplankton and zooplankton dynamics vary spatially and temporally in estuaries due to variation in hydrodynamic exchange and residence time, complicating efforts to understand controls on food web productivity. We conducted approximately monthly (2012–2019; n = 74) longitudinal sampling at 10 fixed stations along a freshwater tidal terminal channel in the San Francisco Estuary, California, characterized by seaward to landward gradients in water residence time, turbidity, nutrient concentrations, and plankton community composition. We used multivariate autoregressive state space (MARSS) models to quantify environmental (abiotic) and biotic controls on phytoplankton and mesozooplankton biomass. The importance of specific abiotic drivers (e.g., water temperature, turbidity, nutrients) and trophic interactions differed significantly among hydrodynamic exchange zones with different mean residence times. Abiotic drivers explained more variation in phytoplankton and zooplankton dynamics than a model including only trophic interactions, but individual phytoplankton–zooplankton interactions explained more variation than individual abiotic drivers. Interactions between zooplankton and phytoplankton were strongest in landward reaches with the longest residence times and the highest zooplankton biomass. Interactions between cryptophytes and both copepods and cladocerans were stronger than interactions between bacillariophytes (diatoms) and zooplankton taxa, despite contributing less biovolume in all but the most landward reaches. Our results demonstrate that trophic interactions and their relative strengths vary in a hydrodynamic context, contributing to food web heterogeneity within estuaries at spatial scales smaller than the freshwater to marine transition.
Altered HLA‐A2‐restricted TP53 epitope induces specific CTL cytotoxicity against hepatocellular carcinoma
Authors: Ye Chunmei , Lin Shengzhe , Hong Jingwen , Liu Fang , Guo Guoxiang , Chen Shuping , Zhou Zhifeng , Lin Wansong , Li Jieyu , Ye Yunbin 
Published: February 2023

AbstractHigh‐frequency mutation of the TP53 tumor suppressor gene is observed in multiple human cancers, which promotes cancer progression. However, the mutated gene‐encoded protein may serve as a tumor antigen to elicit tumor‐specific immune responses. In this study, we detected widespread expression of shared TP53‐Y220C neoantigen in hepatocellular carcinoma with low affinity and low stability of binding to HLA‐A0201 molecules. We substituted the amino acid sequences VVPCEPPEV with VLPCEPPEV in the TP53‐Y220C neoantigen to yield a TP53‐Y220C (L2) neoantigen. This altered neoantigen was found to increase affinity and stability and induce more cytotoxic T lymphocytes (CTLs), indicating improvements in immunogenicity. In vitro assays showed the cytotoxicity of CTLs stimulated by both TP53‐Y220C and TP53‐Y220C (L2) neoantigens against multiple HLA‐A0201‐positive cancer cells expressing TP53‐Y220C neoantigens; however, the TP53‐Y220C (L2) neoantigen showed higher cytotoxicity than the TP53‐Y220C neoantigen against cancer cells. More importantly, in vivo assays demonstrated greater inhibition of hepatocellular carcinoma cell proliferation by TP53‐Y220C (L2) neoantigen‐specific CTLs relative to TP53‐Y220C neoantigen in zebrafish and nonobese diabetic/severe combined immune deficiency mouse models. The results of this study demonstrate enhanced immunogenicity of the shared TP53‐Y220C (L2) neoantigen, which has the potential as dendritic cells or peptide vaccines for multiple cancers.
Mechanism and Origin of CuH‐Catalyzed Regio‐ and Enantioselective Hydrocarboxylation of Allenes
Authors: Ou Yu‐Ru , Ye Qi , Deng Wei , Xu Zheng‐Yang 
Published: February 2023

AbstractThe CuH‐catalyzed hydrocarboxylation of allenes is an enantio‐ and regioselective approach for the synthesis of (S)‐carboxyl‐containing compounds. With density functional theory (DFT) calculations, we elucidate the reaction mechanism and the origins of the enantioselectivity and regioselectivity. The hydrocarboxylation proceeds through the migratory insertion of allenes on CuH complex, the enantioselective addition of fluoroformate, and the β‐fluoride elimination gives the branched carboxylation products. The electron‐donating alkyl and phenyl groups in the allene polarize the C=C bond and thus lead to the anti‐Markovnikov‐selective migratory insertion. In addition, the enantioselective addition of fluoroformate by either (R)‐ or (S)‐addition determines the enantioselectivity. The (S)‐addition is more favorable due to the bulky −tBu group of (R)‐DTBM‐SEGPHOS ligand, which prefers keeping the C=C bond of allene away from the reaction center in six‐membered transition state and thus results in (S)‐carboxyl‐containing products.
A hybrid non‐parametric ground motion model for shallow crustal earthquakes in Europe
Authors: Sreenath Vemula , Podili Bhargavi , Raghukanth S. T. G. 
Published: February 2023

AbstractIn the current study, ground motion models (GMMs) are derived using the European Strong Motion (ESM) database for pseudo‐spectral acceleration (PSA), peak ground acceleration (PGA), peak ground velocity (PGV), peak ground displacement (PGD), cumulative absolute velocity (CAV), arias intensity (Ia), and significant duration. In addition to addressing random effects associated with ground motion regression, such as inter‐event, inter‐site, inter‐locality, and inter‐region variabilities, the current study also aims at reducing the standard deviations (STDs) of the GMMs through development of a hybrid non‐parametric GMM. The hybrid model is derived through an ensemble‐weighted method of five non‐parametric machine learning models: shallow neural network, deep neural network (DNN), gated recurrent unit (GRU), support vector, and random forest (RF) regression techniques; with weights based on model performances. The resulting hybrid model, which also accounts for epistemic uncertainty, is compared against other regional models and is found superior for all output variables. The inter‐event, inter‐site, inter‐locality, and inter‐region deviations, and total ergodic sigma of PSA for the ensemble model lies between 0.3164–0.4478, 0.4156–0.5339, 0.1449–0.3687, 0.0819–0.2421, and 0.668–0.8545, respectively. The coefficient of determination (R2) between predicted and recorded values lies between 0.8435–0.9114 for all the output variables.
Synthesizing Professional Opinion and Published Science to Build a Conceptual Model of Walleye Recruitment
Authors: Krabbenhoft Corey A. , Ludsin Stuart A. , Marschall Elizabeth A. , Budnik Richard R. , Almeida L. Zoe , Cahill Christopher L. , Embke Holly S. , Feiner Zachary S. , Schmalz Patrick J. , Thorstensen Matt J. , Weber Michael J. , Wuellner Melissa R. , Hansen Gretchen J.A. 
Published: February 2023

Abstract
Understanding and predicting recruitment, longstanding goals in fisheries science and ecology, are complicated by variation in the importance of environmental drivers coupled with the dynamic nature of individual ecosystems. Developing an understanding of recruitment from well-monitored stocks offers an opportunity to overcome these complexities. We used a systematic literature review, a survey, and a workshop attended by professionals with expertise in recruitment of Walleye Sander vitreus to identify common environmental drivers of Walleye recruitment and additional sources of variation (i.e., context dependencies) among populations. The importance of individual environmental drivers, as well as the direction of their influence, differed as a function of geographic region, lake surface area, and Walleye life stage. The literature suggested abiotic conditions (e.g., temperature) during the first year of life were influential in determining recruitment. Professional opinion noted the importance of biotic factors, with prey availability and predation risk having the most consistent relationships with recruitment. We synthesized this information to propose a conceptual model that illustrates the suite of characteristics that shape Walleye recruitment over large spatial and temporal scales. Our findings emphasize the importance of first-year growth and system-specific contextual factors, which can alter the relative importance of the environmental drivers of recruitment.
Myelodysplastic syndromes with ring sideroblasts
Authors: Bruzzese Antonella , Vigna Ernesto , Martino Enrica Antonia , Mendicino Francesco , Lucia Eugenio , Olivito Virginia , Bova Carlo , Barbato Angelo , Filippelli Gianfranco , Capodanno Isabella , Neri Antonino , Morabito Fortunato , Gentile Massimo 
Published: February 2023

AbstractMyelodysplastic syndromes (MDS) are acquired bone marrow malignant disorders characterized by ineffective hematopoiesis, resulting from a complex interaction between genetic and epigenetic mutations, alterations of the marrow microenvironment, and the immune system. In 2001, the World Health Organization (WHO) proposed a classification that integrates morphologic and genetic information, considering the MDS with ring sideroblasts (MDS‐RS) as a distinct entity. Considering the strong association between MDS‐RS and SF3B1 mutation and its importance in the development of MDS, the last WHO classification replaced the prior entity of MDS‐RS with MDS with SF3B1 mutation. Several studies were performed to explore this genotype‐phenotype correlation. Mutant SF3B1 protein deregulates the expression of genes implicated in developing hematopoietic stem and progenitor cells. Of paramount importance are PPOX and ABCB7 involved in iron metabolism. Another essential role in hemopoiesis is played by the transforming growth factor‐beta (TGF‐β) receptor. This gene exerts its effects on SMAD pathways, regulating hematopoiesis through effects on balancing proliferation and apoptosis cell inactivity, differentiation, and migration. Luspatercept (ACE‐536) is a soluble fusion protein that inhibits molecules in the TGF‐β superfamily. Since its structure resembles the TGF‐β family receptor, it catches TGF‐β superfamily ligands before binding to the receptor, resulting in reduced activation of SMAD signaling, thus enabling erythroid maturation. Luspatercept was investigated in the phase III trial MEDALIST, showing promising efficacy in treating anemia compared to placebo. Nowadays, further studies are needed to explore the real potential of luspatercept, investigating the biological features likely associated with treatment response, the potential use in combination treatments, and its role in the treatment of naïve MDS.