bluuebunny/crossref_metadata_2025_split huggingface dataset:
[3+2] Cycloaddition of Alkynyl Boronates and in situ Generated Azomethine Ylide
Authors: Liashuk Oleksandr S. , Ryzhov Ihor A. , Hryshchuk Oleksandr V. , Volovenko Yulian M. , Grygorenko Oleksandr O. 
Published: December 2023

AbstractScalable [3+2] cycloaddition of alkynyl boronates and in situ generated unstabilized azomethine ylide is reported for the first time. The selective formation of either 1 : 1 or 1 : 2 cycloaddition products was achieved by carefully optimizing the reaction conditions, mainly by controlling the reactant stoichiometry, catalyst loading, and internal temperature. The developed protocol tolerated many valuable functional groups, including TMS, protected alcohol (as ether or THP derivatives), or aldehyde (as acetal). Further common C−C and C−heteroatom bond‐forming reactions, as well as scaled‐up procedures demonstrate the utility of the prepared compounds as building blocks for organic synthesis and drug discovery.
The impact of stoichiometry on the initial steps of crystal formation: Stability and lifetime of charged triple‐ion complexes
Authors: Koskamp Janou A. , Seepma Sergěj Y. M. H. , Peters Vincent F. D. , Toroz Dimitrios , Di Tommaso Devis , Wolthers Mariette 
Published: December 2023

AbstractMinerals form in natural systems from solutions with varying ratios of their lattice ions, yet non‐stoichiometric conditions have generally been overlooked in investigations of new formation (nucleation) of ionic crystals. Here, we investigated the influence of cation:anion ratio in the solution on the initial steps of nucleation by studying positively and negatively charged triple ion complexes and subsequent particle size evolution. Our model systems are carbonates and sulfates of calcium and barium, as it was recently shown that solution stoichiometry affects the timing and rate of their nucleation. Molecular dynamics (MD) simulations and dynamic light scattering (DLS) flow experiments show that nucleation correlates with the stability and lifetime of the initial complexes, which were significantly impacted by the cation:anion stoichiometry and ion type. Specifically,
was found to have higher association constants and its lifetime was twofold longer than
. Similar trends were observed for
and
. Contrastingly, for
,
was found to have lower association constants and its lifetime was shorter than
. These trends in stability and lifetime follow the same asymmetrical behaviour as observed experimentally for particle formation using techniques like DLS. This suggests a causal relationship between the stability and lifetime of the initial charged complexes and the nucleation under non‐stoichiometric conditions.
Digitalisierung und Simulation sind Teil der Lösung
Authors: Bortz Michael 
Published: December 2023

AbstractWelchen Beitrag kann die Wissenschaft leisten, den großen wirtschaftlichen Veränderungen zu begegnen, denen sich insbesondere die chemische Industrie aktuell stellen muss? Antworten zeigte der zweitägige Workshop “Mathematical Methods in Process Industry” Anfang Oktober am Fraunhofer‐Institut für Techno‐ und Wirtschaftsmathematik ITWM in Kaiserslautern auf. Im Diskurs zeigten Vertreter von Wirtschaft und Wissenschaft Lösungswege auf, die auf Digitalisierung und Simulation basieren und sich in der Praxis anwenden lassen.
Scale‐up begaster Fermenter
Authors: Gezork Klaus , Schorn Annika , Bußmann Niels 
Published: December 2023

AbstractBesonders unter anspruchsvollen Betriebsbedingungen und bei hohen Produktionskapazitäten haben sich gerührte und begaste Fermenter aufgrund ihrer hervorragenden Leistung und Flexibilität weitgehend durchgesetzt. Die langjährige Erfahrung von Ekato und Forschung an diesen Fermentertypen haben das Verständnis erheblich vertieft.
Mit der richtigen Formel vor Cyberangriffen schützen
Authors: Rausse Dirk 
Published: December 2023

AbstractDaten aus Industrieunternehmen sind ein lukratives Ziel für Angreifer, die inzwischen vermehrt auch KI‐Tools einsetzen. Während sich vernetzte Anlagen und Systeme zum Beispiel durch Firewalls, Antivirenprogramme und Co. gegen Hackerangriffe schützen lassen, gibt es noch einen weiteren bedeutenden Risikofaktor: die Mitarbeiter. Für einen effektiven Schutz vor Cybercrime, ist ein regelmäßiges Training nützlich, um für Phishing zu sensibilisieren und den Umgang mit KI‐Tools zu schulen.
Flüchtige Emissionen reduzieren
Authors: Dixon Matt 
Published: December 2023

AbstractDie meisten Anlagenbetreiber streben angesichts heutiger Umweltschutzvorhaben nach einem Netto‐Null‐Ziel. Dieses zu erreichen ist mitunter ein schwieriges Unterfangen. In Raffinerien und Chemieanlagen kann es an vielen Stellen zu einer unbeabsichtigten Freisetzung von Emissionen kommen. Hier spricht man auch von flüchtigen Emissionen. Diese stehen zunehmend im Fokus der Aufsichtsbehörden, was Anlagenbetreiber zusätzlich antreibt, sie zu reduzieren oder gar vollständig zu beseitigen.
Unterbrechungsfreie Gasversorgung
Authors: Karolius Frank‐Detlef 
Published: December 2023

AbstractScheinbar simpel, stellt die Versorgung mit technischen Gasen Nutzer schnell vor technische und logistische Herausforderungen, die innovative und verlässliche Lösungen erfordern. Eine solche Lösung sind Druckregelventile, die die Versorgung mit technischen Gasen in der geforderten Menge selbst bei einem Ausfall von Strom und Instrumentenluft durch eine mechanische Regelung sicherstellen.
In der Praxis erprobt
Authors: Fröhlich Dominik 
Published: December 2023

AbstractWasserstoff gilt als umweltfreundlicher Energieträger der Zukunft, weil er sehr flexibel einsetzbar ist, mit regenerativen Technologien hergestellt werden kann und sich gut transportieren sowie speichern lässt. Fluidische Komponenten, wie Ventile oder Durchflussregler, sind in der gesamten Wertschöpfungskette unerlässlich, bei der Wasserstofferzeugung ebenso wie bei der ‐verteilung und ‐nutzung.
Recent Advances in Pd‐Catalyzed Reactions Involving the “On‐Water” Mechanism†
Authors: Wei Dong , Lin Guo‐Qiang 
Published: December 2023

Comprehensive SummaryAs the chemical industry grapples with the need for more eco‐friendly practices, the use of water as a reaction medium is gaining attraction in organic transformations. This mini‐review delves into Pd‐catalyzed reactions that utilize the "on‐water" mechanism, spanning from 2019 to late 2023. These reactions are neatly categorized into several types: (A) Catalytic C—H activations, (B) Mizoroki‐ Heck‐type reactions, (C) Suzuki‐Miyaura reactions, and (D) Cyclization reactions. By showcasing the potential of water as a sustainable reaction medium for organic transformations, these reactions leave no doubt about the importance of embracing eco‐friendly practices in the chemical industry.
Key ScientistsIn 1980, a seminal work by Breslow et al. showed an acceleration of reaction rate in the Diels‐Alder reaction. Sharpless and co‐workers noted a significant increase in the rate of the [2σ+2σ+2π] cycloaddition of quadricyclane and dimethyl azodicarboxylate (DMAD) when the reaction was conducted in water, as opposed to when it was carried out in organic solvents. The term "on‐water" was then coined to describe this phenomenon. This strategy was further expanded to transition‐metal catalyzed transformations by Ackermann in 2011. Later, Varma and Leazer disclosed a Pd‐catalyzed Mizoroki‐Heck type arylation of alkenes with diaryliodonium salts “on‐water”. The enantioselective version of "on‐water" process was not realized until 2014 by the Zhou group. Later on, the Schaub group described a Pd‐catalyzed Suzuki–Miyaura coupling reaction of electron‐poor aryl chlorides with water, using only 50 ppm of catalyst loading. Very recently, Liu and Lin extended the "on‐water" strategy to Pd‐catalyzed double Mizoroki‐Heck reactions. This mini‐review has focused on Pd‐catalyzed reactions involving the “on‐water” mechanism.
Recent Advances in C—F Bond Formation from Carbon‐Centered Radicals
Authors: Zhang Jihua , Wang Juanjuan , Cheng Qiang 
Published: December 2023

Comprehensive SummaryConstruction of C—F bonds is a direct and efficient method for introducing fluorine into pharmaceuticals, agrochemicals, and materials. Strategies such as nucleophilic, electrophilic, radical, and transition‐metal catalyzed fluorination have been developed to meet the demand of diverse C—F bond formation. Among them, radical fluorination has been witnessed with substantial advancement in a recent decade. Herein, we reviewed methods for formation of C—F bonds with carbon‐centered radicals as key intermediates, especially in recent five years. We introduce in the paper with different fluorinating reagents, strategies for radical generation, and application in late‐stage functionalization and synthesis of PET tracers. We also indicate the current limitations and propose the direction of the field for the future development.
Key ScientistsRadical fluorination was recognized as an old and uncontrolled reaction that may date back to the time when element fluorine was first mixed with organic compounds by Henri Moissan in 1891. The development of the field was slow in combination with discovery of new fluorinating reagents. Substantial changes took place in 2012, when the first example of carbon radical fluorination with robust and mild fluorinating reagents, such as NFSI and Selectfluor, was reported by the Sammis group. In the same year, Groves, Lectka, Li, and Boger led the pioneering works on aliphatic C—H fluorination, decarboxylative fluorination, and fluorofunctionalization of alkenes in a radical manner. Photoredox catalysis was introduced to radical fluorination in 2013 by the Chen group, which opens up a new avenue for diverse fluorinative transformations. Most of the previous works focus on radical fluorination to form C(sp3)–F bonds. In 2018, the challenging non‐directed aromatic C—H fluorination was solved by Ritter and coworkers. Direct arene fluorination with fluoride ion was later disclosed by the Nicewicz group in 2019. There are many other scientists that have also made tremendous contribution to the development of radical fluorination, with too limited space to list them all. We only list those with first discoveries that may point to the new direction of radical fluorination.
Nanomedicine Disrupts Stromal Barriers to Augment Drug Penetration for Improved Cancer Therapy†
Authors: Luo Guo‐Feng , Chen Wei‐Hai , Zhang Xian‐Zheng 
Published: December 2023

Comprehensive SummaryTumor stroma composing diverse extracellular matrixes (ECM) and
stromal cells shapes a condensed physical barrier, which severely hampers the efficient accessibility of nanomedicine to tumor cells, especially these deep‐seated in the core of tumor. Such barrier significantly compromises the antitumor effects of drug‐loaded nanomedicine, revealing the remarkable importance of disrupting stromal barrier for improved tumor therapy with deep penetration ability. To achieve this goal, various nanoparticle‐based strategies have been developed, including direct depleting ECM components via delivering anti‐fibrotic agents or targeting stromal cells to suppress ECM expression, dynamic regulation of nanoparticles’ physicochemical properties (i.e., size, surface charge, and morphology), mechanical force‐driven deep penetration, natural/biomimetic self‐driven nanomedicine, and transcytosis‐inducing nanomedicine. All these nanostrategies were systemically summarized in this review, and the design principles for obtaining admirable nanomedicine were included. With the rapid development of nanotechnology, elaborate design of multifunctional nanomedicine provides new opportunities for overcoming the critical stromal barriers to maximize the therapeutic index of various therapies, such as chemotherapy, photodynamic therapy, and immunotherapy.
Key ScientistsIn 2006, Chan et al. demonstrated that the size and shape of nanoparticles were important for biomedical applications, such as intracellular delivery rate and tissue penetration. In addition, the degradation of the structural collagen was confirmed to increase the diffusion of nanoparticles and macromolecules by Davies et al. in 2010. These findings reveal the importance of chemophysical properties of nanoparticles in determining their diffusion and the critical roles of stromal barrier in hindering nanoparticles penetration. On the basis of this, photoswitchable nanoparticles were developed by Kohane et al. for triggered tissue penetration and efficient drug delivery. In 2015, Nie et al. reported the targeted depletion of cancer‐associated fibroblasts by peptide assembly for enhanced antitumor drug delivery. In 2019, Shen et al. proposed the transcytosis strategy to promote the tumor penetration of nanoparticles. Very recently, Luo et al. reported the specific reversing of the biological function of cancer‐associated fibroblasts to suppress the generation of stromal matrix, greatly increasing the drug perfusion in tumor tissue. All these strategies fueled the design and construction of function‐specific nanoparticles for tumor therapy.
MMP‐2 regulates Src activation via repression of the CHK/MATK tumor suppressor in osteosarcoma
Authors: Maybee Deanna V. , Cromwell Christopher R. , Hubbard Basil P. , Ali Mohammad A. M. 
Published: December 2023

AbstractBackgroundDoxorubicin, a first‐line anticancer drug for osteosarcoma treatment, has been the subject of recent research exploring the mechanisms behind its chemoresistance and its ability to enhance cell migration at sublethal concentrations. Matrix metalloproteinase‐2 (MMP‐2), a type IV collagenase and zinc‐dependent endopeptidase, is well‐known for degrading the extracellular matrix and promoting cancer metastasis. Our previous work demonstrated that nuclear MMP‐2 regulates ribosomal RNA transcription via histone clipping, thereby controlling gene expression. Additionally, MMP‐2 activity is regulated by the non‐receptor tyrosine kinase and oncogene, Src, which plays a crucial role in cell adhesion, invasion, and metastasis. Src kinase is primarily regulated by two endogenous inhibitors: C‐terminal Src kinase (Csk) and Csk homologous kinase (CHK/MATK).AimIn this study, we reveal that the MMP‐2 gene acts as an upstream regulator of Src kinase activity by suppressing its endogenous inhibitor, CHK/MATK, in osteosarcoma cells.Methods and ResultsWe show that enhanced osteosarcoma cell migration which is induced by sublethal concentrations of doxorubicin can be overcome by inactivating the MMP‐2 gene or overexpressing CHK/MATK. Our findings highlight the MMP‐2 gene as a promising additional target for combating cancer cell migration and metastasis. This is due to its role in suppressing on the gene and protein expression of the tumor suppressor CHK/MATK in osteosarcoma.ConclusionBy targeting the MMP‐2 gene, we can potentially enhance the effectiveness of doxorubicin treatment and reduce chemoresistance in osteosarcoma.
Local adaptation and broad performance are synergistic to productivity in modern barley
Authors: Ewing Patrick M. , Kantar Michael B. , Killian Erik , Neyhart Jeffrey L. , Sherman Jamie D. , Williams Jessica L. , Lachowiec Jennifer A. , Eberly Jed O. 
Published: December 2023

AbstractCrop populations have enormous impacts on agricultural productivity, yet decelerating gains from breeding suggest that selection strategies need to be reconsidered to better align priorities of breeders and growers. Breeders benefit from releasing broadly adapted varieties that perform acceptably well across their target region; growers benefit from selecting a variety that specializes in their specific location. We tested whether these interests are compatible using 182 entries in a mega‐population of malting barley (spring, two‐row, multi‐environment trial [S2MET] population; Hordeum vulgare L.), which was grown across the northern United States. We assessed the strength of genetic–environment interactions (G×E), quantified local adaptation benefits, and tested whether local adaptation and genetic yield potential were correlated. Breeding programs favored broad adaptation (p < 0.001). Still, 63% of entries (114) were among the top 10%, best performing at some locations, and among the worst 10% at others. Some of the best overall entries were specialists, performing especially well in their home locations, and in general, genetic potential and local specialization were positively correlated (p < 0.001). These results suggest that breeding for local performance and broad performance are mutually supporting goals. Releasing broadly excellent, locally exceptional varieties may accelerate genetic gain to meet projected global agricultural demand.
Exploring ‘Future three’ curriculum scenarios in practice: Learning from the GeoCapabilities project
Authors: Béneker T. , Bladh G. , Lambert D. 
Published: December 2023

AbstractThis paper has its origins in the EU Comenius funded GeoCapabilities project. From its outset, the project developed and researched the notion of powerful disciplinary knowledge (PDK) as an underlying principle of curriculum making in the context of secondary school geography teaching. The work, led from the UCL Institute of Education and involving school teachers, teacher educators and other stakeholders across eight mainly European jurisdictions, was framed by Young and Muller's ‘three educational scenarios’ (Young & Muller, European Journal of Education, 45, 2010 and 11). The three futures heuristic is discussed as a means to distinguish qualities of curriculum thought. Future 3 scenarios, which posit teachers as curriculum makers with responsibility to engage in essential ‘knowledge work’, provide a principled platform on which to develop ambitious educational classroom encounters. Knowledge working with PDK and (as we go on to argue) other powerful ways of knowing the world, is seen as a bridge between social realist epistemological principles and practical classroom content selections. This opens the possibility of responding to Deng's (Journal of Curriculum Studies, 54, 2022) call for developing practical theories of content with teachers. Although the authors are geographers in education drawing on different international perspectives and traditions, the paper addresses matters of interest applicable to a variety of specialist subject domains across the secondary school curriculum.
A long‐term study of size variation in Northern Goshawk Accipiter gentilis across Scandinavia, with a focus on Norway
Authors: Walker Samuel J. , Lislevand Terje , Meijer Hanneke J. M. 
Published: December 2023

AbstractChanging climate and growing human impacts are resulting in globally rising temperatures and the widespread loss of habitats. How species will adapt to these changes is not well understood. The Northern Goshawk (Accipiter gentilis) can be found across the Holarctic but is coming under more intense pressure in many places. Studies of recent populations in Finland and Denmark have shown a marked decline in body size of Northern Goshawks over the past century. Here we investigate long‐term changes to Norwegian populations of Northern Goshawk by including material from the Middle Ages. We measured 240 skeletons of modern Northern Goshawks from Norway, Sweden, Denmark and Finland, and 89 Medieval Goshawk bones. Our results show that Norwegian and Swedish female Goshawks have decreased in size over the past century, whilst males showed little decline. Medieval female Goshawks were larger than contemporary females. A decline in forest habitats and a concomitant shift towards smaller prey likely drove a shift to smaller body size in Northern Goshawks. Our study shows that significant body size changes in birds can occur over relatively short time spans in response to environmental factors, and that these effects can sometimes differ between sexes.
A neural network model for rapid prediction of analyte focusing in isotachophoresis
Authors: Jangra Amit , Shriyam Shaurya , Santiago Juan G. , Bahga Supreet Singh 
Published: December 2023

AbstractWe present the development and demonstration of a neural network (NN) model for fast and accurate prediction of whether or not a chosen analyte is focused by an isotachophoresis (ITP) buffer system. The NN model is useful in the rapid evaluation of possible ITP chemistries applicable to analytes of interest. We trained and tested the NN model for univalent species based on extensive data sets of over 10,000 anionic and 10,000 cationic ITP simulations. The NN model uses as inputs the mobilities and the acid dissociation constants of leading electrolyte ion, trailing electrolyte ion, counterion, and a single analyte as well as the leading‐to‐counterion concentration ratio of the leading zone. The output then indicates whether the chosen electrolyte system yields stable ITP focusing of the analyte. The prediction accuracy of the NN model is over 97.7%. We demonstrate the applicability of the NN by validating its predictions with reported experimental data for anionic and cationic ITP. We have packaged the NN model in a free, web‐based application named IONN (isotachophoresis on neural network), which can be used to rapidly screen ITP electrolyte systems.
The 1870s Saskatchewan River avulsion: Ice jam or open water flood? A probabilistic approach for cold climate river avulsions
Authors: Kupferschmidt Cody , Arnaud Emmanuelle 
Published: December 2023

AbstractCold climate rivers can experience avulsions due to both open water and ice jam flooding; however, most existing models for evaluating avulsions only consider open water flows. We present a novel approach for determining site‐specific probabilities of avulsion cause (open water vs. ice jam flooding) by combining historical flow data, channel cross‐sections and known avulsion history for the study area. The approach is applied to the Cumberland Marshes region of the Saskatchewan River in Central Canada, which experienced an avulsion in the mid‐1870s that some researchers have suggested may have been triggered by an ice jam. For the study area, overbank flooding was found to occur much more frequently due to ice jams than open‐water floods. Based on an average avulsion return period of 660 years in the study area, the probability of historical avulsions being caused by ice jam flooding was estimated to range from 61% and 80%, using a range of annual ice jam probabilities between 0.1 and 0.5. Results from the study suggest ice jam flooding as the most likely cause of the 1870s avulsion, which is also supported by historical evidence. The developed methodology is relatively simple to apply and could be easily implemented at other cold‐climate sites to evaluate avulsion risks.