bluuebunny/crossref_metadata_2025_split huggingface dataset:
Redox tolerance and metabolic reprogramming in solid tumors
Authors: Mortezaee Keywan 
Published: November 2020

AbstractTumor cells need to cope with the host environment for survival and keep growing in hard conditions. This suggests that tumors must acquire characteristics more potent than what is seen for normal tissue cells, without which they are condemned to disruption. For example, cancer cells have more potent redox tolerance compared with normal cells, which is due to their high adaptation to an oxidative crisis. In addition, increased demand for bioenergetics and biosynthesis can cause a rise in nutrient uptake in tumors. Utilizing nutrients in low nutrient conditions suggests that tumors are also equipped with adaptive metabolic processes. Switching the metabolic demands toward glucose consumption upon exposure to the hypoxic tumor microenvironment, or changing toward using other sources when there is an overconsumption of glucose in the tumor area are examples of fitness metabolic systems in tumors. In fact, cancer cells in cooperation with their nearby stroma (in a process called metabolic coupling) can reprogram their metabolic systems in their favor. This suggests the high importance of stroma for meeting the metabolic demands of a growing tumor, an example in this context is the metabolic symbiosis between cancer‐associated fibroblasts with cancer cells. The point is that redox tolerance and metabolic reprogramming are interrelated, and that, without a doubt, disruption of redox tolerance systems by transient exposure to either oxidative or antioxidative loading, or targeting metabolic rewiring by modulation of tumor glucose availability, controlling tumor/stroma interactions, etc. can be effective from a therapeutic standpoint
Crystallographic Visualization of a Double Water Molecule Addition on a Pt1‐MOF during the Low‐temperature Water‐Gas Shift Reaction
Authors: Bilanin Cristina , Tiburcio Estefanía , Ferrando‐Soria Jesús , Armentano Donatella , Leyva‐Pérez Antonio , Pardo Emilio 
Published: November 2020

AbstractThe low‐temperature water‐gas shift reaction (WGSR, CO+H2O ⇔ H2+CO2) is considered a very promising reaction ‐candidate for fuel cells‐ despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt1) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H2O molecule to CO, with generation of CO2 and H2. Here we show, experimentally, that not one but two H2O molecules are added to CO on the Pt1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measurements, and finally by in‐operando single crystal X‐ray diffraction on a Pt1‐MOF, to visualize the formation of the hemiacetal intermediate on the solid catalytic site. These results confirm our previous DFT predictions and provide a paradigmatic shift in the assumed mechanism of the WGSR, which may open the debate if two H2O molecules are recurrently added during the WGSR, not only for Pt1 catalysts but also for other metal catalysts.
A Compartmentalized‐type Bifunctional Magnetic Catalyst for One‐pot Aerobic Oxysulfonylation and Asymmetric Transfer Hydrogenation
Authors: Wang Shitong , Wang Chengyi , Lv Ning , Tan Chunxia , Cheng Tanyu , Liu Guohua 
Published: November 2020

AbstractUtilization of the confined cavity of the mesoporous silica, the exploration of the synergetic catalysis process for sequential organic transformations has great significance in asymmetric catalysis. In this study, the yolk‐shell‐structured magnetic nanoparticles with the chiral Ru/diamine species within the nanochannels of the outer mesoporous silica shell and the FeCl3 species on the inner magnet core are fabricated. The electron microscopy images and the structural characterizations disclose the uniformly distributed magnetic nanoparticles with the well‐defined single‐site ruthenium/diamine active centers onto the outer silica shell. As a yolk‐shell‐structured bifunctional magnet catalyst, the FeCl3 species enables an efficient aerobic oxysulfonylation between aryl‐substituted terminal alkynes and sodium sulfinates to the β‐keto sulfones intermediates, and the ruthenium/diamine species sequentially reduces the in‐situ generated intermediate to the chiral β‐hydroxysulfones products. As we envision, this one‐pot aerobic oxysulfonylation/asymmetric transfer hydrogenation process affords various chiral β‐hydroxysulfones in high yields with excellent enantioselectivities. Furthermore, this magnetic catalyst can also be conveniently recovered via an additional outer magnet and repeatedly recycled, showing a potential application in industrial interest.
Ruthenium‐Catalyzed Secondary Amine Formation Studied by Density Functional Theory
Authors: Hückmann Lukas , Álvarez‐Barcia Sonia , Fuhrer Marina , Plietker Bernd , Kästner Johannes 
Published: November 2020

AbstractAmines are a ubiquitous class of compounds found in a variety of functional organic building blocks. Within the past years, hydrogen autotransfer catalysis has evolved as a new concept for the synthesis of amines. A through understanding of the mechanism of these reactions is necessary to design optimal catalysts. We investigate secondary amine formation catalyzed by a NNNN(P)Ru‐complex and provide understanding on the three reaction steps involved. We find that the ligand has to open one coordination site in order to allow the formation of a metal hydride intermediate. In a second step, a condensation reaction, which could also happen uncatalyzed in solution, is significantly enhanced by the presence of the ruthenium complex. The back‐transfer of the hydride to the substrate in a third step regenerates the catalyst.
Bond between concrete and rigid foam in precast concrete sandwich construction
Authors: Metje Kevin , Leutbecher Torsten , Weimar Thorsten , Hammer Christian 
Published: November 2020

AbstractIn precast concrete sandwich construction mechanical connectors are used to transfer loads between the two concrete shells. Omitting these connectors seems economically interesting for realizing novel sandwich elements with lightweight facings made of textile‐reinforced concrete or other materials. Then, the adhesion between the isolating layer and the cover layers becomes the decisive parameter. In order to evaluate the basic influence of surface texture and type of concrete on the bond strength, an experimental study including different rigid foams and ordinary performance concrete (OPC) as well as ultra‐high performance concrete (UHPC) was carried out. The results of 120 tensile bond tests and 30 shear tests on concrete‐rigid foam composites show that technically relevant bond strengths can be achieved by pouring the concrete onto the rigid foam. For OPC, the tensile bond strength is 50% higher than the minimum value required for external thermal insulation composite systems without mechanical connectors. For UHPC significantly higher bond strengths are obtained, which can be attributed to a better micromechanical interlock. In some cases, the strength of the composite was limited by the strength of the foam. The results are valuable for identifying promising rigid foam‐concrete configurations.
Use of Crown Ether Functions as Secondary Coordination Spheres for the Manipulation of Ligand–Metal Intramolecular Electron Transfer in Copper–Guanidine Complexes
Authors: Haaf Sebastian , Kaifer Elisabeth , Wadepohl Hubert , Himmel Hans‐Jörg 
Published: November 2020

AbstractInvited for the cover of this issue is the group of Hans‐Jörg Himmel at Ruprecht‐Karls‐Universität Heidelberg. The image depicts the electron transfer process using copper complexes with redox‐active guanidines. Read the full text of the article at 10.1002/chem.202003469.
Covalent Cross‐Linking of 2H‐MoS2 Nanosheets
Authors: Vázquez Sulleiro Manuel , Quirós‐Ovies Ramiro , Vera‐Hidalgo Mariano , Gómez I. Jénnifer , Sebastián Víctor , Santamaría Jesús , Pérez Emilio M. 
Published: November 2020

AbstractThe combination of 2D materials opens a wide range of possibilities to create new‐generation structures with multiple applications. Covalently cross‐linked approaches are a ground‐breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross‐linking method to build 2H‐MoS2–MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide‐based 2D materials.
2‐ and 2,7‐Substituted para‐N‐Methylpyridinium Pyrenes: Syntheses, Molecular and Electronic Structures, Photophysical, Electrochemical, and Spectroelectrochemical Properties and Binding to Double‐Stranded (ds) DNA
Authors: Kole Goutam Kumar , Merz Julia , Amar Anissa , Fontaine Bruno , Boucekkine Abdou , Nitsch Jörn , Lorenzen Sabine , Friedrich Alexandra , Krummenacher Ivo , Košćak Marta , Braunschweig Holger , Piantanida Ivo , Halet Jean‐François , Müller‐Buschbaum Klaus , Marder Todd B. 
Published: November 2020

AbstractTwo N‐methylpyridinium compounds and analogous N‐protonated salts of 2‐ and 2,7‐substituted 4‐pyridyl‐pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm−1. The N‐methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc+ in MeCN. While the reduction process was reversible for the 2,7‐disubstituted compound, it was irreversible for the mono‐substituted one. Experimental findings are complemented by DFT and TD‐DFT calculations. Furthermore, the N‐methylpyridinium compounds show strong interactions with calf thymus (ct)‐DNA, presumably by intercalation, which paves the way for further applications of these multi‐functional compounds as potential DNA‐bioactive agents.
General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones
Authors: Schönauer Timon , Thomä Sabrina L. J. , Kaiser Leah , Zobel Mirijam , Kempe Rhett 
Published: November 2020

AbstractThe development of C−N bond formation reactions is highly desirable due to their importance in biology and chemistry. Recent progress in 3d metal catalysis is indicative of unique selectivity patterns that may permit solving challenges of chemical synthesis. We report here on a catalytic C−N bond formation reaction—the reductive alkylation of nitriles. Aldehydes or ketones and nitriles, all abundantly available and low‐cost starting materials, undergo a reductive coupling to form secondary alkylamines and inexpensive hydrogen is used as the reducing agent. The reaction has a very broad scope and many functional groups, including hydrogenation‐sensitive examples, are tolerated. We developed a novel cobalt catalyst, which is nanostructured, reusable, and easy to handle. The key seems the earth‐abundant metal in combination with a porous support material, N‐doped SiC, synthesized from acrylonitrile and a commercially available polycarbosilane.
Personal social responsibility: Scale development and validation
Authors: Davis Sylvia López , Rives Longinos Marín , Ruiz‐de‐Maya Salvador 
Published: November 2020

AbstractAlthough the literature on consumer behavior has addressed tendencies toward responsible consumption, no research has analyzed responsible behavior as a multidimensional construct in areas not related to consumption, such as paying taxes, children's education, and recycling. It is necessary to develop the concept of personal social responsibility (PSR), which includes human behavior as a whole, beyond consumption. This research develops a reliable and valid scale to measure PSR, a concept that comprises individual behaviors from the perspective of the individual as a citizen. Study 1 (n = 138) suggests that the construct of PSR is made up of the economic, legal, ethical, philanthropic, and environmental dimensions of individual behavior. Study 2 (n = 212) demonstrates the external validity of the scale, revealing that perceived consumer effectiveness and collectivism have a positive influence on personal responsibility behaviors, and that being more responsible leads to higher levels of self‐esteem and satisfaction with life.
Porphyromonas gingivalis and Lactobacillus rhamnosus GG regulate the Th17/Treg balance in colitis via TLR4 and TLR2
Authors: Jia Lu , Wu Ruiqing , Han Nannan , Fu Jingfei , Luo Zhenhua , Guo Lijia , Su Yingying , Du Juan , Liu Yi 
Published: November 2020

AbstractObjectivesCD4+ T cells are the key to many immune–inflammatory diseases mediated by microbial disorders, especially inflammatory bowel disease (IBD). The purpose of this study was to explore how pathogenic and probiotic bacteria directly affect the T helper (Th)17 and T regulatory (Treg) cell balance among CD4+ T cells to regulate inflammation.MethodsPorphyromonas gingivalis (Pg; ATCC 33277) and Lactobacillus rhamnosus GG (LGG; CICC 6141) were selected as representative pathogenic and probiotic bacteria, respectively. Bacterial extracts were obtained via ultrasonication and ultracentrifugation. Flow cytometry, RT‐qPCR, ELISAs, immunofluorescence and a Quantibody cytokine array were used. The dextran sodium sulphate (DSS)‐induced colitis model was selected for verification.ResultsThe Pg ultrasonicate induced the apoptosis of CD4+ T cells and upregulated the expression of the Th17‐associated transcription factor RoRγt and the production of the proinflammatory cytokines IL‐17 and IL‐6, but downregulated the expression of the essential Treg transcription factor Foxp3 and the production of the anti‐inflammatory factors TGF‐β and IL‐10 via the TLR4 pathway. However, LGG extract maintained Th17/Treg homeostasis by decreasing the IL‐17+ Th17 proportion and increasing the CD25+ Foxp3+ Treg proportion via the TLR2 pathway. In vivo, Pg‐stimulated CD4+ T cells aggravated DSS‐induced colitis by increasing the Th17/Treg ratio in the colon and lamina propria lymphocytes (LPLs), and Pg + LGG‐stimulated CD4+ T cells relieved colitis by decreasing the Th17/Treg ratio via the JAK‐STAT signalling pathway.ConclusionsOur findings suggest that pathogenic Pg and probiotic LGG can directly regulate the Th17/Treg balance via different TLRs.
Proteolysis targeting chimera (PROTAC) for epidermal growth factor receptor enhances anti‐tumor immunity in non‐small cell lung cancer
Authors: Wang Kai , Zhou Hongping 
Published: November 2020

AbstractWhile immunotherapy has dramatically revolutionized the treatment of non‐small cell lung cancer (NSCLC), it still faces challenges such as low therapeutic efficacy and immune‐related adverse events, indicating that safe and effective approaches to enhance NSCLC immunotherapy are still highly demanded. Epidermal growth factor receptor (EGFR) is an established target for molecularly targeted therapy of NSCLC. Overexpression and activating mutations of EGFR can promote the resistance of NSCLC to immunotherapy via upregulating inhibitory immune checkpoints such as programmed death receptor ligand 1 (PD‐L1) and indoleamine‐2,3‐dioxygenase‐1 (IDO1). Thus, therapeutic inhibition of EGFR also holds promise in modulating the immune microenvironment to advance NSCLC immunotherapy. In this study, we employed a proteolysis targeting chimera (PROTAC) that degrades EGFRL858R to investigate its potential in dually inhibiting PD‐L1 and IDO1 to potentiate the anti‐tumor immunity in NSCLC. We demonstrated that PROTAC significantly downregulated the protein levels of both PD‐L1 and IDO1 in NSCLC H3255 cell and tumor. We also confirmed that PROTAC significantly suppressed the H3255 tumor growth and enhanced the anti‐tumor immune response in H3255 tumor. Overall, our study provides a novel strategy for future NSCLC therapy.
Detection of ethinyl estradiol and resorcylic acid lactones in poultry meat according to the national residue plan
Authors: Annunziata Loredana , Visciano Pierina , De Massis Maria Rosaria , Schirone Maria , Colagrande Maria Novella , Campana Guido , Migliorati Giacomo 
Published: November 2020

AbstractThe aim of this study was the detection of ethinyl estradiol and resorcylic acid lactones (zeranol and taleranol) in poultry meat samples as unauthorized substances included in the Italian national residue plan. The samples were purified by a solid phase extraction using a C18 column combined with alumina, and the analytes were detected by two specific enzyme‐linked immunosorbent assay (ELISA) kits. As they were collected in the frame of official control activities, the method was also validated according to the Commission Decision 2002/657/EC requirements for screening methods with qualitative purpose. Specificity and detection capability were the performance criteria considered for the validation study, and the latter parameter showed a value of 0.5 μg/kg for both the investigated compounds. Such result was well comparable with the data reported by using chromatographic techniques as confirmation methods, and therefore, the ELISA kits tested in this study could be used for the screening of large numbers of samples.
Demographic modeling to fine‐tune conservation targets: importance of pre‐adults for the decline of an endangered raptor
Authors: Sergio Fabrizio , Tavecchia Giacomo , Blas Julio , Tanferna Alessandro , Hiraldo Fernando 
Published: November 2020

AbstractLarge, long‐lived species with slow life histories and protracted pre‐breeding stages are particularly susceptible to declines and extinction, often for unknown causes. Here, we show how demographic modeling of a medium‐sized raptor, the Red Kite Milvus milvus, can aid to refocus conservation research and attention on the most likely mechanisms driving its decline. Red Kites’ survival and reproduction increased through three sequential stages for 1–2, 3–6, and 7–30 yr of age, mainly corresponding to individuals that are dispersing, attempting to gain a territory, and breeding. As typical of long‐lived species, elasticities were highest for adult (≥7 yr old) survival, but this was high, with little scope for improvement. Instead, the declines were driven by an extremely low survival of pre‐adults in their first years of life, which weakened the whole demographic system by nullifying the offspring contribution of adults and curtailing their replacement by recruits. For example, 27 pairs were necessary to generate a single prime age adult. Simulation of management scenarios suggested that the decline could be halted most parsimoniously by increasing pre‐adult survival to the mean levels recorded for other areas, while only the synergistic, simultaneous improvement of breeding success, adult and pre‐adult survival could generate a recovery. We propose three actions to attain such goals through selective supplementary feeding of both breeding and non‐breeding individuals, and through mortality improvement by GPS remote‐sensing devices employed as surveillance monitoring tools. Our results show how improving demographic models by using real, local vital rates rather than “best guess” vital rates can dramatically improve model realism by refocusing attention on the actual stages and mortality causes in need of manipulation, thus building precious time and resources for conservation management. These results also highlight the frequent key role of pre‐adult survival for the management of long‐lived species, coherent with the idea of demographic systems as integrated chains only as strong as their weakest link.
Disparities in the characteristics and outcomes of patients hospitalized with acute decompensated heart failure admitted to internal medicine and cardiology departments: a single‐centre, retrospective cohort study
Authors: Maymon Shiri Lea , Moravsky Gil , Marcus Gil , Shuvy Mony , Pereg David , Epstein Danny , Litovchik Ilya , Fuchs Shmuel , Minha Sa'ar 
Published: November 2020

AbstractAimsEfforts are constantly made to decrease the rates of readmission after acute decompensated heart failure (ADHF). ADHF admissions to internal medicine departments (IMD) were previously associated with higher risk for readmission compared with those admitted to cardiology departments (CD). It is unknown if the earlier still applies after recent advancement in care over the last decade. This contemporary cohort compares characteristics and outcomes of ADHF patients admitted to IMD with those admitted to CD.Methods and resultsThe data for this single‐centre, retrospective study utilized a cohort of 8332 ADHF patients admitted between 2007 and 2017. We compared patients' baseline characteristics and clinical and laboratory indices of patients admitted to CD and IMD with the outcome defined as 30 day readmission rate. In comparison with those admitted to CD, patients admitted to IMD (89.5% of patients) were older (79 [70–86] vs. 69 [60–78] years; P < 0.001) and had a higher incidence of co‐morbidities and a higher ejection fraction. Readmission rates at 30 days were significantly lower in patients admitted to CD (15.9% vs. 19.6%; P = 0.01). Conflicting results of three statistical models failed to associate between the admitting department and 30 day readmission (odds ratio for 30 day readmission in CD: forced and backward stepwise logistic regression 0.8, 95% confidence interval 0.65–0.97, P = 0.02; stabilized inverse probability weights model odds ratio 1.0, confidence interval 0.75–1.37, P = 0.96).ConclusionsThis contemporary analysis of ADHF patient cohort demonstrates significant differences in the characteristics and outcomes of patients admitted to IMD and CD. Thus, focusing strategies for readmission prevention in patients admitted to IMD may be beneficial.