bluuebunny/crossref_metadata_2025 huggingface dataset:
All‐Electric Nonassociative Learning in Nickel Oxide
Authors: Mondal Sandip , Zhang Zhen , Islam A. N. M. Nafiul , Andrawis Robert , Gamage Sampath , Aghamiri Neda Alsadat , Wang Qi , Zhou Hua , Rodolakis Fanny , Tran Richard , Kaur Jasleen , Chen Chi , Ong Shyue Ping , Sengupta Abhronil , Abate Yohannes , Roy Kaushik , Ramanathan Shriram
Published: September 2022

Habituation and sensitization represent nonassociative learning mechanisms in both non‐neural and neural organisms. They are essential for a range of functions from survival to adaptation in dynamic environments. Design of hardware for neuroinspired computing strives to emulate such features driven by electric bias and can also be incorporated into neural network algorithms. Herein, cellular‐like learning in oxygen‐deficient NiOxdevices is demonstrated. Both habituation learning and sensitization response can be achieved in a single device by simply controlling the magnitude of the electric field. Spontaneous memory relaxations and dynamic redistribution of oxygen vacancies under electric bias enable such learning behavior of NiOxunder sequential training. These characteristics in simple device arrays are implemented to learn alphabets as well as demonstrate simulated algorithmic use cases in digit recognition. Transition metal oxides with carefully prepared defect concentrations can be highly sensitive to electronic structure perturbations under moderate electrical stimulus and serve as building blocks for next‐generation neuroinspired computing hardware.
Implications of RAS mutational status in subsets of patients with newly diagnosed acute myeloid leukemia across therapy subtypes
Authors: Rivera Daniel , Kim Kunhwa , Kanagal‐Shamanna Rashmi , Borthakur Gautam , Montalban‐Bravo Guillermo , Daver Naval , Dinardo Courtney , Short Nicholas J. , Yilmaz Musa , Pemmaraju Naveen , Takahashi Koichi , Jabbour Elias J. , Pierce Sherry , Konopleva Marina , Bhalla Kapil , Garcia‐Manero Guillermo , Ravandi Farhad , Kantarjian Hagop , Kadia Tapan M.
Published: September 2022

Activating mutations in RAS have been reported in about 10–15% of patients with AML; previous studies have not identified a prognostic significance. However, RAS mutations have emerged as a potential resistance mechanism to treatment with inhibitors of FLT3, IDH, and BCL2. We aimed to determine the characteristics and outcomes of patients with RAS‐mutated (RAS‐mut) AML across therapy subsets of 1410 patients newly diagnosed (ND AML). RAS‐mut was observed in 273 (20%) patients. Overall, patients with RAS‐mut AML had an estimated 3‐year survival rate of 38% vs. 28% in those with RAS wild type (RAS‐wt), p = .01. Among patients with RAS‐mut, favorable karyotype and concomitant NPM1 mutations were associated with a higher CR/CRi rate, OR 23.2 (95% CI: 2.7–192.7; p < .001) and OR 2.8 (95% CI: 1.1–6.9; p = .02), respectively, while secondary and treated secondary (ts)‐AML were associated with low response rates, OR 0.34 (95% CI: 0.1–0.9; p = .04) and OR 0.22 (95% CI: 0.09–0.5; p = .001), respectively. Intensive chemotherapy was associated with high response rates OR 5.9 (95% CI: 2.9–12.2; p < .001). Better median OS was observed among those with favorable karyotype, HR 0.28 (95% CI: 0.1–0.6; p = .002), and those treated with intensive chemotherapy, HR 0.42 (95% CI: 0.2–0.6 p < .001). Conversely, ts‐ AML and co‐occurrence of mutations in TP53 were associated with poor median OS; HR 2.3 (95% CI: 1.4–3.9; p = .001) and HR 1.7 (95% CI: 0.9–3.1; p = .06), respectively. The addition of venetoclax was associated with a non‐significant improvement in CR/CRi and OS.
Direct CO2 Transformation to Aliphatic Polycarbonates
Authors: Tamura Masazumi , Nakagawa Yoshinao , Tomishige Keiichi
Published: September 2022

Reduction of CO2 emission is an important issue all over the world, and the development of effective transformation methods of CO2 into valuable chemicals is highly desirable. Among various potential products derived from CO2, polymers are one of the promising target chemicals in terms of the production amount and CO2 fixation to solid materials. Therefore, the direct synthesis of polycarbonates from CO2 has recently attracted much attention because polycarbonates including polycarbonate diols are useful engineering plastics and intermediates for polyurethanes. There are many reports on the synthesis of polycarbonates from CO2 and cyclic ethers such as epoxides and oxetanes, however, the reports on the synthesis from CO2 and diols are limited. In this review, we summarize the recent progress of direct polycarbonate synthesis from CO2 and diols and explain the potential and issues for industrialization based on the characteristics of the reaction systems.
Uncertainty Quantification of Michaelis–Menten Kinetic Rates and Its Application to the Analysis of CRISPR‐Based Diagnostics
Authors: Avaro Alexandre S. , Santiago Juan G.
Published: September 2022

Michaelis–Menten kinetics is an essential model to rationalize enzyme reactions. The quantification of Michaelis–Menten parameters can be very challenging as it is sensitive to even small experimental errors. We here present a quantification of the uncertainty inherent to the experimental determination of kinetic rate parameters for enzymatic reactions. We study the influence of several sources of uncertainty and bias, including the inner filter effect, pipetting errors, number of points in the Michaelis–Menten curve, and flat‐field correction. Using Monte Carlo simulations and analyses of experimental data, we compute typical uncertainties of
,
, and catalytic efficiency
. As a salient example, we analyze the extraction of such parameters for CRISPR‐Cas systems. CRISPR diagnostics have recently attracted much interest and yet reports of these enzymatic kinetic rates have been highly unreliable and inconsistent.
Total Syntheses of (±)‐Dracocephalone A and (±)‐Dracocequinones A and B
Authors: Hwang Taehwan , Tuccinardi Joseph P. , Beard Alexandra A. , Jackson Amy C. , Jung Min J. , Wood John L.
Published: September 2022

Described herein are the first total syntheses of (±)‐dracocephalone A (1) and (±)‐dracocequinones A (4) and B (5). The synthesis was initially envisioned as proceeding through an intramolecular isobenzofuran Diels–Alder reaction, a strategy that eventually evolved into a Lewis acid‐promoted spirocyclization. This highly diastereoselective transformation set the stage for trans‐decalin formation and a late‐stage Suárez oxidation that produced a [3.2.1] oxabicycle suited for conversion to 1. Brønsted acid‐mediated aromatization, followed by a series of carefully choreographed oxidations, allowed for rearrangement to a [2.2.2] oxabicycle poised for conversion to 4 and 5.
HECTD1‐Mediated Ubiquitination and Degradation of Rubicon Regulates Autophagy and Osteoarthritis Pathogenesis
Authors: Liao Shiyao , Zheng Qiangqiang , Shen Haotian , Yang Guang , Xu Yuzi , Zhang Xiaolei , Ouyang Hongwei , Pan Zongyou
Published: September 2022

Objective

Osteoarthritis (OA) is one of the most common degenerative joint diseases and is associated with autophagy suppression. However, the molecular mechanism of autophagy regulation in the context of OA is not fully understood. In this study, we sought to determine the role that HECTD1 plays in the pathogenesis of OA.

Methods

We used RNA sequencing analysis to explore the differential expression of E3 ubiquitin ligase genes in healthy human cartilage and human cartilage affected by OA. Using surgery‐ and aging‐induced OA mouse models, we comprehensively analyzed the function of the screened gene Hectd1 in the development of OA; furthermore, we dissected the mechanism by which HECTD1 regulates autophagy and OA progression using a combination of molecular biologic, cell biologic, and biochemical approaches.

Results

HECTD1 was significantly down‐regulated in human OA cartilage samples compared to healthy cartilage samples. Overexpression of HECTD1 in mouse joints alleviated OA pathogenesis, whereas conditional depletion of Hectd1 in cartilage samples aggravated surgery‐ and aging‐induced OA pathogenesis. Mechanistically, HECTD1 bound to Rubicon and ubiquitinated Rubicon at lysine residue 534, which targets Rubicon for proteasomal degradation. More importantly, HECTD1‐mediated Rubicon degradation regulated chondrocyte autophagy, leading to mitigation of stress‐induced chondrocyte death and the subsequent progression of OA.

Conclusion

HECTD1 plays a crucial role in the pathogenesis of OA, in that HECTD1 regulates chondrocyte autophagy by ubiquitinating and targeting Rubicon for proteasomal degradation.
A promising nanostructured bimetallic catalyst for the production of second‐generation biodiesel: reuse and stability study
Authors: Sánchez Faba Edgar M. , Ferrero Gabriel O. , Eimer Griselda A.
Published: September 2022

The stability and reusability of a promising bimetallic mesoporous catalyst (5Na/20Ce/SBA‐15) to produce first‐ and second‐generation biodiesel was studied. Soybean oil, waste frying oil, and Jatropha hieronymi oil were used as lipid raw materials. Under optimized reaction conditions (10 wt % of catalyst, methanol to oil molar ratio of 40 : 1, 60 °C, and vigorous magnetic stirring), the minimum FAME content required by the EN 14214 standard was achieved in 3 h with soybean oil and waste frying oil. Three alternatives were considered concerning the reuse of the catalyst (without and with regeneration), concluding that washing followed by calcination between each run is suitable for the material to recover its activity. FAME contents over 87 wt % were obtained in five cycles when using waste frying oil. Key quality properties of the produced biofuel were evaluated and found to comply with international standards for its commercialization as automotive diesel fuel without further treatment.
Acceptorless Dehydrogenation of Alcohols and Transfer Hydrogenation of Aldehydes in Water Using a Single Bifunctional, Bistate, Water‐soluble Ruthenium Catalyst
Authors: Hazra Susanta , Nair Abhishek , Dolui Pritam , Malik Ekta , Elias Anil J.
Published: September 2022

A water‐soluble bifunctional, bistate ruthenium catalyst has been developed using the 8‐aminoquinoline ligand which responds to an acid‐base stimuli and is catalytically active for two complementary reactions. The “Ru‐amino state” is highly active for catalytic transfer hydrogenation of various aldehydes using formic acid as the hydrogen source resulting in a range of primary alcohols. On the other hand, the “Ru‐amido state” is active for the acceptorless dehydrogenation of alcohols to yield carboxylate salts or ketones. The reactions can be carried out in air without an inert atmosphere and the products can be purified by simple extraction without the use of any chromatographic techniques. A range of functional groups which include electron‐rich and deficient (hetero)arenes and alkenes, alkynes, halides, esters, cyano, and nitro groups, are all well tolerated, indicating excellent chemoselectivity for transfer hydrogenation.
Design of discrete PID controllers for maximizing stability margins
Authors: Guo Tong‐Yi , Hwang Chyi , Lu Li‐Shin
Published: September 2022

The objective of this paper is to provide a discrete PID controller design procedure for maximizing stability margins. First, a new and complete characterization of the entire set of stabilizing discrete PID controllers for a given plant is presented. Then, based on this characterization, an efficient algorithm is developed for testing if, for a given plant, there exists a digital PID controller gain parameter space corresponding to closed‐loop poles being inside the circle of radius
centered at the origin. The developed algorithm is finally applied along with a bisection strategy to determine, for a specified small positive number
, a minimum value
and the corresponding
discrete PID controller set for achieving at least
of stability margin. To illustrate the features of our new characterization of stabilizing digital PID controller sets and the effectiveness of the presented algorithms to the maximum stability‐margin discrete PID controller design, two numerical examples are provided.
Synthesis, Antifungal Activity, and Molecular Docking Study of Novel 3‐Carene‐Derived 4‐Substituted Phenyl‐1,2,4‐Triazolinthiones Bearing gem‐Dimethylcyclopropane Moiety
Authors: Li Baoyu , Yu Youpei , Duan Wengui , Lin Guishan , Wen Rongzhu , Zhang Zhaolei
Published: September 2022

For exploring new natural product‐based leading compounds with antifungal activity, 15 novel 3‐carene‐derived 4‐substituted phenyl‐1,2,4‐triazolinthiones 7a∼7o bearing gem‐dimethylcyclopropane moiety were synthesized and structurally characterized by UV/VIS, FT‐IR, 1H‐NMR, 13C‐NMR, ESI‐MS and elemental analysis. The preliminary bioassay at 50 μg/mL showed that all of the target compounds exhibited certain in vitro inhibitory activities against the eight tested fungi, in which compound 7g (R=m, p‐Cl) displayed better inhibition activity (85.0 %) against P. piricola than that of the positive control Chlorothalonil. Furthermore, a reasonable and effective 3D structure of phytofungal CYP51 was constructed by homology modeling. Molecular docking study revealed that the total scores of all the target compounds were higher than that of Prothioconazole. In addition, it was found that compound 7g could readily embed into the binding site, and therein shared similar interactions with the case of Prothioconazole. Thus, compound 7g deserved further study as an antifungal leading compound.
Effect of hypoxia and uremia on oxidative stress on erythrocytes from hemodialysis patients
Authors: Dias Gabriela F. , Tozoni Sara S. , Bohnen Gabriela , van Spitzenbergen Beatriz A. K. , Grobe Nadja , Nakao Lia S. , Pecoits‐Filho Roberto , Kotanko Peter , Moreno‐Amaral Andréa N.
Published: September 2022

Oxidative stress (OS) is essential in uremia‐associated comorbidities, including renal anemia. Complications experienced by hemodialysis (HD) patients, such as hypoxemia and uremic toxins accumulation, induce OS and premature death of red blood cells (RBC). We aimed to characterize reactive oxygen species (ROS) production and antioxidant pathways in HD‐RBC and RBC from healthy controls (CON‐RBC) and evaluate the role of uremia and hypoxia in these pathways. ROS production, xanthine oxidase (XO) and superoxide dismutase (SOD) activities, glutathione (GSH), and heme oxygenase‐1 (HO‐1) levels were measured using flow cytometry or spectrophotometry in CON‐RBC and HD‐RBC (pre‐ and post‐HD), at baseline and after 24 h incubation with uremic serum (S‐HD) and/or under hypoxic conditions (5% O2). Ketoprofen was used to inhibit RBC uremic toxins uptake. HD‐RBC showed higher ROS levels and lower XO activity than CON‐RBC, particularly post‐HD. GSH levels were lower, while SOD activity and HO‐1 levels of HD‐RBC were higher than control. Hypoxia per se triggered ROS production in CON‐RBC and HD‐RBC. S‐HD, on top of hypoxia, increased ROS levels. Inhibition of uremic toxins uptake attenuated ROS of CON and HD‐RBC under hypoxia and uremia. CON‐RBC in uremia and hypoxia showed lower GSH levels than cells in normoxia and non‐uremic conditions. Redox mechanisms of HD‐RBC are altered and prone to oxidation. Uremic toxins and hypoxia play a role in unbalancing these systems. Hypoxia and uremia participate in the pathogenesis of OS in HD‐RBC and might induce RBC death and thus compound anemia.
New roles of DNA‐binding and forkhead‐associated domains of Fkh1 and Fkh2 in cellular functions
Authors: Zhou Hui , Shi Bu‐Jun
Published: September 2022

Two yeast forkhead transcription factors Fkh1 and Fkh2 regulate the transcription of CLB2 cluster genes important for mitosis. Both proteins contain a DNA‐binding domain (DBD) and a forkhead‐associated domain (FHAD), which are essential for ternary complex formation with transcription factor Mcm1, the transcription of CLB2 cluster genes and the physical interaction with Ndd1 and Clb2. Fkh2 also contains an additional C′ domain that contains six consensus Cdk phosphorylation sites, but the function of this domain is dispensable. Here, we found new roles of the DBD, the FHAD, and the C′ domain of Fkh1 and Fkh2 in cellular functions. The Fkh2 DBD determines the genetic interaction with NDD1, while both the FHAD and DBD of Fkh1 or Fkh2 determine cell morphology and stability of their own transcripts. Both HFADs, but not DBDs, also mediate physical interaction between Fkh1 and Fkh2. DBD and HFAD of Fkh1 and DBD, but not HFAD, of Fkh2 are also fundamental for nuclear localization. However, the Fkh2‐specific C′ domain has no role in these aspects except in the stability of some fkh mutant transcripts, which is either increased or decreased in the presence of this domain. These findings reveal that Fkh1 and Fkh2 have multiple cellular functions and function mainly via their DBD and FHAD through a domain‐controlled feedback regulation mechanism.
Electro‐assisted Molecular Assembly Giving Atomic‐Scale Catalytic Active‐Site Detection
Authors: Fan Qianqian , Liu Zirui , Qiu Feng , Mao Yong , Liu Qingju , Zhang Longzhou
Published: September 2022

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro‐assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon‐defect electrocatalysis reaction mechanism was first downsized to the single‐atom scale from the experimental perspective. It is expected that this innovative electro‐assisted molecular assembly strategy could be extensively applied in the active structure‐controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.
cis‐Clerodane Diterpenoids with Structural Diversity and Anti‐inflammatory Activity from Tinospora crispa
Authors: You Jin‐Qiu , Liu Yi‐Nan , Zhou Jun‐Su , Sun Xin‐Yu , Lei Chun , Mu Qing , Li Jing‐Ya , Hou Ai‐Jun
Published: September 2022

Comprehensive Summary

Twelve new cis‐clerodane diterpenoids, designated as crispinoids A—L (1—12), together with three known analogues (13—15), were isolated from Tinospora crispa. Their structures were fully assigned by comprehensive spectroscopic techniques, single‐crystal X‐ray diffraction experiments, and electronic circular dichroism (ECD) analyses. The isolated clerodanes displayed diverse heterocyclic frameworks including 6/6/6‐, 6/5/6/6‐, 6/6/5‐, 6/6‐, and 6/5/6‐fused ring systems. Some of the isolates showed ATP‐citrate lyase (ACLY) and nuclear factor kappa B (NF‐κB) pathway inhibition. The NF‐κB inhibitors further suppressed the lipopolysaccharide (LPS)‐induced inflammatory responses in RAW 264.7 cells.
Targeted Management of Perovskite Film by Co(II) Sulfophenyl Porphyrin for Efficient and Stable Solar Cells†
Authors: Feng Xiao‐Xia , Lv Xudong , Cao Jing , Tang Yu
Published: September 2022

Comprehensive Summary

In the lead halide perovskite solar cells (PSCs), the redox reaction of I– and Pb2+ ions in perovskite materials under the fabrication and operation processes causes the formation of defects to destroy the cell efficiency and long‐term stability. Herein, we have employed a Co(II) sulfophenyl porphyrin (CoTPPS) to modify the perovskite film. The sulfonic group could coordinate with Pb2+ to efficiently passivate the uncoordinated Pb2+. Additionally, Co2+ ions in CoTPPS could react with I2 generated under the thermal and light stress to yield the Co3+ and I–, thus achieving the regeneration of I– in perovskite film. Therefore, the CoTPPS could realize the targeted management of the imperfections in perovskite film. As a result, the modified PSCs reveal the remarkably enhanced cell performance. More importantly, the CoTPPS modified device retains 75% of its initial efficiency value storing at 85°C for 2000 h and about 70% of its efficiency when being continuously illuminated at a simulated sunlight for 1200 h. This strategy tackles the chemical reaction and inhibits the defect generation, thus improving the operational stability and efficiency of PSCs.
Precise and Controllable Assembly of Block Copolymers†
Authors: Jin Bixin , Chen Yiqi , Luo Yunjun , Li Xiaoyu
Published: September 2022

Comprehensive Summary

With the development of nanotechnology, the precise synthesis of nanoparticles with nicely‐defined dimensions and structures has been well‐developed, and the functionalization and subsequent applications of the resultant nanostructures are becoming increasingly important. Comparing to inorganic nanoparticles, the nanostructures based on soft matters, especially block copolymer assemblies, are much lower in cost, easier to fabricate and richer in morphology. However, the dimensional control over the block copolymer assemblies is not as easy. Only in recent decade, with the discovery of living Crystallization‐Driven Self‐Assembly (CDSA) by Manners and Winnik, researchers become able to precisely tune the sizes of block copolymer assemblies in a relatively wide range. This discovery has inspired tremendous research effort in the self‐assembly field, and considerable progress has been made recently. This review summarizes the main progress in the precise and controllable self‐assembly field in the past five years, and is mostly focused on four aspects, including in‐depth understanding of the assembly methods, extension of this method to two‐dimensional nanostructures, utilization of this method to fabricate hierarchical structures, and the potential applications of these well‐defined nanostructures. We hope not only to make a periodic systematic summary of previous studies, but also to provide some useful thinking for the future development of this field.
Cardiac metastasis from small cell lung cancer origin: A case report and review of the literature
Authors: Tian Lei , Liu Miaomiao , He Liya , Zhang Qi , Li Qiaofang , Zhang Hongzhen
Published: September 2022

Background

Cardiac metastasis from small cell lung cancer (SCLC) origin is rare, whereas the incidence is anticipated to increase with the extended survival rates. Case: We here describe a case report of a 48‐year‐old male patient diagnosis with SCLC in 2020. In June 2021, he resorted to hospital due to shortness of breath, no obvious changes were found in repeated echocardiography, electrocardiogram and chest computer tomography from June 2021 to September 2021. Due to the persistence of the complaints, cardiac magnetic resonance (CMR) imaging was performed in September 30th, 2021, which showed a mass in the right atrioventricular groove. The patient underwent pericardiocentesis and small cell carcinoma cells were found in the pericardial effusion, confirming the diagnosis of cardiac metastasis.

Conclusion

Patients with a history of SCLC who develop new cardiac symptoms of unknown etiology should undergo imaging studies such as CMR. The importance of CMR for patients with SCLC is highlighted. The literature regarding metastatic cardiac tumors is reviewed.
An intelligent intrusion detection system for distributed denial of service attacks: A support vector machine with hybrid optimization algorithm based approach
Authors: Sokkalingam Sumathi , Ramakrishnan Rajesh
Published: September 2022

Cloud computing offers comfortable service to business sectors as they can concentrate on their products. Over the internet, cloud computing is liable to various security threats and attacks which is a primary obstacle to the growth of cloud computing services. Distributed denial of service (DDoS) is one such attack that exploits cloud computing services using compromised machines; hence, its detection is a significant field of research. Several DDoS detection schemes have been proposed in the past, but they fail to detect real‐time active DDoS attacks because of their growth in severity and volume. Machine learning (ML) techniques are efficient in making predictions; hence, in this study, a hybrid ML intrusion detection system (IDS) model is proposed. The performance of the proposed IDS model is improved by employing a 10‐fold cross‐validation technique to perform feature selection, reducing data dimensions on the publicly available benchmark NSL‐KDD dataset. Performance validation of the proposed hybrid IDS model is done using the confusion matrix. Support vector machine (SVM) parameters are fine‐tuned using hybrid Harris Hawks optimization (HHO) and particle swarm optimization (PSO) algorithms. The performance of these hybrid algorithms is compared with other classical algorithms such as C4.5, K‐nearest neighbor, and SVM using performance metrics such as precision, sensitivity, specificity, F1 score, and accuracy. From these comparisons, it can be inferred that the proposed SVM with hybrid optimization HHO‐PSO machine learning IDS model performs better DDoS detection with good performance metric values.
Effect of Halide Anions on the Electroreduction of CO2 to C2H4: A Density Functional Theory Study**
Authors: Ma Xifei , Xing Lu , Yao Xiaoqian , Zhang Xiangping , Liu Lei
Published: September 2022

The halide anions present in the electrolyte improve the Faradaic efficiencies (FEs) of the multi‐hydrocarbon (C2+) products for the electrochemical reduction of CO2 over copper (Cu) catalysts. However, the mechanism behind the increased yield of C2+ products with the addition of halide anions remains indistinct. In this study, we analysed the mechanism by investigating the electronic structures and computing the relative free energies of intermediates formed from CO2 to C2H4 on the Cu (100) facet based on density functional theory (DFT) calculations. The results show that formyl *CHO from the hydrogenation reaction of the adsorbed *CO acts as the key intermediate, and the C−C coupling reaction occurs preferentially between *CHO and *CO with the formation of a *CHO‐CO intermediate. We then propose a free‐energy pathway of C2H4 formation. We find that the presence of halide anions significantly decreases the free energy of the *CHOCH intermediate, and enhances desorption of C2H4 in the order of I−>Cl−>Br−>F−. Lastly, the obtained results are rationalized through Bader charge analysis.
Benzothiadiazole‐Based Green Hybridized Local and Charge‐Transfer (HLCT) Fluorophores as Solution‐Processed Non‐Doped Emitters for Simple Structured Electroluminescent Devices
Authors: Kongsabay Suwapat , Loythaworn Thidarat , Petdee Sujinda , Chasing Pongsakorn , Funchien Patteera , Waengdongbung Wijitra , Wongkaew Praweena , Sudyodsuk Taweesak , Promarak Vinich
Published: September 2022

Herein, two new solution‐processable HLCT fluorophores (CBzF and CBzFC) based on benzothiadiazole (Bz) derivatives were designed and synthesized (HLCT=hybridized local and charge transfer). Their optical and photophysical properties were experimentally and theoretically studied and verified by the solvatochromic effect and density functional theory calculations. The two molecules demonstrate high solubility, HLCT features, and an intense green fluorescence with solid‐state photoluminescence quantum yields of 63–72 %. Both fluorophores are effectively applied as non‐doped emitters for solution‐processed double‐layered OLEDs, which produce intense green emission colors with low turn‐on voltages (3.0–3.2 V). Specifically, the CBzFC‐based solution‐processed device achieves a high maximum luminescence (24400 cd m−2), high maximum efficiencies (EQEmax=5.59 %, CEmax=12.24 cd A−1, and PEmax=10.54 lm W−1), and decent efficiency low‐off.
Molten Salt‐Assisted Synthesis of Co/N‐Doped Carbon Hybrids for Aqueous‐Phase Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid
Authors: Kumar Reeti , Zhu Zhi , Chen Changzhou , Cai Wenfei , Woon‐Chung Wong Jonathan , Zhao Jun
Published: September 2022

A resource‐efficient and facile method of synthesizing 2,5‐furandicarboxylic acid (FDCA) from biomass‐derived platform chemical 5‐hydroxymethylfurfural (HMF) was explored using cobalt and nitrogen‐doped carbon catalysts (Co/N−C). A molten salts‐assisted method proved to be effective in improving the surface area of the catalysts as well as uniformity and dispersibility of the Co species. Detailed investigation of different combinations of precursors revealed that the formation of Co−Nx species was imperative for high FDCA selectivity, and the nitrogen‐doped carbon matrix enhanced the catalytic activity by providing good electron mobility. A significant observation was made regarding the change in reaction mechanism with the heating rate of Co/N−C. High HMF conversion of 99 % with 68 % FDCA yield was achieved at 120 °C in water at 24 h. This study shows an eco‐friendly and cost‐effective method of FDCA production with high yield that overcomes the use of precious metal‐based catalysts, organic solvents, and severe reaction conditions.
Chemically Bonded Plasmonic Triazole‐Functionalized Au/Zeolitic Imidazole Framework (ZIF‐67) for Enhanced CO2 Photoreduction
Authors: Becerra Jorge , Nguyen Duc‐Trung , Nair Gopalakrishnan Vishnu , Do Trong‐On
Published: September 2022

The design of functionalized metallic nanoparticles is considered an emerging technique to ensure the interaction between metal and semiconductor material. In the literature, this interface interaction is mainly governed by electrostatic or van der Waals forces, limiting the injection of electrons under light irradiation. To enhance the transfer of electrons between two compounds, close contact or chemical bonding at the interface is required. Herein, a new approach was reported for the synthesis of chemically bonded plasmonic Au NPs/ZIF‐67 nanocomposites. The structure of ZIF‐67 was grown on the surface of functionalized plasmonic Au NPs using 1H‐1,2,4‐triazole‐3‐thiol as the capping agent, which acted as both stabilizer of Au nanoparticles and a molecular linker for ZIF‐67 formation. As a result, the synthesized material exhibited outstanding photocatalytic CO2 reduction with a methanol production rate of 2.70 mmol h−1 g−1cat under sunlight irradiation. This work emphasizes that the diligent use of capping agents, with suitable functional groups, could facilitate the formation of intimate heterostructure for enhanced photocatalytic CO2 reduction.
Influence of vegetation structure, seasonality, and soil properties on rodent diversity and community assemblages in west Mount Kilimanjaro, Tanzania
Authors: Thomas Suzana M. , Soka Geofrey E. , Mulungu Loth S.
Published: September 2022

Rodent diversity and community assemblages are affected by several biotic and abiotic factors such as vegetation structure and seasonality. Vegetation structure particularly ground cover influences rodent diversity and community assemblages through provision of food resources and protection from predators. Such information is important for understanding species–habitat relationships for management and conservation. This study was conducted to determine the influence of vegetation structure, seasonality, and soil properties on species richness, abundance, community assemblages, and habitat association of rodents in west Mt Kilimanjaro. Rodent trapping was conducted using removal and capture–mark–recapture (CMR) methods with medium‐sized Sherman's live traps, snap, and Havarhart traps. Rodents were trapped during wet and dry seasons for three consecutive nights at 4 weeks intervals from April 2020 to March 2021. Environmental variables including vegetation structure, soil physical properties, and disturbance levels were recorded for each habitat type. Fourteen species of rodents were trapped in 25,956 trap nights. Rhabdomys pumilio, Praomys delectorum, and Lophuromys verhageni were the most dominant species across all habitats and seasons. L.verhageni occurred in all habitats while R.pumilio was restricted from occurring in montane forests. Moreover, species richness and abundance were influenced by habitat types, seasonality, soil type, and ground cover. Generally, both species richness and abundance were higher in fallows and montane forests and significantly lower in plantation forest and agricultural fields. In addition, rodent diversity was highest in fallows, followed by montane forests, and lowest in agricultural fields. Furthermore, rodents were associated with habitat types and vegetation structure forming two major community assemblages that significantly differed between habitats. Our study conclude that, community assemblages of rodents on Mt. Kilimanjaro were affected by functional spatial heterogeneity of the habitats occupied. Therefore, use of different habitats by rodents may be indicative of the landscape integrity and ecosystem changes based on species assemblages.
Hindcast‐validated species distribution models reveal future vulnerabilities of mangroves and salt marsh species
Authors: Hodel Richard G. J. , Soltis Douglas E. , Soltis Pamela S.
Published: September 2022

Rapid climate change is threatening biodiversity via habitat loss, range shifts, increases in invasive species, novel species interactions, and other unforeseen changes. Coastal and estuarine species are especially vulnerable to the impacts of climate change due to sea level rise and may be severely impacted in the next several decades. Species distribution modeling can project the potential future distributions of species under scenarios of climate change using bioclimatic data and georeferenced occurrence data. However, models projecting suitable habitat into the future are impossible to ground truth. One solution is to develop species distribution models for the present and project them to periods in the recent past where distributions are known to test model performance before making projections into the future. Here, we develop models using abiotic environmental variables to quantify the current suitable habitat available to eight Neotropical coastal species: four mangrove species and four salt marsh species. Using a novel model validation approach that leverages newly available monthly climatic data from 1960 to 2018, we project these niche models into two time periods in the recent past (i.e., within the past half century) when either mangrove or salt marsh dominance was documented via other data sources. Models were hindcast‐validated and then used to project the suitable habitat of all species at four time periods in the future under a model of climate change. For all future time periods, the projected suitable habitat of mangrove species decreased, and suitable habitat declined more severely in salt marsh species.
The contribution of understory and Compositae species to canopy storage capacity of semiarid grassland communities on the Loess Plateau
Authors: Luo Yang , Zhou Junjie , Jian Chunxia , Chen Yang , Wang Shaoyan , Jin Yuan , Xu Peidan , Lei Siyue , Xiong Peifeng , Xu Bingcheng
Published: September 2022

Canopy rainfall interception reduces the effectiveness of limited rainfall resources in arid and semiarid regions. To clarify the effects of species composition and community vertical structure on canopy storage capacity, the artificial wetting and simulated rainfall methods were used to determine the species (C) and community (Cmax) water storage, respectively, in three typical grassland communities on the semiarid Loess Plateau. Results indicated that water storage capacity of 31 grassland species ranged from 0.47 to 3.73 g g−1, with an average of 1.60 g g−1, and leaf storage capacity was significantly higher than the stem. Plant storage capacity was correlated with leaf traits (including leaf fresh weight, length and area). Canopy storage capacity of three grassland communities (Bothriochloa ischaemum, Artemisia gmelinii and Lespedeza davurica) ranged from 0.77 to 1.09 mm and were positively correlated with community leaf area index (LAI), coverage and leaf dry biomass. Leaf and stem water storage accounted for 57.6% and 42.4% of the total community, respectively. The water storage of Compositae, Gramineae, Leguminosae and other species accounted for 35.5%, 27.0%, 23.4% and 14.1%, respectively. The plants in the community with heights of >40, 20–40 and 0–20 cm contributed 5.8%, 30.3% and 63.9% of the water storage, respectively. The field observed canopy storage capacity was significantly higher than the estimated value through scaling up the individual storage data to the community, revealing complex community structure and species composition may increase actual rainfall interception. These results highlighted the species at 0–20 cm height was the key component affecting canopy water storage, and Compositae species may intercept more rainfall within the community, which imply that reducing the understory or Compositae species composition of grassland community would be helpful for increasing limited rainfall partitioning to soil in the drought area.
Ammonium Ferrate‐Catalyzed Cycloaddition of CO2 to Aziridines for the Synthesis of 1,3‐Oxazolidin‐2‐ones
Authors: Panza Nicola , Alberti Matteo , Galiè Simone , Damiano Caterina , Cargnoni Fausto , Italo Trioni Mario , Caselli Alessandro
Published: September 2022

Simple ammonium ferrates are competent catalysts for the CO2 coupling with aziridines to yield 5‐substituted 1,3‐oxazolidin‐2‐ones. Good yields with remarkable selectivity are obtained under mild reaction conditions, room temperature, and atmospheric CO2 pressure, especially for non‐hindered N‐alkyl, N‐benzyl and N‐allyl aziridines, without the need of any co‐catalyst. To shed light on the reaction mechanism, an extensive set of theoretical calculations has been carried out. A viable reaction mechanism involving just one ferrate molecule and where the rate determining step is the 1,3‐oxazolidin‐2‐one ring closure has been found, and the corresponding barrier is compatible with the experimental conditions tested in this study.
Defining the pig microglial transcriptome reveals its core signature, regional heterogeneity, and similarity with human and rodent microglia
Authors: Shih Barbara B. , Brown Sarah M. , Barrington Jack , Lefevre Lucas , Mabbott Neil A. , Priller Josef , Thompson Gerard , Lawrence Alistair B. , McColl Barry W.
Published: September 2022

Microglia play key roles in brain homeostasis as well as responses to neurodegeneration and neuroinflammatory processes caused by physical disease and psychosocial stress. The pig is a physiologically relevant model species for studying human neurological disorders, many of which are associated with microglial dysfunction. Furthermore, pigs are an important agricultural species, and there is a need to understand how microglial function affects their welfare. As a basis for improved understanding to enhance biomedical and agricultural research, we sought to characterize pig microglial identity at genome‐wide scale and conduct inter‐species comparisons. We isolated pig hippocampal tissue and microglia from frontal cortex, hippocampus, and cerebellum, as well as alveolar macrophages from the lungs and conducted RNA‐sequencing (RNAseq). By comparing the transcriptomic profiles between microglia, macrophages, and hippocampal tissue, we derived a set of 239 highly enriched genes defining the porcine core microglial signature. We found brain regional heterogeneity based on 150 genes showing significant (adjusted p < 0.01) regional variations and that cerebellar microglia were most distinct. We compared normalized gene expression for microglia from human, mice and pigs using microglia signature gene lists derived from each species and demonstrated that a core microglial marker gene signature is conserved across species, but that species‐specific expression subsets also exist. Our data provide a valuable resource defining the pig microglial transcriptome signature that validates and highlights pigs as a useful large animal species bridging between rodents and humans in which to study the role of microglia during homeostasis and disease.
The neural correlates of retrieval and procedural strategies in mental arithmetic: A functional neuroimaging meta‐analysis
Authors: Sokolowski H. Moriah , Hawes Zachary , Ansari Daniel
Published: September 2022

Mental arithmetic is a complex skill of great importance for later academic and life success. Many neuroimaging studies and several meta‐analyses have aimed to identify the neural correlates of mental arithmetic. Previous meta‐analyses of arithmetic grouped all problem types into a single meta‐analytic map, despite evidence suggesting that different types of arithmetic problems are solved using different strategies. We used activation likelihood estimation (ALE) to conduct quantitative meta‐analyses of mental arithmetic neuroimaging (n = 31) studies, and subsequently grouped contrasts from the 31 studies into problems that are typically solved using retrieval strategies (retrieval problems) (n = 18) and problems that are typically solved using procedural strategies (procedural problems) (n = 19). Foci were compiled to generate probabilistic maps of activation for mental arithmetic (i.e., all problem types), retrieval problems, and procedural problems. Conjunction and contrast analyses were conducted to examine overlapping and distinct activation for retrieval and procedural problems. The conjunction analysis revealed overlapping activation for retrieval and procedural problems in the bilateral inferior parietal lobules, regions typically associated with magnitude processing. Contrast analyses revealed specific activation in the left angular gyrus for retrieval problems and specific activation in the inferior frontal gyrus and cingulate gyrus for procedural problems. These findings indicate that the neural bases of arithmetic systematically differs according to problem type, providing new insights into the dynamic and task‐dependent neural underpinnings of the calculating brain.
Melanoma differentiation associated gene‐9/syndecan binding protein promotes hepatocellular carcinoma
Authors: Manna Debashri , Reghupaty Saranya Chidambaranathan , Camarena Maria Del Carmen , Mendoza Rachel G. , Subler Mark A. , Koblinski Jennifer E. , Martin Rebecca , Dozmorov Mikhail G. , Mukhopadhyay Nitai D. , Liu Jinze , Qu Xufeng , Das Swadesh K. , Lai Zhao , Windle Jolene J. , Fisher Paul B. , Sarkar Devanand
Published: September 2022

Background and Aims:

The oncogene Melanoma differentiation associated gene‐9/syndecan binding protein (MDA‐9/SDCBP) is overexpressed in many cancers, promoting aggressive, metastatic disease. However, the role of MDA‐9 in regulating hepatocellular carcinoma (HCC) has not been well studied.

Approach and Results:

To unravel the function of MDA‐9 in HCC, we generated and characterized a transgenic mouse with hepatocyte‐specific overexpression of MDA‐9 (Alb/MDA‐9). Compared with wild‐type (WT) littermates, Alb/MDA‐9 mice demonstrated significantly higher incidence of N‐nitrosodiethylamine/phenobarbital‐induced HCC, with marked activation and infiltration of macrophages. RNA sequencing (RNA‐seq) in naive WT and Alb/MDA‐9 hepatocytes identified activation of signaling pathways associated with invasion, angiogenesis, and inflammation, especially NF‐κB and integrin‐linked kinase signaling pathways. In nonparenchymal cells purified from naive livers, single‐cell RNA‐seq showed activation of Kupffer cells and macrophages in Alb/MDA‐9 mice versus WT mice. A robust increase in the expression of Secreted phosphoprotein 1 (Spp1/osteopontin) was observed upon overexpression of MDA‐9. Inhibition of NF‐κB pathway blocked MDA‐9–induced Spp1 induction, and knock down of Spp1 resulted in inhibition of MDA‐9–induced macrophage migration, as well as angiogenesis.

Conclusions:

Alb/MDA‐9 is a mouse model with MDA‐9 overexpression in any tissue type. Our findings unravel an HCC‐promoting role of MDA‐9 mediated by NF‐κB and Spp1 and support the rationale of using MDA‐9 inhibitors as a potential treatment for aggressive HCC.
Serum IgG N‐glycans enable early detection and early relapse prediction of colorectal cancer
Authors: Gu Yong , Duan Bensong , Sha Jichen , Zhang Rongrong , Fan Jiteng , Xu Xiaoyan , Zhao Huijuan , Niu Xiaoyun , Geng Zhi , Gu Jianxin , Huang Ben , Ren Shifang
Published: September 2022

Colorectal cancer (CRC) develops mainly from colorectal advanced adenomas (AA), which are considered precancerous lesions. Novel early diagnostic biomarkers are urgently needed to distinguish CRC and AA from healthy control (HC). Alternative glycosylation of serum IgG has been shown to be closely associated with CRC. We aimed to explore the potential of IgG N‐glycan as biomarkers in the early differential diagnosis of CRC. The study population was strictly matched to the exclusion criteria process. Serum IgG N‐glycan profiles were analyzed by a robust and reliable relative quantitative method based on ultra‐performance liquid chromatography (UPLC). Relative quantification and classification performance of IgG N‐glycans were evaluated by Mann‐Whitney U tests and ROC curve based on directly detected and derived glycan traits, respectively. Six and 14 directly detected glycan traits were significantly changed in AA and CRC, respectively, compared with HC. GP1 and GP3 were able to accurately distinguish AA from HC for early precancerous lesions screening. GP4 and GP14 provided a high value in discriminating CRC from HC. A novel combined index named GlycoF, including GP1, GP3, GP4, GP14 and CEA was developed to provide a potential early diagnostic biomarker in discriminating simultaneously AA (AUC = 0.847) and CRC (AUC = 0.844) from HC. GlycoF also demonstrated a superior CRC detection rate across CRC all stages and conspicuous prediction ability of risk of relapse. Serum IgG N‐glycans analysis provided powerful early screening biomarkers that can efficiently differentiate CRC and AA from HC.
Expanding role of ribosome‐inactivating proteins: From toxins to therapeutics
Authors: Sharma Anuj , Gupta Shelly , Sharma Neeta Raj , Paul Karan
Published: September 2022

Ribosome‐inactivating proteins (RIPs) are toxic proteins with N‐glycosidase activity. RIPs exert their action by removing a specific purine from 28S rRNA, thereby, irreversibly inhibiting the process of protein synthesis. RIPs can target both prokaryotic and eukaryotic cells. In bacteria, the production of RIPs aid in the process of pathogenesis whereas, in plants, the production of these toxins has been attributed to bolster defense against insects, viral, bacterial and fungal pathogens. In recent years, RIPs have been engineered to target a particular cell type, this has fueled various experiments testing the potential role of RIPs in many biomedical applications like anti‐viral and anti‐tumor therapies in animals as well as anti‐pest agents in engineered plants. In this review, we present a comprehensive study of various RIPs, their mode of action, their significance in various fields involving plants and animals. Their potential as treatment options for plant infections and animal diseases is also discussed.