bluuebunny/crossref_metadata_2025_split huggingface dataset:
Constrained density functional theory calculations for estimation of forward and backward intermolecular charge transfer energy
Authors: Kim Junseok , Kim Hyungjun 
Published: April 2023

AbstractCharge transfer (CT) in donor–acceptor complexes can occur in two directions: from donor to acceptor (forward CT, CTF) and from acceptor to donor (backward CT, CTB). For an ethylene and tetrafluoroethylene model system, coupled cluster calculations predict that CTF is more stable than CTB. Meanwhile, density functional theory (DFT) and time‐dependent DFT (TDDFT) employing B3LYP functional show a different CT state order depending on the Hartree–Fock exchange (HFX) contribution. The impact of basis sets as a possible cause to induce such unreasonable CT state reverse along with the increase of HFX was investigated. The physical origin of CT state reversal is examined in terms of molecular orbital energy. We analyzed two additional molecular pairs that feature CT state reversal along with the amount of HFX in B3LYP functional. Despite the reduced gap, we suggest constrained DFT using M06‐HF functional as an effective approach to estimate two CT state energies on equal footing.
Hepatocellular carcinoma in patients cured of chronic hepatitis C: Minimal steatosis
Authors: Rocha Chiara , Doyle Erin H. , Bowman Chip A. , Fiel M‐Isabel , Stueck Ashley E. , Goossens Nicolas , Bichoupan Kian , Patel Neal , Crismale James F. , Makkar Jasnit , Lewis Sara , Perumalswami Ponni V. , Schiano Thomas D. , Hoshida Yujin , Schwartz Myron , Branch Andrea D. 
Published: April 2023

AbstractBackgroundSuccessful treatment of hepatitis C reduces liver inflammation and fibrosis; however, patients remain at risk of developing hepatocellular carcinoma (HCC).AimsTo identify risk factors for new‐onset HCC in patients cured of hepatitis C.MethodsImaging, histological, and clinical data on patients whose first HCC was diagnosed >12 months of post‐SVR were analyzed. Histology of 20 nontumor tissues was analyzed in a blinded manner using the Knodel/Ishak/HAI system for necroinflammation and fibrosis/cirrhosis stage and the Brunt system for steatosis/steatohepatitis. Factors associated with post‐SVR HCC were identified by comparison with HALT‐C participants who did not develop post‐SVR HCC.ResultsHepatocellular carcinoma was diagnosed in 54 patients (45 M/9F), a median of 6 years of post‐SVR [interquartile range (IQR) =1.4‐10y] at a median age of 61 years (IQR, 59–67). Approximately one‐third lacked cirrhosis, and only 11% had steatosis on imaging. The majority (60%) had no steatosis/steatohepatitis in histopathology. The median HAI score was 3 (1.25–4), indicating mild necroinflammation. In a multivariable logistic regression model, post‐SVR HCC was positively associated with non‐Caucasian race (p = 0.03), smoking (p = 0.03), age > 60 years at HCC diagnosis (p = 0.03), albumin<3.5 g/dL (p = 0.02), AST/ALT>1 (p = 0.05), and platelets <100 × 103 cells/μL (p < 0.001). Alpha fetoprotein ≥4.75 ng/mL had 90% specificity and 71% sensitivity for HCC occurrence. Noncirrhotic patients had larger tumors (p = 0.002) and a higher prevalence of vascular invasion (p = 0.016) than cirrhotic patients.ConclusionsOne‐third of patients with post‐SVR HCC did not have liver cirrhosis; most had no steatosis/steatohepatitis. Hepatocellular carcinomas were more advanced in noncirrhotic patients. Results support AFP as a promising marker of post‐SVR HCC risk.
Time trends and survival of marginal zone lymphoma over 25 years in Girona, Spain (1994–2018)
Authors: Auñón Carmen , Sanvisens Arantza , Turon Estel , Vidal‐Vila Anna , Puigdemont Montse , Osca‐Gelis Gemma , Eraso Arantxa , Marcos‐Gragera Rafael 
Published: April 2023

AbstractObjectiveTo analyze the incidence, incidence trends, and survival of marginal zone lymphomas (MZLs) in Girona and to describe these indicators based on the location in the case of extranodal MZLs.MethodsPopulation‐based study of MZL collected in the Girona Cancer Registry, 1994–2018. Sociodemographic data, tumor location, and stage were obtained from clinical records. Crude (CR) and age‐adjusted (ASRE) incidence rates expressed per 100,000 person‐years (p‐y) were calculated. Joinpoint regression models were used for the trend analysis according to the MZL group. Five‐year observed and net survival were analyzed.ResultsA total of 472 MZLs were included, 44 (9.3%) were nodal, 288 (61.0%) extranodal, 122 (25.9%) splenic, and the rest (n = 18) MZL, NOS. The CR for the MZL was 2.89 × 100,000 p‐y (95% CI: 2.63–3.15), the ASRE was 3.26 × 100,000 p‐y (95% CI: 2.97–3.57), and the annual percentage change (APC) was 1.6 (95% CI: 0.5–2.7). The ASRE for nodal MZL was 0.30 × 100,000 p‐y (95% CI: 0.22–0.41) and showed an APC of 2.9% (95% CI: −16.4–26.6). For extranodal MZL, the ASRE was 1.98 × 100,000 p‐y (95% CI: 1.76–2.23) and the APC was −0.4 (95% CI: −2.0–1.2). The most frequent locations of this type of MZL were the gastric (35.4%), skin (13.2%), and respiratory system (11.8%). The ASRE of the splenic MZL was 0.85 (95% CI: 0.71–1.02) with an APC of 12.8 (95% CI: 2.5–24.0). The 5‐year net survival of MZL was 82.1% (95% CI: 76.3–86.5).ConclusionsThis study reveals differences in the incidence and trend of the incidence of MZL according to the subgroup, showing a significant increase in the overall MZL mainly due to splenic MZL type.
Novel predictors of immune checkpoint inhibitor response and prognosis in advanced non‐small‐cell lung cancer with bone metastasis
Authors: Asano Yohei , Yamamoto Norio , Demura Satoru , Hayashi Katsuhiro , Takeuchi Akihiko , Kato Satoshi , Miwa Shinji , Igarashi Kentaro , Higuchi Takashi , Taniguchi Yuta , Morinaga Sei , Sone Takashi , Okuda Miho , Matsumoto Isao , Yano Seiji , Tsuchiya Hiroyuki 
Published: April 2023

AbstractBackgroundsImmune checkpoint inhibitors (ICIs) can significantly prolong the survival of patients with advanced non‐small‐cell lung cancer (NSCLC); however, few studies on the therapeutic effects of ICIs on bone metastases were performed.MethodsThis retrospective study aimed to investigate the therapeutic effects of ICIs and determine predictors of favorable ICI response and prognosis in 55 advanced NSCLC patients with bone metastases who initiated ICI treatment between 2016 and 2019, with a mean follow‐up period of 23.2 months. Patients were classified into responders (complete or partial response) and non‐responders (stable or progressive disease) according to the MD Anderson Cancer Center (MDA) criteria, and the predictors of therapeutic response were identified using multivariate logistic regression analysis. Furthermore, overall survival from the time of ICI administration to the final follow‐up or death was evaluated, and prognostic predictors were identified using Cox proportional hazards regression analysis.ResultsICI response rate was 30.9% (complete in three cases, partial in 14). Median survival time was 9.3 months, with 1‐year and 2‐year survival rates of 40.6% and 19.3%, respectively. Responders survived significantly longer than non‐responders (p = 0.03). Based on the receiver operating characteristic curve, the predictive cutoff value of the pretreatment neutrophil‐to‐lymphocyte ratio (NLR) was 2.1. Multivariate analysis identified female sex (p = 0.03), use of ICIs as first‐line therapy (p < 0.01), and NLR <2.1 (p = 0.03) as significant predictors of therapeutic response, whereas concomitant use of a bone‐modifying agent (p < 0.01), Katagiri score ≤6 points (p < 0.01), and NLR <2.1 (p = 0.02) were identified as significant predictors of good prognosis.ConclusionsThis study identified some novel predictors for favorable therapeutic response and prognosis in advanced NSCLC patients with bone metastases undergoing ICI treatment. Pretreatment NLR less than 2.1 can be considered the most important predictor.
Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide
Authors: Cowie Bradley E. , Häfele Lisa , Phanopoulos Andreas , Said Said A. , Lee Ja Kyung , Regoutz Anna , Shaffer Milo S. P. , Williams Charlotte K. 
Published: April 2023

AbstractThis work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo‐copper precursor, mesitylcopper(I) [CuMes]z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2O or Cu2S nanoparticles. Use of sub‐stoichiometric quantities of protonated ligand (pro‐ligand; 0.1–0.2 equivalents vs. [CuMes]z) allows saturation of surface coordination sites but avoids excess pro‐ligand contaminating the nanoparticle solutions. The pro‐ligands are nonanoic acid (HO2CR1), 2‐[2‐(2‐methoxyethoxy)ethoxy]acetic acid (HO2CR2) or di(thio)nonanoic acid, (HS2CR1), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2O is preferentially coordinated by carboxylate ligands and Cu2S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well‐defined nanoparticles and the need for appropriate ligand selection.
De‐Novo Design of pre‐miR‐21 Maturation Inhibitors: Synthesis and Activity Assessment
Authors: Shcheholeva Iryna , Fernández‐Remacha Daniel , Estrada‐Tejedor Roger , Duca Maria , Michelet Véronique 
Published: April 2023

AbstractTargeting RNA with small molecules is a major challenge of current medicinal chemistry, and the identification and design of original scaffolds able to selectively interact with an RNA target remains difficult. Various approaches have been developed based on classical medicinal chemistry strategies (fragment‐based drug design, dynamic combinatorial chemistry, HTS or DNA‐encoded libraries) as well as on advanced structural biology and biochemistry methodologies (such as X‐ray, cryo‐EM, NMR, or SHAPE). Here, we report the de novo design, synthesis, and biological evaluation of RNA ligands by using a straightforward and sustainable chemistry combined with molecular docking and biochemical and biophysical studies that allowed us to identify a novel pharmacophore for RNA binding. Specifically, we focused on targeting the biogenesis of microRNA‐21, the well‐known oncogene. This led us not only to promising inhibitors but also to a better understanding of the interactions between the small‐molecule compounds and the RNA target paving the way for the rational design of efficient inhibitors with potential anticancer activity.
From Proton to Boron: The Lewis Analogs of Protonated Brønsted Super Acids
Authors: Osi Arnaud , Tumanov Nikolay , Fusaro Luca , Wouters Johan , Berionni Guillaume , Chardon Aurélien 
Published: April 2023

AbstractIsolation and characterization of highly reactive intermediates are crucial to understand the nature of chemical reactivity. Accordingly, the reactivity of weakly coordinating anions (WCA), usually used to stabilized cationic super electrophiles are of fundamental interest. When a variety of WCA are known to form stable σ‐complexes with a proton, inducing Brønsted super acidity, bis‐coordinated weak‐coordinated anions are much more elusive and considered as long‐sought reactive species. In this work, the chemistry of borylated sulfate, triflimidate and triflate anions were scouted in details with the aim of synthetizing the unique analogs of protonated Brønsted superacids. Those complexes were formed by successive borylation with a 9‐boratriptycene derived Lewis super acid paired with a weak coordinated anion, characterized in solution and in the solid state and exhibit unique structures and reactivities.
The Origin of Catalysis and Regioselectivity of Lewis Acid‐Catalyzed Diels‐Alder Reactions with Tropone**
Authors: Tiekink Eveline H. , Vermeeren Pascal , Hamlin Trevor A. 
Published: April 2023

AbstractWe have studied the uncatalyzed and Lewis acid (LA)‐catalyzed cycloaddition reaction between tropone and 1,1‐dimethoxyethene using dispersion‐corrected relativistic density functional theory (DFT). The LA catalysts BF3, B(C6H5)3, and B(C6F5)3efficiently accelerate both the competing [4+2] and [8+2] cycloaddition reactions by lowering the activation barrier up to 12 kcal mol−1compared to the uncatalyzed reaction. Our study reveals that the LA catalyst promotes both cycloaddition reaction pathways byLUMO‐lowering catalysisand demonstrates thatPauli‐lowering catalysisis not always the operative catalytic mechanism in cycloaddition reactions. Judicious choice of the LA catalyst can effectively impart regiocontrol of the cycloaddition: B(C6H5)3furnishes the [8+2] adduct while B(C6F5)3yields the [4+2] adduct. We discovered that the regioselectivity shift finds its origin in the ability of the LA to absorb distortion by adopting a trigonal pyramidal geometry around the boron atom.
Exposure‐Response Analysis to Assess the Concentration‐QTc Relationship of Iberdomide
Authors: Cheng Yiming , Gaudy Allison , Liu Liangang , Ye Ying , Thomas Michael , Xue Yongjun , Zhou Simon , Li Yan 
Published: April 2023

AbstractIberdomide is an orally available cereblon‐modulating agent being developed for the treatment of hematologic malignancies and autoimmune‐mediated diseases. To assess the potential concentration‐QTc relationship in humans and to ascertain or exclude a potential QT effect by iberdomide, a plasma concentration and ΔQTcF (change from baseline of corrected QT interval using the Fridericia formula) model of iberdomide was developed. Iberdomide concentration and paired high‐quality, intensive electrocardiogram signal from a single‐ascending‐dose study in healthy subjects (N = 56) were included in the analysis. The primary analysis was based on a linear mixed‐effect model with ΔQTcF as the dependent variable; iberdomide plasma concentration and baseline QTcF as continuous covariates; treatment (active or placebo) and time as a categorical factor; and a random intercept per subject. The predicted change from baseline and placebo corrected (ΔΔQTcF) at the observed geometric mean maximum plasma concentration and 2‐sided 90% confidence intervals at different dose levels were calculated. The upper bound of the 90% confidence interval of the model‐predicted ΔΔQTcF effect at maximum concentration from the supratherapeutic dose of 6 mg (2.54 milliseconds) is <10‐millisecond threshold, suggesting that iberdomide does not have a clinically relevant QT prolongation liability.
An anomaly detection on blockchain infrastructure using artificial intelligence techniques: Challenges and future directions – A review
Authors: Chithanuru Vasavi , Ramaiah Mangayarkarasi 
Published: April 2023

SummaryRecently, Blockchain cryptographic distributed transaction ledger technology finds its usage in many applications. The application's ledgers implemented through Blockchain, ensures tamper‐proof transactions, and in turn the applications became robust enough against cyber‐attack But still adversaries put forward their efforts in detecting the vulnerabilities in the infrastructure to execute their ill intent. In the literature, many counter measures techniques are presented to address the security breaches on the Blockchain. Detecting as well mitigating from the possible anomalies against on blockchain infrastructure through AI techniques is the greatest attempt of this article, and which is much needed now. Hence, this review article enlightens the readers with the essence of cyber security, the security aspects of Blockchain, its infrastructure vulnerabilities, various Blockchain‐enabled use cases along with the their challenges. Primarily, anomaly detection on Blockchain infrastructure through Artificial Intelligence Techniques is focused. A detailed analysis of Artificial Intelligence Techniques in detecting the anomalies with the help of Blockchain and also how these two technologies complement each other was demonstrated with the help of suitable use cases. The merits, challenges along with the possible future directions, while integrating Blockchain with Artificial Intelligence Techniques are presented for the benefit of research community.
g‐B3C2N3: A Potential Two Dimensional Metal‐free Photocatalyst for Overall Water Splitting**
Authors: Karmakar Sreejani , Adhikary Souren , Dutta Sudipta 
Published: April 2023

AbstractBased on hybrid density functional theory (DFT) calculations, we propose a new two‐dimensional (2D) B‐C‐N material, graphitic‐
(g‐
), with the promising prospect of metal‐free photocatalysis. We find it to be a near ultraviolet (UV) absorbing direct band gap (3.69 eV) semiconductor with robust dynamical and mechanical stability. Estimating the band positions with respect to water oxidation and hydrogen reduction potential levels along with a detailed analysis of reaction mechanism of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), we observe that g‐
monolayer can be efficiently used for hydrogen fuel generation over entire pH range as well as for spontaneous water splitting at basic pH range. Upon biaxial strain application, band positions get realigned along with the free energy change that is involved in HER and OER. Consequently, operational range of pH for OER gets broadened and the proposed material exhibits the ability to perform spontaneous and simultaneous oxidation and reduction even in neutral pH. The combination of pH variation and applied strain can be used as a key to control the reducing and/or oxidizing abilities precisely for diverse photocatalytic reactions to attain environmental sustainability.
The effectiveness of a day hospital mentalization‐based therapy programme for adolescents with borderline personality traits: Findings from Touchstone—Child and Adolescent Mental Health Service
Authors: Gilbey Dylan , Brealey Georgia , Mateo‐Arriero Irene , Waters Zoe , Ansell Megan , Janse van Rensburg Elmie , De Gouveia Belinelo Patricia , Milroy Helen , Pace Giulia , Runions Kevin , Salmin Ivan , Woolard Alix 
Published: April 2023

AbstractBackgroundIndividuals with borderline personality disorder (BPD) are at a substantial risk of harm to themselves and others, experience high levels of functional impairment and typically are high users of tertiary healthcare to address their mental health concerns. As indicators for BPD typically emerge in adolescence, a day therapy service in Bentley, Western Australia, Touchstone Child and Adolescent Mental Health Service (CAMHS), was developed as an intensive intervention for adolescents with indicators for BPD and its associated symptomology. Touchstone utilizes mentalization‐based therapy (MBT) in a therapeutic community setting, where the current study sought to document the anecdotal outcomes using the data provided at Touchstone, to enable a greater understanding of this treatment approach for adolescents with indicators for BPD.MethodForty‐six participants attended the Touchstone programme between 2015 and 2020. The programme involved 6 months of MBT (group and individual), occupational therapy, education and creative therapies. Measures of self‐injury, mood and emergency department presentations were collected pre‐ and post‐programme.ResultsResults indicate that participants show a reduction in non‐suicidal acts and thoughts, as well as a reduction in negative moods and feelings from pre‐Touchstone to post‐Touchstone. There is also a decrease in participant presentation to tertiary emergency departments for mental health concerns.ConclusionsThe current study shows evidence for the efficacy of Touchstone as an MBT therapeutic community intervention to reduce symptoms of emerging BPD and effectively reduce presentations to emergency departments for mental health presentations, alleviating pressure on tertiary hospitals and reducing economic impact of adolescents within this demographic.
Intraindividual variability and emotional change as predictors of sudden gains in imagery rescripting and EMDR for PTSD in adult survivors of childhood abuse
Authors: Kuck Sascha , Arntz Arnoud , Rameckers Sophie A. , Lee Christopher W. , Boterhoven de Haan Katrina L. , Fassbinder Eva , Morina Nexhmedin 
Published: April 2023

AbstractSudden gains, defined as large and stable improvements in symptom severity during psychological treatment, have consistently been found to be associated with better outcomes across treatments and diagnoses. Yet, insights on coherent predictors of sudden gains and on emotional changes around sudden gains in post‐traumatic stress disorder (PTSD) are lacking. We aimed at replicating a measure of intraindividual variability as a predictor for sudden gains and testing its independence from change during treatment. Furthermore, we expected changes in emotions of guilt, shame and disgust prior to sudden gains to predict sudden gains. Data from a pre‐registered randomized controlled trial (RCT) of eye‐movement desensitization and reprocessing (emdr) and Imagery Rescripting (ImRs) for PTSD in 155 adult survivors of childhood abuse were used. Intraindividual variability of PTSD symptoms in both treatments did not predict sudden gains status and was not independent of change during treatment. In the EMDR condition, levels of shame during treatment predicted sudden gains and shame decreased shortly before a sudden gain in both treatments. Reductions in all emotions during sudden gains were significantly higher for participants with sudden gains than for comparable intervals in non‐sudden gainers. Our findings do not support the predictive validity of intraindividual variability for sudden gains. The decrease of guilt, shame and disgust during sudden gains warrants further research on their role as a mechanism of treatment change for PTSD.
Living through war: An oral history of civilians in Sudan
Authors: Rothbart Daniel , Korostelina Karina , Gjeloshi Beltina 
Published: April 2023

AbstractCivilians in Sudan have been devastated by wars for decades, including civil wars that occurred from 1956 to 1972 and from 1983 to 2005, and wars continuing to this day in certain regions. With this article, we offer the findings of an oral history project that showcases the testimony of 116 Sudanese from the following three regions: Darfur, the Nuba Mountains and the Blue Nile state. We focused on their experiences of war and their vision of a just future for Sudan. After presenting summaries of the wars in these regions (Section 1), we identify the project's methodology (Section 2). The respondents' testimony is then analyzed thematically as follows: (a) life before war, (b) experiences of war, (c) becoming refugees, (d) war's impact, and (e) vision of justice in Sudan (Section 3). We then interpret the respondents' vision of justice as expressions of their agency in striving to overcome the systemic inequalities that have ravaged this war‐torn nation. Our analysis reveals the complexity of the respondents' notions of justice as inseparable from peace. Long‐term peace necessities the realization of justice that cannot be achieved without long‐term peace.