bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enhancing the Performance of Dye‐Sensitized Solar Cells with a Gold‐Nanoflowers Box
Authors: Zhang Lu , Wang Zhong‐Sheng 
Published: October 2016

AbstractTo improve the electron collection, electron lifetime, and light‐harvesting efficiency of dye‐sensitized solar cells simultaneously, Au nanoflowers were prepared and used to cover the entire TiO2 film. Deposition of Au nanoflowers around the TiO2 film formed a light‐scattering “box” that covered the entire TiO2 film. Compared with a light‐scattering layer that only covers the top surface of TiO2, the Au‐nanoflowers box exhibited better light‐harvesting efficiency due to omnidirectional light scattering, faster electron transport (attributed to the formation of electron channels between the metallic Au nanoflowers and the electron‐collection electrode), and slower charge recombination. As a consequence, the short‐circuit photocurrent and open‐circuit photovoltage were both enhanced significantly, which improved the power conversion efficiency from 8.12 to 10.91 % (34 %) when an Au‐nanoflowers box was wrapped around the photoanode.
Study on physisorption between G‐actin and amphiphilic polymer‐coated gold nanoparticles
Authors: Du Qiqige , Li Wanrong , Yuan Ming , Gong Pei , Zhang Yi , Zhang Feng 
Published: October 2016

AbstractPhysisorptions occurs everywhere and constantly in living organisms and between nanomaterials and biomolecules. In this study, one of the most important proteins, G‐actin, was selected to investigate its bio‐nano physisorption with a model nanoparticle coated with a amphiphilic polymer. Using a photoluminescence quenching method, both the binding constant and the Hill constant were determined as 1.79 × 107 M−1 and 0.84, respectively. Thermodynamic calculations proved that such a physisorption was a spontaneous procedure. The physisorption‐mediated protein–nanoparticle conjugates were robust enough to resist gel electrophoresis, and protein conformation was kept intact, as revealed using circular dichroism. This conjugate might be a promising candidate for nanofabrication or could play a significant role in actin–related bioactivities.
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

AbstractBackgroundProgressive 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.MethodsWe 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 ResultsWe 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.ConclusionThe 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

AbstractBackground and PurposeClinically, 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.MethodsOur 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.ResultsOur 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.ConclusionsWe 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

AbstractIntroductionCorrelated 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.MethodsFunctional 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.ResultsAs 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.ConclusionOur 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

AbstractThe 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
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 MethodTranscatheter 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.ResultsAll 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.ConclusionRapid 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

AbstractMultimetallic 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

AbstractOperando 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

AbstractNon‐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

AbstractCooperative 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

AbstractSulfur‐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

AbstractIn 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

AbstractBy 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

AbstractBy 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.