bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stabilizing Nitroxide Spin Labels for Structural and Conformational Studies of Biomolecules by Maleimide Treatment
Authors: Wang Xi‐Wei , Zhang Xing , Cui Chao‐Yu , Li Bin , Goldfarb Daniella , Yang Yin , Su Xun‐Cheng 
Published: June 2023

AbstractNitroxide (NO) spin radicals are effective in characterizing structures, interactions and dynamics of biomolecules. The EPR applications in cell lysates or intracellular milieu require stable spin labels, but NO radicals are unstable in such conditions. We showed that the destabilization of NO radicals in cell lysates or even in cells is caused by NADPH/NADH related enzymes, but not by the commonly believed reducing reagents such as GSH. Maleimide stabilizes the NO radicals in the cell lysates by consumption of the NADPH/NADH that are essential for the enzymes involved in destabilizing NO radicals, instead of serving as the solo thiol scavenger. The maleimide treatment retains the crowding properties of the intracellular components and allows to perform long‐time EPR measurements of NO labeled biomolecules close to the intracellular conditions. The strategy of maleimide treatment on cell lysates for the EPR applications has been demonstrated on double electron‐electron resonance (DEER) measurements on a number of NO labeled protein samples. The method opens a broad application range for the NO labeled biomolecules by EPR in conditions that resemble the intracellular milieu.
Bioorthogonal Drug Release from Nanometric Micelles in Living Cells
Authors: Madegard Léa , Girard Melissa , Yaw Benjamin Riss , Porte Karine , Audisio Davide , Papot Sébastien , Taran Frédéric 
Published: June 2023

AbstractWe explored a bioorthogonal approach to release drugs from stimuli‐responsive micelles inside tumor cells. The concept relies on sydnonimine‐based micelles that undergo quantitative cleavage in presence of cyclooctynes, hence releasing their content within living cells. Four cleavable micelles were developed to allow massive burst release of Entinostat, a potent histone deacetylase inhibitor, following their internalization inside cancer cells. A comparative study on the influence of the bioorthogonal‐mediated versus passive drug release from micelles was carried out. The results indicated that a fast release of the drug triggered a stronger antiproliferative activity on tumor cells compared to the passive diffusion of the drug from the micelles core. These finding may be of great interest for the development of new nanomedicines.
Titandioxid
Authors: Schubert Ulrich 
Published: June 2023

ZusammenfassungDie wichtigsten Rohstoffe für TiO2 sind natürliche TiO2‐Vorkommen und das Mineral Ilmenit (FeTiO3). Beim „Chlorid‐Prozess“ werden diese durch Behandlung mit Kohlenstoff und Chlor bei hohen Temperaturen zu TiCl4 aufgeschlossen, das dann durch „Verbrennen“ mit Sauerstoff oder Wasserstoff‐Sauerstoff‐Gemischen zu TiO2 umgesetzt wird. Eine alternative Methode ist die Behandlung der Rohstoffe mit konzentrierter Schwefelsäure und Ausfällen von TiO2 aus den dabei erhaltenen Titanylsulfat‐Lösungen. Neben diesen beiden großtechnischen Prozessen zur Herstellung von TiO2‐Pulvern spielen Sol‐Gel‐Verfahren eine Rolle, beispielsweise zur Synthese von Nanostrukturen, Beschichtungen oder porösem TiO2, bei denen T(OR)4 hydrolysiert wird. TiO2 ist das wichtigste Weißpigment und als solches in unserem Leben allgegenwärtig. Bis vor kurzem wurde TiO2 auch Lebensmitteln als Farbstoff zugesetzt. Diese Verwendung wurde aber mittlerweile in der EU untersagt, da genotoxische Effekte nicht mit Sicherheit ausgeschlossen werden können. Ein zweites wichtiges Anwendungsgebiet ergibt sich aus den Halbleiter‐Eigenschaften von TiO2. Aufgrund der Größe der Bandlücke wird UV‐Strahlung absorbiert. Daraus ergeben sich Anwendungen von Sonnenschutzcremes bis zum photokatalytischen Abbau von organischen Schadstoffen.
Palladium‐Catalyzed [4 + 4] Cycloaddition of Homo‐TMM All‐Carbon 1,4‐Dipole Precursors for Construction of Benzofuro[3,2‐b]azocines and Furo[3,2‐b]azocines
Authors: Chen Ying , Zang Meng , Wang Weijie , Liu Yang‐Zi , Luo Xiaoyan , Deng Wei‐Ping 
Published: June 2023

Comprehensive SummaryWe developed a novel Pd‐catalyzed [4 + 4] cycloaddition of (benzo)furan‐derived azadienes with homo‐TMM all‐carbon 1,4‐dipoles in situ generated from α‐allyl malonate derivatives, affording an array of benzofuro[3,2‐b]azocines and furo[3,2‐b]azocines with good to excellent yields (up to 96%) and exclusive regioselectivities. This methodology featured mild reaction conditions and good functional group tolerance. The synthetic utility was demonstrated by a gram‐scale reaction. Furthermore, the catalytic asymmetric [4 + 4] cycloaddition version has also been explored.
Difluoroalkylation/Lactonization of Alkenes with BrCF2CO2K via Photoredox Catalysis: Access to α,α‐Difluoro‐γ‐lactones†
Authors: Zhang Min , Li Qiang , Lin Jin‐Hong , Xiao Ji‐Chang 
Published: June 2023

Comprehensive SummaryDue to its unique electronic properties, the difluoromethylene group (CF2) has served as a valuable unity in the design of biologically active molecules. Since γ‐lactones display a broad range of biological properties, α,α‐difluoro‐γ‐lactones may exhibit unexpected biological activities, and thus their synthesis has received increasing attention. Traditional synthetic methods suffer from tedious multi‐ step processes, and very few effective methods have been reported recently. Herein, we describe the difunctionalization of alkenes with BrCF2CO2K under photoredox catalysis with the use of a boron‐Lewis acid for the access to α,α‐difluoro‐γ‐lactones. In this transformation, the alkene substrates and the used reagents, including BrCF2CO2K and the boron‐Lewis acid, PhB(OH)2 or BF3·THF, are cheap and widely available. High efficiency and atom economy may make this protocol attractive.
Rapid Access to Free Phenols by Photocatalytic Acceptorless Dehydrogenation of Cyclohexanones at Room Temperature
Authors: Min Lin , Lin Jiani , Shu Wei 
Published: June 2023

Comprehensive SummaryPhenols are ubiquitous substructures in natural products and bioactive compounds. However, practical methods for the direct construction of phenols under mild conditions remain challenging. Herein, a photocatalytic acceptorless hydrogen‐evolution aromatization of cyclohexanones or cyclohexenones at room temperature has been developed. The reaction features the visible‐light and cobalt co‐catalyzed sequential dehydrogenation of in‐situ formed enol silyl ethers, which are regarded as a challenging process. This operationally simple method enables the synthesis of a series of phenols with diverse substitution patterns from cyclohexanones or cyclohexenones. Moreover, diverse substituted 1,2‐, 1,3‐, and 1,4‐benzenediols were obtained from cyclohexanediones, providing a general and straightforward method for the synthesis of phenols from simple starting materials under mild conditions.
Association between diabetes mellitus and reduced efficacy of pembrolizumab in non–small cell lung cancer
Authors: Leshem Yasmin , Dolev Yardenna , Siegelmann‐Danieli Nava , Sharman Moser Sarah , Apter Lior , Chodick Gabriel , Nikolaevski‐Berlin Alla , Shamai Sivan , Merimsky Ofer , Wolf Ido 
Published: June 2023

AbstractBackgroundDiabetes mellitus (DM) is a highly prevalent chronic metabolic disorder. Although DM has been associated with immune dysfunction, the effect of DM on the efficacy of immunotherapy is unknown. This study aimed to evaluate the impact of DM on the efficacy of pembrolizumab in metastatic non–small cell lung cancer (NSCLC).MethodsThe authors reviewed the medical records of consecutive metastatic NSCLC patients treated with first‐line pembrolizumab either alone or in combination with chemotherapy at a single tertiary center. For validation, a computerized data from Maccabi Healthcare Services, a 2.5–million‐member state health service was used.ResultsOf the 203 eligible patients, 51 (25%) had DM. Patients with DM had a significantly shorter median progression‐free survival (PFS) (5.9 vs. 7.1 months, p = .004) and overall survival (OS) (12 vs. 21 months, p = .006). The shorter OS in diabetic patients was more pronounced when pembrolizumab was given alone (12 vs. 27 months, p = .03) than when combined with chemotherapy (14.3 vs. 19.4 months, p = .06). Multivariate analysis confirmed DM as an independent risk factor for shorter PFS (hazard ratio [HR], 1.67; 95% confidence interval [CI], 1.11−2.50, p = .01) and OS (HR, 1.73; 95% CI, 1.09−2.76, p = .02). In a validation cohort of 452 metastatic NSCLC patients, the time on pembrolizumab treatment was shorter in diabetic patients (p = .025), with only 19.6% of patients remaining on treatment at 12 months compared to 31.7% of the nondiabetic patients.ConclusionsThis study suggests immunotherapy is less beneficial in diabetic NSCLC patients. More work is needed to verify our findings and explore similar effects in other cancer entities.
Determinants of frontline tyrosine kinase inhibitor choice for patients with chronic‐phase chronic myeloid leukemia: A study from the Registro Italiano LMC and Campus CML
Authors: Tiribelli Mario , Latagliata Roberto , Breccia Massimo , Capodanno Isabella , Miggiano Maria Cristina , Cavazzini Francesco , Bucelli Cristina , Attolico Immacolata , Crescenzi Sabrina Leonetti , Russo Sabina , Annunziata Mario , Sorà Federica , Bonifacio Massimiliano , Mulas Olga , Loglisci Giuseppina , Maggi Alessandro , Binotto Gianni , Crisà Elena , Scortechini Anna Rita , Leporace Anna Paola , Sancetta Rosaria , Murgano Pamela , Abruzzese Elisabetta , Stagno Fabio , Rapezzi Davide , Luzi Debora , Vincelli Iolanda , Bocchia Monica , Fava Carmen , Malato Alessandra , Crugnola Monica , Pizzuti Michele , Lunghi Francesca , Galimberti Sara , Dalmazzo Matteo , Fanin Renato , Scalzulli Emilia , Foà Robin , Iurlo Alessandra , Saglio Giuseppe , Specchia Giorgina 
Published: June 2023

AbstractBackgroundImatinib, dasatinib, and nilotinib are tyrosine kinase inhibitors (TKIs) approved in Italy for frontline treatment of chronic‐phase chronic myeloid leukemia (CP‐CML). The choice of TKI is based on a combined evaluation of the patient’s and the disease characteristics. The aim of this study was to analyze the use of frontline TKI therapy in an unselected cohort of Italian patients with CP‐CML to correlate the choice with the patient’s features.MethodsA total of 1967 patients with CP‐CML diagnosed between 2012 and 2019 at 36 centers throughout Italy were retrospectively evaluated; 1089 patients (55.4%) received imatinib and 878 patients (44.6%) received a second‐generation (2G) TKI.ResultsSecond‐generation TKIs were chosen for most patients aged <45 years (69.2%), whereas imatinib was used in 76.7% of patients aged >65 years (p < .001). There was a predominant use of imatinib in intermediate/high European long–term survival risk patients (60.0%/66.0% vs. 49.7% in low‐risk patients) and a limited use of 2G‐TKIs in patients with comorbidities such as hypertension, diabetes, chronic obstructive pulmonary disease, previous neoplasms, ischemic heart disease, or stroke and in those with >3 concomitant drugs. We observed a greater use of imatinib (61.1%) in patients diagnosed in 2018–2019 compared to 2012–2017 (53.2%; p = .002). In multivariable analysis, factors correlated with imatinib use were age > 65 years, spleen size, the presence of comorbidities, and ≥3 concomitant medications.ConclusionsThis observational study of almost 2000 cases of CML shows that imatinib is the frontline drug of choice in 55% of Italian patients with CP‐CML, with 2G‐TKIs prevalently used in younger patients and in those with no concomitant clinical conditions. Introduction of the generic formulation in 2018 seems to have fostered imatinib use.
Regulating Efficient and Selective Single‐atom Catalysts for Electrocatalytic CO2 Reduction
Authors: Wang Shuo , Feng Shao‐Yang , Zhao Cong‐Cong , Zhao Ting‐Ting , Tian Yu , Yan Li‐Kai 
Published: June 2023

AbstractAnchoring transition metal (TM) atoms on suitable substrates to form single‐atom catalysts (SACs) is a novel approach to constructing electrocatalysts. Graphdiyne with sp−sp2 hybridized carbon atoms and uniformly distributed pores have been considered as a potential carbon material for supporting metal atoms in a variety of catalytic processes. Herein, density functional theory (DFT) calculations were performed to study the single TM atom anchoring on graphdiyne (TM1−GDY, TM=Sc, Ti, V, Cr, Mn, Co and Cu) as the catalysts for CO2 reduction. After anchoring metal atoms on GDY, the catalytic activity of TM1−GDY (TM=Mn, Co and Cu) for CO2 reduction reaction (CO2RR) are significantly improved comparing with the pristine GDY. Among the studied TM1−GDY, Cu1−GDY shows excellent electrocatalytic activity for CO2 reduction for which the product is HCOOH and the limiting potential (UL) is −0.16 V. Mn1−GDY and Co1−GDY exhibit superior catalytic selectivity for CO2 reduction to CH4 with UL of −0.62 and −0.34 V, respectively. The hydrogen evolution reaction (HER) by TM1−GDY (TM=Mn, Co and Cu) occurs on carbon atoms, while the active sites of CO2RR are the transition metal atoms . The present work is expected to provide a solid theoretical basis for CO2 conversion into valuable hydrocarbons.
Chiral and Luminescent Organic Radicals
Authors: Wang Mengqi , Zhao Engui , He Zikai 
Published: June 2023

AbstractChiral luminescent materials are a class of materials capable of emitting circularly polarized light (CPL). Radicals are unique open‐shell compounds with exceptional photoelectromagnetic properties that can be exploited in constructing novel chiral luminescent materials. This Concept discussed three main catalogues for producing organic CPL radicals, intrinsic chiral luminescent radicals, luminescent radicals with chiral substitutions, and field‐regulation‐induced chiral luminescent radicals. The brief review of their properties aims at providing basic guidelines and supporting further development of novel chiral luminescent radical systems.
UAV‐IoT collaboration: Energy and time‐saving task scheduling scheme
Authors: Banerjee Anuradha , Gupta Sachin Kumar , Gupta Parul , Sufian Abu , Srivastava Ashutosh , Kumar Manoj 
Published: June 2023

SummaryUAVs are capable of providing significant potential to IoT devices through sensors, cameras, GPS systems, and so forth. Therefore, the smart UAV‐IoT collaborative system has become a current hot research topic. However, other concerns require in‐depth investigation and study, such as resource allocation, security, privacy preservation, trajectory optimization, intelligent decision‐making, energy harvesting, and so forth. Here, we suggest a task‐scheduling method that splits IoT devices into distinct clusters based on physical proximity and saves time and energy. Cluster heads can apply an auto regressive moving average (ARMA) model to predict intelligently the timestamp of the arrival of the next task and associated estimated payments. Based on the overall expected payment, a cluster head can smartly advise the UAV about its time of next arrival. According to the findings of the simulation, the proposed ETTS algorithm significantly outperforms Task TSIE and TDMA‐WS in terms of energy use (67%) and delays (36%).
Energy‐optimized cluster head selection based on enhanced remora optimization algorithm in underwater wireless sensor network
Authors: Kumar Tiwari Keshav , Singh Samayveer 
Published: June 2023

SummaryWith the technological advancements, wireless sensor network (WSN) has played an impeccable role in monitoring the underwater applications. Underwater WSN (UWSN) is supported by WSN but subjected to data dissemination in an acoustic medium. Due to challenging conditions in underwater scenario, the limited battery resources of these sensor nodes stem to a crucial research problem that needs to address the energy‐efficient routing in UWSN. In this research work, we intend to propose an energy‐optimized cluster head (CH) selection based on enhanced remora optimization algorithm (ECERO) in UWSN. Since CH devours the maximum energy among the nodes, we perform selection of CH based on EROA while considering energy, Euclidean distance from sink, node density, network's average energy, acoustic path loss model and lastly, the adaptive quantity of CHs in the network. Further, to reduce the load on CH node, we introduce the concept of sleep scheduling among the closely located cluster nodes. The proposed work improves the performance of recently proposed EOCSR algorithm by great magnitude which claims to mitigate hot‐spot problem, but EOCSR still suffers from the same due to relaying a large magnitude of data.
Thoracic SMARCA4‐deficient undifferentiated tumor with associated granulomatous reaction and response to pembrolizumab
Authors: Marshall Mason , Khader Samer , Beasley Scott , Lajara Sigfred 
Published: June 2023

AbstractThoracic SMARCA4‐deficient undifferentiated tumor (SMARCA4‐UT) is a rare entity that was recently described in the current World Health Organization Classification of Tumors. These lesions are highly aggressive with dismal prognosis, and most patients present with metastasis at the time of diagnosis. While there are about 100 cases of SMARCA4‐UT described in the literature, there are only few existing reports that describe the cytomorphology of these lesions. We present a patient with masses involving the mediastinum, right lung, right supraclavicular lymph node and right adrenal gland. Subsequent core‐needle biopsy of the right supraclavicular lymph node showed epithelioid to pleomorphic tumor cells with prominent nucleoli and associated granulomatous inflammation. The tumor cells were positive for CD34 and synaptophysin, and were negative for cytokeratins. SMARCA4 and SMARCA2 both showed loss of expression, which led to the diagnosis of SMARCA4‐UT. The patient underwent treatment with pembrolizumab (PD‐1 blocker), carboplatin, etoposide, and radiotherapy, resulting in an almost 55% reduction in the size of the primary tumor. Our case illustrates that an associated granulomatous inflammation might be an uncommon presentation of an already rare malignancy, and awareness of this phenomenon would prevent from mistaking SMARCA4‐UT for other more well‐known entities that can present with granulomas.
Heart transplantation in patients bridged with mechanical circulatory support: outcome comparison with matched controls
Authors: Bartfay Sven‐Erik , Bobbio Emanuele , Esmaily Sorosh , Bergh Niklas , Holgersson Jan , Dellgren Göran , Bollano Entela , Karason Kristjan 
Published: June 2023

AbstractAimsDue to the shortage of heart donors, increasing numbers of heart transplantation (HTx) candidates are receiving long‐term mechanical circulatory support (MCS) as bridge‐to‐transplantation. Treatment with MCS is associated with increased formation of anti‐human leukocyte antigen antibodies (allosensitization), but whether this affects post‐HTx outcomes is unclear.Methods and resultsWe included all adult patients who received long‐term MCS as bridge‐to‐transplantation and underwent subsequent HTx at our centre between 2008 and 2018. We also enrolled medically treated HTx recipients without prior MCS as controls. These controls were matched by age, sex, diagnosis, and transplantation era. Outcome parameters were compared between the two study groups. A total of 126 patients (48 ± 15 years, 84% male) were included of whom 64 were bridged with MCS and 62 were matched controls. Pre‐HTx allosensitization occurred more frequently in the MCS group than in the control group (27% vs. 11%, P = 0.03). At post‐HTx year 10, the overall survival probability was 84% among patients treated with MCS and 90% among those medically managed (P = 0.32). At post‐HTx year 1, freedom from treated rejections (≥ISHLT 2R) was 69% in the MCS group and 70% in the control group (P = 0.94); and freedom from any rejection was 8% and 5%, respectively (P = 0.98). There were no differences in renal function or cardiac allograft vasculopathy (grade ≥ 1) between groups at 1, 3, and 5 years post‐HTx.ConclusionsAlthough patients treated with MCS had a higher frequency of pre‐HTx allosensitization, there were no significant differences in post‐HTx graft survival, biopsy‐proven rejections, or renal function as compared with patients not bridged with MCS.
Paediatric heart transplantation during the COVID‐19 pandemic in Iran: single‐centre experience
Authors: Mahdavi Mohammad , Hejri Golnar Mortaz , Shahzadi Hossein , Dehaki Maziar Gholampour , Houshmand Golnaz 
Published: June 2023

AbstractAimsTransplant services were imposed to the multiple challenges of insufficient facilities and resources during the COVID‐19 pandemic. Thus, each centre modified and altered its routine practice to maintain the service. We report our experience in Iran's single‐centre paediatric heart transplantation unit during the 2 year pandemic in transplant rate and early transplant outcomes.Methods and resultsWe retrospectively reviewed all paediatric heart transplants performed at our centre between 19 February 2020 and February 2022. We studied the number and percentage of paediatric transplanted patients who developed COVID‐19, in‐hospital outcome, 30 day survival and left ventricular function during the first month of the follow‐up visit. From February 2020 to February 2022, 59 transplants were performed compared with 62 patients from February 2018 to 2020. Compared with the year before the pandemic, the heart transplant rate was reduced by 34% in the first year of the pandemic; however, it bounced back in the second year with a 19% increase. The in‐hospital mortality rate during the 2 year pandemic was (11.8%). One death occurred related to COVID‐19 acute respiratory distress syndrome. The in‐hospital COVID‐19 infection rate was 11 patients (18%). In the 30 day follow‐up, the overall 30 day survival rate was 88%, and the 30 day rejection rate was 10%. The mean left ventricular ejection fraction was (53.6 ± 4.9), the mean left ventricular global longitudinal strain was −16.9 ± 3.3, and the mean right ventricular global longitudinal strain was −17.0 ± 3.8 with no significant difference between patients with in‐hospital COVID and other recipients (P = 0.1, P = 0.2 and P = 0.2).ConclusionsThroughout the pandemic, although we experienced a reduction in the transplant rate in the first year, with the increasing vaccination rate in health care and later in the general population, we continued to maintain our transplant rate by incorporating safety protocols and more resources.
Short‐chain polyphosphates: Extraction effects on migration and size estimation of Saccharomyces cerevisiae extracts with polyacrylamide gel electrophoresis
Authors: Manoukian Lori , Stein Robin S. , Correa José A. , Frigon Dominic , Omelon Sidney 
Published: June 2023

AbstractPolyacrylamide gel electrophoresis is commonly used to characterize the chain length of polyphosphates (polyP), more generally called condensed phosphates. After separation, nonradioactive, optical polyP staining is limited to chain lengths greater than 15 monomers with toluidine blue or 4′,6‐diamidino‐2‐phenylindole. PolyP chain lengths longer than 62monomers were correlated to the shortest DNA ladders. In this study, synthetic linear polyPs (Sigma‐Aldrich “Type 45”, estimated mean length of 45 monomers), trimetaphosphate (trimetaP: 3 ring), tripolyphosphate (tripolyP), pyrophosphate (PPi), and inorganic orthophosphate (o‐Pi) were visualized after separation by an in situ hydrolytic degradation process to o‐Pi that was subsequently stained with methyl green. Statistically insignificant migration reduction of synthetic short‐chain polyP after perchloric acid or phenol–chloroform extraction was confirmed with the Friedman test. 31P diffusion–ordered NMR spectroscopy confirmed that extraction also reduced PPi diffusivity by <10%. Linear regression between the Rf peak migration value and the logarithm of synthetic polyP molecular weights enabled estimation of extracted polyP chain lengths from 2 to 45 monomers. Linear polyP extracts from Saccharomyces cerevisiae grown in aerobic conditions were generally shorter than extracts cultured in anaerobic conditions. Extractions from both aerobic and anaerobic S. cerevisiae included tripolyP and o‐Pi, but no PPi.