bluuebunny/crossref_metadata_2025_split huggingface dataset:
Theory‐Guided Machine Learning to Predict the Performance of Noble Metal Catalysts in the Water‐Gas Shift Reaction
Authors: Chattoraj Joyjit , Hamadicharef Brahim , Kong Jian Feng , Pargi Mohan Kashyap , Zeng Yingzhi , Poh Chee Kok , Chen Luwei , Gao Fei , Tan Teck Leong 
Published: May 2022

AbstractMachine learning (ML) has widespread applications in catalyst discovery and reaction optimization. We present a theory‐guided machine learning framework to evaluate the carbon monoxide (CO) conversion performance of noble metal catalysts in water‐gas shift (WGS) reaction. Our study is based on an open source WGS dataset, which we modify significantly to be consistent with the chemical reaction principles. We apply state‐of‐the‐art ML models including artificial neural networks, extreme gradient boosting to predict CO conversion percentage. These models show superior regression performance than the previously reported results in the literature. We further generalize the existing data structure by including physical, chemical and surface chemistry properties as fingerprint features that rationalize the importance of all the input features for CO conversion. We noticed that purely data‐driven ML models frequently violate the thermodynamic equilibrium principle and predict unphysical CO conversion percentage. We address these two problems by developing a custom loss function and an additional activation function in our neural networks architecture. Our proposed theory‐guided ML model displays high accuracy (R2 score is 0.95 and root mean square error is 6.87) and physically robust predictions. The model also opens up promising possibilities to improve CO conversion percentage, which were previously unexplored in experiments.
The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
Authors: Grimm Laura M. , Spicher Sebastian , Tkachenko Boryslav , Schreiner Peter R. , Grimme Stefan , Biedermann Frank 
Published: May 2022

AbstractThe rationalization of non‐covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host‐guest binding mechanism remains ambiguous despite their symmetric and simple macrocyclic structure and the wealth of literature reports. We herein report experimental thermodynamic binding parameters (ΔG, ΔH, TΔS) for CB7 and CB8 with a set of hydroxylated adamantanes, di‐, and triamantanes as uncharged, rigid, and spherical/ellipsoidal guests. Binding geometries and binding energy decomposition were obtained from high‐level theory computations. This study reveals that neither London dispersion interactions, nor electronic energies or entropic factors are decisive, selectivity‐controlling factors for CBn complexes. In contrast, peculiar host‐related solvation effects were identified as the major factor for rationalizing the unique behavior and record‐affinity characteristics of cucurbit[n]urils.
Micro‐CT visualization of the CNS: Performance of different contrast‐enhancing techniques for documenting the spider brain
Authors: Rivera‐Quiroz Francisco Andres , Miller Jeremy A. 
Published: May 2022

AbstractSpider brain and central nervous system (CNS) have remained unexplored, due in part to the difficulty of observing these organs, usually only possible through histological preparations. Recently, internal anatomy studies have been supplemented by the inclusion of X‐ ray micro‐CT. Unmineralized tissue such as the body of invertebrates requires a staining process to enhance tissue X‐ray absorption and improve contrast during observation. Many current protocols are based on iodine staining requiring critical point drying (CPD) of the sample for optimal contrast. This process induces shrinking of the soft tissue generating artifacts in the morphology, volume, and even position of internal structures. Phosphotungstic acid (PTA) is an alternative staining agent recently used in marine invertebrate and plant studies. Here, we used several specimens of the common spider Araneus diadematus to visualize the spider brain and compare both contrast‐enhancing ethanol‐based solutions. We assessed a gradient of staining times, observed and tested the repercussions of CPD, and examined the use of vacuum to accelerate PTA diffusion. We show that PTA provides the best contrast on micro‐CT scans in ethanol eliminating the need for CPD, and offering more realistic in situ visualizations of the internal organs. In combination with different scanning settings, PTA allowed observation of internal organs like the CNS, digestive system, muscles, and finer structures like the retina, visual nerves, and optic neuropiles. This fast and less invasive method could facilitate the proper documentation of the internal anatomy in the context of evolutionary, developmental and functional studies.
Basic color terms in Thai
Authors: Panitanang Nischanade , Phuangsuwan Chanprapha , Ikeda Mitsuo 
Published: May 2022

AbstractThis psycholinguistic study explored whether the inventory of color names and, in particular, basic color terms (BCTs) in the Thai language has changed since the seminal study of Berlin and Kay (1969), who reported 10 BCTs in Thai. We collected color‐naming data from 161 Thai native speakers from across Thailand. The speakers were requested to name each of the 330 Munsell color chips, similar to those employed in the World Color Survey, using monolexemic color terms. Mean number of color terms offered per speaker was 19.2 ± 5.2. We found that 12 color terms were offered by ≥80% of the speakers. The BCT inventory exceeded the BCTs reported by Berlin and Kay, by nam‐ngoen “dark blue”, fa “sky/light blue”, and thao “gray”; furthermore, som “orange” appears to have supplanted saet “orange trumpet”. We also found that three non‐BCTs, with Thai‐specific referents, were offered frequently: khi‐ma “horse feces” (75%), lueat‐mu “pig blood” (68%), and ban‐yen “four o'clock flower/magenta” (50%). Further scrutiny of color term object referents prompts that most Thai non‐BCTs refer to flora (31.72%) and inanimate nature (17.54%).
Pharmacometric and Electrocardiographic Evaluation of Chloroquine and Azithromycin in Healthy Volunteers
Authors: Chotsiri Palang , Tarning Joel , Hoglund Richard M. , Watson James A. , White Nicholas J. 
Published: May 2022

Chloroquine and azithromycin were developed in combination for the preventive treatment of malaria in pregnancy, and more recently were proposed as coronavirus disease 2019 (COVID‐19) treatment options. Billions of doses of chloroquine have been administered worldwide over the past 70 years but concerns regarding cardiotoxicity, notably the risk of torsades de pointes (TdP), remain. This investigation aimed to characterize the pharmacokinetics and electrocardiographic effects of chloroquine and azithromycin observed in a large previously conducted healthy volunteer study. Healthy adult volunteers (n = 119) were randomized into 5 arms: placebo, chloroquine alone (600 mg base), or chloroquine with either 500 mg, 1,000 mg, or 1,500 mg of azithromycin all given daily for 3 days. Chloroquine and azithromycin levels, measured using liquid‐chromatography tandem mass spectrometry, and electrocardiograph intervals were recorded at frequent intervals. Time‐matched changes in the PR, QRS, and heart rate‐corrected JT, and QT intervals were calculated and the relationship with plasma concentrations was evaluated using linear and nonlinear mixed‐effects modeling. Chloroquine and azithromycin pharmacokinetics were described satisfactorily by two‐ and three‐compartment distribution models, respectively. No drug–drug interaction between chloroquine and azithromycin was observed. Chloroquine resulted in concentration‐dependent prolongation of the PR, QRS, JTc and QTc intervals with a minimal additional effect of azithromycin. QRS widening contributed ~ 28% of the observed QT prolongation. Chloroquine causes significant concentration‐dependent delays in both ventricular depolarization and repolarization. Co‐administration of azithromycin did not significantly increase these effects. The arrhythmogenic risk of TdP associated with chloroquine may have been substantially overestimated in studies which did not separate electrocardiograph QRS and JT prolongation.
The genetics of adaptation in freshwater Eurasian shad (Alosa)
Authors: Sabatino Stephen J. , Pereira Paulo , Carneiro Miguel , Dilytė Jolita , Archer John Patrick , Munoz Antonio , Nonnis‐Marzano Francesco , Murias Antonio 
Published: May 2022

AbstractStudying the genetics of phenotypic convergence can yield important insights into adaptive evolution. Here, we conducted a comparative genomic study of four lineages (species and subspecies) of anadromous shad (Alosa) that have independently evolved life cycles entirely completed in freshwater. Three naturally diverged (A. fallax lacustris, A. f. killarnensis, and A. macedonica), and the fourth (A. alosa) was artificially landlocked during the last century. To conduct this analysis, we assembled and annotated a draft of the A. alosa genome and generated whole‐genome sequencing for 16 anadromous and freshwater populations of shad. Widespread evidence for parallel genetic changes in freshwater populations within lineages was found. In freshwater A. alosa, which have only been diverging for tens of generations, this shows that parallel adaptive evolution can rapidly occur. However, parallel genetic changes across lineages were comparatively rare. The degree of genetic parallelism was not strongly related to the number of shared polymorphisms between lineages, thus suggesting that other factors such as divergence among ancestral populations or environmental variation may influence genetic parallelism across these lineages. These overall patterns were exemplified by genetic differentiation involving a paralog of ATPase‐α1 that appears to be under selection in just two of the more distantly related lineages studied, A. f. lacustris and A. alosa. Our findings provide insights into the genetic architecture of adaptation and parallel evolution along a continuum of population divergence.
Empagliflozin reduces markers of acute kidney injury in patients with acute decompensated heart failure
Authors: Thiele Kirsten , Rau Matthias , Hartmann Niels‐Ulrik Korbinian , Möller Marcus , Möllmann Julia , Jankowski Joachim , Keszei András P. , Böhm Michael , Floege Jürgen , Marx Nikolaus , Lehrke Michael 
Published: May 2022

AbstractAimsIn this prospective, placebo‐controlled, double‐blind, exploratory study, we examined early and more delayed effects of empagliflozin treatment on haemodynamic parameters (primary endpoint: cardiac output) and kidney function including parameters of acute kidney injury (AKI) in patients with acute decompensated heart failure (HF).Methods and resultsPatients with acute decompensated HF with or without diabetes were randomized to empagliflozin 10 mg or placebo for 30 days. Haemodynamic, laboratory, and urinary parameters were assessed after 6 h, 1 day, 3 days, 7 days, and 30 days of treatment. Median time between hospital admission and randomization was 72 h. Baseline characteristics were not different in the empagliflozin (n = 10) and placebo (n = 9) groups. Empagliflozin led to a significant increase in urinary glucose excretion throughout the study (baseline: 37 ± 15 mg/24 h; Day 1: 14 565 ± 8663 mg/24 h; P = 0.001). Empagliflozin did not affect the primary endpoint of cardiac index or on systemic vascular resistance index at any time point. However, empagliflozin significantly reduced parameters of AKI (urinary TIMP‐2 and IGFBP7 by NephroCheck® as indicators of tubular kidney damage), which became significant after 3 days of treatment [placebo: 1.1 ± 1.1 (ng/mL)2/1000; empagliflozin: 0.3 ± 0.2 (ng/mL)2/1000; P = 0.02] and remained significant at the 7 day time point [placebo: 2.5 ± 3.8 (ng/mL)2/1000; empagliflozin: 0.3 ± 0.2 (ng/mL)2/1000; P = 0.003].ConclusionsIn this study, empagliflozin treatment did not affect haemodynamic parameters but significantly reduced markers of tubular injury in patients with acute decompensated HF.
Antigen targeting to dendritic cells: Still a place in future immunotherapy?
Authors: Stoitzner Patrizia , Romani Nikolaus , Rademacher Christoph , Probst Hans Christian , Mahnke Karsten 
Published: May 2022

AbstractThe hallmark of DCs is their potent and outstanding capacity to activate naive resting T cells. As such, DCs are the sentinels of the immune system and instrumental for the induction of immune responses. This is one of the reasons, why DCs became the focus of immunotherapeutical strategies to fight infections, cancer, and autoimmunity. Besides the exploration of adoptive DC‐therapy for which DCs are generated from monocytes or purified in large numbers from the blood, alternative approaches were developed such as antigen targeting of DCs. The idea behind this strategy is that DCs resident in patients' lymphoid organs or peripheral tissues can be directly loaded with antigens in situ. The proof of principle came from mouse models; subsequent translational studies confirmed the potential of this therapy. The first clinical trials demonstrated feasibility and the induction of T‐cell immunity in patients. This review will cover: (i) the historical aspects of antigen targeting, (ii) briefly summarize the biology of DCs and the immunological functions upon which this concept rests, (iii) give an overview on attempts to target DC receptors with antibodies or (glycosylated) ligands, and finally, (iv) discuss the translation of antigen targeting into clinical therapy.
Asymmetric Dual‐State Emitters Featuring Thiazole Acceptors
Authors: Belmonte‐Vázquez José L. , Hernández‐Morales Ernesto A. , Hernández Federico. , García‐González Ma. Carmen , Miranda Luis D. , Crespo‐Otero Rachel , Rodríguez‐Molina Braulio 
Published: May 2022

AbstractThis work describes a new approach to construct highly conjugated molecules with asymmetric donor‐acceptor‐donor’ architectures (D−A−D’). Five new emissive compounds featuring thiazole, a scarcely used acceptor, were synthesized using a three‐component Rh(II) catalytic reaction. The asymmetric fluorescent compounds show significant emission in solution (QY=73 %–100 %) and the solid‐state (QY=14 %–59 %), and therefore considered Dual‐State Emitters (DSE). We also evaluate the impact of O‐alkyl chains with varying lengths in the photophysical properties in solution, aggregates, and solid‐state. Computational studies indicate that the involved electronic transitions have a significant charge transfer character produced almost exclusively from the triphenylamine donors. According to the single crystal X‐ray data of compounds8and9, the conjugated structures have a twisted molecular conformation that contributes to the observed emission in the solid‐state. These findings show a systematic approach to design DSE materials, which may help to stimulate their use in biological or optoelectronic applications.
Structurally Forced Ion Binding Affinity: Tetraurea‐Based Macrocycle as a Receptor for Ion Pairs
Authors: Ramírez Cortés Fabricio , Eigner Václav , Cuřínová Petra , Himl Michal 
Published: May 2022

AbstractA urea‐based complexation site represents a building block customarily used in the design of receptors for anion recognition. Here we report a cyclization driven change of complexation preferences, leading to a urea‐based macrocyclic receptor with selectivity for heavier alkali metal cations. Moreover, thorough 1H and 19F NMR, HRMS and X‐ray diffraction studies of the complexes revealed an inherent capability of the macrocycle to interact with selected ion pairs.
Effect of pretreatment on solid‐state fermentation of natural lignocellulose by Aspergillus fumigatus G‐13
Authors: Feng Qian , Guo Gaijuan , Yan Hong , Li Fen 
Published: May 2022

AbstractIn order to efficiently utilize lignocellulosic materials, different treatment methods were used to pretreat lignin. In this research, three pretreatment methods, physical pretreatment, chemical pretreatment, and combined physical and chemical pretreatment, were used to investigate the effect of different pretreatment ways on the solid‐state fermentation of lignocellulosic biomass (straw, locust, and walnut shell) by Aspergillus fumigatus G‐13, and the physical and chemical structure changes of the materials before and after pretreatment and fermentation were also analyzed. The study concluded that physical–chemical combined pretreatment was most beneficial to enzyme production. The optimized pretreatment method is that the particle size is 60–80 mesh, the solid‐to‐liquid volume ratio is 1:1.5, and the 8% Ca(OH)2 solution is pretreated at 60°C for 48 h. The maximum enzyme activity was increased by 4.81–28.91 times for the locust, with 7.68–35.20 times for the walnut shell. Research indicated that the combined pretreatment could change the crystallinity and microcrystalline size of lignocellulose samples. In addition, it broke the ester and ether bonds between lignin and hemicellulose as well as weakened the hydrogen bond between hemicellulose and cellulose.
Effect of biomethane substitution on combustion noise and performance of a dual fuel common rail direct injection diesel engine
Authors: Abdul Hameed Nadeem , Kurien Caneon , Kaipakam Jaychandra Ramesh , Mittal Mayank 
Published: May 2022

AbstractRising pollution levels and stringent emission regulations have raised the requirement for the utilization of alternative green fuels as a sustainable energy source for engine applications. The economic and environmental benefits of using biomethane or renewable natural gas (>95% methane) in diesel engines have made it a promising solution. Sound levels caused by combustion noise, however, is an area of concern in the early stages of engine development process, and to the best of our knowledge studies related to the impact of gaseous fuel energy share on combustion noise in dual fuel diesel engines have not been reported in the literature. In the present work, experimental research on the combustion noise of a biomethane augmented dual fuel common‐rail direct injection (CRDI) diesel engine has been carried out with a correlational design of its performance and combustion characteristics at various engine operating conditions. Comparative results on combustion and performance characteristics of different fuel compositions at various engine loads revealed that there is a better utilization of gaseous fuel at full load conditions resulting in improved power output and reduced heat transfer losses. Cylinder pressure spectra derived from recorded in‐cylinder pressure were used for carrying out the quantitative analysis of sound levels. The results suggested that an increment in methane share is effective in controlling the sound pressure levels to 95 dB (at 1.5 Newton‐meter [Nm] and 13.5 Nm loading conditions) and it is lower than the diesel‐only operational levels at all loading conditions.
A rice protein hydrolase from Serratia marcescens and its specificity in preparation of oligopeptide‐enriched rice protein hydrolysates
Authors: Yan Zheng‐Fei , Zhou Jian‐Qiao , Yuan Shuai , Tang Cheng‐Ye , Wu Jing 
Published: May 2022

AbstractA secreted 50‐kDa metalloprotease from Serratia marcescens D15 was identified as rice protein hydrolase (SeMPase), which reached the highest proteolytic activity (477.3 U/ml) in basal medium with 1.5% rice protein (RP) at 35°C and 150 rpm for 48 h. SeMPase exhibited a highest catalytic number for RP (275.8 min−1, Kcat), which contained a highly conserved Zn2+‐binding (HEIGH) domain, Met‐turn (SLMSY), and Ca2+ binding domain (GGAGND). RP hydrolysates that prepared by SeMPase showed the highest content of oligopeptides at 72.3%, compared to 64.1% from neutrase, 63.0% from alcalase, 50.2% from trypsin, 47.1% from flavourzyme, and 2.41% from pepsin. Our results showed that cleavage sites of SeMPase exposed in RP are more than those of other proteases because both SeMPase cleavage sites and the amino acid composition of RP are rich in Leu, Val, Phe, Glu, and Ala. SeMPase has significant specificity for the preparation of oligopeptide‐enriched RP hydrolysates, which provides a new and highly valued option for industrial preparation of oligopeptide‐enriched protein hydrolysates.
Provenance, production, and distribution of basalt and volcanic glass artifacts in Leeward Kohala, Hawaiʻi Island
Authors: Mills Peter R. , Lundblad Steven P. , Cauley Christina , Coleman Drew S. , Field Julie S. , Hafner Alison L. , Kahn Jennifer G. , Sinton John M. , Kirch Patrick V. 
Published: May 2022

AbstractWe examined 2947 basalt and volcanic glass artifacts from 38 sites in leeward Kohala. Nondestructive energy‐dispersive X‐ray fluorescence provided initial geochemical characterizations. Wavelength‐dispersive X‐ray fluorescence (WDXRF) and thermal ionization mass spectrometry (TIMS) analyses were completed on samples from ambiguously sourced groups. No more than 13.9% of the probable and definite adze‐related debitage originated in leeward Kohala. Notably absent are lithic materials from the nearby Pololū Adze Quarry in windward Kohala. Material from the more distant Mauna Kea Adze Quarry accounts for 41.6% of the adze debitage. Another 38.8% of the adze debitage matches with a tholeiitic source or sources long assumed to be Kīlauea Volcano in Kaʻū, but WDXRF and TIMS isotopic data do not support a Kīlauea source. Centralized adze production and distribution networks best explain adze distribution. Scoria abraders appear to have been regularly transported from the Kona district to leeward Kohala. Volcanic glass sources loosely align with distance‐decay trends, but show greater reliance on Puʻuwaʻawaʻa material by 1650 CE.
Eliminating METTL1‐mediated accumulation of PMN‐MDSCs prevents hepatocellular carcinoma recurrence after radiofrequency ablation
Authors: Zeng Xuezhen , Liao Guanrui , Li Shumin , Liu Haining , Zhao Xiao , Li Shuang , Lei Kai , Zhu Shenghua , Chen Zhihang , Zhao Yi , Ren Xuxin , Su Tianhong , Cheng Alfred Sze‐Lok , Peng Sui , Lin Shuibin , Wang Ji , Chen Shuling , Kuang Ming 
Published: May 2022

Background and Aims:
Radiofrequency ablation (RFA) is an important curative therapy in hepatocellular carcinoma (HCC), but recurrence rate remains as high as all the other HCC therapeutic modalities. Methyltransferase 1 (METTL1), an enzyme for m7G tRNA modification, was reported to promote HCC development. Here, we assessed the role of METTL1 in shaping the immunosuppressive tumor microenvironment after insufficient RFA (iRFA).

Approach and Results:
By immunohistochemistry and multiplex immunofluorescence (mIF) staining, we showed that METTL1 expression was enhanced in post‐RFA recurrent HCC, accompanied by increased CD11b+CD15+ polymorphonuclear‐myeloid–derived suppressor cells (PMN‐MDSCs) and decreased CD8+ T cells. Mechanistically, heat‐mediated METTL1 upregulation enhanced TGF‐β2 translation to form the immunosuppressive environment by induction of myeloid‐derived suppressor cell. Liver‐specific overexpression or knockdown of Mettl1 significantly affected the accumulation of PMN‐MDSCs and subsequently affected CD8+ T cell infiltration. Complete RFA successfully eliminated the tumor, whereas iRFA‐treated mice exhibited enhanced tumor growth and metastasis with increased PMN‐MDSC accumulation and decreased CD8+ T cells compared to sham surgery. Interrupting METTL1‐TGF‐β2‐PMN‐MDSC axis by anti‐Ly6G antibody, or knockdown of hepatoma‐intrinsic Mettl1 or Tgfb2, or TGF‐β signaling blockade significantly mitigated tumor progression induced by iRFA and restored CD8+ T cell population.

Conclusions:
Our study sheds light on the pivotal role of METTL1 in modulating an immunosuppressive microenvironment and demonstrated that interrupting METTL1‐TGF‐β2‐PMN‐MDSC axis could be a therapeutic strategy to restore antitumor immunity and prevent HCC recurrence after RFA treatment, meriting further clinical studies.