bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ru Nanoparticles Supported on Oxygen‐Deficient 3DOM BiVO4: High‐Performance Catalysts for the Visible‐Light‐Driven Selective Oxidation of Benzyl Alcohol
Authors: Zhang Kunfeng , Liu Yuxi , Deng Jiguang , Jing Lin , Pei Wenbo , Han Zhuo , Zhang Xing , Dai Hongxing 
Published: October 2019

AbstractDeveloping novel photocatalysts for green synthesis of important organic intermediates under mild conditions is of great significance in industry. In this work, we synthesized the oxygen‐deficient three‐dimensionally ordered macroporous (3DOM) BiVO4‐supported nanosized Ru (xRu/3DOM BiVO4, x=0.24–2.16 wt %) catalysts by the polymethyl methacrylate‐templating, ethylene glycol reduction, and post‐thermal treatment methods. Physicochemical properties of the materials were characterized using the various techniques, and their catalytic activities for the visible‐light‐driven selective oxidation of benzyl alcohol to benzaldehyde were measured. It is found that the Ru nanoparticles (NPs) with a size of 1.2–1.5 nm were uniformly dispersed on the surface of 3DOM BiVO4, which gave rise to a significant enhancement in photocatalytic activity. Benzyl alcohol conversion first went up and then dropped down with the rise in loading of Ru NPs. The 0.95Ru/3DOM BiVO4−Ar‐300 sample was thermally treated in an Ar flow at 300 °C for 4 h showed the highest benzyl alcohol conversion (78 %) with a benzaldehyde selectivity of 100 % (benzaldehyde formation rate was 1380 μmol/(g h) after 6 h of illumination) and good photocatalytic stability. The high dispersion of Ru NPs and formation of oxygen vacancies in 3DOM BiVO4 improved separation and transfer efficiency of the photogenerated electrons/holes and increased the superoxide radical concentration. In addition, the possible mechanism of benzyl alcohol oxidation over 0.95Ru/3DOM BiVO4−Ar‐300 was also discussed. The oxygen‐deficient 3DOM BiVO4‐supported Ru NPs have promising applications for selective oxidation of organics.
Influence of Coordination Environment of Anchored Single‐Site Cobalt Catalyst on CO2 Hydrogenation
Authors: Jimenez Juan D. , Wen Cun , Royko Michael M. , Kropf Arthur J. , Segre Carlo , Lauterbach Jochen 
Published: October 2019

AbstractHeterogeneous catalysts generally have a variety of active‐site structures due to the innate heterogeneity of the surface, resulting in complicated correlations between activity and active‐site structure. Single site heterogeneous cobalt catalysts with a uniform catalytic surface were utilized as a platform to probe surface sensitive reactions; in this case CO2 hydrogenation. It was found that atomically isolated cobalt single sites, which exist solely in the tetrahedral Co2+ coordination, exclusively form CO under typical CO2 methanation conditions, while cobalt clusters yielded the highest rate of CO2 reaction and began to form methane. Utilizing the principles of Ostwald Ripening to probe the ensemble effects for CO2 hydrogenation, the transition from atomic isolation to small clusters of atoms to nanoparticles was explored. The chemical structure of the cobalt was elucidated primarily via X‐Ray Absorption Spectroscopy (XANES/EXAFS) and X‐Ray Photoelectron Spectroscopy (XPS).
Bimetallic Selenide LiInSe2 Decorated with a Uniform Carbon Layer with Superior Lithium Storage Performance
Authors: Zhang Mengqi , Liu Yangyang , Zhang Yupeng , Bai Xue , Zhu He , Li Xuesong , Liu Yang , Cui Deliang , Li Bo , Tao Xutang 
Published: October 2019

AbstractOwing to their relatively high electronic conductivity and electrochemical activity, bimetallic chalcogenides exhibit promising applications in advanced lithium‐ion batteries. Herein, for the first time, a uniform thin carbon layer (about 2–3 nm) derived from citric acid coating bimetallic selenide, LiInSe2, is designed. When used as an anode material for lithium‐ion batteries, the novel carbon‐coated LiInSe2 anode delivers high initial charge/discharge capacities of 545.2/732.0 mAh g−1 at a current density of 100 mA g−1. Even after 800 cycles at 1500 mA g−1, a high reversible capacity of 333 mAh g−1 can be achieved, suggesting its superior rate capability and cycling stability. The excellent electrochemical performance of the carbon‐coated LiInSe2 anode is ascribed to the improved electronic/ionic conductivity, electrochemical activity, and reaction kinetics. This remarkable lithium storage property indicates the potential application of bimetallic selenide for future lithium‐ion batteries.
Differentiating and Quantifying Dead Lithium.
Authors: Sun Fu , Manke Ingo 
Published: October 2019

AbstractThe current Highlight emphasizes the significance of a recently published Nature paper (Nature 2019, 572, 511–515) and sheds light onto future research activities on Li anodes, for example, the solid electrolyte interphase Li, the dead Li, the morphology of the electrodeposited Li, as well as the correlation between the dead Li and battery performance degradation.
Control of Chemical Reactions by Using Molecules that Buffer Non‐aqueous Solutions
Authors: Sohail Muhammad , Tanaka Fujie 
Published: October 2019

AbstractControl of chemical reactions is necessary to obtain designer chemical transformation products and for preventing decomposition and isomerization reactions of compounds of interest. For the control of chemical events in aqueous solutions, the use of aqueous buffers is a common practice. However, no molecules that buffer non‐aqueous solutions were commonly used. Herein, we demonstrate that 1,3‐cyclohexanedione derivatives have buffering functions in non‐aqueous solutions. It was also shown that these molecules can be utilized to alter and control chemical reactions. 1,3‐Cyclohexanedione derivatives inhibited both acid‐ and base‐catalyzed isomerizations and decompositions in organic solvents. The reaction products obtained in the presence of the buffering molecule 2‐methyl‐1,3‐cyclohexanedione differed from those obtained in the absence of the buffering molecule. The use of buffering molecules that work in organic solvents provides a strategy to control chemical reactions and expands the range of compounds that can be synthesized.
Decomposition of Picolyl Radicals at High Temperature: A Mass Selective Threshold Photoelectron Spectroscopy Study
Authors: Reusch Engelbert , Holzmeier Fabian , Gerlach Marius , Fischer Ingo , Hemberger Patrick 
Published: October 2019

AbstractThe reaction products of the picolyl radicals at high temperature were characterized by mass‐selective threshold photoelectron spectroscopy in the gas phase. Aminomethylpyridines were pyrolyzed to initially produce picolyl radicals (m/z=92). At higher temperatures further thermal reaction products are generated in the pyrolysis reactor. All compounds were identified by mass‐selected threshold photoelectron spectroscopy and several hitherto unexplored reactive molecules were characterized. The mechanism for several dissociation pathways was outlined in computations. The spectrum of m/z=91, resulting from hydrogen loss of picolyl, shows four isomers, two ethynyl pyrroles with adiabatic ionization energies (IEad) of 7.99 eV (2‐ethynyl‐1H‐pyrrole) and 8.12 eV (3‐ethynyl‐1H‐pyrrole), and two cyclopentadiene carbonitriles with IE′s of 9.14 eV (cyclopenta‐1,3‐diene‐1‐carbonitrile) and 9.25 eV (cyclopenta‐1,4‐diene‐1‐carbonitrile). A second consecutive hydrogen loss forms the cyanocyclopentadienyl radical with IE′s of 9.07 eV (T0) and 9.21 eV (S1). This compound dissociates further to acetylene and the cyanopropynyl radical (IE=9.35 eV). Furthermore, the cyclopentadienyl radical, penta‐1,3‐diyne, cyclopentadiene and propargyl were identified in the spectra. Computations indicate that dissociation of picolyl proceeds initially via a resonance‐stabilized seven‐membered ring.
π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes
Authors: Miki Koji , Ohe Kouichi 
Published: October 2019

AbstractAngle‐strained alkyne‐containing π‐conjugated macrocycles are attractive compounds both in functional materials chemistry and biochemistry. Their interesting reactivity as well as photophysical and supramolecular properties have been revealed in the past three decades. This review highlights the recent advances in angle‐strained alkyne‐containing π‐conjugated macrocycles, especially their synthetic methods, the bond angles of alkynes (∠sp at C≡C−C), and their functions. The theoretical and experimental research on cyclo[n]carbons and para‐cyclophynes consisting of ethynylenes and para‐phenylenes are mainly summarized. Related macrocycles bearing other linkers, such as ortho‐phenylenes, meta‐phenylenes, heteroaromatics, biphenyls, extended aromatics, are also overviewed. Bond angles of strained alkynes in π‐conjugated macrocycles, which are generable, detectable, and isolable, are summarized at the end of this review.
Photoinduced Electron Transfer Involving a Naphthalimide Chromophore in Switchable and Flexible [2]Rotaxanes
Authors: Colasson Benoit , Credi Alberto , Ventura Barbara 
Published: October 2019

AbstractThe interlocking of ring and axle molecular components in rotaxanes provides a way to combine chromophoric, electron‐donor and electron‐acceptor moieties in the same molecular entity, in order to reproduce the features of photosynthetic reaction centers. To this aim, the photoinduced electron transfer processes involving a 1,8‐naphthalimide chromophore, embedded in several rotaxane‐based dyads, were investigated by steady‐state and time‐resolved absorption and luminescence spectroscopic experiments in the 300 fs–10 ns time window. Different rotaxanes built around the dialkylammonium/ dibenzo[24]crown‐8 ether supramolecular motif were designed and synthesized to decipher the relevance of key structural factors, such as the chemical deactivation of the ammonium‐crown ether recognition, the presence of a secondary site for the ring along the axle, and the covalent functionalization of the macrocycle with a phenothiazine electron donor. Indeed, the conformational freedom of these compounds gives rise to a rich dynamic behavior induced by light and may provide opportunities for investigating and understanding phenomena that take place in complex (bio)molecular architectures.
Iron Coordination to Hollow Microporous Metal‐Free Disalphen Networks: Heterogeneous Iron Catalysts for CO2 Fixation to Cyclic Carbonates
Authors: Cho Kyoungil , Lee Sang Moon , Kim Hae Jin , Ko Yoon‐Joo , Kang Eun Joo , Son Seung Uk 
Published: October 2019

AbstractThis work shows that a hollow and microporous metal‐free N,N′‐phenylenebis(salicylideneimine) (salphen) network (H‐MSN) can be engineered by Sonogashira coupling of [tetraiodo{di(Zn‐salphen)}] building blocks with 1,4‐diethynylbenzene in the presence of silica templates and by successive Zn and silica etching. Iron(III) ions could be incorporated into the H‐MSN to form hollow and microporous Fe–disalphen networks (H‐MFeSN) with enhanced microporosity and surface area. The H‐MFeSN showed efficient catalytic performance and recyclability in the CO2 conversion to cyclic carbonates.
Facile Generation of Thermally Activated Delayed Fluorescence and Fabrication of Highly Efficient Non‐Doped OLEDs Based on Triazine Derivatives
Authors: Chih Hsin‐Yun , Chen Ying‐Wei , Hsieh Yi‐Chun , Li Wei‐Cheng , Liao Chia‐Wei , Lin Chun‐Han , Chiu Ting‐Ya , Tsai Wei‐Wen , Lu Chin‐Wei , Chang Chih‐Hao 
Published: October 2019

AbstractA series of donor–acceptor–donor triazine‐based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain highly efficient blue‐emitting OLEDs with non‐doped emitting layers (EMLs). The targeted molecules use a triazine core as the electron acceptor, and a benzene ring as the conjugated linker with different electron donors to alternate the energy level of the HOMO to further tune the emission color. The introduction of long alkyl chains on the triazine core inhibits the unwanted intermolecular D–D/A–A‐type π–π interactions, resulting in the intermolecular D–A charge transfer. The weak aggregation‐caused quenching (ACQ) effect caused by the suppressed intermolecular D–D/A–A‐type π–π interaction further enhances the emission. The crowded molecular structure allows the electron donor and acceptor to be nearly orthogonal, thereby reducing the energy gap between triplet and singlet excited states (ΔEST). As a result, blue‐emitting devices with TH‐2DMAC and TH‐2DPAC non‐doped EMLs showed satisfactory efficiencies of 12.8 % and 15.8 %, respectively, which is one of the highest external quantum efficiency (EQEs) reported for blue TADF emitters (λpeak<475 nm), demonstrating that our tailored molecular designs are promising strategies to endow OLEDs with excellent electroluminescent performances.
Supramolecular Nanowires from an Acceptor–Donor–Acceptor Conjugated Chromophore
Authors: Chakraborty Saptarshi , Varghese Shinto , Ghosh Suhrit 
Published: October 2019

AbstractOligothiophene derivatives have been extensively studied as p‐type semiconducting materials in organic electronics applications. This work reports the synthesis, self‐assembly and photophysical properties of acceptor–donor–acceptor (A–D–A)‐type oligothiophene derivatives by end‐group engineering of quaterthiophene (QT) with naphthalene monoimide (NMI) chromophores that are further connected to a trialkoxy benzamide wedge. Conjugation to the NMI units reduces the HOMO–LUMO gap significantly, and consequently the absorption spectrum exhibits a bathochromic shift of about 50 nm compared with QT. Furthermore, extended H‐bonding interactions among the amido groups of the peripheral wedges produce entangled fibrillar nanostructures and gelation in hydrocarbon solvents such as methylcyclohexane, wherein the A–D–A chromophore exhibits typical H‐aggregation. On the contrary, the fact that the same chromophore, lacking only the amido units, does not produce gels or H‐aggregates indicates strong impact of H‐bonding on the self‐assembly. Computational studies revealed the electronic properties of the chromophore and predicted the geometry of a dimer in the H‐aggregate that reasonably matches with the experimental results. Bulk electrical conductivity measurements determined an excellent conductivity of 2.3×10−2 S cm−1 for the H‐aggregated system (OT‐1), which is two orders of magnitude higher than that of the same chromophore lacking the amido groups (OT‐2).
Dehydrative Glycosylation Enabled by a Comproportionation Reaction of 2‐Aryl‐1,3‐dithiane 1‐Oxide†
Authors: Cai Lei , Zeng Jing , Li Ting , Xiao Ying , Ma Xiang , Xiao Xiong , Zhang Qin , Meng Lingkui , Wan Qian 
Published: October 2019

Summary of main observation and conclusionA new dehydrative glycosylation reaction has been established by capitalizing on the comproportionation reaction of 2‐aryl‐1,3‐dithiane 1‐oxides promoted by triflic anhydride (Tf2O). By wedding the high potency of thiophilic promoter system with the step efficiency of dehydrative glycosylation, this reagent underwent facile intermolecular oxothio acetalization with C1‐hemiacetal donor to install a temporary leaving group, rendering a transient electrophilic center at the remote site to the anomeric position. The sulfenyl triflate tethered at the terminus concomitantly activated the sulfide intramolecularly to afford the oxocarbenium ion, thereby facilitating the title glycosylation. Aside from accommodating broad range functional groups and inactive hemiacetal substrates, the present activation protocol also proved expedient for 1,3‐diol protection. Most importantly, this method further provided a fresh perspective for the application of sulfur chemistry to carbohydrate chemistry.
Facilities that service economically advantaged neighborhoods perform surgical metastasectomy more often for patients with colorectal liver metastases
Authors: Uppal Abhineet , Smieliauskas Fabrice , Sharma Manish R. , Maron Steven B. , Polite Blase N. , Posner Mitchell C. , Turaga Kiran 
Published: October 2019

BackgroundMetastasectomy of isolated colorectal liver metastases (CRLM) requires significant clinical expertise and may not be readily available or offered. The authors hypothesized that hospitals that treat a greater percentage of patients from higher income catchment areas are more likely to perform metastasectomies regardless of patient or tumor characteristics.MethodsUsing the National Cancer Data Base, the authors classified facilities into facility income quartiles (FIQs) based on the percentage of patients from the wealthiest neighborhoods (by zip code). Quartile 1 included facilities with <2.1% of the patients residing within the highest income zip codes, quartile 2 included facilities with 2.2% to 15.6% of patients residing within the highest income zip codes, quartile 3 included facilities with 15.7% to 40.2% of patients residing within the highest income zip codes, and quartile 4 included facilities with 40.3% to 90.5% of patients residing within the highest income ZIP codes. Patient, tumor, and facility characteristics were analyzed using a multivariate logistic regression to identify associations between metastasectomy and FIQ.ResultsPatients with CRLM were more likely to undergo metastasectomy at facilities in the highest FIQ compared with the lowest FIQ (18% vs 11% in FIQ4; P = .001). This trend was not observed in the resection of primary tumors for nonmetastatic CRLM (rates of 95% vs 93%; P = .94). After adjusting for individual insurance status, distance traveled, zip code–level individual income, tumor, and host, patients who were treated at the highest FIQ facilities were found to be more likely to undergo metastasectomy (odds ratio, 1.29; 95% CI, 1.02‐1.72 [P = .03]).ConclusionsMetastasectomy for CRLM is more likely to occur at facilities that serve a greater percentage of patients from high‐income catchment areas, regardless of individual patient characteristics. This disparity uniquely affects those patients with advanced cancers for which specialized expertise for therapy is necessary.
Rapid Detection of AIB1 in Breast Cancer Cells Based on Aptamer‐Functionalized Nanomotors
Authors: Beltrán‐Gastélum Mara , Esteban‐Fernández de Ávila Berta , Gong Hua , Venugopalan Pooyath Lekshmy , Hianik Tibor , Wang Joseph , Subjakova Veronika 
Published: October 2019

AbstractHerein, we report ultrasound‐propelled graphene‐oxide coated gold nanowire motors, functionalized with fluorescein‐labeled DNA aptamers (FAM‐AIB1‐apt), for qualitative detection of overexpressed AIB1 oncoproteins in MCF‐7 breast cancer cells. The movement of nanomotors under the ultrasound field facilitated intracellular uptake and resulted in a faster aptamer binding with the target protein and thus faster fluorescence recovery. The propulsion behavior of the aptamer functionalized nanomotors greatly enhanced the fluorescence intensity compared to static conditions. The new aptamer@nanomotor‐based strategy offers considerable potential for further development of sensing methodologies towards diagnosis of breast cancer.
Miniaturized Energy Storage Devices Based on Two‐Dimensional Materials
Authors: Jiang Kang , Weng Qunhong 
Published: October 2019

AbstractA growing demand for miniaturized biomedical sensors, microscale self‐powered electronic systems, and many other portable, wearable, and integratable electronic devices is continually stimulating the rapid development of miniaturized energy storage devices (MESDs). Miniaturized batteries (MBs) and supercapacitors (MSCs) were considered to be suitable energy storage devices to power microelectronics uninterruptedly with reasonable energy and power densities. However, in addition to similar challenges encountered with electrode materials in conventional energy storage devices, their performances are also greatly affected by microfabrication technologies, as well as the challenges of how to realize stable and high‐performance MESDs in such a limited footprint area. Benefiting from the unique architectural engineering of two‐dimensional materials and the emergence of precise and controllable microfabrication techniques, the output electrochemical performances of MSCs and MBs are improving rapidly. This minireview summarizes recent advances in MSCs and MBs built from two‐dimensional materials, including electrode/device configuration designs, material synthesis, microfabrication processes, smart function incorporations, and system integrations. An introduction to configurations of the MESDs, from linear fibrous shapes, planar sandwich thin‐film or interdigital structures, to three‐dimensional configurations, is presented. The fundamental influences of the electrode material and configuration designs on the exhibited MB/MSC electrochemical performances are also highlighted.
Automatically Controlled Microfluidic System for Continuous Separation of Rare Bacteria from Blood
Authors: Yoon Taehee , Moon Hui‐Sung , Song Jae‐Woo , Hyun Kyung‐A , Jung Hyo‐Il 
Published: October 2019

AbstractBloodstream infection by microorganisms is a major public health concern worldwide. Millions of people per year suffer from microbial infections, and current blood culture‐based diagnostic methods are time‐consuming because of the low concentration of infectious microorganisms in the bloodstream. In this study, we introduce an efficient automated microfluidic system for the continuous isolation of rare infectious bacteria (Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa) from blood. Bacteria received a balanced force between a fluidic drag force and a periodically controlled dielectrophoretic (DEP) force from tilted electrodes to minimize cell adhesion to the electrodes, which prevented the loss of rare infectious bacteria. Target bacteria were efficiently segregated from the undesired blood cells to ensure that only the bacteria received the DEP force under the hypotonic condition, while the blood cells received no DEP force and exited the channel via a laminar flow. Thus, the bacteria were successfully extracted from the blood with a high recovery yield of 91.3%, and the limit of the bacteria concentration for isolation was 100 cfu/ml. We also developed an automated system that performed every step from blood‐sample loading to application of electricity to the microfluidic chip for bacteria separation. It reduced the standard deviation of the bacteria recovery yield from 6.16 to 2.77 compared with the conventional batch process, providing stable bacteria‐extraction performance and minimizing errors and bacteria loss caused by user mistakes. © 2019 International Society for Advancement of Cytometry