bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anwendungen der C−H‐Aktivierung im präparativen Maßstab in der medizinischen Chemie
Authors: de Jesus Rita , Hiesinger Kerstin , van Gemmeren Manuel 
Published: June 2023

AbstractDie C−H‐Aktivierung ist eine attraktive Methode zur Steigerung der molekularen Komplexität, ohne Vorfunktionalisierung des Substrats. Im Gegensatz zu den etablierten Kreuzkupplungsmethoden ist die C−H‐Aktivierung in großem Maßstab weniger erforscht und ihre Anwendung bei der Herstellung von Arzneimitteln ist mit erheblichen Hürden verbunden. Die inhärenten Vorteile, wie kürzere Synthesewege und einfachere Ausgangsmaterialien, motivieren Medizinal‐ und Prozesschemiker jedoch dazu, diese Herausforderungen zu überwinden und C−H‐Aktivierungsschritte für die Synthese pharmazeutisch relevanter Verbindungen zu nutzen. In diesem Aufsatz werden wir Beispiele von Arzneimitteln/Wirkstoffkandidaten behandeln, bei denen die C−H‐Aktivierung in einem präparativen Synthesemaßstab (zwischen 355 mg und 130 kg) durchgeführt wurden. Die Optimierungsprozesse werden beschrieben und jedes Beispiel wird im Hinblick auf seine Vor‐ und Nachteile untersucht, um dem Leser ein umfassendes Verständnis der Herausforderungen und des Potenzials von C−H‐Aktivierungsmethoden für die Herstellung von Arzneimitteln zu vermitteln.
Pure and Metal‐confining Carbon Nanotubes through Electrochemical Reduction of Carbon Dioxide in Ca‐based Molten Salts
Authors: Cao Jin , Jing Shuangxi , Wang Hongwei , Xu Wangyue , Zhang Mingen , Xiao Juanxiu , Peng Yuhao , Ning Xiaohui , Wang Zhangjie , Xiao Wei 
Published: June 2023

AbstractTo be successfully implemented, an efficient conversion, affordable operation and high values of CO2‐derived products by electrochemical conversion of CO2 are yet to be addressed. Inspired by the natural CaO‐CaCO3 cycle, we herein introduce CaO into electrolysis of SnO2 in affordable molten CaCl2‐NaCl to establish an in situ capture and conversion of CO2. In situ capture of anodic CO2 from graphite anode by the added CaO generates CaCO3. The consequent co‐electrolysis of SnO2 and CaCO3 confines Sn in carbon nanotube (Sn@CNT) in cathode and increases current efficiency of O2 evolution in graphite anode to 71.9 %. The intermediated CaC2 is verified as the nuclei to direct a self‐template generation of CNT, ensuring a CO2‐CNT current efficiency and energy efficiency of 85.1 % and 44.8 %, respectively. The Sn@CNT integrates confined responses of Sn cores to external electrochemical or thermal stimuli with robust CNT sheaths, resulting in excellent Li storage performance and intriguing application as nanothermometer. The versatility of the molten salt electrolysis of CO2 in Ca‐based molten salts for template‐free generation of advanced carbon materials is evidenced by the successful generation of pure CNT, Zn@CNT and Fe@CNT.
Mechanistic Characterisation of the Bacterial Sesterviridene Synthase from Kitasatospora viridis
Authors: Xu Houchao , Schnakenburg Gregor , Goldfuss Bernd , Dickschat Jeroen S. 
Published: June 2023

AbstractA gene coding for a terpene synthase homolog from Kitasatospora viridis was cloned and expressed in Escherichia coli. The purified recombinant protein possessed sesterterpene synthase activity and efficiently converted geranylfarnesyl diphosphate (GFPP) with 19 % yield into the sesterterpene hydrocarbon sesterviridene A. Large scale enzymatic conversions also allowed for the isolation of two side products that are generated with very low yields of ca. 0.1 %. Several derivatives of sesterviridene A were obtained by chemical transformations, securing the NMR‐based structural assignments. The absolute configuration of sesterviridene A was determined by chemical correlation using stereoselectively deuterated precursors and by anomalous dispersion X‐ray crystallography. The cyclisation mechanism from GFPP to sesterviridene A was extensively studied through isotopic labelling experiments and DFT calculations.
Taguchi optimized sliding wear behavior and hardness of novelGrewia optiva/Basalt fiber reinforced hybrid polyester composites
Authors: Bijlwan Pramod Prabhakar , Prasad Lalta , Sharma Anshul , Kumar Sanjeev 
Published: June 2023

AbstractThis research paper investigated the hardness and tribological performance of novelGrewia optiva/Basalt fiber reinforced hybrid polymer composites. Two different configuration of hybrid composite that is, woven and chopped fiber reinforced composite are considered for the study. The chopped fiber configuration of the composite is further divided into two types based on fiber length and wt%. The fiber lengths studied are 6 and 12 mm while the wt% studied are 0, 6, and 12 wt%. Woven fiber reinforced composite is divided into five configurations based on wt% ofG. optivafiber with 0, 3, 6, 9, and 12 wt%. In all configurations, maximum fiber content of 12 wt% is maintained. B6/GO6 composite exhibits minimum specific wear rate and maximum hardness among all the compositions. Wear experimental results are analyzed by Taguchi optimization technique and based on the five levels and four control factors (sliding velocity, fiber loading, sliding distance, and normal load) L25partial orthogonal array was suggested for the woven fiber reinforced composites. Fiber content is the main control parameter for hardness testing and L9orthogonal array was suggested according to four control factors and three levels.
The impact of ‘bursary tourism’ or the desire for a ‘fulfilling, challenging, and emotionally rewarding career’? Career entry motivations and perceptions of preservice teachers from England
Authors: George Sindu , Thornby John 
Published: June 2023

AbstractWhy teachers choose their career has been a popular topic of research in many contexts since the introduction of the FIT‐Choice framework by Watt and Richardson in 2007 to study teacher motivations. Although altruistic motivations have been identified as the common driving factor behind preservice teachers' (PSTs') decision to enter the field, there are other motivational factors—such as teaching being a career that fits well with family commitments, or choosing teacher education as a ‘fallback’ option—that are widely reported in different contexts. The introduction of incentives for student teachers in certain subjects has been subject to media criticism in England as promoting ‘bursary tourism’. This study investigates the career entry motivations and teaching perceptions of PSTs from a university that is one of the key teacher education providers in the country, using the FIT‐Choice framework. The paper discusses the findings (N = 115), including validation of the FIT‐Choice scale, collecting data on 12 motivations and six perceptions, along with preliminary findings. It was identified that intrinsic career values were the highest rated motivation, followed by altruistic values such as the desire to make a social contribution and being a part of shaping the future of children and adolescents. Perceived abilities were also rated higher, while personal utility values and task returns— including monetary rewards—were rated very low. While the participants agreed that the job is professionally and emotionally demanding, it was promising to note that they were highly satisfied with their career choice, implicitly indicating their intention to continue in the teaching profession. Gender differences, along with field of study and training pathway differences in motivations and teaching perceptions are also discussed, with practical implications.
Rissreibung in Biegeschubrissen
Authors: Jauk Vladimir , Rombach Günter A. 
Published: June 2023

AbstractZur Bestimmung der Querkrafttragfähigkeit von Stahl‐ und Spannbetonbauteilen ohne Schubbewehrung wurden zahlreiche Rechenmodelle entwickelt. Dabei gehen manche Ansätze davon aus, dass die einwirkende Querkraft im Wesentlichen über die Rissreibung abgetragen wird. Andere sehen die ungerissene Betondruckzone als maßgebenden Tragmechanismus an. Um diese Frage zu klären, wurden zehn Versuche mit Stahlbetonbalken ohne Bügelbewehrung durchgeführt. Hierbei lag der Schwerpunkt bei der genauen Aufzeichnung der Rissentwicklung sowie bei der Messung von Rissöffnung und ‐gleitung. Mithilfe konventioneller und moderner Messmethoden, wie der digitalen Bildkorrelation (DIC), wurde das Tragverhalten umfänglich aufgezeichnet und ausgewertet. Des Weiteren erfolgten eine Begutachtung der Rissoberflächen sowie eine Bestimmung der Rissreibungskräfte. Nach den durchgeführten Untersuchungen scheint die Rissreibung nur einen geringen Anteil der Querkraft aufzunehmen. Die Ergebnisse des Forschungsvorhabens liefern damit einen Beitrag zu einem besseren Verständnis des Querkraftabtrags in Stahlbetonbauteilen ohne Querkraftbewehrung.
Doppelkopfanker als Querkraft‐ und Durchstanzbewehrung – Aktueller Stand und Ausblick
Authors: Fingerloos Frank , Lindorf Alexander , Meyer Lars 
Published: June 2023

AbstractAls eine sehr effektive Durchstanzbewehrung haben sich seit Jahrzehnten Doppelkopfanker etabliert, da bei diesen für Querkraft‐ und Durchstanzbeanspruchungen optimierten Bewehrungselementen eine besonders hohe Verankerungsleistung mit einer praktikablen Einbaubarkeit kombiniert werden kann. In diesem Beitrag wird ein Überblick über aktuelle Verwendbarkeits‐ und Anwendbarkeitsnachweise für Doppelkopfanker in Deutschland gegeben. Danach werden die aktuell geltenden Bemessungs‐ und Konstruktionsregeln für die Verwendung der Doppelkopfanker als Querkraft‐ sowie als Durchstanzbewehrung zusammengestellt. Abschließend wird auf die nächste Eurocode‐2‐Generation 2023+geblickt, wobei auszugsweise einige wesentliche Neuerungen bei der zukünftigen Einbindung der Doppelkopfanker in die Querkraft‐ und Durchstanzregelungen vorgestellt werden.
A joint control intervention for the acquisition of group exercise sequences
Authors: Baker Natalie , Jackson Marianne L. , Smith Nicole J. 
Published: June 2023

AbstractDespite the health problems associated with a lack of physical activity, most adults in the U.S. do not meet recommended levels. One barrier often cited is lack of relevant skills, and a small number of studies have suggested that instructional forms of self‐talk may be an important aspect of skill acquisition in physical activity. The process of joint control may provide a conceptually accurate account of this type of intervention and suggest new applications. Five undergraduate students participated in this study and attended a group exercise class created for this purpose. Following baseline sessions, all participants completed joint control training on a novel exercise sequence and then returned to the group exercise setting. All participants showed a noticeable increase in the accuracy of their movements in the post‐training phase and demonstrated continued improvements in the generalization phase. Limitations of covert responses and the contrived setting are discussed.
Health insurance and neighborhood poverty as mediators of racial disparities in advanced disease stage at diagnosis and nonreceipt of surgery for women with breast cancer
Authors: Hines Robert B. , Zhu Xiang , Lee Eunkyung , Eames Bradley , Chmielewska Karolina , Johnson Asal M. 
Published: June 2023

AbstractBackgroundIn our recent study, advanced disease stage and nonreceipt of surgery were the most important mediators of the racial disparity in breast cancer survival. The purpose of this study was to quantify the racial disparity in these two intermediate outcomes and investigate mediation by the more proximal mediators of insurance status and neighborhood poverty.MethodsThis was a cross‐sectional study of non‐Hispanic Black and non‐Hispanic White women diagnosed with first primary invasive breast cancer in Florida between 2004 and 2015. Log‐binomial regression was used to obtain prevalence ratios (PR) with 95% confidence intervals (CIs). Multiple mediation analysis was used to assess the role of having Medicaid/being uninsured and living in high‐poverty neighborhoods on the race effect.ResultsThere were 101,872 women in the study (87.0% White, 13.0% Black). Black women were 55% more likely to be diagnosed with advanced disease stage at diagnosis (PR, 1.55; 95% CI, 1.50–1.60) and nearly twofold more likely to not receive surgery (PR, 1.97; 95% CI, 1.90–2.04). Insurance status and neighborhood poverty explained 17.6% and 5.3% of the racial disparity in advanced disease stage at diagnosis, respectively; 64.3% remained unexplained. For nonreceipt of surgery, insurance status explained 6.8% while neighborhood poverty explained 3.2%; 52.1% was unexplained.ConclusionsInsurance status and neighborhood poverty were significant mediators of the racial disparity in advanced disease stage at diagnosis with a smaller impact on nonreceipt of surgery. However, interventions designed to improve breast cancer screening and receipt of high‐quality cancer treatment must address additional barriers for Black women with breast cancer.
Ten principles of counselling: Grounded theory in a mixed methods research project
Authors: Rohr Dirk , Becker‐Neu Josephine 
Published: June 2023

AbstractThis grounded theory (GT) study is part of an extensive mixed methods research project to develop general principles for counselling. Nine hundred counselling protocols were examined. The material is characterised by a quantitative amount of data with a qualitative character. The research is based on the systemic‐constructivist research paradigm. The variety of perspectives is an important aspect of the work. Therefore, it is important that the entire research process with GT takes place in exchange with other research settings in order to minimise the limitations caused by the perspective of the researchers. During the research process, there was an intensive examination of GT in order to adapt it to the research project. By using the GT to analyse the extensive qualitative material, the actions of the counsellors were observed and 10 counselling principles were developed. This article presents the research process and the findings.
Supervision experiences of trans/gender expansive counselors‐in‐training: An interpretative phenomenological analysis
Authors: Degenstein Megan , Tangen Jodi , Danielson Jessica 
Published: June 2023

AbstractClinical supervisors should be culturally competent working with transgender or gender expansive (TGE) counselors‐in‐training; however, minimal research exists regarding TGE counselors’ experiences in supervision. This interpretative phenomenological analysis study explored the supervision experiences of five TGE counselors‐in‐training. Findings revealed four super‐ordinate themes and two sub‐themes, and implications are discussed.
Photobioelectrocatalysis of Intact Photosynthetic Bacteria Exposed to Dinitrophenol
Authors: de Moura Torquato Lilian Danielle , Matteucci Rosa Maria , Stufano Paolo , Vona Danilo , Farinola Gianluca M. , Trotta Massimo , Boldrin Zanoni Maria Valnice , Grattieri Matteo 
Published: June 2023

AbstractInvited for this issue's Front Cover is the international collaborative team with researchers from Università degli Studi di Bari “Aldo Moro” (Italy), São Paulo State University (UNESP, Brasil), and Consiglio Nazionale delle Ricerche (Italy). The cover picture shows purple bacterial cells that hit, or miss, their “target electrode” with photo‐induced electrons depending on the concentration of dinitrophenol at which they are exposed. Under low dinitrophenol concentration, the electrons can reach the target, while under high dinitrophenol concentrations the electrons are diverted away from the electrode. Read the full text of the Research Article at 10.1002/celc.202300013.
A Domino Radical Amidation/Semipinacol Approach to All‐Carbon Quaternary Centers Bearing an Aminomethyl Group
Authors: Dhak Mandeep S. , Arunprasath Dhanarajan , Argent Stephen P. , Cuthbertson James D. 
Published: June 2023

AbstractA photoredox‐mediated radical amidation ring‐expansion sequence that enables the generation of all‐carbon quaternary centers bearing a protected aminomethyl substituent is described. The methodology can be applied to both styrene and unactivated alkene substrates generating structurally diverse sp3‐rich amine derivatives in a concise manner.
Diffundierter Sauerstoff als dominierender flacher Akzeptor in p‐Typ Kupferiodid‐Dünnfilmen
Authors: Lorenz Michael , Storm Philipp , Gierth Stephan , Selle Susanne , von Wenckstern Holger , Grundmann Marius 
Published: June 2023

AbstractDie Langzeitstabilität des optisch transparenten p‐Typ‐Halbleiters Kupferiodid ist eine aktuelle Herausforderung, da die elektrische Leitfähigkeit von CuI‐Dünnfilmen empfindlich auf Umgebungseinflüsse reagiert. Deckschichten aus Aluminiumoxid erhöhen die Stabilität beträchtlich. Systematische Untersuchungen von Al2O3/CuI‐Heterostrukturen in Abhängigkeit der N2‐ oder O2‐Partialdrücke bei der Oxid‐Abscheidung zeigen, dass die elektrische Leitfähigkeit der CuI‐Filme durch die Sauerstoff‐Diffusion in Al2O3 und CuI bestimmt wird. Sauerstoff scheint somit als dominierender Akzeptor in CuI zu wirken. Die Diffusion des Umgebungs‐Sauerstoffs in CuI wurde mittels des 18O‐Isotopes verfolgt.
The essential molecular requirements for the transformation of normal cells into established cancer cells, with implications for a novel anti‐cancer agent
Authors: Warenius Hilmar M. 
Published: June 2023

AbstractBackgroundNormal adult mammalian cells can respond to oncogenic somatic mutations by committing suicide through a well‐described, energy dependent process termed apoptosis. Cancer cells avoid oncogene promoted apoptosis. Oncogenic somatic mutations are widely acknowledged to be the cause of the relentless unconstrained cell proliferation which characterises cancer. But how does the normal cell with the very first oncogenic mutation survive to proliferate without undergoing apoptosis?New findingsThe phenomena of malignant transformation by somatic mutation, apoptosis, aneuploidy, aerobic glycolysis and Cdk4 upregulation in carcinogenesis have each been extensively discussed separately in the literature but an overview explaining how they may be linked at the initiation of the cancer process has not previously proposed.ConclusionA hypothesis is presented to explain how in addition to the initial oncogenic mutation, the expression of certain key normal genes is, counter‐intuitively, also required for successful malignant transformation from a normal cell to a cancer cell. The hypothesis provides an explanation for how the cyclic amphiphilic peptide HILR‐056, derived from peptides with homology to a hexapeptide in the C‐terminal region of Cdk4, kill cancer cells but not normal cell by necrosis rather than apoptosis.
The stationary AKPZ equation: Logarithmic superdiffusivity
Authors: Cannizzaro Giuseppe , Erhard Dirk , Toninelli Fabio 
Published: June 2023

AbstractWe study the two‐dimensional Anisotropic KPZ equation (AKPZ) formally given by
where ξ is a space‐time white noise and λ is a strictly positive constant. While the classical two‐dimensional KPZ equation, whose nonlinearity is , can be linearised via the Cole‐Hopf transformation, this is not the case for AKPZ. We prove that the stationary solution to AKPZ (whose invariant measure is the Gaussian Free Field (GFF)) is superdiffusive: its diffusion coefficient diverges for large times as up to corrections, in a Tauberian sense. Morally, this says that the correlation length grows with time like . Moreover, we show that if the process is rescaled diffusively (), then it evolves non‐trivially already on time‐scales of order approximately . Both claims hold as soon as the coefficient λ of the nonlinearity is non‐zero. These results are in contrast with the belief, common in the mathematics community, that the AKPZ equation is diffusive at large scales and, under simple diffusive scaling, converges to the two‐dimensional Stochastic Heat Equation (2dSHE) with additive noise (i.e., the case ).
Effect of Choline Amino Acid‐Based Ionic Liquids on Stability and Structure of Hemoglobin
Authors: Devi Tulsiyan Kiran , Rani Prusty Mallika , Biswal Himansu S. 
Published: June 2023

AbstractIonic liquids (ILs) can stabilize or destabilize proteins, which motivates us to examine their effect on hemoglobin. The native state of hemoglobin (Hb) is disrupted at different physical conditions such as pressure, temperature, and solvents. Herein, we have monitored the stability of Hb in a nontoxic and biocompatible IL, i. e., choline amino acid‐based Ils (ChAAILs), using various spectroscopic techniques like UV‐Vis and fluorescence spectroscopy, circular dichroism (CD), and isothermal titration calorimetry (ITC) measurements. It was observed that Hb stays neither in its native state nor in its fully denatured state; rather, it achieves an intermediate state in the presence of ChAAILs. The research on the intermediate state of Hb is still unexplored. Research has been pursued to find a suitable ligand or IL that can stabilize the intermediate state of Hb. In that context, ChAAILs are among the best choices. Molecular docking studies unravel the binding of ChAAILs with Hb. The obtained binding energies of the docked complex are −7.2 kcal/mol and −8.7 kcal/mol for binding of Hb with [Chl][Gly] and [Chl][Met], respectively, which was in line with the ITC results. The quantum chemical calculations show that H‐bond plays a significant role for the interaction between Hb and ChAAILs.
Chiral Pyrrolidinium Ionic Liquids with (−)‐Borneol Fragment in the Cation – Synthesis, Physicochemical Properties and Application in Diels‐Alder Reaction
Authors: Gano Marcin , Janus Ewa , Schilf Wojciech 
Published: June 2023

AbstractA series of chiral pyrrolidinium salts containing (1 S)‐endo‐(−)‐born‐2‐yloxymethyl substituent in the structure of the cation and six different anions: chloride, tetrafluoroborate [BF4]−, hexafluorophosphate [PF6]−, trifluoromethanesulfonate [OTf]−, bis(trifluoromethylsulfonyl)imide [NTf2]−, bis(pentafluoroethylsulfonyl)imide [NPf2]− and perfluorobutanesulfonate [C4FS]− were efficiently prepared and extensively characterized. The enantiomeric purity of them was confirmed by NMR analysis with a chemical shift reagent. All salts were characterized with the specific rotation, the solubility in commonly used solvents, thermal properties, including phase transition temperatures and thermal stability. Salts with [PF6]−, [C4FS]−, [NTf2]− and [NPf2]− anions were classified as chiral ionic liquids (CILs). Moreover, salts with [NTf2]− and [NPf2]− anions were in the liquid state at room temperature and below. Therefore, density and dynamic viscosity, the surface tension and the contact angle on three different surfaces were also measured for them. Additionally, these chiral ionic liquids were tested as solvents in Diels‐Alder reaction.