bluuebunny/crossref_metadata_2025 huggingface dataset:
Exciton and Charge Carrier Dynamics in Highly Crystalline PTQ10:IDIC Organic Solar Cells
Authors: Cha Hyojung , Zheng Yizhen , Dong Yifan , Lee Hyun Hwi , Wu Jiaying , Bristow Helen , Zhang Jiangbin , Lee Harrison Ka Hin , Tsoi Wing C. , Bakulin Artem A. , McCulloch Iain , Durrant James R.
Published: July 2020

Herein the morphology and exciton/charge carrier dynamics in bulk heterojunctions (BHJs) of the donor polymer PTQ10 and molecular acceptor IDIC are investigated. PTQ10:IDIC BHJs are shown to be particularly promising for low cost organic solar cells (OSCs). It is found that both PTQ10 and IDIC show remarkably high crystallinity in optimized BHJs, with GIWAXS data indicating pi‐pi stacking coherence lengths of up to 8 nm. Exciton‐exciton annihilation studies indicate long exciton diffusion lengths for both neat materials (19 nm for PTQ10 and 9.5 nm for IDIC), enabling efficient exciton separation with half lives of 1 and 3 ps, despite the high degree of phase segregation in this blend. Transient absorption data indicate exciton separation leads to the formation of two spectrally distinct species, assigned to interfacial charge transfer (CT) states and separated charges. CT state decay is correlated with the appearance of additional separate charges, indicating relatively efficient CT state dissociation, attributed to the high crystallinity of this blend. The results emphasize the potential for high material crystallinity to enhance charge separation and collection in OSCs, but also that long exciton diffusion lengths are likely to be essential for efficient exciton separation in such high crystallinity devices.
High‐Temperature Shock Enabled Nanomanufacturing for Energy‐Related Applications
Authors: Dou Shuming , Xu Jie , Cui Xiaoya , Liu Weidi , Zhang Zhicheng , Deng Yida , Hu Wenbin , Chen Yanan
Published: July 2020

Functional nanomaterials are playing a crucial role in the emerging field of energy‐related devices. Recently, as a novel synthesis method, high‐temperature shock (HTS), which is rapid, low cost, eco‐friendly, universal, scalable, and controllable, has provided a promising option for the rational design and synthesis of various high‐quality nanomaterials. In this report, the HTS technique, including the equipment setup and operating principle, is systematically introduced, and recent progress in the synthesis of nanomaterials for energy storage and conversion applications using this HTS method is summarized. The growth mechanisms of nanoparticles and carbonaceous nanomaterials are thoroughly discussed, followed by the summary of the characteristic advantages of the HTS strategy. A series of nanomaterials prepared by the HTS method, including carbon‐based films, metal nanoparticles and compound nanoparticles, show high performance in the diverse applications of storage energy batteries, highly active catalysts, and smart energy devices. Finally, the future perspectives and directions of HTS in nanomanufacturing for broader applications are presented.
Phase 1 study of combinatorial sorafenib, G‐CSF, and plerixafor treatment in relapsed/refractory, FLT3‐ITD‐mutated acute myelogenous leukemia patients
Authors: Borthakur Gautam , Zeng Zhihong , Cortes Jorge E. , Chen Hsiang‐Chun , Huang Xuelin , Konopleva Marina , Ravandi Farhad , Kadia Tapan , Patel Keyur P. , Daver Naval , Kelly Mary A. , McQueen Teresa , Wang Ru‐Yiu , Kantarjian Hagop , Andreeff Michael
Published: July 2020

Stroma‐leukemia interactions mediated by CXCR4, CD44, VLA4, and their respective ligands contribute to therapy resistance in FLT3‐ITD‐mutated acute myelogenous leukemia (AML). We conducted a phase 1 study with the combination of sorafenib (a FLT3‐ITD inhibitor), plerixafor (a SDF‐1/CXCR4 inhibitor), and G‐CSF (that cleaves SDF‐1, CD44, and VLA4). Twenty‐eight patients with relapsed/refractory FLT3‐ITD‐mutated AML were enrolled from December 2010 to December 2013 at three dose levels of sorafenib (400, 600, and 800 mg twice daily) and G‐CSF and plerixafor were administered every other day for seven doses starting on day one. Sorafenib 800 mg twice daily was selected for the expansion phase. While no dose‐limiting toxicities (DLT) were encountered in the four‐week DLT window, hand‐foot syndrome and rash were seen beyond the DLT window, which required dose reductions in most patients. The response rate was 36% (complete response (CR) = 4, complete remission with incomplete platelet recovery (CRp) = 4, complete remission with incomplete hematologic recovery (CRi) = 1, and partial response (PR) = 1) for the intention to treat population. Treatment resulted in 58.4 and 47 mean fold mobilization of blasts and CD34 /38‐ stem/progenitor cells, respectively, to the circulation. Expression of the adhesion molecules CXCR4, CD44, and VLA4 on circulating leukemia cells correlated negatively with the mobilization of CD34+/38‐, CD34+/38−/123+ “progenitor” cells (all P ≤ .002). Mass cytometry analysis of sequential samples from two patients demonstrated resistance emerging early on from sub‐clones with persistent Akt and/or ERK signaling. In conclusion, the strategy of combined inhibition of FLT3 kinase and stromal adhesive interactions has promising activity in relapsed/refractory, FLT3‐ITD‐mutated AML, which warrants further evaluation in the front‐line setting.
Cocrystallization Tailoring Multiple Radiative Decay Pathways for Amplified Spontaneous Emission
Authors: Bolla Geetha , Liao Qing , Amirjalayer Saeed , Tu Zeyi , Lv Shaokai , Liu Jie , Zhang Shuai , Zhen Yonggang , Yi Yuanping , Liu Xinfeng , Fu Hongbing , Fuchs Harald , Dong Huanli , Wang Zhaohui , Hu Wenping
Published: July 2020

Amplified spontaneous emission (ASE) is intrinsically associated with lasing applications. Inefficient photon energy transfer to ASE is a long‐standing issue for organic semiconductors that consist of multiple competing radiative decay pathways, far from being rationally regulated from the perspective of molecular arrangements. Herein, we achieve controllable molecular packing motifs by halogen‐bonded cocrystallization, leading to ten times increased radiative decay rate, four times larger ASE radiative decay selectivity and thus remarkable ASE threshold decrease from 223 to 22 μJ cm−2, albeit with a low photoluminescence quantum yield. We have made an in‐depth investigation on the relationship among molecular arrangements, vibration modes, radiative decay profiles and ASE properties. The results suggest that cocrystallization presents a powerful approach to tailor the radiative decay pathways, which is fundamentally important to the development of organic ASE and lasing materials.
N‐Bridged Acyclic Trimeric Poly‐Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks
Authors: Shi Xiaoyan , León Felix , Sim Ying , Quek Shina , Hum Gavin , Khoo Yi Xin Joycelyn , Ng Zi Xuan , Par Mian Yang , Ong How Chee , Singh Varun K. , Ganguly Rakesh , Clegg Jack K. , Díaz Jesús , García Felipe
Published: July 2020

We have synthesized a completely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, NiPr, NtBu and NPh bridging groups. In addition, the first NH‐bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species display highly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from ≈6 to ≈10 Å). Moreover, these species exhibit pronounced topological changes when a weak non‐bonding NH⋅⋅⋅π aryl interaction is introduced. Finally, the NH‐bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes. Our results underscore these species as promising hydrogen bond donors for supramolecular host–guest applications.
Ambient Moisture Accelerates Hydroamination Reactions of Vinylarenes with Alkali‐Metal Amides under Air
Authors: Mulks Florian F. , Bole Leonie J. , Davin Laia , Hernán‐Gómez Alberto , Kennedy Alan , García‐Álvarez Joaquín , Hevia Eva
Published: July 2020

A straightforward alkali‐metal‐mediated hydroamination of styrenes using biorenewable 2‐methyltetrahydrofuran as a solvent is reported. Refuting the conventional wisdom of the incompatibility of organolithium reagents with air and moisture, shown here is that the presence of moisture is key in favoring formation of the target phenethylamines over competing olefin polymerization products. The method is also compatible with sodium amides, with the latter showing excellent promise as highly efficient catalysts under inert atmosphere conditions.
Co3O4 Hollow Nanoparticles Embedded in Mesoporous Walls of Carbon Nanoboxes for Efficient Lithium Storage
Authors: Huang Yi , Fang Yongjin , Lu Xue Feng , Luan Deyan , Lou Xiong Wen (David)
Published: July 2020

Confining nanostructured electrode materials in porous carbon represents an effective strategy for improving the electrochemical performance of lithium‐ion batteries. Herein, we report the design and synthesis of hybrid hollow nanostructures composed of highly dispersed Co3O4 hollow nanoparticles (sub‐20 nm) embedded in the mesoporous walls of carbon nanoboxes (denoted as H‐Co3O4@MCNBs) as an anode material for lithium‐ion batteries. The facile metal–organic framework (MOF)‐engaged strategy for the synthesis of H‐Co3O4@MCNBs involves chemical etching‐coordination and subsequent two‐step annealing treatments. Owing to the unique structural merits including more active interfacial sites, effectively alleviated volume variation, good and stable electrical contact, and easy access of Li+ ions, the H‐Co3O4@MCNBs exhibit excellent lithium‐storage performance in terms of high specific capacity, excellent rate capability, and cycling stability.
Manipulating the Click Reactivity of Dibenzoazacyclooctynes: From Azide Click Component to Caged Acylation Reagent by Silver Catalysis
Authors: Shi Wei , Tang Feng , Ao Jiwei , Yu Qun , Liu Junjie , Tang Yubo , Jiang Bofeng , Ren Xuelian , Huang He , Yang Weibo , Huang Wei
Published: July 2020

Strain‐promoted azide–alkyne cycloaddition using dibenzoazacyclooctyne (DBCO) is widely applied in copper‐free bioorthogonal reactions. Reported here is the efficient acid‐promoted rearrangement and silver‐catalyzed amidation of DBCO, which alters its click reactivity robustly. In the switched click reaction, DBCO, as a caged acylation reagent, enables rapid peptide/protein modification after decaging facilitated by silver catalysts, rendering site‐specific conjugation of an IgG antibody by a Fc‐targeting peptide.
Adsorptive Separation of Benzene, Cyclohexene, and Cyclohexane by Amorphous Nonporous Amide Naphthotube Solids
Authors: Yao Huan , Wang Yu‐Mei , Quan Mao , Farooq M. Umar , Yang Liu‐Pan , Jiang Wei
Published: July 2020

Benzene hydrogenation is an important industrial process. The reaction is incomplete, resulting in a mixture of benzene, cyclohexane, and/or cyclohexene that have to be separated before any further reactions. The currently used extractive and azeotropic distillations are operationally complex and energy intensive. Adsorptive separation provides an alternative energy‐efficient method. However, the separation of the ternary mixture by adsorptive separation has not yet been reported. In the present research, we report two macrocyclic hosts with hydrogen‐bonding sites in their cavities that are able to separate the ternary mixture of benzene, cyclohexene, and cyclohexane. N−H⋅⋅⋅π interactions were found to play a key role in the selective separation. In addition, fast adsorption, high loading ratios, and easy recycling are achieved with the present system, which is promising for practical applications.
Efficient Trapping of Trace Acetylene from Ethylene in an Ultramicroporous Metal–Organic Framework: Synergistic Effect of High‐Density Open Metal and Electronegative Sites
Authors: Zhang Zhaoqiang , Peh Shing Bo , Wang Yuxiang , Kang Chengjun , Fan Weidong , Zhao Dan
Published: July 2020

Acetylene (C2H2) removal from ethylene (C2H4) is a crucial step in the production of polymer‐grade C2H4but remains a daunting challenge because of the similar physicochemical properties of C2H2and C2H4. Currently energy‐intensive cryogenic distillation processes are used to separate the two gases industrially. A robust ultramicroporous metal–organic framework (MOF), Ni3(pzdc)2(7 Hade)2, is reported for efficient C2H2/C2H4separation. The MOF comprises hydrogen‐bonded linked one‐dimensional (1D) chains, and features high‐density open metal sites (2.7 nm−3) and electronegative oxygen and nitrogen sites arranged on the pore surface as cooperative binding sites. Theoretical calculations, in situ powder X‐ray diffraction and Fourier‐transform infrared spectroscopy revealed a synergistic adsorption mechanism. The MOF possesses S‐shaped 1D pore channels that efficiently trap trace C2H2at 0.01 bar with a high C2H2uptake of 60.6 cm3 cm−3and C2H2/C2H4selectivity.
Probing CO2 Reduction Pathways for Copper Catalysis Using an Ionic Liquid as a Chemical Trapping Agent
Authors: Zhang Gui‐Rong , Straub Sascha‐Dominic , Shen Liu‐Liu , Hermans Yannick , Schmatz Patrick , Reichert Andreas M. , Hofmann Jan P. , Katsounaros Ioannis , Etzold Bastian J. M.
Published: July 2020

The key to fully leveraging the potential of the electrochemical CO2 reduction reaction (CO2RR) to achieve a sustainable solar‐power‐based economy is the development of high‐performance electrocatalysts. The development process relies heavily on trial and error methods due to poor mechanistic understanding of the reaction. Demonstrated here is that ionic liquids (ILs) can be employed as a chemical trapping agent to probe CO2RR mechanistic pathways. This method is implemented by introducing a small amount of an IL ([BMIm][NTf2]) to a copper foam catalyst, on which a wide range of CO2RR products, including formate, CO, alcohols, and hydrocarbons, can be produced. The IL can selectively suppress the formation of ethylene, ethanol and n‐propanol while having little impact on others. Thus, reaction networks leading to various products can be disentangled. The results shed new light on the mechanistic understanding of the CO2RR, and provide guidelines for modulating the CO2RR properties. Chemical trapping using an IL adds to the toolbox to deduce the mechanistic understanding of electrocatalysis and could be applied to other reactions as well.
Efficient Reduction of Dioxygen with Ferrocene Catalyzed by Thiocarbohydrazone Tetranuclear Cobalt(III) Coordination Compound
Authors: Kamyabi Mohammad Ali , Alirezaei Fariba , Soleymani‐Bonoti Fatemeh , Bikas Rahman , Siczek Milosz , Lis Tadeusz
Published: July 2020

The synthesis, characterization and crystal structure of a tetranuclear cobalt(III) coordination compound, [Co4(L)4](HSO4)2(SO4)·4.1(CH3OH)·H2O (1), with thiocarbohydrazone based ligand is reported. This compound can efficiently catalyze the reduction of oxygen (O2) by a weak electron donor ferrocene, (Fc), at the polarized water/dichloroethane interface which was investigated by voltammetry and biphasic shake‐flask experiments. Compound1contains four cobalt cores which are connected together by sulphur atoms. By having four cobalt cores this coordination compound provides a multi‐electron transfer system for oxygen reduction reactions. The results also suggest that compound1catalyzes decomposition of H2O2at the interface.
Biological Applications of Macrocyclic Schiff Base Ligands and Their Metal Complexes: A Survey of the Literature (2005–2019)
Authors: Golbedaghi Reza , Tabanez Andreia M. , Esmaeili Somayeh , Fausto Rui
Published: July 2020

This article aims to provide a survey of biological applications of Schiff base macrocycles and their metal complexes, with emphasis given to the synthesis of the compounds and to their uses as antibacterial and antifungal agents. The literature on the subject, published during the 2005–2019 period, is shortly reviewed. This is an informed report collecting information on the addressed topic in a concise systematic way, and can be expected to be useful as a fast literature catalogue for researchers working on this and related domains.
Movement ecology of imperilled fish in a novel ecosystem: River‐reservoir movements by razorback sucker and translocations to aid conservation
Authors: Pennock Casey A. , McKinstry Mark C. , Cathcart Charles N. , Gido Keith B. , Francis Travis A. , Hines Brian A. , MacKinnon Peter D. , Hedden Skyler C. , Gilbert Eliza I. , Cheek Christopher A. , Speas David W. , Creighton Katherine , Elverud Darek S. , Schleicher Benjamin J.
Published: July 2020

Reservoirs and associated river fragments are novel ecosystems not experienced by fishes in their evolutionary history, yet they are now commonplace across the globe. Understanding how fishes use these novel habitats is vital to conservation efforts in contemporary riverscapes.

Movement patterns of the endangered razorback sucker (Xyrauchen texanus) synthesized from tagging efforts in the upper Colorado River basin, USA, illustrate the applications of tagging technology and data sharing by multiple agencies to better understand the spatial ecology of large river fishes.

Tagging studies between 2014 and 2018 in Lake Powell and its two main tributary rivers, the Colorado (unfragmented) and San Juan (waterfall‐fragmented), were used to quantify movement of razorback sucker within this river–reservoir habitat complex. In addition, facilitated translocations of fish upstream of a waterfall barrier in the San Juan River were assessed in 2016–2017.

Extensive movement of fish occurred within and across river and reservoir habitats. Of 722 fish captured in the Colorado River arm of Lake Powell, 36% of re‐encounters occurred upstream in the Colorado or Green rivers, or fish dispersed through the reservoir and were detected in the San Juan River arm. Fourteen fish moved more than 600 km. In the San Juan arm of the reservoir, 29% and 20% of fish in 2017 and 2018, respectively, had moved ~30–40 km upstream below the waterfall in the San Juan River within a year. In 2016–2017, 303 fish were translocated upstream of the waterfall into the San Juan River, but 80% were re‐encountered downstream of the waterfall within a year.

Long‐distance movements by razorback sucker were common within and among rivers and reservoirs illustrating how large river fish, in general, might maintain population connectivity in highly altered ecosystems.
Understanding the Glycopeptide Antibiotic Crosslinking Cascade: In Vitro Approaches Reveal the Details of a Complex Biosynthesis Pathway
Authors: Zhao Yongwei , Ho Y. T. Candace , Tailhades Julien , Cryle Max
Published: July 2020

The glycopeptide antibiotics (GPAs) are a fascinating example of complex natural product biosynthesis, with the nonribosomal synthesis of the peptide core coupled to a cytochrome P450‐mediated cyclisation cascade that crosslinks aromatic side chains within this peptide. Given that the challenges associated with the synthesis of GPAs stems from their highly crosslinked structure, there is great interest in understanding how biosynthesis accomplishes this challenging set of transformations. In this regard, the use of in vitro experiments has delivered important insights into this process, including the identification of the unique role of the X‐domain as a platform for P450 recruitment. In this minireview, we present an analysis of the results of in vitro studies into the GPA cyclisation cascade that have demonstrated both the tolerances and limitations of this process for modified substrates, and in turn developed rules for the future reengineering of this important antibiotic class.
Photo‐biohydrogen Production by Photosensitization with Biologically Precipitated Cadmium Sulfide in Hydrogen‐Forming Recombinant Escherichia coli
Authors: Honda Yuki , Shinohara Yuka , Watanabe Motonori , Ishihara Tatsumi , Fujii Hiroshi
Published: July 2020

An inorganic‐biological hybrid system that integrates features of both stable and efficient semiconductors and selective and efficient enzymes is attractive for facilitating the conversion of solar energy to hydrogen. In this study, we aimed to develop a new photocatalytic hydrogen‐production system based on Escherichia coli whole‐cell genetically engineered as a biocatalysis for highly active hydrogen formation. The photocatalysis part was obtained by bacterial precipitation of cadmium sulfide (CdS), which is a visible‐light‐responsive semiconductor. The recombinant E. coli cells were sequentially subjected to CdS precipitation and heterologous [FeFe]‐hydrogenase synthesis to yield a CdS@E. coli hybrid capable of light energy conversion and hydrogen formation in a single cell. The CdS@E. coli hybrid achieved photocatalytic hydrogen production with a sacrificial electron donor, thus demonstrating the feasibility of our system and expanding the current knowledge of photosensitization using a whole‐cell biocatalyst with a bacterially precipitated semiconductor.
Epistaxis management on COVID‐19–positive patients: Our early case experience and treatment
Authors: Bathula Samba Siva R. , Patrick Tyler , Srikantha Luxman
Published: July 2020

Epistaxis management on COVID‐19 patients is concerning for otolaryngologists due to the highly virulence and increased concentration within respiratory droplets and nasal secretions. Authors suggest initial management with oxymetazoline nasal drops and local pressure before considering nasal packing with absorbable material to prevent COVID‐19 transmission to surrounding healthcare workers.
Recent progress and challenges of carbon materials for Zn‐ion hybrid supercapacitors
Authors: Liu Qiyu , Zhang Haozhe , Xie Jinhao , Liu Xiaoqing , Lu Xihong
Published: July 2020

Zinc‐ion hybrid supercapacitors (ZHSCs) have garnered increasing attention as promising energy storage devices in recent years, as they combine the advantages of high‐energy Zn‐ion batteries and high‐power supercapacitors. However, the development of ZHSCs is still in its infancy and there are many bottlenecks to overcome. In particular, the challenge induced by the limited ion adsorption capability of carbon‐positive electrodes severely restricts the energy density of ZHSCs. Therefore, it has become a key issue to design novel carbon‐positive electrodes that enable high energy density yet do not deteriorate the intrinsic power capability and long‐term durability. This study focuses on recent achievements in synthesis, morphology, and electrochemical performance of various carbon materials applied in ZHSCs. The modification strategies to optimize their electrochemical performance are briefly summarized. In addition, current challenges and future opportunities in this field are also outlined. This review will be beneficial to provide an organized framework for the research systems of carbon‐positive electrodes and develop novel ZHSCs with high energy density.
Synthesis and Applications of Cinchona Squaramide‐Modified Poly(Glycidyl Methacrylate) Microspheres as Recyclable Polymer‐Grafted Enantioselective Organocatalysts
Authors: Nagy Sándor , Fehér Zsuzsanna , Kárpáti Levente , Bagi Péter , Kisszékelyi Péter , Koczka Béla , Huszthy Péter , Pukánszky Béla , Kupai József
Published: July 2020

This work presents the immobilization of cinchona squaramide organocatalysts on poly(glycidyl methacrylate) solid supports. Preparation of the well‐defined monodisperse polymer microspheres was facilitated by comprehensive parameter optimization. By exploiting the reactive epoxy groups of the polymer support, three amino‐functionalized cinchona derivatives were immobilized on this carrier. To explore the effect of the amino linker, these structurally varied precatalysts were synthesized by modifying the cinchona skeleton at different positions. The catalytic activities of the immobilized organocatalysts were tested in the Michael addition of pentane‐2,4‐dione and trans‐β‐nitrostyrene with excellent yields (up to 98 %) and enantioselectivities (up to 96 % ee). Finally, the catalysts were easily recovered five times by centrifugation without loss of activity.
Distinct Helical Molecular Orbitals through Conformational Lock**
Authors: Ozcelik Ani , Aranda Daniel , Gil‐Guerrero Sara , Pola‐Otero Xaquín A. , Talavera Maria , Wang Liangxuan , Behera Santosh Kumar , Gierschner Johannes , Peña‐Gallego Ángeles , Santoro Fabrizio , Pereira‐Cameselle Raquel , Alonso‐Gómez J. Lorenzo
Published: July 2020

Several theoretical studies have proposed strategies to generate helical molecular orbitals (Hel‐MOs) in [n]cumulenes and oligoynes. While chiral even‐[n] cumulenes feature Hel‐MOs, odd‐[n] cumulenes may also present them if the terminal groups lie in different planes. However, the proposed systems have been either experimentally unfeasible or resulted in opposite pseudo‐degenerated Hel‐MOs. We hereby demonstrate the introduction of a remarkable energy difference between helical orbitals of opposite twist by fixing the torsion angle between the terminal groups in butadiyne fragments. To experimentally lock the conformation of the terminal groups, we designed and synthesized cyclic architectures by combining acetylenes with chiral spirobifluorenes. The high stability of these systems with distinct helical orbitals allowed their isolation and full characterization. In our view, these results constitute a step further in the development of real systems presenting helical molecular orbitals.
A Reversible Liquid‐to‐Liquid Organic Hydrogen Carrier System Based on Ethylene Glycol and Ethanol
Authors: Zhou Quan‐Quan , Zou You‐Quan , Ben‐David Yehoshoa , Milstein David
Published: July 2020

Liquid organic hydrogen carriers (LOHCs) are powerful systems for the efficient unloading and loading molecular hydrogen. Herein, a liquid‐to‐liquid organic hydrogen carrier system based on reversible dehydrogenative coupling of ethylene glycol (EG) with ethanol catalysed by ruthenium pincer complexes is reported. Noticeable advantages of the current LOHC system is that both reactants (hydrogen‐rich components) and the produced esters (hydrogen‐lean components) are liquids at room temperature, and the dehydrogenation process can be performed under solvent and base‐free conditions. Moreover, the hydrogenation reaction proceeds under low hydrogen pressure (5 bar), and the LOHC system has a relatively high theoretical gravimetric hydrogen storage capacity (HSC>5.0 wt %), presenting an attractive hydrogen storage system.
Copper‐Catalyzed Oxidative Cross‐Coupling of Electron‐Deficient Polyfluorophenylboronate Esters with Terminal Alkynes
Authors: Liu Zhiqiang , Budiman Yudha P. , Tian Ya‐Ming , Friedrich Alexandra , Huang Mingming , Westcott Stephen A. , Radius Udo , Marder Todd B.
Published: July 2020

We report herein a mild procedure for the copper‐catalyzed oxidative cross‐coupling of electron‐deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cross‐coupled alkynyl(fluoro)arene products in moderate to excellent yields. Thus, it represents a simple alternative to the conventional Sonogashira reaction.
Computational Analysis of Mesomerism in para‐Substituted mer‐NCN Pincer Platinum(II) Complexes, Including its Relationships with Hammett σp Substituent Parameters
Authors: Canty Allan J. , Ariafard Alireza , van Koten Gerard
Published: July 2020

Density Functional Theory studies of square‐planar PtII pincer structures, (4‐Z‐NCN)PtCl ([4‐Z‐NCN]−=[4‐Z‐2,6‐(Me2NCH2)2C6H2‐N,C,N]−, Z=H, NO2, CF3, CO2H, CHO, Cl, Br, I, F, SMe, SiMe3, tBu, OH, NH2, NMe2), enable characterisation of mesomerism for the pincer‐Pt interaction. Relationships between Hammett σp substituent parameters of Z and DFT data obtained from NBO6 and AOMix computation are used to probe the interaction of the 5dyz orbital of platinum with π‐orbitals of the arene ring. Analogous computation for 2,6‐(Me2CH2)2C6H3Z (Z=H, CF3, CHO, Cl, Br, I, F, SMe, SiMe3, tBu, OH, NH2) and (4‐H‐NCN)PtZ allows an estimation of the relative substituent effects of “(CH2NMe2)2PtZ” on π‐delocalisation in the pincer system.
Survival and clinical outcomes of patients with ovarian cancer who were treated on phase 1 clinical trials
Authors: Corr Bradley R. , Moroney Marisa , Sheeder Jeanelle , Eckhardt S. Gail , Sawyer Brandon , Behbakht Kian , Diamond Jennifer R.
Published: July 2020

Background

Patients with ovarian cancer who are enrolled on phase 1 trials typically have platinum‐resistant and heavily pretreated disease, with a poor prognosis. In the current study, the authors assessed prognostic factors and survival in women with recurrent ovarian cancer who were treated on phase 1 clinical trials.

Methods

The authors performed a retrospective analysis of patients treated from 2008 through 2018 at the University of Colorado Cancer Center. Patient characteristics and treatment and toxicity‐related survival data were assessed. Descriptive statistics and Cox proportional hazards models were used to identify risk factors associated with survival time.

Results

A total of 132 patients were treated on phase 1 clinical trials. Patients had a median age of 59 years (range, 33‐88 years) with a median of 5.5 previous chemotherapy lines (range, 1‐13 lines). Of the 132 patients, 53 (40%) were treated on multiple phase 1 trials with a median of 1 (range, 0‐5) prior phase 1 trial. The overall response rate was 14.7%. The median overall survival was 11.3 months (95% CI, 9.1‐13.4 months). Two patients died on trial due to progression of disease whereas no patients died of treatment‐related toxicity. Independent risk factors found to be predictive of shorter survival were an elevated cancer antigen 125 (CA 125) level (hazard ratio [HR], 2.8; 95% CI, 1.6‐5.2) and albumin <3.5 g/dL (HR, 2.5; 95% CI, 1.65‐3.79). A body mass index >25 kg/m2 was predictive of longer survival (HR, 0.65; 95% CI, 0.44‐0.96).

Conclusions

In the current single‐institution series, patients with heavily pretreated ovarian cancer who were treated on phase 1 clinical trials experienced a median overall survival of 11.3 months. When available, phase 1 clinical trials represent a reasonable treatment option for patients with heavily pretreated ovarian cancer with a preserved performance status.
Effect of Hepatic Impairment on Cobimetinib Pharmacokinetics: The Complex Interplay Between Physiological Changes and Drug Characteristics
Authors: Cheeti Sravanthi , Deng Yuzhong , Chang Ilsung , Georgescu Isabela , Templeton Ian , Choong Nicholas , Cheung Kit Wun Kathy , Girish Sandhya , Musib Luna
Published: July 2020

Cobimetinib is a kinase inhibitor indicated for use in combination with vemurafenib for treatment of unresectable/metastatic melanoma with specific BRAF mutations. Cobimetinib is extensively metabolized in liver; thus, patients with hepatic impairment (HI) might have increased cobimetinib exposure. In this study, we investigated the impact of HI on the pharmacokinetics (PK) and safety of cobimetinib. Subjects with normal hepatic function and mild to severe HI were enrolled. All subjects received a single oral dose of 10 mg cobimetinib, and serial blood samples were collected at specified times. Cobimetinib PK in subjects with mild and moderate HI was similar to that in those with normal liver function. However, subjects with severe HI, on average, showed ∼30% lower total AUC0‐∞ and ∼2‐fold higher unbound AUC0‐∞ compared with those with normal hepatic function. These exposure differences can be explained by lower albumin levels observed in subjects with severe HI, the strong correlation between albumin level and the unbound fraction and the general PK variability of cobimetinib. In addition, previous studies with cobimetinib showed a lack of an exposure‐response relationship for efficacy and safety. Therefore, collectively, our results suggest that the starting dose for patients with hepatic impairment can be the same as that for those with normal hepatic function.
Molecular Mobility of Tert‐butyl Alcohol Confined in a Breathing MIL‐53 (Al) Metal‐Organic Framework
Authors: Khudozhitkov Alexander E. , Toktarev Alexander V. , Arzumanov Sergei S. , Gabrienko Anton A. , Kolokolov Daniil I. , Stepanov Alexander G.
Published: July 2020

We present a detailed solid‐state NMR characterization of the molecular dynamics of tert‐butyl alcohol (TBA) confined inside breathing metal‐organic framework (MOF) MIL‐53(Al). 27Al MAS NMR has demonstrated that TBA adsorption induces the iX phase of MIL‐53 material with partially shrunk channels. 2H solid‐state NMR has shown that the adsorbed alcohol exhibits anisotropic rotations of the methyl groups around two
axes and librations of the molecule as a whole about the axis passing through the TBA C−O bond. These librations are realized by two distinct ways: fast molecule orientation change during the translational jump diffusion along the channel with characteristic time τD of about 10−9 s at 300 K; slow local librations at a single coordination site, representing framework hydroxyl groups, with τl≈10−6 s at 300 K. Self‐diffusion coefficient of the alcohol in the MOF has been estimated: D=3.4×10−10 m2 s−1 at 300 K. It has been inferred that both the framework flexibility and the interaction with framework hydroxyl groups define the dynamics of TBA confined in the channels of MIL‐53 (Al).
Insights into Nitrogenase Bioelectrocatalysis for Green Ammonia Production
Authors: Rapson Trevor D. , Gregg Christina M. , Allen Robert S. , Ju HyungKuk , Doherty Cara M. , Mulet Xavier , Giddey Sarbjit , Wood Craig C.
Published: July 2020

There is a growing interest in using ammonia as a liquid carrier of hydrogen for energy applications. Currently, ammonia is produced industrially by the Haber‐Bosch process, which requires high temperature and high pressure. In contrast, bacteria have naturally evolved an enzyme known as nitrogenase, that is capable of producing ammonia and hydrogen at ambient temperature and pressure. Therefore, nitrogenases are attractive as a potentially more efficient means to produce ammonia via harnessing the unique properties of this enzyme. In recent years, exciting progress has been made in bioelectrocatalysis using nitrogenases to produce ammonia. Here, the prospects for developing biological ammonia production are outlined, key advances in bioelectrocatalysis by nitrogenases are highlighted, and possible solutions to the obstacles faced in realising this goal are discussed.
Effects on Carbon Molecular Sieve Membrane Properties for a Precursor Polyimide with Simultaneous Flatness and Contortion in the Repeat Unit
Authors: Liang Jiachen , Wang Zhenggong , Huang Menghui , Wu Shanshan , Shi Yanshu , Zhang Yatao , Jin Jian
Published: July 2020

Carbon molecular sieve (CMS)‐based membrane separation is a promising solution for hydrogen separation due to its great advantages on perm‐selectivity, thermal stability, and chemical stability. To prepare high‐performance CMS membranes, the molecular structure of polymer precursors and their arrangements should be primarily considered. In this work, a benzimidazole‐based 6FDA (2,2′‐bis(3,4′‐dicarboxyphenyl) hexafluoropropane dianhydride)‐type polyimide (PABZ‐6FDA‐PI) is chosen as precursor to prepare the CMS membrane. Effects of chain flatness and contortion in the polyimide precursor on gas‐separation performance of CMS membranes were studied in detail by gas adsorption and permeation experiment. The H2 permeability of CMS is up to 9500 Barrer and ideal selectivity of gas pairs of H2/CH4 and H2/CO2 is up to 3800 and 13, respectively. The comprehensive performance of hydrogen separation including H2/CO2, H2/N2, and H2/CH4 gas pairs is located well above previously reported upper bounds for polymers.
Synthesis of Dicarboxylic Acids from Aqueous Solutions of Diols with Hydrogen Evolution Catalyzed by an Iridium Complex
Authors: Toyooka Genki , Fujita Ken‐ichi
Published: July 2020

Invited for this month′s cover is the group of Prof. Ken‐ichi Fujita at Kyoto University, Japan. The image shows an ordinary bird that has been transformed into a phoenix, which we metaphorically compare to the conversion of readily available diols to industrially important dicarboxylic acids. The Communication itself is available at 10.1002/cssc.202001052.
A hybrid elephant herding optimization and cultural algorithm for energy‐balanced cluster head selection scheme to extend the lifetime in WSNs
Authors: Murugadass Gopal , Sivakumar Poruran
Published: July 2020

Clustering‐based optimal cluster head selection in wireless sensor networks (WSNs) is considered as the efficient technique essential for improving the network lifetime. But enforcing optimal cluster head selection based on energy stabilization, reduced delay, and minimized distance between sensor nodes always remain a crucial challenge for prolonging the network lifetime in WSNs. In this paper, a hybrid elephant herding optimization and cultural algorithm for optimal cluster head selection (HEHO‐CA‐OCHS) scheme is proposed to extend the lifetime. This proposed HEHO‐CA‐OCHS scheme utilizes the merits of belief space framed by the cultural algorithm for defining a separating operator that is potent in constructing new local optimal solutions in the search space. Further, the inclusion of belief space aids in maintaining the balance between an optimal exploitation and exploration process with enhanced search capabilities under optimal cluster head selection. This proposed HEHO‐CA‐OCHS scheme improves the characteristic properties of the algorithm by incorporating separating and clan updating operators for effective selection of cluster head with the view to increase the lifetime of the network. The simulation results of the proposed HEHO‐CA‐OCHS scheme were estimated to be superior in percentage of alive nodes by 11.21%, percentage of dead nodes by 13.84%, residual energy by 16.38%, throughput by 13.94%, and network lifetime by 19.42% compared to the benchmarked cluster head selection schemes.
Eco‐evolutionary dynamics of range expansion
Authors: Miller Tom E. X. , Angert Amy L. , Brown Carissa D. , Lee‐Yaw Julie A. , Lewis Mark , Lutscher Frithjof , Marculis Nathan G. , Melbourne Brett A. , Shaw Allison K. , Szűcs Marianna , Tabares Olivia , Usui Takuji , Weiss‐Lehman Christopher , Williams Jennifer L.
Published: July 2020

Understanding the movement of species’ ranges is a classic ecological problem that takes on urgency in this era of global change. Historically treated as a purely ecological process, range expansion is now understood to involve eco‐evolutionary feedbacks due to spatial genetic structure that emerges as populations spread. We synthesize empirical and theoretical work on the eco‐evolutionary dynamics of range expansion, with emphasis on bridging directional, deterministic processes that favor evolved increases in dispersal and demographic traits with stochastic processes that lead to the random fixation of alleles and traits. We develop a framework for understanding the joint influence of these processes in changing the mean and variance of expansion speed and its underlying traits. Our synthesis of recent laboratory experiments supports the consistent role of evolution in accelerating expansion speed on average, and highlights unexpected diversity in how evolution can influence variability in speed: results not well predicted by current theory. We discuss and evaluate support for three classes of modifiers of eco‐evolutionary range dynamics (landscape context, trait genetics, and biotic interactions), identify emerging themes, and suggest new directions for future work in a field that stands to increase in relevance as populations move in response to global change.
Rationale and design of a risk‐guided strategy for reducing readmissions for acute decompensated heart failure: the Risk‐HF study
Authors: Zisis Georgios , Huynh Quan , Yang Yang , Neil Christopher , Carrington Melinda J. , Ball Jocasta , Maguire Graeme , Marwick Thomas H.
Published: July 2020

Aims

Heart failure (HF) readmission commonly arises owing to insufficient patient knowledge and failure of recognition of the early stages of recurrent fluid congestion. In previous work, we developed a score to predict short‐term hospital readmission and showed that higher‐risk patients benefit most from a disease management programme (DMP) that included enhancing knowledge and education by a nurse. We aim to evaluate the effectiveness of a novel, nurse‐led HF DMP in selected patients at high risk of short‐term hospital readmission, using ultrasound‐guided diuretic management and artificial intelligence to enhance HF knowledge in an outpatient setting.

Methods and results

Risk‐HF is a prospective multisite randomized controlled trial that will allocate 404 patients hospitalized with acute decompensated HF, and ≥33% risk of readmission and/or death at 30 days, into risk‐guided nurse intervention (DMP‐Plus group) compared with usual care. Intervention elements include (i) fluid management with a handheld ultrasound (HHU) device at point of care; (ii) post‐discharge follow‐up; (iii) optimal programmed drug titration; (iv) better transition of care; (v) intensive self‐care education via an avatar‐based ‘digital health coach’; and (vi) exercise guidance through the digital coach. Usual care involves standard post‐discharge hospital care. The primary outcome is reduced death and/or hospital readmissions at 30 days post‐discharge, and secondary outcomes include quality of life, fluid management efficacy, and feasibility and patient engagement. Assuming that our intervention will reduce readmissions and/or deaths by 50%, with a 1:1 ratio of intervention vs. usual care, we plan to randomize 404 patients to show a difference at a statistical power of 80%, using a two‐sided alpha of 0.05. We anticipate this recruitment will be achieved by screening 2020 hospitalized HF patients for eligibility. An 8 week pilot programme of our digital health coach in 21 HF patients, age > 75 years, showed overall improvements in quality of life (13 of 21), self‐care (12 of 21), and HF knowledge (13 of 21). A pilot of the use of HHU by nurses showed that it was feasible and accurate.

Conclusions

The Risk‐HF trial will evaluate the effectiveness of a risk‐guided intervention to improve HF outcomes and will evaluate the efficacy of trained HF nurses delivering a fluid management protocol that is guided by lung ultrasound with an HHU at point of care.
Iso‐maleimycin, a Constitutional Isomer of Maleimycin, from Streptomyces sp. QL37
Authors: Uiterweerd Michiel T. , Santiago Isabel Nuñez , van der Heul Helga , van Wezel Gilles P. , Minnaard Adriaan J.
Published: July 2020

Iso‐maleimycin, a previously unknown constitutional isomer of the antibiotic maleimycin, has been detected in an extract of Streptomyces sp. QL37. Chemical synthesis of both maleimycin (20 % yield over seven steps) and iso‐maleimycin, (15 % yield over six steps) allowed access to reference materials for identification. Gas Chromatography coupled Mass Spectrometry (GC‐MS) analysis demonstrated that of the two isomers, only iso‐maleimycin was present in the extract. This finding supports our hypothesis that iso‐maleimycin is a biosynthetic intermediate of lugdunomycin. Iso‐maleimycin displays low antibiotic activity, with a Minimum Inhibitory Concentration (MIC) value on both E. coli and B. subtilis of 250 µg/mL.
Base‐Promoted Double Amination of 1‐Haloalkynes: Direct Synthesis of Ene‐1,1‐diamines
Authors: Gulia Nurbey , Pigulski Bartłomiej , Szafert Sławomir
Published: July 2020

Selective and efficient synthetic procedure for highly reactive ene‐1,1‐diamines was developed by systematic investigation of double amination of 1‐haloalkynes. High yields, without the need for transition metal and simple isolation make the reported procedure superior compared to synthetic approaches reported so far. The reaction demonstrates high functional group tolerance, but its efficiency depends on the electronic properties of 1‐haloalkyne and the steric hindrance of an amine. The selected diamine and its corresponding protonated form – amidinium salt – have been examined for the first time by means of single‐crystal X‐ray diffraction. Finally, a new mechanism explaining selective formation of ene‐1,1‐diamines was proposed.
Regulation of Macrocycle Shuttling Rates in [2]Rotaxanes by Amino‐Acid Speed Bumps in Organic–Aqueous Solvent Mixtures
Authors: Douarre Maxime , Martí‐Centelles Vicente , Rossy Cybille , Pianet Isabelle , McClenaghan Nathan D.
Published: July 2020

A homologous series of two‐station [2]rotaxanes incorporating amino‐acid units in the molecular thread has been developed. The degenerate [2]rotaxanes exhibit amino‐acid specific shuttling rates between two fumaric stations related to the steric factor associated to the amino‐acid side chain, as demonstrated by variable‐temperature 1H NMR spectroscopy and exchange spectroscopy (EXSY). This allows tuning of the macrocycle shuttling rate over 4 orders of magnitude, which has a relatively small solvent dependency.
Hall and ion‐slip effects on MHD mixed convection flow in a vertical microchannel with asymmetric wall heating
Authors: Jha Basant K. , Malgwi Peter B.
Published: July 2020

In this article, a theoretical analysis is carried out on hydromagnetic mixed convection flow of viscous incompressible and electrically conducting fluid in a vertical microchannel in the existence of Hall current and ion‐slip effects. The walls of the microchannels are preheated and the flow is prompted by the combination of buoyancy forces and pressure gradient. The governing dimensional equations are obtained and reduced to dimensionless form using suitable transformations. The flow equations are solved analytically, and their solutions are obtained in dimensionless form. Some interesting effects of the relevant flow parameters on the flow formation and volume flow rates, in both primary and secondary flow directions, are showed. The results show that, in the presence of Hall current and pressure gradient, the ion‐slip current supports flow formation along the primary flow direction, while destabilizing it along the secondary direction. In addition, it is also highlighted that, in the presence of pressure gradient and buoyancy forces, the ion‐slip current increases the volume flow rate in both primary and secondary flow directions, whereas the Hall current destabilizes the volume flow rate along the primary direction.
Rock‐breaking mechanism and efficiency of straight‐swirling mixed nozzle for the nondiagenetic natural gas hydrate in deep‐sea shallow
Authors: Tang Yang , Sun Peng , Wang Guorong , Fu Biwei , Yao Jiaxin
Published: July 2020

Jet breaking using a high‐pressure nozzle is one solution for breaking natural gas hydrate (NGH) formations, creating a larger breaking volume and fluidizing broken solid fragments. Based on the analysis of various jet breaking mechanisms for the variation of the flow velocity of the internal and outlet sections of different nozzles, a straight‐swirling mixed nozzle (SSMN) was designed. We obtained different jet breaking effects for a single nozzle, including the influences of the working pressure and target distance on the hole shape, as well as working pressure on hole parameters and target distance on hole parameters. In addition, we analyzed the influences of the nozzle number, type of NGH rock, and construction parameters on the rock‐breaking efficiency and selected the best combination mode of multiple nozzles. The research results of the rock‐breaking mechanism and efficiency of the SSMN promotes the development of commercial mining technology for nondiagenetic NGH in deep‐sea shallow areas.