bluuebunny/crossref_metadata_2025_split huggingface dataset:
Construction of Catalytic Covalent Organic Frameworks with Redox‐Active Sites for the Oxygen Reduction and the Oxygen Evolution Reaction
Authors: Liu Minghao , Liu Sijia , Cui Cheng‐Xing , Miao Qiyang , He Yue , Li Xuewen , Xu Qing , Zeng Gaofeng 
Published: October 2022

AbstractConstruction of catalytic covalent organic frameworks (COFs) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is significant but rarely demonstrated. In this work, we have first constructed bifunctional COFs towards ORR and OER by integrating diarylamine derivatives into the Co‐porphyrin based frameworks. Both of the new COFs (CoTAPP‐PATA‐COF and CoTAPP‐BDTA‐COF) have good ordered structures, high surface areas, and robust chemical stability. The diarylamine units, as a typical electron donor and redox‐active cores, promote intramolecular electron transport along the frameworks and improve the electrochemically active surface areas. Thus, the COFs showed higher catalytic activities than that of the COF without redox‐active units. CoTAPP‐PATA‐COF had a halfwave potential of 0.80 V towards ORR, and delieved an overpotential of 420 mV for OER in 0.1 M KOH. The theoretical calculation revealed introducing diarylamine unites improved the oxygen electrocatalysis.
Photoexcited Enzymes for Asymmetric Csp3−Csp3 Cross‐Electrophile Couplings
Authors: Schmidt Sandy 
Published: October 2022

AbstractEnzymes have several advantages over conventional catalysts for organic synthesis. Over the last two decades, much effort has been made to further extend the scope of biocatalytic reactions available to synthetic chemists, particularly by expanding the repertoire of enzymes for abiological transformations. In this regard, exciting new developments in the area of photobiocatalysis enable now the introduction of non‐natural reactivity in enzymes to solve long‐standing synthetic challenges. A recently described example from the Hyster group demonstrates in an unprecedented way how the combination of photochemistry with enzyme catalysis empowers the catalytic asymmetric construction of Csp3−Csp3 bonds with high chemo‐ and enantioselectivity.
A Sensitive and Nonoptical CRISPR Detection Mechanism by Sizing Double‐Stranded λ DNA Reporter
Authors: Mohammad Noor , Katkam Shrinivas S. , Wei Qingshan 
Published: October 2022

AbstractCRISPR‐based biosensors often rely on colorimetric, fluorescent, or electrochemical signaling mechanism, which involves expensive reporters and/or sophisticated equipment. Here, we demonstrated a simple, inexpensive, nonoptical, and sensitive CRISPR‐Cas12a‐based sensing platform to detect ssDNA targets by sizing double‐stranded λ DNA as novel report molecules. In this platform, the size reduction of λ DNA was quantified by gel electrophoresis analysis. We hypothesize that the massive trans‐nuclease activity of Cas12a toward λ DNA is due to the presence of single‐stranded looped structures along the λ DNA sequence. In addition, we observed a strong binding affinity between Cas12a and λ DNA, which further promotes the trans‐cleavage activity and helps achieve sub‐picomolar detection sensitivity, ≈100 times more sensitive than the fluorescent counterpart. The concept of utilizing the physical size change of λ DNA unlocks the possibility of using a variety of dsDNA as CRISPR reporters.
Improving culture initiation of mature oak shoots through use of silver thiosulfate
Authors: Winkeljohn Max , Pence Valerie C. , Culley Theresa M. 
Published: October 2022

AbstractPremiseOf the approximately 430 species of oaks (Quercus spp.) that have been assessed, 31% are threatened with extinction and in need of safeguarding. However, oak seeds cannot be seed banked, and thus rely on alternative strategies such as in vitro culture for ex situ conservation. One challenge to this approach is low culture initiation rates. Our objective was to identify factors that may improve the establishment of shoot cultures in vitro using new growth collected from mature trees.MethodsShoot cuttings were harvested from individuals of five different oak species (Q. alba, Q. bicolor, Q. macrocarpa, Q. muehlenbergii, and Q. palustris). Shoots were cultured onto medium with or without 50 µM silver thiosulfate (STS), a known inhibitor of the stress hormone ethylene. Cultures were grown for one month, at which point shoots were assessed for survival.ResultsShoot survival was significantly greater in shoots cultured on medium containing STS compared to the control group, with the overall survival rate increasing from 65% to 73%.DiscussionIncreasing the survival rate of newly established cultures is important in ensuring that material collected from endangered species has the best chance for survival, which is critical for successful ex situ conservation.
Comparing an interdependent and dependent group contingency to increase physical activity in students during recess
Authors: Asaro Madeline M. , Zonneveld Kimberley L. M. , Frijters Jan C. 
Published: October 2022

AbstractPhysical activity produces important physiological, mental health, academic, and cognitive benefits in children and youth. Despite these advantages, a large proportion of this population does not meet the recommended amount of physical activity. Recent studies have shown that the interdependent (IGC) and dependent (DGC) group contingencies improve physical activity; however, no comparison of the effects of these contingencies on physical activity has been conducted. We used a multielement within a concurrent multiple baseline design across three classes to compare the effectiveness of group contingencies on physical activity. Both group contingencies increased physical activity, with the IGC producing slightly higher overall levels of physical activity at the classwide and individual levels of analyses. We also compared participants' positive and negative statements and found that, regardless of the group contingency in effect, participants emitted higher levels of positive statements about the contingency when they earned the reward than when they did not, suggesting that reward delivery influenced statements more so than the group contingency arrangement. Results are discussed within the context of treatment decisions and future research.
Adjuvant 5‐Fluorouracil/leucovorin, capecitabine, and oxaliplatin‐related regimens for stage II/III colon cancer patients 66 years or older
Authors: Jones Emily , Duan Zhigang , Nguyen Thinh T. , Giordano Sharon H. , Zhao Hui 
Published: October 2022

AbstractAdjuvant chemotherapy of leucovorin‐modulated 5‐fluorouracil (5‐FU/LV), capecitabine, and adding oxaliplatin to 5‐FU/LV or capecitabine (FLOX/OX) have been standard regimens for high‐risk stage II or III colon cancer (CC). We aimed to evaluate their patterns of use, association with survival, and rate of emergency room visit (ER) or hospitalization during the treatment period. High‐risk stage II or III patients aged >65 years diagnosed between 2007 and 2015, underwent colectomy, and received any of these three regimens were selected from SEER and Texas Cancer Registry (TC) linked with Medicare data. Chi‐square test, Kaplan–Meier survival curves, Cox regression, and logistic regression were used in data analysis. A total of 5621 (1080 stage II and 4541 stage III) patients with median age of 72 years were included in this study. For stage II, 24.4% used 5‐FU/LV, 31.2% used capecitabine, and 44.4% used FLOX/OX; the respective numbers for stage III were 13.8%, 17.9%, and 68.3%. Patients aged <70 years, not in the West region, not in Medicare state‐buy‐in program, and with no comorbidity were more likely to use FLOX/OX. FLOX/OX was associated with improved overall survival (OS) in stage II and III patients and improved cancer‐specific survival in stage III patients compared with 5‐FU/LV. The survival benefit of FLOX/OX was sustained in stage III patients aged ≥70 years. Capecitabine had the lowest ER/hospitalization rate with 19.2% in stage II and 28.9% in III. The use of FLOX/OX was associated with improved survival compared with 5‐FU/LV among CC patients. Capecitabine was associated with the lowest ER/hospitalization rate.
Long noncoding RNA THRIL promotes foam cell formation and inflammation in macrophages
Authors: Song Xiaosu , Gao Fen , Li Hong , Qin Weiwei , Chai Chanjuan , Shi Guojuan , Yang Huiyu 
Published: October 2022

AbstractTumor necrosis factor‐α (TNF‐α) and heterogenous nuclear ribonucleoprotein L (hnRNPL)‐related immunoregulatory lincRNA (THRIL) is a long noncoding RNA (lncRNA) involved in various inflammatory diseases. However, its role in atherosclerosis is not known. In this study, we aimed to investigate the function of THRIL in mediating macrophage inflammation and foam cell formation. The expression of THRIL was quantified in THP‐1 macrophages after treatment with oxidized low‐density lipoprotein (oxLDL). The effect of THRIL overexpression and knockdown on oxLDL‐induced inflammatory responses and lipid accumulation was determined. THRIL‐associated protein partners were identified by RNA pull‐down and RNA immunoprecipitation assays. We show that THRIL is upregulated in macrophages after oxLDL treatment. Knockdown of THRIL blocks oxLDL‐induced expression of interleukin‐1β (IL‐1β), IL‐6, and TNF‐α and lipid accumulation. Conversely, ectopic expression of THRIL enhances inflammatory gene expression and lipid deposition in oxLDL‐treated macrophages. Moreover, THRIL depletion increases cholesterol efflux from macrophages and the expression of ATP‐binding cassette transporter (ABC) A1 and ABCG1. FOXO1 is identified as a protein partner of THRIL and promotes macrophage inflammation and lipid accumulation. Furthermore, overexpression of FOXO1 restores lipid accumulation and inflammatory cytokine production in THRIL‐depleted macrophages. In conclusion, our data suggest a model where THRIL interacts with FOXO1 to promote macrophage inflammation and foam cell formation. THRIL may represent a therapeutic target for atherosclerosis.
Effects of fall stocking rates on naturalized cool‐season stockpiled pastures
Authors: Bailey Bobbi , Griggs Thomas C. , Felton Eugene , Krause Karen Marie 
Published: October 2022

AbstractThe potential of tall fescue (Schedonorus arundinaceus Dumort) and orchardgrass (Dactylis glomerata L.) as stockpiled forages has been documented; however, limited information describes the characteristics of other species, especially complex mixtures of cool‐season naturalized pastures. A 3‐yr study assessed the herbage mass, forage quality, and botanical composition of mixed cool‐season naturalized pastures [orchardgrass, tall fescue, clover (Trifolium spp.), narrowleaf plantain (Plantago lanceolata L.), and quackgrass (Elymus repens [L.] Gould)] in response to two stocking rates based on daily herbage allowances of 3.5% (low) or 7.0% (high) of heifer bodyweight. The stocking rate for the entire pasture area, including unoccupied paddocks during the grazing period, was 2.4 and 1.3 heifers acre−1 for the low and high treatments, respectively. Stockpiling began in August; grazing began in early November. The initial herbage mass and botanical composition were determined at the end of the stockpiling period. Herbage samples were taken throughout the fall grazing period at intervals of 11 to 19 d. The stocking rate had no effect on changes in botanical composition. Total legume percentage increased from 6% in Year 1 to 31% in Year 3 (P < .05). Herbage mass declined more quickly in Year 3 than in Years 1 and 2 (P < .05), probably because of the high percentage of legumes. As fall grazing progressed, crude protein content and in vitro true dry matter digestibility declined, and neutral detergent fiber content increased. Mixed cool‐season naturalized pastures could be used for stockpiling and grazed intensively without detrimental effects on subsequent stockpiling periods.
Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C−H Functionalization and Allylic Alkylation
Authors: Ge Zhaoliang , Lu Bin , Teng Huailong , Wang Xiaoming 
Published: October 2022

AbstractA three‐component reaction ofN, N‐disubstituted aniline,α‐diazo ester, and an allylic electrophile has been realized by [Rh(II)]2/Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identifiedα,α‐diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp2)−H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.
Dielectric Relaxation and Dielectric Switching Behaviors in (N,N‐Diisopropylethylamine) Tetrachloroantimonate(III)
Authors: Wei Wen‐Juan , Gao Hong‐Qiang , Luo Xiao‐Hua , Tang Yun‐Zhi 
Published: October 2022

AbstractDielectric switches have drawn renewed attention to the study of their many potential applications with the adjustable switch temperatures (Ts). Herein, a novel antimony‐based halide semiconductor, (N,N‐diisopropylethylamine) tetrachloroantimonate ((DIPEA)SbCl4, DIPEA+=N,N‐diisopropylethylamine), with dielectric relaxation behavior and dielectric switches has been successfully synthesized. This compound, consisting of coordinated anion
chains and isolated DIPEA+ cations, undergoes an isostructural order‐disorder phase transition and shows a step‐like dielectric anomaly, which can function as a frequency‐tuned dielectric switch with highly adjustable switch temperature (Ts). Variable‐temperature single‐crystal structure analyses and first‐principles molecular dynamics simulations give information about the general mechanisms of molecular dynamics. This work enriches the dielectric switch family and proves that hybrid metal halides are promising candidates for switchable physical or chemical properties.
Improving cervical cancer survival–A multifaceted strategy to sustain progress for this global problem
Authors: Markovina Stephanie , Rendle Katharine A. , Cohen Alexander C. , Kuroki Lindsay M. , Grover Surbhi , Schwarz Julie K. 
Published: October 2022

AbstractCervical cancer is associated with profound socioeconomic and racial disparities in incidence, mortality, morbidity, and years of life lost. The last standard‐of‐care treatment innovation for locally advanced cervical cancer occurred in 1999, when cisplatin chemotherapy was added to pelvic radiation therapy (chemoradiation therapy). Chemoradiation therapy is associated with a 30%–50% failure rate, and there is currently no cure for recurrent or metastatic disease. The enormity of the worldwide clinical problem of cervical cancer morbidity and mortality as well as the egregiously unchanged mortality rate over the last several decades are recognized by the National Institutes of Health as urgent priorities. This is reflected within the Office of Research on Women's Health effort to advance National Institutes of Health research on the health of women, as highlighted in a recent symposium. In the current review, the authors address the state of the science and opportunities to improve cervical cancer survival with an emphasis on improving access, using technology in innovative and widely implementable ways, and improving current understanding of cervical cancer biology.Lay summaryCervical cancer is associated with profound socioeconomic and racial disparities in incidence, mortality, morbidity, and years of life lost.In this review, the state of the science and opportunities to improve cervical cancer survival are presented with an emphasis on improving access, using technology in innovative and widely implementable ways, and improving current understanding of cervical cancer biology.
When IV−VI Meets I−V−VI2: A Reinvigorating Thermoelectric Strategy for Tin Monochalcogenides
Authors: Shi Xin , Ren Zhifeng 
Published: October 2022

AbstractResembling the widely studied PbTe−AgSbTe2(LAST) and GeTe−AgSbTe2(TAGS) thermoelectric materials, alloying group I−V−VI2compounds to tin monochalcogenides (SnTe, SnSe, and SnS) was also initially studied in the 1960s. Nevertheless, this thermoelectric strategy has regained popularity only in recent years, and boosted performance is now generally expected in these alloys. Given its encouraging revival and the absence of a corresponding research summary, here we carefully review current advances in this system, which is categorized into three major subgroups, that is, I−Sb−VI2‐alloyed SnTe, I−Bi−VI2‐alloyed SnTe, and I−Sb−VI2‐alloyed SnSe. Emphasis is placed on exploring the underlying mechanisms of this system in addition to its thermoelectric properties. Some future directions of this reinvigorating strategy are also proposed in the hope that they can serve as a guide for its further exploration.
Understanding Conformational Properties and Role of Hydrogen Bonds in Glycosaminoglycans‐Interleukin8 Complexes in Aqueous Medium by Molecular Dynamics Simulation
Authors: Dhurua Shakuntala , Jana Madhurima 
Published: October 2022

AbstractAtomistic molecular dynamics simulations were performed under ambient conditions to explore the conformational features and binding affinities of hexameric glycosaminoglycans (GAGs) with chemokine Interleukin8 (IL8) in an aqueous medium. We tried to understand the role of hydrogen bonds (HBs) involving conserved water in mediating the interactions. The Luzar‐Chandler model was adopted to study the kinetics of HB breaking and formation concerning different water‐mediated HBs. The conformational flexibilities of bound GAGs are due to the flexible glycosidic linkages than the occasional/rare ring pucker conformation. The free energy landscape constructed with ϕ, and ψ, depicted that different conformational minima associated with the glycosidic linkage flexibility of the GAGs in bound states are separated by energy barriers. The binding affinities of IL8 towards GAGs are favored through the electrostatic and non‐polar solvation interactions. 4‐different types of conserved water were explored in the solvent‐mediated binding of GAGs with IL8. The average lifetime of the IL8‐GAG direct HB pairs was ∼ten times less than the IL8‐GAG‐shared water HBs. This is due to the rapid establishment of HB breaking and reformation kinetics involving water of a shared layer. We find that despite the highly negatively charged surface of GAGs, the IL8 surface populated by non‐cationic amino acids could serve as a promising binding site in addition to the cationic surface of the protein.
An In Vivo Mouse Model for Chronic Inflammation–Induced Immune Suppression: A “Factory” for Myeloid‐Derived Suppressor Cells (MDSCs)
Authors: Ben‐Meir Kerem , Twaik Nira , Meirow Yaron , Baniyash Michal 
Published: October 2022

AbstractMyeloid‐derived suppressor cells (MDSCs) represent a heterogeneous population of immature myeloid cells known to play a role in perpetuating a wide range of pathologies, such as chronic infections, autoimmune diseases, and cancer. MDSCs were first identified in mice by the markers CD11b+Gr1+, and later, based on their morphology, they were classified into two subsets: polymorphonuclear MDSCs, identified by the markers CD11b+Ly6G+Ly6CLow, and monocytic MDSCs, detected as being CD11b+Ly6G–Ly6CHi. MDSCs are studied as immunosuppressive cells in various diseases characterized by chronic inflammation and are associated with disease causes/triggers such as pathogens, autoantigens, and cancer. Therefore, different diseases may diversely affect MDSC metabolism, migration, and differentiation, thus influencing the generated MDSC functional features and ensuing suppressive environment. In order to study MDSCs in a pathology‐free environment, we established and calibrated a highly reproducible mouse model that results in the development of chronic inflammation, which is the major cause of MDSC accumulation and immune suppression. The model presented can be used to study MDSC phenotypes, functional diversity, and plasticity. It also permits study of MDSC migration from the bone marrow to peripheral lymphatic and non‐lymphatic organs and MDSC crosstalk with extrinsic factors, both in vivo and ex vivo. Furthermore, this model can serve as a platform to assess the effects of anti‐MDSC modalities. © 2022 The Authors. Current Protocols published by Wiley Periodicals LLC.Basic Protocol: Repetitive M.tb immunizations for the induction of chronic inflammationAlternate Protocol 1: Creating a lower grade of inflammation by changing the site of immunizationAlternate Protocol 2: In vivo evaluation of immune statusSupport Protocol 1: Preparation of reconstituted M.tb aliquots and M.tb‐IFA emulsions for each of the three injectionsSupport Protocol 2: Preparation of an ovalbumin lentiviral expression vectorSupport Protocol 3: Fluorescence titering assay for the lentiviral expression vectorSupport Protocol 4: Spleen excision, tissue dissociation, and preparation of a single‐cell suspensionSupport Protocol 5: Labeling of splenocytes with CFSE proliferation dye
Synthesis of Aluminum N,N‐Dialkylcarbamates by Insertion of CO2 into Al−N Bonds
Authors: Schumann Erik , Brendler Erica , Böhme Uwe , Mertens Florian 
Published: October 2022

AbstractDespite decades of research on various carbamates and their important applications, only one aluminum N,N‐dialkylcarbamate (ADC) with an aluminum:carbamate ratio of 1 : 3 has been structurally described and comprehensively studied so far, namely tris(diisopropyl)carbamate. The reasons for this situation include problems with the used synthetic routes. The process of CO2 insertion into Al−N bonds of tris(dialkylamido)alanes resolved these difficulties. Using this advantageous synthetic route, the dimethyl and diethyl, as well as the pyrrolidino, piperidino, and N‐methylpiperazino derivatives were now successfully prepared. These ADCs were investigated by solid‐state NMR spectroscopy, where line‐shape analyses of the 27Al NMR spectra allowed conclusions with respect to the determination of the quadrupole coupling parameters. Furthermore, data of an intermediate during the CO2 insertion into tris(diisopropylamido)alane were obtained by in‐situ IR spectroscopy, which were complemented by NMR measurements of samples periodically taken during the reaction. Partial hydrolysis of tris(pyrrolidino)carbamate revealed a complex Al3(μ3‐O) cluster structure, which was elucidated by single crystal X‐ray diffraction.
Small‐Molecule Activation by Heteroleptic Metallasilylenes
Authors: Schoening Juliane , Wölper Christoph , Schulz Stephan 
Published: October 2022

AbstractWe report on reactions of heteroleptic metallasilylenes L1(Cl)MSiL2(M=Al1, Ga2, L1=HC[C(Me)NDipp]2, Dipp=2,6‐iPr2C6H3; L2=PhC(NtBu)2) with CO2, N2O, and Me3SiN3, yielding the corresponding carbonate complexes L1(Cl)MOSi(CO3‐κ2O,O−)L2(M=Al3, Ga4), silanoic esters L1(Cl)MOSi(O)L2(M=Al5, Ga6), and silaimine L1(Cl)GaSi(NSiMe3)L2(8), whereas {L2Si[N(SiMe3)Al(Cl)C(Me)NDipp][CHC(Me)N(Dipp)]}7was formed by C−C bond cleavage of the L1ligand. Compounds3–8were characterized by NMR (1H,13C) and IR spectroscopy, elemental analysis and single crystal X‐ray diffraction.
Room Temperature DBN Initiated Phospha‐Brook Rearrangement of α‐Hydroxyphosphonates to Phosphates
Authors: Mahandru‐Gill Muskaan , Iqbal Aleema , Damai Margarita , Spiedo Francesco , Kasonde Edward K. , Sykes Daniel , Devine Kevin G. , Patel Bhaven 
Published: October 2022

AbstractA series of substituted aryl phosphate esters have been synthesized from their α‐hydroxyphosphonates substrates, using DBN (1,5 diazabicyclo(4.3.0)non‐5‐ene) at room temperature, via a phospha‐Brook rearrangement. The aryl‐substrate dependence of the rearrangement was explored, and excellent yields of the phosphate esters were achieved irrespective of whether the aryl moiety was activated or unactivated. A plausible mechanism for the rearrangement has been proposed. Based on the low temperature 31P‐NMR, the mechanism of the phospha‐Brook rearrangement is proposed to take place via an oxaphosphirane intermediate.