bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Thermodynamic Model for the Insertion Electrochemistry of Battery Cathodes
Authors: Malaie Keyvan , Scholz Fritz , Schröder Uwe 
Published: January 2023

AbstractThe transition to Ni‐based battery cathodes enhances the energy density and reduces the cost of batteries. However, this comes at the expense of losing energy efficiency which could be a consequence of charge–discharge hysteresis. Here, a thermodynamic model is developed to understand the extent and origin of charge–discharge hysteresis in battery cathodes based on their cyclic voltammograms (CVs). This was possible by defining a Gibbs energy function that weights random ion insertion/expulsion, i. e., a solid solution pathway, against selective ion insertion/expulsion, i. e., a phase separation route. The model was verified experimentally by the CVs of CoOOH and Ni(OH)2 as solid‐solution and phase‐separating cathodes, respectively. Finally, a microscopic view reveals that phase separation and hysteresis are a consequence of large ionic radii difference of the reduced and oxidized central metal atoms.
C versus O Protonation in Zincate Anions: A Simple Gas‐Phase Model for the Surprising Kinetic Stability of Organometallics
Authors: Rahrt Rene , Koszinowski Konrad 
Published: January 2023

AbstractFor better understanding the intrinsic reactivity of organozinc reagents, we have examined the protolysis of the isolated zincate ions Et3Zn−, Et2Zn(OH)−, and Et2Zn(OH)2Li− by 2,2,2‐trifluoroethanol in the gas phase. The protonation of the hydroxy groups and the release of water proceed much more efficiently than the protonation of the ethyl groups and the liberation of ethane. Quantum‐chemical computations and statistical‐rate theory calculations fully reproduce the experimental findings and attribute the lower reactivity of the more basic ethyl moiety to higher intrinsic barriers, which override the thermodynamic preference for its protonation. Thus, our minimalistic gas‐phase model provides evidence for the intrinsically low reactivity of organozinc reagents toward proton donors and helps to explain their remarkable kinetic stability against moisture and even protic media.
Diastereoselectivity Switch During Alkene Reductions: Diastereodivergent Syntheses of Molecular Fossils via MHAT or Homogeneous Catalytic Hydrogenation Reactions
Authors: Maior Christian R. S. , Costa Paulo C. S. , Ligiéro Carolina B. P. , de Moraes Lygia S. , Sousa Gustavo R. , Lima Sidney G. , Esteves Pierre M. , Miranda Paulo C. M. L. 
Published: January 2023

AbstractSixteen geosterane derivatives were synthesized in up to 57 % overall yields in four steps harnessing the olefin cross‐metathesis (OCM) and Metal hydride H atom transfer (MHAT) or homogeneous hydrogenation reactions as key steps. Drawing on this strategy, the diastereomeric ratio (d. r.) reached up to 24 : 1 for the thermodynamic isomer and 7 : 1 for the other isomer in the hydrogenation step. In a geological sample from northeast Brazil, we confirmed the putative structures previously assumed as methyl 2‐(3α‐5αH‐cholestan) acetate, methyl 2‐(3β‐5αH‐cholestan)acetate, and methyl 6‐(3β‐5αH‐cholestan)hexanoate, as well three new molecular fossils of approximately 120 million years old. We also proved the migration marking ability of those carboxylic acids derived from forerunner geosteranes during an oil migration event, which suggests their aptitudes as molecular odometers. Our approach demonstrated swiftness and effectiveness in preparing a molecular library of geological biomarkers would also be appropriate to generate stereochemical diversity in molecular libraries for medicinal chemistry and natural product anticipation.
Induced CPL‐Active Materials Based on Chiral Supramolecular Co‐Assemblies
Authors: Zhang Yuxia , Yu Wenting , Li Hang , Zheng Wenhua , Cheng Yixiang 
Published: January 2023

AbstractCircularly polarized luminescence (CPL) has attracted much interest due to its potential applications on chiral photonic techniques and optoelectronic materials science. As known, dissymmetry factor (gem) of CPL is one essential factor for evaluating the features of CPL‐active materials. Much attention has focused on how to increase thegemvalue, which is one of the most important issues for CPL practical applications. Recently, more and more works have demonstrated that chiral supramolecular could provide the significant strategy to improve thegemvalue through the orderly helical superstructure of chiral building blocks. Normally, this kind of chiral supramolecular assembly process can be accompanied by chirality transfer and induction mechanism, which can promote the amplification effect on the induced CPL of achiral dyes. In this review, we fully summarized recent advances on the induced CPL‐active materials of chiral supramolecular co‐assemblies, their applications in circularly polarized organic light‐emitting diodes (CP‐OLEDs) and current challenges.
Maytansinol Functionalization: Towards Useful Probes for Studying Microtubule Dynamics
Authors: Boiarska Zlata , Pérez‐Peña Helena , Abel Anne‐Catherine , Marzullo Paola , Álvarez‐Bernad Beatriz , Bonato Francesca , Santini Benedetta , Horvath Dragos , Lucena‐Agell Daniel , Vasile Francesca , Sironi Maurizio , Díaz J. Fernando , Prota Andrea E. , Pieraccini Stefano , Passarella Daniele 
Published: January 2023

AbstractInvited for the cover of this issue are the groups of Professors Passarella and Pieraccini at the University of Milan, in collaboration with some of the members of TubInTrain consortium. The image depicts work with the elements of nature, in particular the destabilising effect of maytansinol (the constellation) on microtubules (the trees). Read the full text of the article at 10.1002/chem.202203431.
Palladium(0)‐Catalyzed Anti‐Selective Addition‐Cyclizations of Alkynyl Electrophiles
Authors: Tsukamoto Hirokazu , Ito Kazuya , Ueno Tatsuhiko , Shiraishi Mitsugu , Kondo Yoshinori , Doi Takayuki 
Published: January 2023

AbstractInvited for the cover of this issue is the group of Hirokazu Tsukamoto at Tohoku University (current affiliation: Yokohama University of Pharmacy). The image depicts anti‐selective arylative cyclization reactions of alkynyl aldehydes with arylboronic acids under palladium catalysis in methanol to afford endo‐ and exo‐cyclic products. Read the full text of the article at 10.1002/chem.202203068.
Brønsted Acid/Base Site Isolated in a Pentanuclear Scaffold
Authors: Tomoda Misa , Kondo Mio , Izu Hitoshi , Masaoka Shigeyuki 
Published: January 2023

AbstractInvited for the cover of this issue is the group of Shigeyuki Masaoka at Osaka University. The image depicts a Brønsted acid/base pair based on a pentanuclear scaffold, and the formation thermodynamically metastable state of H+ by the steric isolation of a Brønsted acid/base site. Read the full text of the article at 10.1002/chem.202203253.
Risk factors based vessel‐specific prediction for stages of coronary artery disease using Bayesian quantile regression machine learning method: Results from the PARADIGM registry
Authors: Park Hyung‐Bok , Lee Jina , Hong Yongtaek , Byungchang So , Kim Wonse , Lee Byoung K. , Lin Fay Y. , Hadamitzky Martin , Kim Yong‐Jin , Conte Edoardo , Andreini Daniele , Pontone Gianluca , Budoff Matthew J. , Gottlieb Ilan , Chun Eun Ju , Cademartiri Filippo , Maffei Erica , Marques Hugo , Gonçalves Pedro de A. , Leipsic Jonathon A. , Shin Sanghoon , Choi Jung H. , Virmani Renu , Samady Habib , Chinnaiyan Kavitha , Stone Peter H. , Berman Daniel S. , Narula Jagat , Shaw Leslee J. , Bax Jeroen J. , Min James K. , Kook Woong , Chang Hyuk‐Jae 
Published: January 2023

AbstractBackground and HypothesisThe recently introduced Bayesian quantile regression (BQR) machine‐learning method enables comprehensive analyzing the relationship among complex clinical variables. We analyzed the relationship between multiple cardiovascular (CV) risk factors and different stages of coronary artery disease (CAD) using the BQR model in a vessel‐specific manner.MethodsFrom the data of 1,463 patients obtained from the PARADIGM (NCT02803411) registry, we analyzed the lumen diameter stenosis (DS) of the three vessels: left anterior descending (LAD), left circumflex (LCx), and right coronary artery (RCA). Two models for predicting DS and DS changes were developed. Baseline CV risk factors, symptoms, and laboratory test results were used as the inputs. The conditional 10%, 25%, 50%, 75%, and 90% quantile functions of the maximum DS and DS change of the three vessels were estimated using the BQR model.ResultsThe 90th percentiles of the DS of the three vessels and their maximum DS change were 41%–50% and 5.6%–7.3%, respectively. Typical anginal symptoms were associated with the highest quantile (90%) of DS in the LAD; diabetes with higher quantiles (75% and 90%) of DS in the LCx; dyslipidemia with the highest quantile (90%) of DS in the RCA; and shortness of breath showed some association with the LCx and RCA. Interestingly, High‐density lipoprotein cholesterol showed a dynamic association along DS change in the per‐patient analysis.ConclusionsThis study demonstrates the clinical utility of the BQR model for evaluating the comprehensive relationship between risk factors and baseline‐grade CAD and its progression.
Inhibition Studies on Carbonic Anhydrase Isoforms I, II, IX, and XII with a Series of Sulfaguanidines
Authors: Abdoli Morteza , De Luca Viviana , Capasso Clemente , Supuran Claudiu T. , Žalubovskis Raivis 
Published: January 2023

AbstractTwo novel sulfaguanidine series, six N‐(N,N′‐dialkyl/dibenzyl‐carbamimidoyl) benzenesulfonamide derivatives and nine N‐(N‐alkyl/benzyl‐carbamimidoyl) benzenesulfonamide derivatives, were obtained by desulfidative amination of easily accessible dimethyl arylsulfonylcarbonimidodithioates under catalyst‐ and base‐free conditions. The newly synthesized compounds were tested for the inhibition of four different isozymes of human carbonic anhydrase (hCA I, II, IX and XII, EC 4.2.1.1). Both series reported here were inactive against the off‐target isozymes hCA I and II (Ki>100 μM). Interestingly, all investigated compounds inhibited both target isozymes hCA IX and XII in the submicromolar to micromolar ranges in which Ki values spanned from 0.168 to 0.921 μM against hCA IX and from 0.335 to 1.451 μM against hCA XII. The results indicated that N‐(N‐alkyl/benzyl‐carbamimidoyl) benzenesulfonamides were slightly more potent inhibitors than N‐(N,N′‐dialkyl/dibenzyl‐carbamimidoyl) benzenesulfonamides. Among the evaluated compounds, N‐n‐octyl‐substituted N‐carbamimidoylbenzenesulfonamide showed the most significant activity with a Ki value of 0.168 μM against hCA IX, which was four‐fold more selective toward this isozyme versus hCA XII. Again, another derivative from N‐(N‐alkyl/benzyl‐carbamimidoyl) benzenesulfonamide series, N‐p‐methylbenzyl‐substituted N‐carbamimidoylbenzenesulfonamide, demonstrated superior inhibitory activity against hCA XII with a Ki value of 0.335 μM.
AVALON: The Italian cohort study on real‐life efficacy of hypomethylating agents plus venetoclax in newly diagnosed or relapsed/refractory patients with acute myeloid leukemia
Authors: Todisco Elisabetta , Papayannidis Cristina , Fracchiolla Nicola , Petracci Elisabetta , Zingaretti Chiara , Vetro Calogero , Martelli Maria Paola , Zappasodi Patrizia , Di Renzo Nicola , Gallo Susanna , Audisio Ernesta , Griguolo Davide , Cerchione Claudio , Selleri Carmine , Mattei Daniele , Bernardi Massimo , Fumagalli Monica , Rizzuto Giuliana , Facchini Luca , Basilico Claudia Maria , Manfra Ilenia , Borlenghi Erika , Cairoli Roberto , Salutari Prassede , Gottardi Michele , Molteni Alfredo , Martini Vincenza , Lunghi Monia , Fianchi Luana , Cilloni Daniela , Lanza Francesco , Abruzzese Elisabetta , Cascavilla Nicola , Rivellini Flavia , Ferrara Felicetto , Maurillo Luca , Nanni Jacopo , Romano Alessandra , Cardinali Valeria , Gigli Federica , Roncoroni Elisa , Federico Vincenzo , Marconi Giovanni , Volpi Roberta , Sciumè Mariarita , Tarella Corrado , Rossi Giuseppe , Martinelli Giovanni ,   for the AVALON Cooperative Group
Published: January 2023

AbstractBackgroundVenetoclax in combination with hypomethylating agents (HMA) is revolutionizing the therapy of acute myeloid leukemia (AML). However, evidence on large sets of patients is lacking, especially in relapsed or refractory leukemia.MethodsAVALON is a multicentric cohort study that was conducted in Italy on patients with AML who received venetoclax‐based therapies from 2015 to 2020. The study was approved by the ethics committee of the participating institution and was conducted in accordance with the Declaration of Helsinki. The effectiveness and toxicity of venetoclax + HMA in 190 (43 newly diagnosed, 68 refractory, and 79 relapsed) patients with AML are reported here.ResultsIn the newly diagnosed AML, the overall response rate and survival confirmed the brilliant results demonstrated in VIALE‐A. In the relapsed or refractory AML, the combination demonstrated a surprisingly complete remission rate (44.1% in refractory and 39.7% in relapsed evaluable patients) and conferred to treated patients a good expectation of survival. Toxicities were overall manageable, and most incidents occurred in the first 60 days of therapy. Infections were confirmed as the most common nonhematologic adverse event.ConclusionsReal‐life data show that the combination of venetoclax and HMA offers an expectation of remission and long‐term survival to elderly, newly diagnosed patients, and to relapsed or chemoresistant AML, increasing the chance of cure through a different mechanism of action. The venetoclax + HMA combination is expected to constitute the base for triplet combinations and integration of target therapies. Our data contribute to ameliorate the understanding of venetoclax + HMA effectiveness and toxicities in real life.
Ethnic‐specific predictors of neurotoxicity among patients with pediatric acute lymphoblastic leukemia after high‐dose methotrexate
Authors: Harris Rachel D. , Bernhardt Melanie Brooke , Zobeck Mark C. , Taylor Olga A. , Gramatges Maria Monica , Schafer Eric S. , Lupo Philip J. , Rabin Karen R. , Scheurer Michael E. , Brown Austin L. 
Published: January 2023

AbstractBackgroundHigh‐dose methotrexate (HD‐MTX; 5000 mg/m2) is an important component of curative therapy in many treatment regimens for high‐risk pediatric acute lymphoblastic leukemia (ALL). However, methotrexate therapy can result in dose‐limiting neurotoxicity, which may disproportionately affect Latino children. This study evaluated risk factors for neurotoxicity after HD‐MTX in an ethnically diverse population of patients with ALL.MethodsThe authors retrospectively reviewed the medical records of patients who were diagnosed with ALL and treated with HD‐MTX at Texas Children's Cancer Center (2010–2017). Methotrexate neurotoxicity was defined as a neurologic episode (e.g., seizures or stroke‐like symptoms) occurring within 21 days of HD‐MTX that resulted in methotrexate treatment modifications. Mixed effects multivariable logistic regression was used to estimate the odds ratio (OR) and corresponding 95% confidence interval (CI) for the association between clinical factors and neurotoxicity.ResultsOverall, 351 patients (58.1% Latino) who received 1183 HD‐MTX infusions were evaluated. Thirty‐five patients (10%) experienced neurotoxicity, 71% of whom were Latino. After adjusting for clinical risk factors, the authors observed that serum creatinine elevations ≥50% of baseline were associated with a three‐fold increased odds (OR, 3.32; 95% CI, 0.98–11.21; p = .05) for neurotoxicity compared with creatinine elevation <25%. Notably, predictors of neurotoxicity differed by ethnicity. Specifically, Latino children experienced a nearly six‐fold increase in neurotoxicity odds (OR, 5.80; 95% CI, 1.39–24.17; p = .02) with serum creatinine elevation ≥50% compared with creatinine elevation <25%.ConclusionsThe current findings indicate that serum creatinine elevations ≥50% may be associated with an increased risk for neurotoxicity among Latino children with ALL and may identify potential candidates for therapeutic or supportive care interventions.
Top advances of the year: Head and neck cancer
Authors: Verma Avanti , Burtness Barbara 
Published: January 2023

AbstractAdvances in treatment deintensification for human papillomavirus‐associated oropharyngeal cancer include use of transoral surgery to permit reduction in pathologic risk‐based postoperative therapy after transoral resection. The E3311 cooperative group trial demonstrated 3‐year progression‐free survival (PFS) of 95% for intermediate risk patients treated with 50 Gy radiation alone, with no decrement for those with a smoking history. Favorable risk patients could be observed, with a 3‐year PFS of 93%. Reduction in radiation dose is also feasible for favorable risk patients (low or no smoking history and low stage) treated with chemoradiation on the NRG HN002 trial, where 2‐year PFS was 90.7%. For those favorable risk patients treated with radiation alone, 2‐year PFS was 87.7% and this arm did not meet criteria for further testing. Important phase 3 trials of immunotherapy in first‐line treatment of recurrent and/or metastatic head and neck cancer were also reported in 2022. For patients with nonnasopharyngeal sites of disease, the combination of the programmed death‐1–directed antibody nivolumab plus the anti–CTLA‐4 agent ipilimumab was not superior to chemotherapy plus cetuximab in the Checkmate 651 trial. However, in an important breakthrough for patients with nasopharyngeal cancer, the JUPITER‐02 trial, conducted in China, Singapore, and Taiwan among patients with predominantly Epstein‐Barr virus‐related cancers, demonstrated a significant improvement in PFS (hazard ratio, 0.52) when toripalimab was added to gemcitabine/cisplatin chemotherapy. Immature survival data indicate overall survival will likely also be impacted.
An active defense model based on situational awareness and firewalls
Authors: Li Di , Hu Yikun , Xiao Guoqing , Duan Mingxing , Li Kenli 
Published: January 2023

SummaryWith the rapid development of the internet, cyberspace security issues have become increasingly prominent. The importance of constructing a cyberspace security system is self‐evident, but compared with attackers, defenders in cyberspace are in a castle‐like passive defense state in most cases. Therefore, building a reliable, accurate, timely, and active defense system is challenging. The key is to accurately focus on defense priorities, the anticipation of attackers who will likely succeed, and blocking attacks in a timely manner. In this article, we propose an active defense model based on the interaction of situational awareness and firewalls. First, by biasing the integrity, confidentiality, and availability of assets to get the score of assets, and using the Common Vulnerability Scoring System to assess the threat level of assets, we combine the two to determine the maximum system damage that the asset will suffer if it is lost, and then focus on defense. Meanwhile, log analysis of the network situational awareness platform can predict successful attackers, and then the linked firewall strategy can block these attacks in time before the attackers obtain attack gains. After that, we force the attackers to give up their attacks on the target by increasing the attack cost. We compared our model with iptables auto‐blocking and nginx auto‐blocking, and our model excelled them across the board in terms of comprehensiveness and false positive rate. The experimental results verify thar our active defense model proposed in this article can better reduce the defense cost and increase the attack cost, thus achieving the relatively defense goal.
Landslide identification using water cycle particle swarm optimization‐based deep generative adversarial network
Authors: Lekshmanan Lijesh , George Arockia Selva Saroja 
Published: January 2023

SummaryA natural vulnerability called a landslide threatens people, property, and infrastructure in many different places all over the world. Various landslide identification techniques are developed to assess the landslide hazard, but accurate identification of landslide occurrence particularly in certain regions remains a challenging issue, due to the complex scale‐dependent processes among geomorphometric features and landslides. To solve the shortcomings of landslide identification, the water cycle particle swarm optimization‐based deep generative adversarial network (WCPSO‐based Deep GAN) hybridization technique is presented. To develop the developed WCPSO, the water cycle algorithm (WCA) and particle swarm optimization (PSO) were hybridized. The landslide rainfall dataset is used as the source of the input data in this instance, and the Manhattan distance approach is then used to do feature selection. After performing data augmentation based on the results of the feature selection, the proposed WCPSO‐based deep GAN approach accurately detects the landslides. The developed WCPSO‐driven deep GAN's performance is also measured using the three metrics accuracy, specificity, and sensitivity, with a maximum accuracy of 0.937, higher specificity of 0.919, and higher sensitivity of 0.952.
Robust malware clustering of windows portable executables using ensemble latent representation and distribution modeling
Authors: Rizvi Syed Khurram Jah , Fraz Muhammad Moazam 
Published: January 2023

SummaryMalware is a malicious program used for unauthorized access to organizational infrastructure and systems. To overcome challenges of exponential growth of malware, notable research has been made for unsupervised clustering of Windows‐based portable executable (PE). Nevertheless, to the best of our knowledge there has been no research for robust cluster prediction of Windows based PEs using static features. To this end, we proposed an ensemble neural network architecture for unsupervised feature learning and its distribution modeling for robust clustering of PE(s). The novel architecture is a cascaded formation of a deep autoencoder (AE) network and latent distribution modeling (LDM) network. The AE performs feature learning using latent representation and LDM performs the distribution modeling of latent representation using Gaussian approximation. An objective function is also devised for model optimization. The network adjusts the Gaussian components to optimize the distribution modeling. It also performs adjustments for data representations toward related Gaussian centers to make the model behave in adaptive manner. A novel malware dataset has also been collected by employing endpoint security management solution over enterprise network to assess proposed architecture. The dataset contains 21,486 samples including 14,497 malicious and 6989 benign ones. We also performed the evaluation of proposed architecture over publicly available benchmark malware dataset including 138,047 samples comprising 96,742 malicious and 41,323 benign PEs. The experimental results demonstrated that the proposed architecture yielded more than 95% accuracy for cluster prediction. The novel architecture has achieved superior performance and outperformed progressive techniques. The dataset along with implementation are accessible at
bit.ly/3J6ZF8S.