bluuebunny/crossref_metadata_2025_split huggingface dataset:
Advanced simulation technology for etching process design for CMOS device applications
Authors: Kuboi Nobuyuki , Fukasawa Masanaga , Tatsumi Tetsuya 
Published: June 2016

Abstract
Plasma etching is a critical process for the realization of high performance in the next generation of CMOS devices. To predict and control fluctuations in the etching properties accurately during mass production, it is essential that etching process simulation technology considers fluctuations in the plasma chamber wall conditions, the effects of by-products on the critical dimensions, the Si recess dependence on the wafer open area ratio and local pattern structure, and the time-dependent plasma-induced damage distribution associated with the three-dimensional feature scale profile at the 100 nm level. This consideration can overcome the issues with conventional simulations performed under the assumed ideal conditions, which are not accurate enough for practical process design. In this article, these advanced process simulation technologies are reviewed, and, from the results of suitable process simulations, a new etching system that automatically controls the etching properties is proposed to enable stable CMOS device fabrication with high yields.
Extreme dry spell detection and climatology over the Mediterranean Basin during the wet season
Authors: Raymond Florian , Ullmann Albin , Camberlin Pierre , Drobinski Philippe , Smith Carmela Chateau 
Published: June 2016

AbstractThe E‐OBS precipitation gridded data set v.10.0 is used to detect very long dry spell (VLDS) events over the entire Mediterranean Basin for the 1957–2013 period, during the wet season (September to April). The main objective is to characterize these events as climatic objects, in terms of location, spatial extent, duration, and temporal variability. In this study, 76 VLDS events were detected in the Mediterranean Basin and grouped into four spatial patterns: scattered localized (with 25 events), northeast Mediterranean (11 events), West Mediterranean (15 events), and southeast Mediterranean (25 events). Each pattern shows seasonality in events. Most of the scattered localized, northeast, and southeast events begin in September, at the beginning of the wet season. In contrast, most of the West Mediterranean events begin in the middle of the wet season. Over time, there is a slight but not significant increase in the cumulative number of days per season affected by VLDS events.
Advancing the Evolution of Sexual Offender Risk Assessment
Authors: Thornton David , D'Orazio Deirdre M. 
Published: June 2016

AbstractThis chapter explores the nature and role of psychological factors in assessing the risk presented by sexual offenders. It is argued that it is incumbent upon those tasked with assessing risk to conduct a comprehensive assessment of psychological factors as an essential aspect of effective sexual offender risk assessment. Not only do instruments that provide comprehensive assessment of psychological risk factors afford a similar level of predictive accuracy compared with that afforded by traditional static actuarial instruments, but the combination of static and psychological risk factors leads to even better prediction than either alone. Moreover, the predictive properties of the static actuarial instruments become unstable if either the density of psychological risk factors or the degree of external control prevailing in the release environment varies. Psychological risk factors have both enduring and more actively dynamic aspects and assessors are cautioned not to overweight recent functioning in rendering risk predictions. The chapter articulates a model of these temporal aspects of risk factors and their interaction. Risk reduction is understood in terms of managing long‐term vulnerabilities through improved self‐regulation and the development of resources supportive of prosocial goals.
Monofluoralkenylierung von Dimethylaminoverbindungen durch Radikal‐Radikal‐Kreuzkupplung
Authors: Xie Jin , Yu Jintao , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K. 
Published: June 2016

AbstractEine neuartige und schwierige Radikal‐Radikal‐Kreuzkupplung von α‐Aminoalkylradikalen mit von gem‐Difluoralkenen abgeleiteten Monofluoralkenylradikalen wurde erreicht. Dieses erste Beispiel einer Tandem‐C(sp3)‐H/C(sp2)‐F‐Bindungsfunktionalisierung über Photoredoxkatalyse mit sichtbarem Licht eröffnet einen leichten und flexiblen Zugang zu privilegierten, tetrasubstituierten Monofluoralkenen unter sehr milden Reaktionsbedingungen. Die besonderen Eigenschaften dieses redoxneutralen Verfahrens bezüglich der Anwendungsbreite, der Toleranz gegenüber funktionellen Gruppen und Regioselektivität zeigen sich durch die Fluoralkenylierungen von komplexen molekularen Architekturen wie dem bioaktiven (+)‐Filtiazem, Rosiglitazon, Dihydroartemisinin, Oleanolsäure und einem Androsteron‐Derivat; dies sind wichtige neue α‐Amino‐C‐H‐Monofluoralkenylierungen.
Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines
Authors: Kim Sang Bok , Yang Chuanxi , Powers Tamara , Davis Luke M. , Lou Xiabing , Gordon Roy G. 
Published: June 2016

AbstractWe have prepared two new CaII amidinates, which comprise a new class of ALD precursors. The syntheses proceed by a direct reaction between Ca metal and the amidine ligands in the presence of ammonia. Bis(N,N′‐diisopropylformamidinato)calcium(II) (1) and bis(N,N′‐diisopropylacetamidinato)calcium(II) (2) adopt dimeric structures in solution and in the solid state. X‐ray crystallography revealed asymmetry in one of the bridging ligands to afford the structure [(η2‐L)Ca(μ‐η2:η2‐L)(μ‐η2:η1‐L)Ca(η2‐L)]. These amidinate complexes showed unprecedentedly high volatility as compared to the widely employed and commercially available CaII precursor, [Ca3(tmhd)6]. In CaS ALD with 1 and H2S, the ALD window was approximately two times wider and lower in temperature by about 150 °C than previously reported with [Ca3(tmhd)6] and H2S. Complexes 1 and 2, with their excellent volatility and thermal stability (up to at least 350 °C), are the first homoleptic CaII amidinates suitable for use as ALD precursors.
Selective Protein Hyperpolarization in Cell Lysates Using Targeted Dynamic Nuclear Polarization
Authors: Viennet Thibault , Viegas Aldino , Kuepper Arne , Arens Sabine , Gelev Vladimir , Petrov Ognyan , Grossmann Tom N. , Heise Henrike , Etzkorn Manuel 
Published: June 2016

AbstractNuclear magnetic resonance (NMR) spectroscopy has the intrinsic capabilities to investigate proteins in native environments. In general, however, NMR relies on non‐natural protein purity and concentration to increase the desired signal over the background. We here report on the efficient and specific hyperpolarization of low amounts of a target protein in a large isotope‐labeled background by combining dynamic nuclear polarization (DNP) and the selectivity of protein interactions. Using a biradical‐labeled ligand, we were able to direct the hyperpolarization to the protein of interest, maintaining comparable signal enhancement with about 400‐fold less radicals than conventionally used. We could selectively filter out our target protein directly from crude cell lysate obtained from only 8 mL of fully isotope‐enriched cell culture. Our approach offers effective means to study proteins with atomic resolution in increasingly native concentrations and environments.
Photo‐induced Substitutive Introduction of the Aldoxime Functional Group to Carbon Chains: A Formal Formylation of Non‐Acidic C(sp3)−H Bonds
Authors: Kamijo Shin , Takao Go , Kamijo Kaori , Hirota Masaki , Tao Keisuke , Murafuji Toshihiro 
Published: June 2016

AbstractA photo‐induced substitutive introduction of an aldoxime functional group to carbon chains was achieved using photo‐excited 4‐benzoylpyridine as a C(sp3)−H bond cleaving agent and arylsulfonyl oxime as an aldoxime precursor. The non‐acidic C−H bonds in various substances, including cycloalkanes, ethers, azacycles, and cyclic sulfides, were chemoselectively converted at ambient temperature under neutral conditions. The present transformation is a formal formylation of non‐acidic C(sp3)−H bonds in a single step.
Unidirectional Threading into a Bowl‐Shaped Macrocyclic Trimer of Boron–Dipyrrin Complexes through Multipoint Recognition
Authors: Nakamura Takashi , Yamaguchi Gento , Nabeshima Tatsuya 
Published: June 2016

AbstractBowl‐shaped macrocycles have the distinctive feature that their two sides are differentiated, and thus can be developed into elaborate hosts that fix a target molecule in a controlled geometry through multipoint interactions. We now report the synthesis of a bowl‐shaped macrocyclic trimer of the boron–dipyrrin (BODIPY) complex and its unidirectional threading of guest molecules. Six polarized Bδ+−Fδ‐ bonds are directed towards the center of the macrocycle, which enables strong recognition of cationic guests. Specifically, the benzylbutylammonium ion is bound in a manner in which the benzyl group is located at the convex face of the bowl and the butyl group at its concave face. Furthermore, adrenaline was strongly captured on the convex side of the bowl by hydrogen bonding, Coulomb forces, and C−H⋅⋅⋅π interactions.
Supramolecular Control over Split‐Luciferase Complementation
Authors: Bosmans Ralph P. G. , Briels Jeroen M. , Milroy Lech‐Gustav , de Greef Tom F. A. , Merkx Maarten , Brunsveld Luc 
Published: June 2016

AbstractSupramolecular split‐enzyme complementation restores enzymatic activity and allows for on–off switching. Split‐luciferase fragment pairs were provided with an N‐terminal FGG sequence and screened for complementation through host‐guest binding to cucurbit[8]uril (Q8). Split‐luciferase heterocomplex formation was induced in a Q8 concentration dependent manner, resulting in a 20‐fold upregulation of luciferase activity. Supramolecular split‐luciferase complementation was fully reversible, as revealed by using two types of Q8 inhibitors. Competition studies with the weak‐binding FGG peptide revealed a 300‐fold enhanced stability for the formation of the ternary heterocomplex compared to binding of two of the same fragments to Q8. Stochiometric binding by the potent inhibitor memantine could be used for repeated cycling of luciferase activation and deactivation in conjunction with Q8, providing a versatile module for in vitro supramolecular signaling networks.
Synthesis of Diversely Functionalized Oxindoles Enabled by Migratory Insertion of Isocyanide to a Transient σ‐Alkylpalladium(II) Complex
Authors: Kong Wangqing , Wang Qian , Zhu Jieping 
Published: June 2016

AbstractPalladium‐catalyzed intramolecular carbopalladation of N‐aryl acrylamides followed by migratory insertion of an isocyanide‐coordinated C(sp3)−Pd intermediate afforded an alkylimidoyl−PdII complex, which can be intercepted by a nucleophile, including heteroarenes. In addition to amides, the alkylimidoyl−PdII complex was successfully converted into esters, ketones, and bis‐heterocyclic compounds. An unprecedented palladium‐catalyzed enantioselective domino process involving isocyanide was also documented.
Biomimetic Transmembrane Channels with High Stability and Transporting Efficiency from Helically Folded Macromolecules
Authors: Lang Chao , Li Wenfang , Dong Zeyuan , Zhang Xin , Yang Feihu , Yang Bing , Deng Xiaoli , Zhang Chenyang , Xu Jiayun , Liu Junqiu 
Published: June 2016

AbstractMembrane channels span the cellular lipid bilayers to transport ions and molecules into cells with sophisticated properties including high efficiency and selectivity. It is of particular biological importance in developing biomimetic transmembrane channels with unique functions by means of chemically synthetic strategies. An artificial unimolecular transmembrane channel using pore‐containing helical macromolecules is reported. The self‐folding, shape‐persistent, pore‐containing helical macromolecules are able to span the lipid bilayer, and thus result in extraordinary channel stability and high transporting efficiency for protons and cations. The lifetime of this artificial unimolecular channel in the lipid bilayer membrane is impressively long, rivaling those of natural protein channels. Natural channel mimics designed by helically folded polymeric scaffolds will display robust and versatile transport‐related properties at single‐molecule level.
Rapid Access to Orthogonally Functionalized Naphthalenes: Application to the Total Synthesis of the Anticancer Agent Chartarin
Authors: Unzner Teresa A. , Grossmann Adriana S. , Magauer Thomas 
Published: June 2016

AbstractWe report the synthesis of orthogonally functionalized naphthalenes from simple, commercially available indanones in four steps. The developed method proceeds through a two‐step process that features a thermally induced fragmentation of a cyclopropane indanone with simultaneous 1,2‐chloride shift. Migration of the chloride substituent occurs in a regioselective manner to preferentially afford the para‐chloronaphthol substitution pattern. The obtained naphthols are versatile building blocks that can be selectively modified and used for the efficient construction of biologically active molecules. This has enabled the total synthesis of the potent anticancer natural product chartarin through a highly convergent retrosynthetic bond disconnection.
Mechanical behavior of palm oil–based composite foam and its sandwich structure with a flax–epoxy composite
Authors: Teo Siew Cheng , Lan Du Ngoc Uy , Teh Pei Leng , Tran Le Quan Ngoc 
Published: June 2016

ABSTRACTEmpty fruit bunch fiber (EFB), an abundant biomass waste from the palm oil industry, is used to reinforce palm oil–based polyurethane foam (POPU), and the mechanical properties of the composite foams are also assessed. The fiber–foam interfacial adhesion is also investigated by SEM images and Fourier transform infrared spectrometry. The results show that the composite foam reinforced by 15–30% EFB volume fractions could be enhanced by up to 10 times in flexural strength and twice in compressive strength compared to neat POPU. The composite foams with 20% and 30% volume fraction of EFB are exploited as a core in a sandwich construction with unidirectional flax fiber–reinforced epoxy composites (as face sheets). Sandwiches using EFB/POPU composite foam cores exhibited better toughness and achieved higher flexural energy at break compared to that using a commercial poly(ethylene terephthalate (PET) foam core. Furthermore, the failure mechanisms occurred under a combination of flexural and shear deformation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43977.
Reinforcement of ethylene‐acrylic elastomer with a dispersion of grafted PA6 droplets
Authors: Oriani S. R. 
Published: June 2016

ABSTRACTCured elastomers are commonly dispersed in thermoplastics, but the reverse morphology has received little attention. The present work examines dispersions of 0.5–2 μm PA6 droplets in ethylene‐acrylic elastomer (AEM), created by melt blending. After cooling, the blends are compounded with amine curative and crosslinked. Uncrosslinked blends exhibit high bound rubber levels compared to N990 carbon black filled AEM, but similar viscosity at equal filler volume fraction. Crosslinking the blends produces strong, heat resistant vulcanizates with minimal Payne effect and good compression set resistance. These properties result from extensive AEM‐PA6 grafting, absence of filler‐filler contacts, and beneficial modification of the oxidation profile under diffusion limited conditions. The data show rubber‐filler grafting strongly influences filler reinforcing ability, but does not directly influence the Payne effect. Relative to unfilled AEM, silica and carbon black fillers accelerate oxidative degradation in proportion to their reinforcing ability, whereas PA6 has a stabilizing effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43995.
Structural modeling of tumor necrosis factor: A protein of immunological importance
Authors: Roy Urmi 
Published: June 2016

AbstractTumor necrosis factor (TNF) is a multifunctional pro‐inflammatory cytokine responsible for various immunoregulatory activities. Upon binding with its receptor, TNF triggers multiple complex signaling pathways such as the activations of nuclear factor kappa B and caspase cascade, which are the leading determining factors for cell survival or cell death. The present work studies certain modeling aspects of the TNF, with comparative structural analyses of the wild and mutant types of this protein. Additionally, nanoscale molecular dynamics simulations are performed to assess the structure–property relationships of proteins as functions of time.
Local influence diagnostics for hierarchical count data models with overdispersion and excess zeros
Authors: Rakhmawati Trias Wahyuni , Molenberghs Geert , Verbeke Geert , Faes Christel 
Published: June 2016

We consider models for hierarchical count data, subject to overdispersion and/or excess zeros. Molenberghs et al. () and Molenberghs et al. () extend the Poisson‐normal generalized linear‐mixed model by including gamma random effects to accommodate overdispersion. Excess zeros are handled using either a zero‐inflation or a hurdle component. These models were studied by Kassahun et al. (). While flexible, they are quite elaborate in parametric specification and therefore model assessment is imperative. We derive local influence measures to detect and examine influential subjects, that is subjects who have undue influence on either the fit of the model as a whole, or on specific important sub‐vectors of the parameter vector. The latter include the fixed effects for the Poisson and for the excess‐zeros components, the variance components for the normal random effects, and the parameters describing gamma random effects, included to accommodate overdispersion. Interpretable influence components are derived. The method is applied to data from a longitudinal clinical trial involving patients with epileptic seizures. Even though the data were extensively analyzed in earlier work, the insight gained from the proposed diagnostics, statistically and clinically, is considerable. Possibly, a small but important subgroup of patients has been identified.
Endothioxopeptides: A conformational overview
Authors: De Zotti Marta , Peggion Cristina , Biondi Barbara , Crisma Marco , Formaggio Fernando , Toniolo Claudio 
Published: June 2016

AbstractAlthough thionamides would have been first prepared two centuries ago and their chemical and spectroscopic properties extensively investigated, only much more recently (since about 1985) a well deserved but still insufficient attention has been paid to their endothioxopeptide subfamily which nonetheless currently represents a rapidly emerging area of great scientific interest in the broader field of foldameric compounds based on biologically relevant building blocks. After two brief sections offering information on the unfortunately still limited number of endothioxopeptides discovered from natural sources but also on the impressive advancements registered in the last few years in their synthetic methods, this review article outlines the results of a detailed literature survey on the ongoing great, but not systematic, progress related to the conformational consequences generated by incorporating one (or more) thionamide group(s) into a polypeptide chain. Finally, a short discussion of the growing, but still in its infancy, class of the endoselenoxopeptide congeners is also presented.
A current perspective on applications of macrocyclic‐peptide‐based high‐affinity ligands
Authors: Leenheer Daniël , ten Dijke Peter , Hipolito Christopher John 
Published: June 2016

AbstractMonoclonal antibodies can bind with high affinity and high selectivity to their targets. As a tool in therapeutics or diagnostics, however, their large size (∼150 kDa) reduces penetration into tissue and prevents passive cellular uptake. To overcome these and other problems, minimized protein scaffolds have been chosen or engineered, with care taken to not compromise binding affinity or specificity. An alternate approach is to begin with a minimal non‐antibody scaffold and select functional ligands from a de novo library. We will discuss the structure, production, applications, strengths, and weaknesses of several classes of antibody‐derived ligands, that is, antibodies, intrabodies, and nanobodies, and nonantibody‐derived ligands, that is, monobodies, affibodies, and macrocyclic peptides. In particular, this review is focussed on macrocyclic peptides produced by the Random non‐standard Peptides Integrated Discovery (RaPID) system that are small in size (typically ∼2 kDa), but are able to perform tasks typically handled by larger proteinaceous ligands.
Enantioselective Cu‐Catalyzed Functionalizations of Unactivated Alkenes
Authors: Sorádová Zuzana , Šebesta Radovan 
Published: June 2016

AbstractCopper hydride or copper boranyl species have already been used in reactions with Michael acceptors. Recently, notable advances have been described and the methodology extended to unactivated alkenes as well. In situ generated copper hydride ligated with chiral ligands is able to catalyze enantioselective aminations of alkenes. Furthermore, transient organocopper species formed upon initial hydrocupration of the alkene can be intercepted by other electrophiles such as imines, organohalides, or boranes.
Three‐Dimensional Metal–Organic Framework Graphene Nanocomposite as a Highly Efficient and Stable Electrocatalyst for the Oxygen Reduction Reaction in Acidic Media
Authors: Sohrabi Samaneh , Dehghanpour Saeed , Ghalkhani Masoumeh 
Published: June 2016

AbstractWe report on the design of a bio‐inspired composite as a noble‐metal‐free electrocatalyst for the oxygen reduction reaction (ORR). The composite is made from the assembly of pyridine‐functionalized graphene (G‐py) and a 3 D metal–organic framework (MOF) deposited onto a glassy carbon electrode (GCE). The 3 D heme‐like MOF was synthesized from tetrakis(4‐carboxyphenyl)porphyrin iron(III) chloride and Zr6 clusters for the assembly of the stable porous coordination network. G‐py, which possesses an axial ligand to anchor to the centers of porphyrin in the MOF, results in a significant change in the electronic and geometric structure of centers, which enhances the rate of ORR and durability during cycling in acidic media. The occurrence potential of the ORR by the composite is shifted to the positive potential near 100 mV. Our results introduce a new strategy for the rational design of inexpensive and highly stable oxygen reduction electrocatalysts for fuel cells without the requirement of pyrolysis.
Corrole and Porphyrin Amino Acid Conjugates: Synthesis and Physicochemical Properties
Authors: Karikis Kostas , Georgilis Evangelos , Charalambidis Georgios , Petrou Athanasia , Vakuliuk Olena , Chatziioannou Theodore , Raptaki Iliana , Tsovola Sofia , Papakyriacou Ioanna , Mitraki Anna , Gryko Daniel T. , Coutsolelos Athanassios G. 
Published: June 2016

AbstractA series of conjugates of amino acids with porphyrins and corroles was synthesized. Their self‐assembling ability under defined conditions was investigated by scanning electron microscopy. The morphology and photophysical properties of these molecules were studied by absorption and fluorescence spectroscopy in solid, liquid, and self‐assembled forms. We observed that both corrole and porphyrin conjugated with the l‐phenylalanine–l‐phenylalanine peptide to form spherical nanostructures with bathochromic shifts in the emission spectra, indicating the formation of aggregates. These aggregates are characterized by the impressive absorption of light over nearly the whole visible range. The broadening of all bands was particularly strong in the case of corroles. The fluorescence lifetimes of self‐assembled species were longer as compared to the solid‐state form.