bluuebunny/crossref_metadata_2025_split huggingface dataset:
Copper‐Catalyzed Acyloxycyanation of Alkynes with Acetonitrile: Regioselective Construction of Cyclic Acrylonitriles by 6‐endo or 5‐exo Cyclization
Authors: Zhu Yamin , Shen Zengming 
Published: August 2017

AbstractAn efficient difunctionalization of alkynes by tandem iodolactonization and copper‐catalyzed cyanation using acetonitrile as a cyanating reagent is reported for the first time. This approach can afford cyano‐containing isocoumarin or phthalide derivatives in good yields by careful choice of the carboxylate nucleophiles and electrophilic iodine sources. Thus, an acyloxycyanation strategy can be achieved in good yields and high regioselectivity of either 6‐endo or 5‐exo cyclization products.magnified image
Correlating Electrode–Electrolyte Interface and Battery Performance in Hybrid Solid Polymer Electrolyte‐Based Lithium Metal Batteries
Authors: Pan Qiwei , Barbash Dmitri , Smith Derrick M. , Qi Hao , Gleeson Sarah E. , Li Christopher Y. 
Published: August 2017

AbstractSolid polymer electrolytes (SPEs) are desirable in lithium metal batteries (LMBs) since they are nonflammable and show excellent lithium dendrite growth resistance. However, fabricating high performance polymer LMBs is still a grand challenge because of the complex battery system. In this work, a series of tailor‐designed hybrid SPEs are used to prepare LMBs with a LiFePO4‐based cathode. High performance LMBs with both excellent rate capability and long cycle life are obtained at 60 and 90 °C. The well‐controlled network structure in this series of hybrid SPEs offers a model system to study the relationship between the SPE properties and the LMB performance. It is shown that the cycle life of the polymer LMBs is closely correlated with the SPE–Li interface ionic conductivity, underscoring the importance of the solid electrolyte interface in LMB operation. LMB performance is further correlated with the molecular network structure. It is anticipated that results from this study will shed light on designing SPEs for high performance LMB applications.
Redoxneutrale Mangan(I)‐katalysierte C‐H‐Aktivierung: regioselektive Anellierung mithilfe einer spurlosen dirigierenden Gruppe
Authors: Lu Qingquan , Greßies Steffen , Cembellín Sara , Klauck Felix J. R. , Daniliuc Constantin G. , Glorius Frank 
Published: August 2017

AbstractEine Strategie, die spurlose dirigierende Gruppen (SDGs) zur redoxneutralen MnI‐katalysierten regioselektiven Synthese von N‐Heterocyclen verwendet, wird vorgestellt. Alkine als Kupplungspartner, die eine spurlose dirigierende Gruppe tragen, die sowohl zur Chelatisierung als auch als internes Oxidationsmittel fungiert, wurden zur Kontrolle der Regioselektivität der Anellierungsreaktionen eingesetzt. Dieser neuartige Ansatz ermöglicht die Verwendung von bisher anspruchsvollen unsymmetrischen Alkinen, einschließlich zweifach Alkyl‐substituierter Alkine, mit perfekter Regioselektivität. Die einfachen Reaktionsbedingungen und der gezeigte Gramm‐Maßstab unterstreichen die Nützlichkeit dieser Methode. Die Anwendung dieser Strategie wurde durch die Synthese der bioaktiven Verbindung PK11209 und des Naturstoffes Moxaverin gezeigt.
Redox‐Neutral Manganese(I)‐Catalyzed C−H Activation: Traceless Directing Group Enabled Regioselective Annulation
Authors: Lu Qingquan , Greßies Steffen , Cembellín Sara , Klauck Felix J. R. , Daniliuc Constantin G. , Glorius Frank 
Published: August 2017

AbstractA strategy is reported in which traceless directing groups (TDGs) are used to promote the redox‐neutral MnI‐catalyzed regioselective synthesis of N‐heterocycles. Alkyne coupling partners bearing a traceless directing group, which serves as both the chelator and internal oxidant, were used to control the regioselectivity of the annulation reactions. This operationally simple approach is highly effective with previously challenging unsymmetrical alkyne systems, including unbiased dialkyl alkynes, with perfect regioselectivity. The simple conditions and the ability to carry out synthesis on a gram scale underscore the usefulness of this method. The application of this strategy in the concise synthesis of the bioactive compound PK11209 and the pharmaceutical moxaverine is also described.
Self‐Cyclizing Antioxidants to Prevent DNA Damage Caused by Hydroxyl Radical
Authors: AbdulSalam Safnas F. , Gurjar Purujit N. , Zhu Haizhou , Liu Jing , Johnson Emma S. , Kadekaro Ana Luisa , Landero‐Figueroa Julio , Merino Edward J. 
Published: August 2017

AbstractAntioxidant therapy is a promising treatment strategy for protecting DNA from the damage caused by reactive oxygen species (ROS). Here, we report new self‐cyclizing antioxidant reagents that are selective for the hydroxyl radical. Our mechanistic investigation revealed that the reagents react with three equivalents of oxidant in a cascade reaction to form a bicyclic final product. Among the reagents synthesized, 1 c showed favorable properties in vitro and in cellular studies. Using As2O3, which triggers ROS production, we showed that 1 c prevents formation of the guanine oxidation product 2,2,4‐triamino‐2H‐oxazol‐5‐one‐2′‐deoxyribonucleoside and lowers cellular levels of reactive oxygen. The described self‐cyclizing antioxidants are efficient, flexible, and tunable reagents with the potential to limit toxic oxidative stress.
Central nervous system Tuberculosis in a man from Cambodia with worsening headaches
Authors: Krauth Daniel S. , Stone‐Garza Kristi K. , Amaro Deirdre E. , Reed Sharon L. , Katsivas Theodoros F. 
Published: August 2017

Key Clinical MessageCentral nervous system (CNS) tuberculosis should be considered in patients from endemic nations with worsening neurological symptoms. If imaging reveals possible CNS tuberculomas, potentially life‐threatening lesions should be excised and analyzed. When disease is less severe, other tissues possibly infected should be biopsied first for diagnosis to avoid neurosurgery.
123I‐BMIPP single‐photon emission computed tomography for diagnosing chest pain in patients with nonobstructive coronary angiograms: Takotsubo or vasospasm?
Authors: Seko Yuta , Sasaki Kenichi , Kato Takao , Inoko Moriaki 
Published: August 2017

Key Clinical MessageThe decreased 123I‐BMIPP uptake, while having normal perfusion, in the correspondent coronary artery territory is caused by a delayed metabolic recovery after the recovery of perfusion. This phenomenon termed ischemic memory can clearly differentiate vasospastic angina from other chest pain syndromes.
Late onset of unilateral optic disk edema secondary to treatment with imatinib mesylate
Authors: Napolitano Mariasanta , Santoro Marco , Mancuso Salvatrice , Carlisi Melania , Raso Simona , Tarantino Giuseppe , Accurso Vincenzo , Siragusa Sergio 
Published: August 2017

Key Clinical MessagePrompt ophthalmology evaluation and immediate imatinib suspension should be suggested at any time of tyrosine kinase inhibitor therapy in patients with visual deficit, as it may be a clinical manifestation of optic disk edema, and suspension may help in prompt recovery.
Theoretical Studies on the Charging and Discharging of Poly(acrylonitrile)‐Based Lithium‐Sulfur Batteries
Authors: Zhu Tianwei , Mueller Jonathan E. , Hanauer Matthias , Sauter Ulrich , Jacob Timo 
Published: August 2017

AbstractBased on a previous study where key structural motifs of poly(acrylonitrile) (PAN) and sulfur/PAN (SPAN) were identified and their energies evaluated by using density functional theory, here plausible mechanisms for battery charging and discharging at a SPAN cathode were identified. Based on a simplified model for battery operation, we find that discharging the battery involves the formation of lithium polysulfide intermediates and the reductive adsorption of Li+ ions onto SnPAN. In both discharging and charging, Li atoms preferentially coordinate with N atoms on the backbone, leading to strong Li‐SnPAN adsorption energies. Furthermore, we found that spatially separating a dissociated SnLi fragment from the backbone is difficult, providing a plausible explanation for the ability of a SPAN cathode to hinder polysulfides from diffusing to the cathode, leading to a reduction of the polysulfide shuttle mechanism.
Directing Nanostructure Formation of Gold through the In Situ Underpotential Deposition of a Secondary Metal for the Detection of Nitrite Ions
Authors: Lertanantawong Benchaporn , Hoshyargar Faegheh , O'Mullane Anthony P. 
Published: August 2017

AbstractIn this work, the underpotential deposition of metals such as copper and lead during the electrochemical deposition of gold is investigated to understand the influence that the incorporation of a second metal has on the morphology of gold nanostructures. The incorporation of Pb or Cu, even at concentrations as low as 0.2 %, significantly influences the morphology of the deposit, where the formation of elongated structures from a central gold structure is favored. These nanostructures are characterized by cyclic voltammetry, X‐ray diffraction, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy and are tested for their suitability as a sensing layer for the electrochemical detection of nitrite ions in aqueous solution. A limit of detection of 0.3 μM is achieved with a linear range up to 1 mM, which is adequate for the determination of nitrite contained within food products.
In‐Situ Fabrication of MOF‐Derived Co−Co Layered Double Hydroxide Hollow Nanocages/Graphene Composite: A Novel Electrode Material with Superior Electrochemical Performance
Authors: Bai Xue , Liu Jingyuan , Liu Qi , Chen Rongrong , Jing Xiaoyan , Li Bin , Wang Jun 
Published: August 2017

AbstractRational design of a transition metal layered double hydroxide (LDH) and graphene composite is vitally important for designing high‐performance supercapacitor electrodes. Although various methods are performed, the realization of high‐performance is still impeded by the agglomeration of graphene and layered double hydroxide. Here, metal–organic framework derived cobalt–cobalt layered double hydroxide (Co−Co LDH) hollow nanocages, uniformly deposited on graphene nanosheets, are fabricated through facile in situ co‐deposition and thermal ion‐exchange reaction. Electrochemical investigation reveals that Co−Co LDH/15 mg graphene is rather outstanding, which delivers high specific capacitance of 1205 F g−1, excellent rate capability (60.3 % capacitance retention is obtained after the current density increased 6.67 times), and cycling stability. The excellent performance of electrode is also confirmed by assembling an asymmetric supercapacitor, which delivers high energy density of 49.5 Wh kg−1 as well as the maximum power density of 7000 W kg−1. The Co−Co LDH/graphene composite proves a promising concept for constructing hierarchical structure materials in the future.
Design and Fabrication of Temperature‐Sensitive Nanogels with Controlled Drug Release Properties for Enhanced Photothermal Sterilization
Authors: Li Luoyuan , Fu Limin , Ai Xicheng , Zhang Jianping , Zhou Jing 
Published: August 2017

AbstractFor better removal of excessive free radicals and harmful bacteria from the human body, the development of synergistic antioxidant and antibacterial agents is urgently required. Herein, we designed novel temperature‐sensitive, curcumin (Cur)‐loaded nanogels for the application of scavenging reactive oxygen species and killing pathogenic bacteria. Photothermal sterilization, different from traditional antibiotics, is a promising and effective treatment for pathogenic bacterial infection. The nanogels were fabricated by using poly(N‐isopropylacrylamide) (a temperature‐sensitive hydrogel) to encapsulate poly(3,4‐ethylenedioxythiophene) nanoparticles (photothermal agents) and Cur through a reformative precipitation polymerization. When triggered by near‐IR light, the Cur‐loaded nanogels exhibited high (56.8 %), and excellent temperature‐sensitive effects. Moreover, the light‐induced temperature increase can also weaken the interaction between the networks of PNIPAAm and Cur, to show excellent antioxidant and antibacterial performance (90 % cell death) of the nanogels.
Diagnosing the Internal Architecture of Zeolite Ferrierite
Authors: Schmidt Joel E. , Hendriks Frank C. , Lutz Martin , Post L. Christiaan , Fu Donglong , Weckhuysen Bert M. 
Published: August 2017

AbstractLarge crystals of zeolite ferrierite (FER) are important model systems for spatially resolved catalysis and diffusion studies, though there is considerable variation in crystal habit depending on the chemical composition and employed synthesis conditions. A synergistic combination of techniques has been applied, including single crystal X‐ray diffraction, high‐temperature in situ confocal fluorescence microscopy, fluorescent probe molecules, wide‐field microscopy and atomic force microscopy to unravel the internal architecture of three distinct FER zeolites. Pyrolyzed template species can be used as markers for the 8‐membered ring direction as they are trapped in the terraced roof of the FER crystals. This happens as the materials grow in a layer‐by‐layer, defect‐free manner normal to the large crystal surface, and leads to a facile method to diagnose the pore system orientation, which avoids tedious single crystal X‐ray diffraction experiments.
Different localizations of drugs simultaneously administered in a strand of hair by micro‐segmental analysis
Authors: Kuwayama Kenji , Miyaguchi Hajime , Iwata Yuko T. , Kanamori Tatsuyuki , Tsujikawa Kenji , Yamamuro Tadashi , Segawa Hiroki , Inoue Hiroyuki 
Published: August 2017

AbstractSegmental hair analysis is used to estimate the time of drug intake at monthly precision in drug‐related crimes. Previously, we advanced this analytical method to specify the day of drug intake by cutting a strand of hair into 0.4‐mm segments, which correspond to daily hair growth. Herein, we investigated the distributions of 7 compounds in a strand of hair using micro‐segmental analysis. Several strands of hair were collected 33.1−229.4 days after subjects were administered 4 pharmaceutical products that contained 10 drugs in single doses within 32 hours. The administered drugs and resulting metabolites were extracted from 0.4‐mm hair segments and quantified using liquid chromatography–tandem mass spectrometry. Acidic and neutral compounds were detected at low amounts in any of the hair segments analyzed. Epinastine, fexofenadine, dihydrocodeine, chlorpheniramine, and the chlorpheniramine metabolite, desmethylchlorpheniramine each was localized to 2 regions within a strand of hair. By contrast, methylephedrine and its metabolite, ephedrine, each was localized to only a region. Among 20 individual strands of hair associated with different subjects and head regions, few differences in the shapes of drug concentration–hair segment curves for each compound were detected. Our data indicated that 2 mechanisms for drug uptake into hair can operate depending on drug properties and that co‐administered drugs can be localized to different regions in a strand of hair. Micro‐segmental analysis may aid in the identification of the day of drug intake and help to elucidate the mechanisms of drug uptake into hair.
Allosteric modulation of α4β2* nicotinic acetylcholine receptors: Desformylflustrabromine potentiates antiallodynic response of nicotine in a mouse model of neuropathic pain
Authors: Bagdas D. , Ergun D. , Jackson A. , Toma W. , Schulte M.K. , Damaj M.I. 
Published: August 2017

AbstractBackgroundNeuronal nicotinic acetylcholine receptors (nAChRs) are ligand‐gated ion channels. The α4β2 subtype of nAChRs plays an important role in the mediation of pain and several nicotine‐evoked responses. Agonists and partial agonists of α4β2 nAChRs show efficacy in animal pain models. In addition, the antinociceptive properties of nicotine, a non‐selective nAChR agonist with a high affinity for α4β2 nAChRs, is well‐known. There is a growing body of evidence pointing to allosteric modulation of nAChRs as an alternative treatment strategy in experimental pain. Desformylflustrabromine (dFBr) is a positive allosteric modulator (PAM) at α4β2 nAChRs that enhances agonist responses without activating receptors. We hypothesized that dFBr may enhance nicotine‐induced antinociception.MethodsThe present study investigated whether dFBr could attenuate mouse chronic constriction injury (CCI)‐induced neuropathic pain by increasing endogenous cholinergic tone or potentiating the nicotine‐evoked antiallodynic response.ResultsWe found that subcutaneous administration of dFBr failed to reduce pain behaviour on its own. However, the combination of dFBr with nicotine significantly reversed neuropathic pain behaviour dose‐ and time‐dependently without motor impairment. Our data revealed that this effect was mediated by the α4β2 nAChRs by using competitive α4β2 antagonist dihydro‐β‐erythroidine. In addition, dFBr failed to potentiate the antiallodynic effect of morphine, which shows the effect of dFBr is unique to α4β2 nAChRs.ConclusionsThe present results suggest that allosteric modulation of α4β2 nAChR may provide new strategies in chronic neuropathic pain.Significanceα4β2 nAChRs are involved in pain modulation. dFBr, a PAM at α4β2 nAChRs, potentiates the nicotine response dose‐dependently in neuropathic pain. Thus, the present results suggest that allosteric modulation of α4β2* nAChR may provide new strategies in chronic neuropathic pain.
Evaluating hydrologic performance of bioretention cells in shallow groundwater
Authors: Zhang Kun , Chui Ting Fong May 
Published: August 2017

AbstractBioretention cells, which are generally effective in controlling surface runoff and recharging groundwater, have been widely adopted as low impact development practices. However, shallow groundwater has limited their implementation in some locations due to the potential problems of a reduction in surface runoff control, groundwater pollution, and continuous groundwater drainage through the underdrain. Many guidelines have established minimum requirements for the groundwater depth below bioretention cells, but they may not be optimized for certain environmental conditions and bioretention cell designs. This study made use of a variably saturated flow model to examine the hydrologic performance of a single bioretention cell in shallow groundwater with event‐based simulations, considering a wide range of initial groundwater depths, media and in situ soil types, surface runoff loads, and underdrain sizes. Performance indicators (e.g., runoff reduction, time for infiltrated water to reach the bioretention cell bottom and the groundwater table, and height and dissipation time of groundwater mound) were evaluated to examine the processes of runoff generation, the formation and dissipation of groundwater mounds, and the bioretention cell's performance in a shallow groundwater environment. The most influential factors were the initial groundwater depth, the hydraulic conductivity of the media soil, and the rainfall runoff load. With a deeper initial groundwater table, infiltrated water took longer to reach the bioretention cell bottom and groundwater table. Groundwater mounds, however, took longer to dissipate even though they were smaller. The groundwater quality can be better protected if relatively less‐permeable soil types (e.g., sandy loam) are used as the media, although it may compromise the performance in runoff quantity control. However, only very high surface runoff loads would cause concerns regarding a reduction in runoff quantity control and possible groundwater contamination due to the shallow groundwater. A distance of 1.5–3 m between the bioretention cell bottom and the groundwater table is generally sufficient. The results of this study could help to guide the planning and design of bioretention cells in areas of shallow groundwater.
Therapeutic monoclonal antibodies and clinical laboratory tests: When, why, and what is expected?
Authors: Zhang Zhanhu , Hu Wenjie , Li Linlin , Ding Hongxia , Li Haibo 
Published: August 2017

BackgroundWe herein provide an overview of the clinical laboratory tests that should be performed before, during and after using therapeutic monoclonal antibodies (mAbs) and the clinical laboratory tests that may be affected by mAbs.MethodsThe labels of FDA‐approved therapeutic mAbs were downloaded from DailyMed (the official website for drug labels) and were used as the sources of data for this review.ResultsIt was found that most of the labels provided information relevant to the clinical laboratory tests, including the tests needed before mAbs treatment to check the patients’ background status and to identify potentially sensitive patients, the tests needed during or after the treatment to evaluate the patients’ response, and the mAbs that may lead to false positive or negative results for clinical laboratory tests.ConclusionsThe present findings will be of interest to physicians, laboratory scientists, those involved in drug development and surveillance and individuals making health care policy.
Computationally efficient modeling for assessing the energy efficiency of electric drivetrains using convex formulations
Authors: Vandeputte Matthias , De Keyser Arne , Crevecoeur Guillaume 
Published: August 2017

AbstractHigh‐fidelity models capturing the dynamical behavior can be engaged for the analysis of complex mechatronic systems. Determining the optimal control parameters and design characteristics of such systems necessitates solving multiple interconnected models acting on their respective physical domains and time scales. In this paper, high‐fidelity physics‐based models are constructed for several electrical subsystems. Loss mechanisms in the various components are inferred because these are key when performing optimal design and control in terms of energy‐efficient conversion from power source to actuation. The complexity of the analyzed models is then reduced by introducing convex approximations for the occurring dissipation during power transfers, allowing abstracting the complicated dynamic behavior into a tractable convex formulation, specifically suited for time‐efficient numerical simulation. The effectiveness of the strategy is demonstrated on a case study originating from the field of all‐electric vehicles, embodying a series interconnection of a battery stack, a buck‐boost converter, a voltage source inverter, and an asynchronous electric motor. Results show that the dynamic simulation of the proposed system, composed of multiple time scales, can be reliably computed using the composed convex mappings, hereby reducing the computational time approximately by a factor 461, compromising only 1.8% accuracy regarding energy consumption assessment. The introduced convex formulation can therefore constitute the foundation for optimal control and design of complex mechatronic drives.