bluuebunny/crossref_metadata_2025 huggingface dataset:
Prevalence of progressive supranuclear palsy in Yonago: change throughout a decade
Authors: Takigawa Hiroshi , Kitayama Michio , Wada‐Isoe Kenji , Kowa Hisanori , Nakashima Kenji
Published: October 2016

Background

Progressive supranuclear palsy (PSP) is a neurodegenerative disorder that is sometimes confused with Parkinson's disease, multiple system atrophy, and other disorders. The typical clinical features are categorized as Richardson's syndrome (RS), but other clinical subtypes include PSP‐parkinsonism (PSP‐P) and PSP‐pure akinesia with gait freezing (PSP‐PAGF). In this study, we determined the prevalence of PSP in a Japanese rural area compared to our previous 1999 report.

Methods

We collected data in Yonago City from 2009 to 2014 using a service‐based study of PSP. We collected case history data from PSP patients in the area from our hospital. The crude prevalence and 95% confidence interval (CI) were calculated using the population demographics on the prevalence day of 1 October 2010. Age‐ and sex‐adjusted prevalence was calculated by direct standardization to the population demographics in Yonago City on the prevalence day of 1 April 1999.

Material and Results

We identified 25 patients: 16 with probable RS, 4 with possible RS, 3 with clinical PSP‐P, and 2 with clinical PSP‐PAGF. The prevalence per 100,000 was 17.90 (male = 18.05; female = 17.76). The prevalence of PSP in Yonago in 2010 increased compared to the measurements from 1999.

Conclusion

The prevalence of PSP in Japan increased from 1999 to 2010.
Cortical asymmetry in Parkinson's disease: early susceptibility of the left hemisphere
Authors: Claassen Daniel O. , McDonell Katherine E. , Donahue Manus , Rawal Shiv , Wylie Scott A. , Neimat Joseph S. , Kang Hakmook , Hedera Peter , Zald David , Landman Bennett , Dawant Benoit , Rane Swati
Published: October 2016

Background and Purpose

Clinically, Parkinson's disease (PD) presents with asymmetric motor symptoms. The left nigrostriatal system appears more susceptible to early degeneration than the right, and a left‐lateralized pattern of early neuropathological changes is also described in several neurodegenerative conditions, including Alzheimer's disease, frontotemporal dementia, and Huntington's disease. In this study, we evaluated hemispheric differences in estimated rates of atrophy in a large, well‐characterized cohort of PD patients.

Methods

Our cohort included 205 PD patients who underwent clinical assessments and T1‐weighted brain MRI's. Patients were classified into Early (n = 109) and Late stage (n = 96) based on disease duration, defined as greater than or less than 10 years of motor symptoms. Cortical thickness was determined using FreeSurfer, and a bootstrapped linear regression model was used to estimate differences in rates of atrophy between Early and Late patients.

Results

Our results show that patients classified as Early stage exhibit a greater estimated rate of cortical atrophy in left frontal regions, especially the left insula and olfactory sulcus. This pattern was replicated in left‐handed patients, and was not influenced by the degree of motor symptom asymmetry (i.e., left‐sided predominant motor symptoms). Patients classified as Late stage exhibited greater atrophy in the bilateral occipital, and right hemisphere‐predominant cortical areas.

Conclusions

We show that cortical degeneration in PD differs between cerebral hemispheres, and findings suggest a pattern of early left, and late right hemisphere with posterior cortical atrophy. Further investigation is warranted to elucidate the underlying mechanisms of this asymmetry and pathologic implications.
Effects of isoflurane anesthesia on resting‐state fMRI signals and functional connectivity within primary somatosensory cortex of monkeys
Authors: Wu Tung‐Lin , Mishra Arabinda , Wang Feng , Yang Pai‐Feng , Gore John C. , Chen Li Min
Published: October 2016

Introduction

Correlated low‐frequency fluctuations of resting‐state functional magnetic resonance imaging (rsfMRI) signals have been widely used for inferring intrinsic brain functional connectivity (FC). In animal studies, accurate estimate of anesthetic effects on rsfMRI signals is demanded for reliable interpretations of FC changes. We have previously shown that inter‐regional FC can reliably delineate local millimeter‐scale circuits within digit representations of primary somatosensory cortex (S1) subregions (areas 3a, 3b, and 1) in monkeys under isoflurane anesthesia. The goals of this study are to determine (1) the general effects of isoflurane on rsfMRI signals in the S1 circuit and (2) whether the effects are functional‐ and regional‐ dependent, by quantifying the relationships between isoflurane levels, power and inter‐regional correlation coefficients in digit and face regions of distinct S1 subregions.

Methods

Functional MRI data were collected from male adult squirrel monkeys at three different isoflurane levels (1.25%, 0.875%, and 0.5%). All scans were acquired on a 9.4T magnet with a 3‐cm‐diameter surface transmit‐receive coil centered over the S1 cortex. Power and seed‐based inter‐regional functional connectivity analyses were subsequently performed.

Results

As anesthesia level increased, we observed (1) diminishing amplitudes of signal fluctuations, (2) reduced power of fluctuations in the low‐frequency band used for connectivity measurements, (3) decreased inter‐voxel connectivity around seed regions, and (4) weakened inter‐regional FC across all pairs of regions of interest (digit‐to‐digit). The low‐frequency power measures derived from rsfMRI signals from control muscle regions, however, did not exhibit any isoflurane level‐related changes. Within the isoflurane dosage range we tested, the inter‐regional functional connectivity differences were still detectable, and the effects of isoflurane did not differ across region‐of‐interest (ROI) pairs.

Conclusion

Our data demonstrate that isoflurane induced similar dose‐dependent suppressive effects on the power of rsfMRI signals and local fine‐scale FC across functionally related but distinct S1 subregions.
Sustainable Corporate Entrepreneurship: Performance and Strategies Toward Innovation
Authors: Provasnek Anna Katharina , Schmid Erwin , Geissler Bernhard , Steiner Gerald
Published: October 2016

The field of sustainable corporate entrepreneurship is in a nascent stage. By developing a position matrix of companies with respect to their corporate entrepreneurship and sustainability performance, we make conceptual contributions to an integrated perspective on elements supporting a sustainable corporate entrepreneurship process. We propose that such a process without evolving corporate sustainability is misleading. Methodologically, we investigate publicly available index ratings to assess strategies for and qualitative measurement of the sustainable development and innovation performance of eight top‐ranked international companies. Findings show that the strategies of the identified companies correspond well to our typology and allow suggestions of where efforts for corporate sustainability and/or entrepreneurship could be reinforced to gain or maintain a benchmark position. The article will clarify underlying elements of, and help to advance strategies for the implementation of, a sustainable corporate entrepreneurship process. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Opossum peptide that can neutralize rattlesnake venom is expressed in Escherichia coli
Authors: Komives Claire F. , Sanchez Elda E. , Rathore Anurag S. , White Brandon , Balderrama Michael , Suntravat Montamas , Cifelli Angela , Joshi Varsha
Published: October 2016

An eleven amino acid ribosomal peptide was shown to completely neutralize Western Diamondback Rattlesnake (Crotalus atrox) venom in mice when a lethal dose of the venom was pre‐incubated with the peptide prior to intravenous injection. We have expressed the peptide as a concatenated chain of peptides and cleaved them apart from an immobilized metal affinity column using a protease. After ultrafiltration steps, the mixture was shown to partially neutralize rattlesnake venom in mice. Preliminary experiments are described here that suggest a potential life‐saving therapy could be developed. To date, no recombinant therapies targeting cytotoxic envenomation have been reported. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:81–86, 2017
Did student‐athlete have a defamation case against a national magazine?
Authors: Gelpi Aileen
Published: October 2016

Sports Illustrated published a highly critical article in March 2012 about the University of California, Los Angeles men's basketball program.
Rapid pacing using the 0.035‐in. Retrograde left ventricular support wire in 208 cases of transcatheter aortic valve implantation and balloon aortic valvuloplasty
Authors: Hilling‐Smith Roland , Cockburn James , Dooley Maureen , Parker Jessica , Newton Andrea , Hill Andrew , Trivedi Uday , de Belder Adam , Hildick‐Smith David
Published: October 2016

Introduction and Method

Transcatheter aortic valve implantation (TAVI) and balloon aortic valvuloplasty (BAV) are now well established percutaneous procedures. These procedures almost always require bursts of rapid ventricular pacing to temporarily reduce cardiac output to facilitate the procedure, usually done via a temporary pacing wire inserted into the right ventricle. We describe a case series of 132 cases of TAVI and 76 BAV done using ventricular pacing via the left ventricular lead by simply connecting one electrode to the patient's skin and one electrode through the left ventricular (LV) wire.

Results

All of the 132 TAVI cases (a mixture of Edwards Sapien, Medtronic CoreValve and Boston Scientific Lotus) and 76 BAV were successfully performed using pacing through the LV wire. No BAV patients required temporary pacing wire (TPW) or permanent pacemaker (PPM) insertion. Of the TAVI patients, 6 (4.5%) required TPW during the procedure due to complete heart block to facilitate removal of the LV wire. 1 patient (0.8%) required a PPM urgently due to complete heart block and haemodynamic instability. Twenty eight Patients (21.2%) required PPM following TAVI, 9 of which were within the first 24 hr. Average time to pacemaker implantation was 3.7 days.

Conclusion

Rapid ventricular pacing via the LV wire is a simple, safe and effective strategy for percutaneous aortic valve intervention and balloon aortic valvuloplasty. It eliminates the need for a temporary pacing wire with its attendant risks in the vast majority of cases. Furthermore, most pacemakers following TAVI are required late, after the first 24 hr period, by which time the TPW has already usually been removed. © 2016 Wiley Periodicals, Inc.
Structural Analysis and Electrochemical Properties of Bimetallic Palladium–Platinum Aerogels Prepared by a Two‐Step Gelation Process
Authors: Oezaslan Mehtap , Herrmann Anne‐Kristin , Werheid Matthias , Frenkel Anatoly I. , Nachtegaal Maarten , Dosche Carsten , Laugier Bonnaud Céline , Yilmaz Hale Ceren , Kühn Laura , Rhiel Erhard , Gaponik Nikolai , Eychmüller Alexander , Schmidt Thomas Justus
Published: October 2016

Multimetallic aerogels have emerged as promising unsupported and high‐surface‐area metal materials for different applications in heterogeneous catalysis and electrochemistry, which are fabricated using a gelation process characterized by the controlled aggregation of metallic nanoparticles to form a macroscopic network structure in aqueous solution. However, the achievement of the structural homogeneity of the multimetallic aerogels in terms of the diameter of the nanochains and the chemical composition at the nano‐ and the macro‐scale is still a great challenge. In this paper, we investigated two Pd‐Pt aerogels prepared by the two‐step gelation method. The structural homogeneity and chemical distribution of both metals inside the aerogels were analyzed by using high‐resolution (scanning) transmission microscopy, energy‐dispersive X‐ray spectroscopy, extended X‐ray absorption fine structure spectroscopy and cyclic voltammetry. The Pd‐Pt aerogels show the presence of Pd/Pt‐rich domains inside the long‐range framework. It is evident that the initial monometallic features dominate over alloying during the gelation process. Although the same synthetic approach for Pd‐Pt aerogels with different atomic ratios was used, we observed that the sizes of these monometallic domains varied strongly between the Pd‐rich and Pt‐rich aerogels. The presence of such metal clusters influenced the electrochemical robustness of the Pd‐Pt aerogels dramatically. Electrochemical durability investigations revealed that the aerogels with a high content of Pd are less stable because of the gradual dissolution of the less noble metal particularly inside the Pd‐rich domains. A chemical and structural homogeneity might improve the lifetime of the Pd‐Pt aerogels under electrochemical conditions. In this work, we provide a better understanding of the structure and chemical distribution of the bimetallic aerogel framework prepared by the two‐step gelation process.
Effect of Feedstock and Catalyst Impurities on the Methanol‐to‐Olefin Reaction over H‐SAPO‐34
Authors: Vogt Charlotte , Weckhuysen Bert M. , Ruiz‐Martínez Javier
Published: October 2016

Operando UV/Vis spectroscopy with on‐line mass spectrometry was used to study the effect of different types of impurities on the hydrocarbon pool species and the activity of H‐SAPO‐34 as a methanol‐to‐olefins (MTO) catalyst. Successive reaction cycles with different purity feedstocks were studied, with an intermittent regeneration step. The combined study of two distinct impurity types (i.e., feed and internal impurities) leads to new insights into MTO catalyst activation and deactivation mechanisms. In the presence of low amounts of feed impurities, the induction and active periods of the process are prolonged. Feed impurities are thus beneficial in the formation of the initial hydrocarbon pool, but also aid in the unwanted formation of deactivating coke species by a separate, competing mechanism favoring coke species over olefins. Further, feedstock impurities strongly influence the location of coke deposits, and thus influence the deactivation mechanism, whereas a study of the organic impurities retained after calcination reveals that these species are less relevant for catalyst activity and function as “seeds” for coke formation only.
Metal Dicyanamides as Efficient and Robust Water‐Oxidation Catalysts
Authors: Nune Satya Vijaya Kumar , Basaran Aysun Tekin , Ülker Emine , Mishra Rupali , Karadas Ferdi
Published: October 2016

Non‐oxide cobalt‐based water‐oxidation electrocatalysts have received attention recently for their relative ease of preparation, they are stable both in acidic and basic media, and they have higher turnover frequencies than cobalt oxides. Recent studies show that one of the main bottlenecks in the implementation of non‐oxide systems to water splitting is the low number of active metal sites, which is in the order of nmol cm−2. Herein, a new series of non‐oxide water‐oxidation catalysts has been introduced to the field. Cobalt dicyanamides are observed to have around four times higher surface active sites and better catalytic performances than cyanide‐based systems. Long‐term catalytic studies (70 h) at an applied potential of 1.2 V and electrochemical studies performed in solutions in pH values of 3.0–12.0 indicate that the compounds are robust and retain their structures even under harsh conditions. Moreover, the addition of Ni impurities to cobalt dicyanamides is a feasible method to improve their catalytic activities.
Bifunctional Polymer Architectures for Cooperative Catalysis: Tunable Acid–Base Polymers for Aldol Condensation
Authors: Hoyt Caroline B. , Lee Li‐Chen , Cohen Aaron E. , Weck Marcus , Jones Christopher W.
Published: October 2016

Cooperative catalysts combining weak acids and basic amines have been utilized to effectively catalyze aldol and related coupling reactions under mild conditions. Most cooperative chemical catalysts for the aldol reaction have been based on silica‐supported amines. In this work, an alternate approach is demonstrated whereby cooperative amine/acid interactions are tailored through the implementation of polymeric supports. By using linear poly(styrene) supports, this work demonstrates that the design and spacing of monomer units plays an essential role in the cooperativity of the acid–base sites in the aldol condensation. The monomer sequence of each polymer catalyst dramatically affects the catalytic activity, with a random copolymer displaying optimal cooperativity between the acid and base, and block copolymers drastically reducing catalyst activity. Trends established in the silica‐supported systems, such as use of stronger acid monomers demonstrating reduced activity, are verified and extended to these polymer‐supported systems. Overall, this first generation polymer‐supported system is not as efficient as the optimal silica‐supported catalysts developed over the last decade, with the polymers studied here being poorly soluble, leading to inefficient use of the amine sites.
Thermal Decomposition of Sulfur Compounds and their Role in Coke Formation during Steam Cracking of Heptane
Authors: Olahova Natalia , Djokic Marko R. , Van de Vijver Ruben , Ristic Nenad D. , Marin Guy B. , Reyniers Marie‐Françoise , Van Geem Kevin M.
Published: October 2016

Sulfur‐containing compounds play a key role in many industrial processes. Particularly for the steam cracking process, they have been linked with increased olefin selectivity, CO formation, and coke inhibition. The influence of four different sulfur‐containing additives, methanedithione, (methyldisulfanyl)methane, (methylsulfanyl)methane, and dimethyl sulfoxide, on product selectivity, coke deposition, and CO production during steam cracking of a surrogate light naphtha feed is investigated. The use of online comprehensive 2D gas chromatography with sulfur chemiluminescence detection (GC×GC‐SCD) is the key enabling technology to characterize the sulfur compounds. Steam cracking in a pilot‐plant unit revealed that all studied sulfur compounds are efficient in reducing the CO yield. Simultaneously, they strongly promote coke.
Gold‐Catalyzed Enantioselective Annulations
Authors: Li Yangyan , Li Wenbo , Zhang Junliang
Published: October 2016

In the past decade, there have been many extraordinary advances in the development of gold‐catalyzed enantioselective annulations, such as cycloadditions, cyclizations, cycloisomerizations, and tandem annulations, which are of particular interest owing to their potential for rapid construction of optically active hetero‐ and carbocyclic molecules. This Review summarizes the methods to construct chiral cyclic compounds by gold‐catalyzed enantioselective annulations reported since 2005. The Review is organized according to the general annulation types catalyzed by chiral gold complexes or chiral gold salts, which have four main types (cycloadditions, cyclizations of C−C multiple bonds with tethered nucleophiles, cycloisomerization or cyclization of enynes, and tandem annulations), as well as some other strategies. The general reaction mechanisms of each subcategory, key intermediates for some unusual transformations, and the application of several novel ligands and chiral gold salts are also discussed.
Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization, HF‐HFEPR Studies, First‐Principles Calculations, and Orbital Modeling
Authors: Charron Gaëlle , Malkin Elena , Rogez Guillaume , Batchelor Luke J. , Mazerat Sandra , Guillot Régis , Guihéry Nathalie , Barra Anne‐Laure , Mallah Talal , Bolvin Hélène
Published: October 2016

By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy (1), (NCS−)2 (2), C2O42− (3), NO3− (4)). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ (5; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from −1 to −10 cm−1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3, on one hand, and 4 and 5, on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3− and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1–3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model.
Fused Helicene Chains: Towards Twisted Graphene Nanoribbons
Authors: Pradhan Anirban , Dechambenoit Pierre , Bock Harald , Durola Fabien
Published: October 2016

By taking advantage of an unexpected regioselectivity of intramolecular Scholl reactions on pentaphenylene compounds that favors distorted [5]helicenes over their flat counterparts, a new synthetic approach to twisted graphene nanoribbons has been designed based on side‐fused di‐tert‐butyl‐[5]helicene fragments. Syntheses of both small monomers and dimers have been achieved and their structures have been studied. An iterative synthetic strategy has been developed for the formation of longer flexible precursors, which relies on the step‐by‐step elongation of mono‐functionalized oligomeric chains. The flexible trimer and tetramer have, thus, been synthesized and submitted to intramolecular Scholl reactions, which revealed important purification and characterization issues.
NMR Hyperpolarization Techniques of Gases
Authors: Barskiy Danila A. , Coffey Aaron M. , Nikolaou Panayiotis , Mikhaylov Dmitry M. , Goodson Boyd M. , Branca Rosa T. , Lu George J. , Shapiro Mikhail G. , Telkki Ville‐Veikko , Zhivonitko Vladimir V. , Koptyug Igor V. , Salnikov Oleg G. , Kovtunov Kirill V. , Bukhtiyarov Valerii I. , Rosen Matthew S. , Barlow Michael J. , Safavi Shahideh , Hall Ian P. , Schröder Leif , Chekmenev Eduard Y.
Published: October 2016

Nuclear spin polarization can be significantly increased through the process of hyperpolarization, leading to an increase in the sensitivity of nuclear magnetic resonance (NMR) experiments by 4–8 orders of magnitude. Hyperpolarized gases, unlike liquids and solids, can often be readily separated and purified from the compounds used to mediate the hyperpolarization processes. These pure hyperpolarized gases enabled many novel MRI applications including the visualization of void spaces, imaging of lung function, and remote detection. Additionally, hyperpolarized gases can be dissolved in liquids and can be used as sensitive molecular probes and reporters. This Minireview covers the fundamentals of the preparation of hyperpolarized gases and focuses on selected applications of interest to biomedicine and materials science.
Amine Catalysis for the Organocatalytic Diboration of Challenging Alkenes
Authors: Farre Albert , Soares Kaline , Briggs Rachel A. , Balanta Angelica , Benoit David M. , Bonet Amadeu
Published: October 2016

The generation of in situ sp2–sp3 diboron adducts has revolutionised the synthesis of organoboranes. Organocatalytic diboration reactions have represented a milestone in terms of unpredictable reactivity of these adducts. However, current methodologies have limitations in terms of substrate scope, selectivity and functional group tolerance. Here a new methodology based on the use of simple amines as catalyst is reported. This methodology provides a completely selective transformation overcoming current substrate scope and functional/protecting group limitations. Mechanistic studies have been included in this report.
Supra‐dendron Gelator Based on Azobenzene–Cyclodextrin Host–Guest Interactions: Photoswitched Optical and Chiroptical Reversibility
Authors: Xie Fan , Ouyang Guanghui , Qin Long , Liu Minghua
Published: October 2016

A novel amphiphilic dendron (AZOC8GAc) with three l‐glutamic acid units and an azobenzene moiety covalently linked by an alkyl spacer has been designed. The compound formed hydrogels with water at very low concentration and self‐assembled into chiral‐twist structures. The gel showed a reversible macroscopic volume phase transition in response to pH variations and photo‐irradiation. During the photo‐triggered changes, although the gel showed complete reversibility in its optical absorptions, only an incomplete chiroptical property change was achieved. On the other hand, the dendron could form a 1:1 inclusion complex through a host–guest interaction with α‐cyclodextrin (α‐CD), designated as supra‐dendron gelator AZOC8GAc/α‐CD. The supra‐dendron showed similar gelation behavior to that of AZOC8GAc, but with enhanced photoisomerization‐transition efficiency and chiroptical switching capacity, which was completely reversible in terms of both optical and chiroptical performances. The self‐assembly of the supra‐dendron is a hierarchical or multi‐supramolecular self‐assembling process. This work has clearly illustrated that the hierarchical and multi‐supramolecular self‐assembling system endows the supramolecular nanostructures or materials with superior reversible optical and chiroptical switching.
Metal–Metal Single Bonds with the Magnetic Anisotropy of Quadruple Bonds: A Systematic Series of Heterobimetallic Bismuth(II)–Rhodium(II) Formamidinate Complexes
Authors: Sunderland Travis L. , Berry John F.
Published: October 2016

The first set of five heterobimetallic MM′(form)4 (form=formamidinate) complexes containing a BiRh core has been successfully synthesized. The Bi−Rh bond lengths lie between 2.5196(6) and 2.572(2) Å, consistent with Bi−Rh single bonds. All complexes have rich electrochemistry, with the [BiRh]4+/5+ redox couples spanning approximately 700 mV and showing a strong correlation to remote ligand substitution. Visible spectroscopy showed two features for complexes 1–5 at approximately 459 and 551 nm, unique to BiRh paddlewheel complexes that are attributed to LMCT bands into the Bi−Rh σ* orbital. The large spin–orbit coupling (SOC) of Bi creates a massive Bi−Rh magnetic anisotropy, Δχ, approximately −4800×10−36 m3molecule−1, which is the largest value reported for any single bond to date.
Structurally Divergent Lithium Catalyzed Friedel–Crafts Reactions on Oxetan‐3‐ols: Synthesis of 3,3‐Diaryloxetanes and 2,3‐Dihydrobenzofurans
Authors: Croft Rosemary A. , Mousseau James J. , Choi Chulho , Bull James A.
Published: October 2016

The first examples of 3,3‐diaryloxetanes are prepared in a lithium‐catalyzed and substrate dependent divergent Friedel–Crafts reaction. para‐Selective Friedel–Crafts reactions of phenols using oxetan‐3‐ols afford 3,3‐diaryloxetanes by displacement of the hydroxy group. These constitute new isosteres for benzophenones and diarylmethanes. Conversely, ortho‐selective Friedel–Crafts reactions of phenols afford 3‐aryl‐3‐hydroxymethyl‐dihydrobenzofurans by tandem alkylation–ring‐opening reactions; the outcome of the reaction diverging to structurally distinct products dependent on the substrate regioselectivity. Further reactivity of the oxetane products is demonstrated, suitable for incorporation into drug discovery efforts.
Synthesis of Potent and Selective HDAC6 Inhibitors Bearing a Cyclohexane‐ or Cycloheptane‐Annulated 1,5‐Benzothiazepine Scaffold
Authors: De Vreese Rob , Galle Lisa , Depetter Yves , Franceus Jorick , Desmet Tom , Van Hecke Kristof , Benoy Veronick , Van Den Bosch Ludo , D'hooghe Matthias
Published: October 2016

Selective inhibitors of histone deacetylase 6 (HDAC6) are an emerging class of pharmaceuticals due to the involvement of HDAC6 in different pathways related to neurodegenerative diseases, cancer, and immunology. Herein, the synthesis of ten new benzohydroxamic acids, constructed by employing the tetrahydrobenzothiazepine core as a privileged pharmacophoric unit, is described. This is the first report on the synthesis and isolation of octahydrodibenzothiazepines and octahydro‐6H‐benzocycloheptathiazepines, which were then used to develop a new class of HDAC6 inhibitors. Evaluations of their HDAC‐inhibiting activity resulted in the identification of cis‐N‐(4‐hydroxycarbamoylbenzyl)‐1,2,3,4,4a,5,11,11a‐octahydrodibenzo[b,e][1,4]thiazepine‐10,10‐dioxide and cis‐N‐(4‐hydroxycarbamoylbenzyl)‐7‐trifluoromethyl‐1,2,3,4,4a,5,11,11a‐octahydrodibenzo[b,e][1,4]thiazepine‐10,10‐dioxide as highly potent and selective HDAC6 inhibitors with activity in the low nanomolar range, which also show excellent selectivity on the enzymatic and cellular levels. Furthermore, four promising inhibitors were subjected to an Ames fluctuation assay, which revealed no mutagenic effects associated with these structures.
Li+/Mg2+ Hybrid‐Ion Batteries with Long Cycle Life and High Rate Capability Employing MoS2 Nano Flowers as the Cathode Material
Authors: Ju Yanming , Meng Yuan , Wei Yingjin , Bian Xiaofei , Pang Qiang , Gao Yu , Du Fei , Liu Bingbing , Chen Gang
Published: October 2016

The demand for large‐scale and safe energy storage is increasing rapidly due to the strong push for smartphones and electric vehicles. As a result, Li+/Mg2+ hybrid‐ion batteries (LMIBs) combining a dendrite‐free deposition of Mg anode and Li+ intercalation cathode have attracted considerable attention. Here, a LMIB with hydrothermal‐prepared MoS2 nano flowers as cathode material was prepared. The battery showed remarkable electrochemical properties with a large discharge capacity (243 mAh g−1 at the 0.1 C rate), excellent rate capability (108 mAh g−1 at the 5 C rate), and long cycle life (87.2 % capacity retention after 2300 cycles). Electrochemical analysis showed that the reactions occurring in the battery cell involved Mg stripping/plating at the anode side and Li+ intercalation at the cathode side with a small contribution from Mg2+ adsorption. The excellent electrochemical performance and extremely safe cell system show promise for its use in practical applications.
Local A‐Site Layering in Rare‐Earth Orthochromite Perovskites by Solution Synthesis
Authors: Daniels Luke M. , Kashtiban Reza J. , Kepaptsoglou Demie , Ramasse Quentin M. , Sloan Jeremy , Walton Richard I.
Published: October 2016

Cation size effects were examined in the mixed A‐site perovskites La0.5Sm0.5CrO3 and La0.5Tb0.5CrO3 prepared through both hydrothermal and solid‐state methods. Atomically resolved electron energy loss spectroscopy (EELS) in the transmission electron microscope shows that while the La and Sm cations are randomly distributed, increased cation‐radius variance in La0.5Tb0.5CrO3 results in regions of localised La and Tb layers, an atomic arrangement exclusive to the hydrothermally prepared material. Solid‐state preparation gives lower homogeneity resulting in separate nanoscale regions rich in La3+ and Tb3+. The A‐site layering in hydrothermal La0.5Tb0.5CrO3 is randomised upon annealing at high temperature, resulting in magnetic behaviour that is dependent on synthesis route.
Time‐Gated Detection of Cystathionine γ‐Lyase Activity and Inhibition with a Selective, Luminogenic Hydrogen Sulfide Sensor
Authors: Yao Yao , Kong Chen , Yin Liang , Jain Atul D. , Ratia Kiira , Thatcher Gregory R. J. , Moore Terry W. , Driver Tom G. , Miller Lawrence W.
Published: October 2016

Herein, we report the design, synthesis, and characterization of a lanthanideIII complex‐based probe for the time‐gated luminescence detection of hydrogen sulfide (H2S) in aqueous media. The probe's unique sensing mechanism relies on the selective reduction of azide to amine by sulfide, followed by intramolecular cyclization to form a quinolinone. The quinolinone is a sensitizer that absorbs near‐UV light and transfers excitation energy to coordinated TbIII or EuIII ions to trigger a strong “turn‐on” luminescence response with ms‐scale lifetimes characteristic of lanthanide complexes. Using this probe, we developed a robust, high throughput screening (HTS) assay for detecting H2S generated by cystathionine γ‐lyase (CSE), one of the main producers of H2S in mammalian cells. In a 240‐compound screen to identify potential CSE inhibitors, the EuIII analogue of the sensor showed a low false‐positive rate and high Z′‐factor (>0.7).
ChemInform Abstract: Low‐Temperature Cationic Rearrangement in a Bulk Metal Oxide.
Authors: Greenblatt Martha , et al.
Published: October 2016

Cationic rearrangement in bulk Mn2FeMoO6 at 150—300 °C leads to a transition from the Ni3TeO6‐type to an ordered ilmenite structure, and dramatic changes of the electrical and magnetic properties as evidenced by powder X‐ray and neutron diffraction, and second harmonic generation.
ChemInform Abstract: Crystal Structure of Strontium Dicobalt Iron(III) Tris(orthophosphate): SrCo2Fe(PO4)3.
Authors: Bouraima Adam , Makani Thomas , Assani Abderrazzak , Saadi Mohamed , El Ammari Lahcen
Published: October 2016

Single crystals of the title compound are prepared by solid state reaction of a 1:2:1:3 molar mixture of Sr, Co, and Fe nitrates along with NH4H2PO4 (Pt crucible, 1343 K; cooling to 273 K at a rate of 5 K/h).
ChemInform Abstract: Cu3V2O8 Nanoparticles as Intercalation‐Type Anode Material for Lithium‐Ion Batteries.
Authors: Li Malin , Gao Yu , Chen Nan , Meng Xing , Wang Chunzhong , Zhang Yaoqing , Zhang Dong , Wei Yingjin , Du Fei , Chen Gang
Published: October 2016

Cu3V2O8 nanoparticles (40‐50 nm) are prepared by addition of NH4VO3 to an aqueous 0.1 M Cu(NO3)2 solution followed by drying and sintering of the Cu3V2O7 (OH)2·2H2O precipitate in air (400 °C, 1 h).
ChemInform Abstract: New Clathrates of Rb7.50(1)Tl0.50(1)Ge46 and K7.62(1)Tl0.38(1)Ge45.34(3).
Authors: Zhang Hui , Mu Gang , Huang Fuqiang , Xie Xiaoming
Published: October 2016

The title type‐I clathrates are synthesized by solid state reactions of the elements (Ta tubes, 650 °C, 14 d) and characterized by powder XRD, SEM, and DFT calculations.
ChemInform Abstract: RbZnFe(PO4)2: Synthesis and Crystal Structure.
Authors: Badri Abdessalem , Ben Amara Mongi
Published: October 2016

Single crystals of the new title compound are grown in a flux of Rb2Mo2O7 starting with Rb2CO3, Zn(NO3)2, Fe(NO3)3, (NH4)2HPO4, and MoO3 dissolved in HNO3 (353 K, 24 h) followed by heating of the dried residue (Pt crucible, 1173 K, 1 h).
ChemInform Abstract: Ternary Arsenides RECo5As3 (RE: Y, Gd, Tb, Dy, Ho, Er).
Authors: Zhak O. , Senkiv I. , Babyzhetskyy V. , Dzevenko M. , Bigun I. , Havela L. , Maskova S. , Paukov M.
Published: October 2016

LnCo5As3 (Ln: Y, Gd, Tb, Dy, Ho, Er) compounds are prepared by solid state reaction of stoichiometric amounts of the elements (evacuated silica tubes, 970 K, 10 d) followed by pelletizing, arc melting, and a final annealing (evacuated silica tubes, 970 K, 4 weeks).
ChemInform Abstract: Palladium Nanoparticles in Water: A Reusable Catalytic System for the Cycloetherification or Benzannulation of α‐Allenols.
Authors: Alcaide Benito , Almendros Pedro , Gonzalez Ana M. , Luna Amparo , Martinez‐Ramirez Sagrario
Published: October 2016

Palladium nanoparticles freshly generated from PdCl2, K2CO3 and Bu4NBr, are described as highly efficient catalytic system for the chemoselective cyclization reaction of various allenyl substituted secondary alcohols.
ChemInform Abstract: Highly Efficient and Recyclable Magnetic Nanoparticles‐Supported Gold(III)‐bipy Catalyst for Oxidative α‐Cyanation of Tertiary Amines.
Authors: Yang Weisen , Wei Li , Yi Feiyan , Cai Mingzhong
Published: October 2016

The title reaction renders possible the direct synthesis of various α‐aminonitriles if the amine substrates bear at least one aromatic substituent.
ChemInform Abstract: Organocatalytic Regioselective Chlorosilylation of Oxirane Derivatives: Mild and Effective Insertion of Bulky Silyl Chloride by Using 4‐Methoxypyridine N‐Oxide.
Authors: Yoshida Keisuke , Suzuki Hina , Inoue Hiroki , Matsui Kohei , Fujino Yuta , Kanoko Yohei , Itatsu Yukihiro , Takao Ken‐ichi
Published: October 2016

4‐Methoxypyridine N‐oxide is an efficient catalyst for the chlorosilylation of epoxides (I).
ChemInform Abstract: Copper Catalyzed Alkynylation of Tertiary Amines with CaC2 via sp3 C—H Activation.
Authors: Teong Siew Ping , Yu Dingyi , Sum Yin Ngai , Zhang Yugen
Published: October 2016

The copper‐catalyzed alkynylation of tertiary amines with CaC2 is described.
ChemInform Abstract: Highly Active Multidentate Ligand‐Based Alkyne Metathesis Catalysts.
Authors: Du Ya , Yang Haishen , Zhu Chengpu , Ortiz Michael , Okochi Kenji D. , Shoemaker Richard , Jin Yinghua , Zhang Wei
Published: October 2016

The catalyst combination MOC/BDMC can be successfully applied for homodimerization, ring closing alkyne metathesis and cyclooligomerization.
ChemInform Abstract: Catalytic, Diastereoselective 1,2‐Difluorination of Alkenes.
Authors: Banik Steven M. , Medley Jonathan William , Jacobsen Eric N.
Published: October 2016

A direct, catalytic approach to the 1,2‐difluorination of alkenes is described.
ChemInform Abstract: Efficient Synthesis of Unsymmetrical Sulfamides via a Lossen‐Like Rearrangement.
Authors: Pantaine Loic , Richard Francois , Marrot Jerome , Moreau Xavier , Coeffard Vincent , Greck Christine
Published: October 2016

A direct synthesis of unsymmetrical sulfamides is achieved by Et3N‐promoted reaction of N,O‐bissulfonyl hydroxylamines with primary amines or diphenylamine.
ChemInform Abstract: Rhodium‐Catalyzed Enantioselective Arylation of Aliphatic Imines.
Authors: Kato Naoya , Shirai Tomohiko , Yamamoto Yasunori
Published: October 2016

A broad spectrum of N‐sulfonyl aldimines is found to be suitable for the title reaction under either conditions A) or B).
ChemInform Abstract: The Multiple Facets of Iodine(III) Compounds in an Unprecedented Catalytic Auto‐Amination for Chiral Amine Synthesis.
Authors: Buendia Julien , Grelier Gwendal , Darses Benjamin , Jarvis Amanda G. , Taran Frederic , Dauban Philippe
Published: October 2016

Diacetoxyiodoarene (III) is used both as an oxidant and a substrate for the C(sp3)—H amination reaction leading to chiral iodide (V).
ChemInform Abstract: Synthesis of Pyrrolidinone Derivatives from Aniline, an Aldehyde and Diethyl Acetylenedicarboxylate in an Ethanolic Citric Acid Solution under Ultrasound Irradiation.
Authors: Ahankar Hamideh , Ramazani Ali , Slepokura Katarzyna , Lis Tadeusz , Joo Sang Woo
Published: October 2016

Compared to the conventional method, the utilization of ultrasound irradiation is shown to give slightly higher yields in significantly shorter reaction times.
ChemInform Abstract: Intramolecular Alkene Aminocarbonylation Using Concerted Cycloadditions of Amino‐Isocyanates.
Authors: Ivanovich Ryan A. , Clavette Christian , Vincent‐Rocan Jean‐Francois , Roveda Jean‐Gregoire , Gorelsky Serge I. , Beauchemin Andre M.
Published: October 2016

The title reaction proceeds via amino‐isocyanate intermediates to produce bi‐ or tricyclic N‐heterocycles which include an aminocarbonyl segment.
ChemInform Abstract: Efficient Synthesis of Dimeric Oxazoles, Piperidines and Tetrahydroisoquinolines from N‐Substituted 2‐Oxazolones.
Authors: Nicolaou K. C. , et al.
Published: October 2016

Different types of N‐substituted 2‐oxazolone substrates are subjected to a boron trifluoride etherate promoted reaction under slightly modified conditions to produce the title heterocycles (investigation and discussion of the cascade mechanisms).
ChemInform Abstract: A Carboxylative Cyclization of Propargylic Amines with Carbon Dioxide Catalyzed by the N‐Heterocyclic Carbene 1,3‐Di‐tert‐butylimidazol‐2‐ylidene (ItBu).
Authors: Fujita Ken‐ichi , Sato Junichi , Fujii Akira , Onozawa Shun‐ya , Yasuda Hiroyuki
Published: October 2016

Depending on the pressure of carbon dioxide employed, the carboxylative cyclization of propargylic amines gives selectively 2‐oxazolidiones (III) or 2‐oxazolones (IV).
ChemInform Abstract: Metal‐Free Autoxidative Nitrooxylation of Alkenyl Oximes with Molecular Oxygen.
Authors: Zhang Xiao‐Wei , Xiao Zu‐Feng , Zhuang Yan‐Jun , Wang Mei‐Mei , Kang Yan‐Biao
Published: October 2016

A series of nitrooxyisoxazolines (II), (IV), and (VI) is prepared by nitrooxylation of alkenyl oximes under air atmosphere.
ChemInform Abstract: Ytterbium Triflate Promoted Coupling of Phenols and Propiolic Acids: Synthesis of Coumarins.
Authors: Fiorito Serena , Epifano Francesco , Taddeo Vito A. , Genovese Salvatore
Published: October 2016

The improved method using microwave irradiation under solvent‐free conditions allows the synthesis of coumarins from phenols or hydroxycoumarins and propiolic acid derivatives.
ChemInform Abstract: Synthesis of 6‐Aryl/Heteroaryl‐4‐oxo‐4H‐chromene‐2‐carboxylic Ethyl Ester Derivatives.
Authors: Fernandes Carlos , Soares Pedro , Gaspar Alexandra , Martins Daniel , Gomes Ligia R. , Low John N. , Borges Fernanda
Published: October 2016

An expeditious two‐step procedure to synthesize the title compounds is developed.
ChemInform Abstract: Broensted Acid Promoted One‐Pot Synthesis of 4‐Aryl‐3,4‐dihydrocoumarins.
Authors: Chen Cheng , Zhang Rui , Lin Long , Yang Guang‐Fu , Wu Qiong‐You
Published: October 2016

A mild and facile approach to the title compounds, which are of interest in natural product and medicinal chemistry, becomes optimal in the presence of HClO4.
ChemInform Abstract: Metal‐Free C—H Arylation of Aminoheterocycles with Arylhydrazines.
Authors: Taniguchi Toshihide , Imoto Mitsutaka , Takeda Motonori , Matsumoto Fukashi , Nakai Takeo , Mihara Masatoshi , Mizuno Takumi , Nomoto Akihiro , Ogawa Akiya
Published: October 2016

Heterocyclic amines and diamine (Ib) are successfully arylated under atmospheric conditions in the presence of an inexpensive base.
ChemInform Abstract: Rh(III)‐Catalyzed Double Molecular Alkyne Imine C—H Activation: A Facile and Efficient Synthesis of Functionalized Acridine Compounds.
Authors: Shan Yingying , Yan Weidong
Published: October 2016

A facile protocol is developed for the synthesis of polyfunctionalized benzo‐ and thienoacridine derivatives from readily available imine substrates.
ChemInform Abstract: NBS Mediated One‐Pot Regioselective Synthesis of 2,3‐Disubstituted Imidazo[1,2‐a]pyridines and Their Unambiguous Characterization Through 2D NMR and X‐Ray Crystallography.
Authors: Aggarwal Ranjana , Singh Gulshan , Sanz Dionisia , Claramunt Rosa M. , Torralba M. Carmen , Torres M. Rosario
Published: October 2016

The access to the required heterocycles of type (III) proceeds via brominated 1,3‐diketones.
ChemInform Abstract: Synthesis of 3‐Substituted Indolizidines from Amino‐ynones Derivatives.
Authors: Vu Huy‐Dinh , Renault Jacques , Roisnel Thierry , Gouault Nicolas , Uriac Philippe
Published: October 2016

This study demonstrates access to indolizidines from racemic pipecolic acid with amino‐ynones as key intermediates.
ChemInform Abstract: One‐Pot Synthesis of Polyhydropyrido[1,2‐a]indoles and Tetracyclic Quinazolinones from 2‐Arylindoles Using Copper‐Mediated Oxidative Tandem Reactions.
Authors: Yamashita Mitsuaki , Nishizono Yukari , Himekawa Seiya , Iida Akira
Published: October 2016

The approach to the title heterocycles proceeds via C‐acylimine intermediates followed by aza‐Diels—Alder reactions or oxidative ring expansion and opens the way to important polycyclic systems.
ChemInform Abstract: A New Convenient Synthetic Approach to Diarylpyrimidines.
Authors: Guirado Antonio , Alarcon Enrique , Vicente Yesica , Andreu Raquel , Bautista Delia , Galvez Jesus
Published: October 2016

Two pathways to the desired compounds are presented: a stepwise and a one‐pot procedure which both are operationally simple.
ChemInform Abstract: Acceptorless Dehydrogenative Coupling of o‐Aminobenzamides with the Activation of Methanol as a C1 Source for the Construction of Quinazolinones.
Authors: Li Feng , Lu Lei , Liu Pengcheng
Published: October 2016

This method is applied in a synthesis of tyrosine kinase inhibitor erlotinib (X).
ChemInform Abstract: A Facile, Regioselective Synthesis of Pyrazolo[1, 5‐a]pyrimidine Analogues in the Presence of KHSO4 in Aqueous Media Assisted by Ultrasound and Their Antiinflammatory and Anticancer Activities.
Authors: Kaping Shunan , Kalita Utpalparna , Sunn Melboureen , Singha Laishram Indira , Vishwakarma Jai Narain
Published: October 2016

The pyrimidine derivatives are screened for their anti‐inflammatory and anticancer activities.
ChemInform Abstract: Synthesis of Derivatives of Methoxydibenzo[b,f]oxepine in the Presence of Sodium Azide.
Authors: Krawczyk Hanna , Wrzesinski Michal , Mielecki Damian , Szczecinski Przemyslaw , Grzesiuk Elzbieta
Published: October 2016

Sodium azide promotes the formation of the pharmaceutically important ring system (mechanism and theoretical calculations).
ChemInform Abstract: Total Synthesis of (—)‐Stemoamide by Sequential Overman/Claisen Rearrangement.
Authors: Nakayama Yasuaki , Maeda Yuichiro , Hama Naoto , Sato Takaaki , Chida Noritaka
Published: October 2016

The enantioselective total synthesis of (—)‐stemoamide using Overman/Claisen rearrangement of an allylic 1,2‐diol is reported.
ChemInform Abstract: Why Do Lithium—Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect
Authors: Yao Xiahui , Dong Qi , Cheng Qingmei , Wang Dunwei
Published: October 2016

Review: 90 refs.
ChemInform Abstract: Dilute Ferromagnetic Semiconductors Prepared by the Combination of Ion Implantation with Pulse Laser Melting
Authors: Zhou Shengqiang
Published: October 2016

Review: 183 refs.
ChemInform Abstract: Ferrocenyl‐Nucleobase Complexes: Synthesis, Chemistry and Applications
Authors: Kowalski Konrad
Published: October 2016

Review: 119 refs.
ChemInform Abstract: A Decade of Advance in the Asymmetric Vinylogous Mannich Reaction
Authors: Sanchez Rosello Maria , del Pozo Carlos , Fustero Santos
Published: October 2016

Review: [70 refs.
ChemInform Abstract: Functionalization of Pyrene to Prepare Luminescent Materials — Typical Examples of Synthetic Methodology
Authors: Feng Xing , Hu Jian‐Yong , Redshaw Carl , Yamato Takehiko
Published: October 2016

Review: [95 refs.
ChemInform Abstract: Recent Developments in Transition Metal Catalysis for Quinazolinone Synthesis
Authors: Maiden T. M. M. , Harrity J. P. A.
Published: October 2016

Review: 54 refs.
ChemInform Abstract: 3‐Hydrazinoindolin‐2‐one Derivatives: Chemical Classification and Investigation of Their Targets as Anticancer Agents
Authors: Ibrahim Hany S. , Abou‐Seri Sahar M. , Abdel‐Aziz Hatem A.
Published: October 2016

Review: 91 refs.
ChemInform Abstract: Application of Ionic Liquids in Pot‐in‐Pot Reactions
Authors: Cinar Simge , Schulz Michael D. , Oyola‐Reynoso Stephanie , Bwambok David K. , Gathiaka Symon M. , Thuo Martin
Published: October 2016

Review: critical role of ionic liquids in site‐isolation of multiple catalyzed reactios in a standard pot‐in‐pot reaction; 71 refs.
ChemInform Abstract: Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse
Authors: Neeve Emily C. , Geier Stephen J. , Mkhalid Ibraheem A. I. , Westcott Stephen A. , Marder Todd B.
Published: October 2016

Review: 917 refs.
ChemInform Abstract: Blood—Brain Barrier Shuttle Peptides: An Emerging Paradigm for Brain Delivery
Authors: Oller‐Salvia Benjami , Sanchez‐Navarro Macarena , Giralt Ernest , Teixido Meritxell
Published: October 2016

Review: 195 refs.
ChemInform Abstract: Discovery and Development of Natural Product Oridonin‐Inspired Anticancer Agents
Authors: Ding Ye , Ding Chunyong , Ye Na , Liu Zhiqing , Wold Eric A. , Chen Haiying , Wild Christopher , Shen Qiang , Zhou Jia
Published: October 2016

Review: 130 refs.