bluuebunny/crossref_metadata_2025_split huggingface dataset:
Controllable Multiemission with Ultralong Organic Phosphorescence in Crystal by Isomerization
Authors: Ling Kun , Shi Huifang , Wang He , Fu Lishun , Lv Anqi , Huang Kaiwei , Ye Wenpeng , Gu Mingxing , Ma Chaoqun , Yao Xiaokang , Jia Wenyong , Zhi Jiahuan , Yao Wei , An Zhongfu , Ma Huili , Huang Wei 
Published: September 2019

AbstractOrganic multiemissive materials with different lifetimes have attractive applications in sensors, bioimaging, data encryption, and so on. However, it is a formidable challenge to achieve multiemission with ultralong organic phosphorescence (UOP) in a single molecule. Here, reported is a series of isomers (o‐CzPh, m‐CzPh, and p‐CzPh) with multiemissive behavior under ambient conditions. All phosphors emit both fluorescence and UOP in crystal. Beyond that, o‐CzPh also displays thermally activated delayed fluorescence with a lifetime of 2.56 µs, which can be ascribed to the fast reverse intersystem crossing process from T2 to S1 states. Impressively, m‐CzPh crystal exhibits another phosphoresce emission with a lifetime of 0.24 ms assigned as single molecule phosphorescence, which is rarely reported. This finding enables the development of new organic phosphors with diverse lifetimes within a single molecule for potential applications.
Electrochemical Cross‐Coupling of C(sp2)−H with Aryldiazonium Salts via a Paired Electrolysis: an Alternative to Visible Light Photoredox‐Based Approach
Authors: Jiang Yang‐ye , Dou Gui‐yuan , Zhang Luo‐sha , Xu Kun , Little R. Daniel , Zeng Cheng‐chu 
Published: September 2019

AbstractPhotoredox‐based C−H bond functionalization constitutes one of the most powerful and atom‐economical approaches to organic syntheses. During this type of reaction, single electron transfer takes place between the photocatalyst (PC) and redox‐ active substrates. Electrosynthesis also involves electron transfer between substrates and electrodes. In this paper, we focus upon electrochemical cross‐coupling of C(sp2)−H with aryldiazonium salts and have developed an efficient electrochemical approach to the Minisci‐type arylation reaction. The constant current paired electrosynthesis proceeds in a simple undivided cell without external supporting electrolyte, features a wide range of substrates and is easy to scale‐up. These results demonstrate that photoredox‐based cross‐coupling of C(sp2)−H with aryldiazonium salts can also proceed successfully under paired electrolysis conditions, thereby contributing to understanding of the parallels between photosynthesis and electrosynthesis.magnified image
A Reversible Electron Relay to Exclude Sacrificial Electron Donors in the Photocatalytic Oxygen Atom Transfer Reaction with O2 in Water
Authors: Vo Nhat Tam , Mekmouche Yasmina , Tron Thierry , Guillot Régis , Banse Frédéric , Halime Zakaria , Sircoglou Marie , Leibl Winfried , Aukauloo Ally 
Published: September 2019

AbstractUsing light energy and O2 for the direct chemical oxidation of organic substrates is a major challenge. A limitation is the use of sacrificial electron donors to activate O2 by reductive quenching of the photosensitizer, generating undesirable side products. A reversible electron acceptor, methyl viologen, can act as electron shuttle to oxidatively quench the photosensitizer, [Ru(bpy)3]2+, generating the highly oxidized chromophore and the powerful reductant methyl‐viologen radical MV+.. MV+. can then reduce an iron(III) catalyst to the iron(II) form and concomitantly O2 to O2.− in an aqueous medium to generate an active iron(III)‐(hydro)peroxo species. The oxidized photosensitizer is reset to its ground state by oxidizing an alkene substrate to an alkenyl radical cation. Closing the loop, the reaction of the iron reactive intermediate with the substrate or its radical cation leads to the formation of two oxygenated compounds, the diol and the aldehyde following two different pathways.
Activation and Characterization of Cryptic Gene Cluster: Two Series of Aromatic Polyketides Biosynthesized by Divergent Pathways
Authors: Ji Zhen‐Yu , Nie Qiu‐Yue , Yin Yue , Zhang Mei , Pan Hai‐Xue , Hou Xian‐Feng , Tang Gong‐Li 
Published: September 2019

AbstractOne biosynthetic gene cluster (BGC) usually governs the biosynthesis of a series of compounds exhibiting either the same or similar molecular scaffolds. Reported here is a multiplex activation strategy to awaken a cryptic BGC associated with tetracycline polyketides, resulting in the discovery of compounds having different core structures. By constitutively expressing a positive regulator gene in tandem mode, a single BGC directed the biosynthesis of eight aromatic polyketides with two types of frameworks, two pentacyclic isomers and six glycosylated tetracyclines. The proposed biosynthetic pathway, based on systematic gene inactivation and identification of intermediates, employs two sets of tailoring enzymes with a branching point from the same intermediate. These findings not only provide new insights into the role of tailoring enzymes in the diversification of polyketides, but also highlight a reliable strategy for genome mining of natural products.
Artificial Enzyme Catalyzed Cascade Reactions: Antitumor Immunotherapy Reinforced by NIR‐II Light
Authors: Wen Mei , Ouyang Jiang , Wei Chuanwan , Li Hui , Chen Wansong , Liu You‐Nian 
Published: September 2019

AbstractCurrent cancer therapy is seriously challenged by tumor metastasis and recurrence. One promising solution to these problems is to build antitumor immunity. However, immunotherapeutic efficacy is highly impeded by the immunosuppressive state of the tumors. Here a new strategy is presented, catalytic immunotherapy based on artificial enzymes. Cu2−xTe nanoparticles exhibit tunable enzyme‐mimicking activity (including glutathione oxidase and peroxidase) under near‐infrared‐II (NIR‐II) light. The cascade reactions catalyzed by the Cu2−xTe artificial enzyme gradually elevates intratumor oxidative stress to induce immunogenic cell death. Meanwhile, the continuously generated oxidative stress by the Cu2−xTe artificial enzyme reverses the immunosuppressive tumor microenvironment, and boosts antitumor immune responses to eradicate both primary and distant metastatic tumors. Moreover, immunological memory effect is successfully acquired after treatment with the Cu2−xTe artificial enzyme to suppress tumor relapse.
Polymerizations Mediated by Well‐Defined Rhodium Complexes
Authors: Tan Nicholas Sheng Loong , Lowe Andrew B. 
Published: September 2019

AbstractThis Minireview details the current state‐of‐the‐art relating to (co)polymerizations mediated by well‐defined RhI‐ethynyl, vinyl, and aryl complexes. In particular, we focus on RhI species suitable for the (co)polymerization of phenylacetylenes, arylisocyanides, as well as propargyl esters and amides.
Autonomous Discovery in the Chemical Sciences Part II: Outlook
Authors: Coley Connor W. , Eyke Natalie S. , Jensen Klavs F. 
Published: September 2019

AbstractThis two‐part Review examines how automation has contributed to different aspects of discovery in the chemical sciences. In this second part, we reflect on a selection of exemplary studies. It is increasingly important to articulate what the role of automation and computation has been in the scientific process and how that has or has not accelerated discovery. One can argue that even the best automated systems have yet to “discover” despite being incredibly useful as laboratory assistants. We must carefully consider how they have been and can be applied to future problems of chemical discovery in order to effectively design and interact with future autonomous platforms. The majority of this Review defines a large set of open research directions, including improving our ability to work with complex data, build empirical models, automate both physical and computational experiments for validation, select experiments, and evaluate whether we are making progress towards the ultimate goal of autonomous discovery. Addressing these practical and methodological challenges will greatly advance the extent to which autonomous systems can make meaningful discoveries.
Multi‐Resonance Induced Thermally Activated Delayed Fluorophores for Narrowband Green OLEDs
Authors: Zhang Yuewei , Zhang Dongdong , Wei Jinbei , Liu Ziyang , Lu Yang , Duan Lian 
Published: September 2019

AbstractHigh‐color‐purity emissions with small a full‐width at half‐maximum (FWHM) are an ongoing pursuit for high‐resolution displays. Though the flourishment of narrow‐band emissive materials with multi‐resonance induced thermally activated delayed fluorescence (MR‐TADF) in the blue region, such materials have not validated their potential in other color regions. By amplifying the influence of skeleton and peripheral units, a series of highly efficient green‐emitting MR‐TADF materials are firstly reported. Peripheral units with electron‐deficit properties can significantly narrow the energy gap for bathochromic emission without compromising the color fidelity. MR‐TADF emitters with photo‐luminance quantum yields of above 90 % with FWHMs of ≤25 nm are developed. The corresponding organic light‐emitting diodes show maximum external quantum efficiency/ power efficiency of 22.02 %/ 69.82 lm W−1 with excellent long‐term stability.
Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase
Authors: Muramatsu Satoru , Tsukuda Tatsuya 
Published: September 2019

AbstractMetal atoms and clusters exhibit chemical properties that are significantly different or totally absent in comparison to their bulk counterparts. Such peculiarity makes them potential building units for the generation of novel catalysts. Investigations of the gas‐phase reactions between size‐ and charge‐selected atoms/clusters and small molecules have provided fundamental insights into their intrinsic reactivity, thus leading to a guiding principle for the rational design of the single‐atom and cluster‐based catalysts. Especially, recent gas‐phase studies have elucidated that small molecules such as O2, CO2, and CH3I can be catalytically activated by negatively‐charged atoms/clusters via donation of a partial electronic charge. This Minireview showcases typical examples of such “reductive activation” processes promoted by anions of metal atoms and clusters. Here, we focus on anionic atoms/clusters of coinage metals (Cu, Ag, and Au) owing to the simplicity of their electronic structures. The determination of a correlation between their activation modes and the electronic structures might be helpful for the future development of innovative coinage metal catalysts.
Dissecting the Binding Interactions of Teixobactin with the Bacterial Cell‐Wall Precursor Lipid II
Authors: Chiorean Sorina , Antwi Isaac , Carney Daniel W. , Kotsogianni Ioli , Giltrap Andrew M. , Alexander Francesca M. , Cochrane Stephen A. , Payne Richard J. , Martin Nathaniel I. , Henninot Antoine , Vederas John C. 
Published: September 2019

AbstractThe prevalence of life‐threatening, drug‐resistant microbial infections has challenged researchers to consider alternatives to currently available antibiotics. Teixobactin is a recently discovered “resistance‐proof” antimicrobial peptide that targets the bacterial cell wall precursor lipid II. In doing so, teixobactin exhibits potent antimicrobial activity against a wide range of Gram‐positive organisms. Herein we demonstrate that teixobactin and several structural analogues are capable of binding lipid II from both Gram‐positive and Gram‐negative bacteria. Furthermore, we show that when combined with known outer membrane‐disrupting peptides, teixobactin is active against Gram‐negative organisms.
Selective Photo‐Oxygenation of Light Alkanes Using Iodine Oxides and Chloride
Authors: Liebov Nichole S. , Goldberg Jonathan M. , Boaz Nicholas C. , Coutard Nathan , Kalman Steven E. , Zhuang Thompson , Groves John T. , Gunnoe T. Brent 
Published: September 2019

AbstractPartial oxidation of light alkanes to generate alkyl esters has been achieved under photochemical conditions using mixtures of iodine oxides and chloride salts in trifluoroacetic acid (HTFA). The reactions are catalytic in chloride and are successful using compact fluorescent light, but higher yields are obtained using a mercury lamp. In this photo‐initiated oxyesterification process, the robust alkyl ester products are resistant to over‐oxidation, and under optimized conditions yields for alkyl ester production of ∼50 % based on methane, ∼60 % based on ethane (with a total functionalized yield of EtX (X=TFA or Cl) of 80 %) and ∼30 % based on propane have been demonstrated. The reaction also proceeds in aqueous HTFA and dichloroacetic acid with lower yields. Mechanistic studies indicate that the process likely operates by a chlorine hydrogen atom abstraction pathway wherein alkyl radicals are generated, trapped by iodine, and converted to alkyl trifluoroacetates in situ.
Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single‐Atom Alloys
Authors: Hannagan Ryan T. , Patel Dipna A. , Cramer Laura A. , Schilling Alex C. , Ryan Paul T. P. , Larson Amanda M. , Çınar Volkan , Wang Yicheng , Balema Tedros A. , Sykes E. Charles H. 
Published: September 2019

AbstractSingle‐atom alloys are a new class of heterogeneous catalyst in which trace amounts of metal dopants exist as individual, isolated sites in a host metal. In this study, we examine RhCu, a new single‐atom alloy with a combination of scanning tunneling microscopy, reflectance absorption infrared spectroscopy, and temperature programed desorption to understand the atomic structure of the alloy and correlate this with the behavior of CO, a common probe molecule. We find that Rh alloys into Cu(111) preferentially from step edges. As such, step density plays an important role in the vibrational structure of CO on isolated Rh sites. We find that atomically dispersed Rh sites can be close enough together to have dipole‐dipole coupling interactions. Together, this combined experimental approach enables us to understand the alloying mechanism of Rh with Cu and yields important signatures of the atomic sites that are useful in benchmarking CO vibrational data.
Long‐term follow‐up of lower dose dasatinib (50 mg daily) as frontline therapy in newly diagnosed chronic‐phase chronic myeloid leukemia
Authors: Naqvi Kiran , Jabbour Elias , Skinner Jeffrey , Anderson Kristin , Dellasala Sara , Yilmaz Musa , Ferrajoli Alessandra , Bose Prithviraj , Thompson Philip , Alvarado Yesid , Jain Nitin , Takahashi Koichi , Burger Jan , Estrov Zeev , Borthakur Gautam , Pemmaraju Naveen , Paul Shilpa , Cortes Jorge , Kantarjian Hagop M. 
Published: September 2019

BackgroundDasatinib, a potent Bcr‐Abl tyrosine kinase inhibitor, is approved for the treatment of chronic‐phase chronic myeloid leukemia (CML‐CP) in the frontline and salvage settings. Notable side effects include pleural effusions and myelosuppression. Dasatinib at 50 mg daily has previously been reported to be active and better tolerated than the approved 100‐mg daily dose. The aim of this study was to update the long‐term follow‐up results of dasatinib at 50 mg daily as frontline therapy for CML‐CP.MethodsEighty‐three patients with newly diagnosed CML‐CP received dasatinib at 50 mg daily. Eligibility and response criteria were standards used in previous protocols.ResultsAfter a minimum follow‐up of 12 months, 81 patients were evaluable. Two patients came off the study in less than 3 months. The rates of BCR‐ABL1 transcript levels (International Standard) at ≤10% and ≤1% at 3 months were 96% and 77%, respectively. The cumulative rates for a complete cytogenetic response by 6 and 12 months were 77% and 95%, respectively. The cumulative rates for a major molecular response, a molecular response with a 4.0‐log reduction, and a molecular response with a 4.5‐log reduction by 12 months were 81%, 55%, and 49%, respectively. Twenty‐one patients (25%) had treatment interruptions for a median of 13 days (range, 4‐64 days). Five patients (6%) developed pleural effusions; 4 of these patients (80%) required a dose reduction. Two patients (2%) failed to achieve any cytogenetic or molecular response and were taken off the study. At a median follow‐up of 24 months, none of the patients had disease transformation to an accelerated or blastic phase. The 2‐year event‐free and overall survival rates were 100%.ConclusionsThese updated results continue to support 50 mg of dasatinib daily as an effective and safe dose for early CML‐CP.
Mapping child and adolescent self‐reported symptom data to clinician‐reported adverse event grading to improve pediatric oncology care and research
Authors: McFatrich Molly , Brondon Jennifer , Lucas Nicole R. , Hinds Pamela S. , Maurer Scott H. , Mack Jennifer W. , Freyer David R. , Jacobs Shana S. , Baker Justin N. , Mowbray Catriona , Wang Mian , Castellino Sharon M. , Barz Leahy Allison , Reeve Bryce B. 
Published: September 2019

BackgroundClinicians are the standard source for adverse event (AE) reporting in oncology trials, despite the subjective nature of symptomatic AEs. The authors designed a pediatric patient‐reported outcome (PRO) instrument for symptomatic AEs to support the National Cancer Institute's Common Terminology Criteria for Adverse Events (CTCAE) (the Pediatric PRO‐CTCAE). The current study developed a standardized algorithm that maps all possible Pediatric PRO‐CTCAE response patterns to recommended CTCAE grades to improve the accuracy of AE reporting in pediatric oncology trials.MethodsTwo rounds of surveys were administered to experienced cancer clinicians across 9 pediatric hospitals. In round 1, pediatric oncologists assigned CTCAE grades to all 101 possible Pediatric PRO‐CTCAE response patterns. The authors evaluated clinician agreement of CTCAE grades across response patterns and categorized each response pattern as having high or low agreement. In round 2, a survey was sent to a larger clinician group to examine clinician agreement among a select set of Pediatric PRO‐CTCAE response patterns, and the authors examined how clinical context influenced grade assignment.ResultsA total of 10 pediatric oncologists participated in round 1. Of the 101 possible patterns, 89 (88%) had high agreement. The Light weighted kappa was averaged across the 10 oncologists (Light kappa = 0.73; 95% CI, 0.66‐0.81). A total of 139 clinicians participated in round 2. High clinician agreement remained for the majority of generic response patterns and the clinical context did not typically change grades but rather improved agreement.ConclusionsThe current study provides a framework for integrating child self‐reported symptom data directly into mandated AE reporting in oncology trials. Translating Pediatric PRO‐CTCAE responses into clinically meaningful metrics will guide future cancer care and toxicity grading.
Use of Insulin and the Risk of Progression of Pancreatitis: A Population‐Based Cohort Study
Authors: Cho Jaelim , Scragg Robert , Petrov Maxim S. 
Published: September 2019

Acute pancreatitis (AP) often progresses to recurrent acute pancreatitis (RAP) and chronic pancreatitis (CP). We investigated the relationship between the use of insulin after AP and progression from AP to RAP or CP, as well as the effect of diabetes status on the relationship. Using nationwide pharmaceutical dispensing data and hospital discharge data, insulin‐naïve individuals were followed from first AP admission. Multivariable time‐dependent Cox regression analyses were conducted. In the overall cohort (n = 10,190), ever‐use of insulin was associated with an increased risk of progression to RAP or CP (adjusted hazard ratio (HR), 1.70; 95% confidence interval (CI), 1.31–2.20). This risk remained increased in individuals with preexisting diabetes (adjusted HR, 1.45; 95% CI, 1.04–2.00), those with diabetes after AP (3.87; 1.20–12.46), and those without diabetes (2.80; 1.25–6.25). The findings suggest that individuals with AP who receive insulin are at a heightened risk of progression of pancreatitis, irrespective of diabetes status.
Decline in the strength of genetic controls on aspen environmental responses from seasonal to century‐long phenomena
Authors: Drobyshev I. , Picq S. , Ganivet E. , Tremblay F. , Bergeron Y. 
Published: September 2019

AbstractUnderstanding intra‐specific variation in climate sensitivity could improve the prediction of tree responses to climate change. We attempted to identify the degree of genetic control of tree phenology and growth of trembling aspen (Populus tremuloides Mchx.) in a natural stand of this species in northwestern Quebec. We mapped and genotyped 556 aspen trees growing within the plot, using seven nuclear microsatellite loci for clone identification. We selected 13 clones (n of trees per clone >5, in total 350 trees) and evaluated the explanatory power of clone identity in (a) variability of spring leaf phenology and (b) short‐ and long‐term growth responses. The clone's identity explained 43% of the variability in spring leaf phenology, between 18% and 20% of variability in response to monthly climate variables significantly affecting growth, between 8% and 26% of growth response to insect outbreaks, and 12% in the long‐term growth rates. Strong clonal control of aspen phenology and moderate control of growth responses to monthly weather do not result in an equally large impact on long‐term growth rates. The result suggests an important role of environmental extremes and within community interactions as factors averaging aspen growth performance at the stand level.
Protein kinase Akt2/PKBβ is involved in blastomere proliferation of preimplantation mouse embryos
Authors: Fiorenza Maria Teresa , Russo Giandomenico , Narducci Maria Grazia , Bresin Antonella , Mangia Franco , Bevilacqua Arturo 
Published: September 2019

AbstractActivation of Akt/Protein Kinase B (PKB) by phosphatidylinositol‐3‐kinase (PI3K) controls several cellular functions largely studied in mammalian cells, including preimplantation embryos. We previously showed that early mouse embryos inherit active Akt from oocytes and that the intracellular localization of this enzyme at the two‐cell stage depends on the T‐cell leukemia/lymphoma 1 oncogenic protein, Tcl1. We have now investigated whether Akt isoforms, namely Akt1, Akt2 and Akt3, exert a specific role in blastomere proliferation during preimplantation embryo development. We show that, in contrast to other Akt family members, Akt2 enters male and female pronuclei of mouse preimplantation embryos at the late one‐cell stage and thereafter maintains a nuclear localization during later embryo cleavage stages. Depleting one‐cell embryos of single Akt family members by microinjecting Akt isoform‐specific antibodies into wild‐type zygotes, we observed that: (a) Akt2 is necessary for normal embryo progression through cleavage stages; and (b) the specific nuclear targeting of Akt2 in two‐cell embryos depends on Tcl1. Our results indicate that preimplantation mouse embryos have a peculiar regulation of blastomere proliferation based on the activity of the Akt/PKB family member Akt2, which is mediated by the oncogenic protein Tcl1. Both Akt2 and Tcl1 are essential for early blastomere proliferation and embryo development.