bluuebunny/crossref_metadata_2025_split huggingface dataset:
Daily pain in adults with sickle cell disease—a different perspective
Authors: van Tuijn Charlotte F. J. , Sins Joep W. R. , Fijnvandraat Karin , Biemond Bart J. 
Published: November 2016

AbstractPrevious reports demonstrated that patients with sickle cell disease (SCD) experience pain on more than half of the observed days. Yet, these high incidences do not seem to match observations in our population. In this prospective cohort study, we aimed to assess the frequency and characteristics of daily, self‐reported pain among adult SCD patients in the Netherlands. Consecutive patients were enrolled during routine outpatient visits and followed up to 6 months. A total of 55 patients completed 5,982 diary observation days. Median age was 27 years (IQR 23‐43). Patients reported SCD related pain on 17% of the observed days; on 13% of these days this pain was not defined as a painful crisis, while 3% was reported as a painful crisis but managed at home, and on 1% of the observed days patients were admitted to the hospital. Analgesics were used on 52% of days with pain with a relatively infrequent use of oral opioids (9% of pain days). This first European study on pain in SCD indicates that pain appears to be significantly less frequent in our population as compared to previous study cohorts from the United States, and may be more representative for current SCD populations in other Western countries. Besides a more widespread use of hydroxycarbamide in modern disease management, differences in organization and accessibility of healthcare between countries may also explain this discrepancy.
Highly Site‐Selective and Direct Ortho‐C−H Nitration, Trifluoromethylation and Cyanation at the C1‐Position of Carbazole Frameworks
Authors: Reddy Ganapam Manohar , Rao Naidu Sambasiva , Hariharasarma Maheswaran 
Published: November 2016

AbstractWe report a concise, versatile, and practical method for ortho‐C−H mononitration, monotrifluoromethylation and monocyanation of carbazole cores via a transition‐metal‐catalyzed reaction using an appropriate functional group source. The significant advantage of this transformation is the generation of highly site‐selective direct C1–heteroatom bonds that are geometrically difficult to access, in good to excellent yields.
Aufklärung entscheidender struktureller Aspekte einer enantioselektiven Peptid‐katalysierten Acylierung mittels moderner NMR‐Techniken
Authors: Procházková Eliška , Kolmer Andreas , Ilgen Julian , Schwab Mira , Kaltschnee Lukas , Fredersdorf Maic , Schmidts Volker , Wende Raffael C. , Schreiner Peter R. , Thiele Christina M. 
Published: November 2016

AbstractWir stellen eine umfassende NMR‐spektroskopische Untersuchung der Katalysator‐Substrat‐Wechselwirkungen eines hochselektiven Oligopeptid‐Katalysators vor, welcher für die kinetische Racematspaltung von trans‐Cycloalkan‐1,2‐diolen via Monoacylierung verwendet wird. Die außerordentliche Selektivität wurde basierend auf Molekulardynamik‐Simulationen sowie DFT‐Rechnungen erklärt. In dieser Arbeit beschreiben wir die Konformationsanalyse des Organokatalysators durch Kombination des Kern‐Overhauser‐Effekts (NOE) mit residualen dipolaren Kopplungen (RDC), wobei ein Ensemble aus vier Konformeren erhalten wurde. Zur Bestätigung des postulierten Mechanismus untersuchten wir den Katalysator in Mischungen mit dem jeweiligen Enantiomer des trans‐Cyclohexan‐1,2‐diols. Zur Charakterisierung der molekularen Aggregation wurden weiterführende NMR‐Methoden, wie die Messung von T1‐Relaxationszeiten und DOSY‐Experimente, angewendet. Bei der Messung quantitativer NOEs konnte eine Änderung der intramolekularen Abstände innerhalb des Katalysators nach Zugabe des Diols festgestellt werden. Schließlich erlaubte die Entwicklung eines pure‐shift‐EASY‐ROESY‐Experiments auf der Basis von PSYCHE‐Homoentkopplung die direkte Beobachtung intermolekularer NOE‐Kontakte zwischen dem trans‐1,2‐Diol und dem Cyclohexyl‐Rest des Katalysators, welche zuvor aufgrund von Signalüberlagerung in konventionellen NMR‐Spektren nicht beobachtbar waren. Sämtliche experimentellen NMR‐Daten bestätigen die zuvor durch Berechnungen aufgestellten Modelle. Dies beinhaltet auch die vorgeschlagene Schlüsselrolle von Dispersionswechselwirkungen.
2‐Substituted dATP Derivatives as Building Blocks for Polymerase‐Catalyzed Synthesis of DNA Modified in the Minor Groove
Authors: Matyašovský Ján , Perlíková Pavla , Malnuit Vincent , Pohl Radek , Hocek Michal 
Published: November 2016

Abstract2′‐Deoxyadenosine triphosphate (dATP) derivatives bearing diverse substituents (Cl, NH2, CH3, vinyl, ethynyl, and phenyl) at position 2 were prepared and tested as substrates for DNA polymerases. The 2‐phenyl‐dATP was not a substrate for DNA polymerases, but the dATPs bearing smaller substituents were good substrates in primer‐extension experiments, producing DNA substituted in the minor groove. The vinyl‐modified DNA was applied in thiol–ene addition and the ethynyl‐modified DNA was applied in a CuAAC click reaction to form DNA labelled with fluorescent dyes in the minor groove
Combining Organocatalysis and Lanthanide Catalysis: A Sequential One‐Pot Quadruple Reaction Sequence/Hetero‐Diels–Alder Asymmetric Synthesis of Functionalized Tricycles
Authors: Dochain Simon , Vetica Fabrizio , Puttreddy Rakesh , Rissanen Kari , Enders Dieter 
Published: November 2016

AbstractA stereoselective one‐pot synthesis of functionalized complex tricyclic polyethers has been achieved using the combination of secondary amine and lanthanide catalysis. This one‐pot quadruple reaction/Hetero‐Diels–Alder sequence gave good yields (per step) as well as excellent diastereo‐ and enantioselectivities. Furthermore, the particular combination of lanthanide complexes with organocatalysis is one of the first examples described for sequential catalysis.
Uncovering Key Structural Features of an Enantioselective Peptide‐Catalyzed Acylation Utilizing Advanced NMR Techniques
Authors: Procházková Eliška , Kolmer Andreas , Ilgen Julian , Schwab Mira , Kaltschnee Lukas , Fredersdorf Maic , Schmidts Volker , Wende Raffael C. , Schreiner Peter R. , Thiele Christina M. 
Published: November 2016

AbstractWe report on a detailed NMR spectroscopic study of the catalyst‐substrate interaction of a highly enantioselective oligopeptide catalyst that is used for the kinetic resolution of trans‐cycloalkane‐1,2‐diols via monoacylation. The extraordinary selectivity has been rationalized by molecular dynamics as well as density functional theory (DFT) computations. Herein we describe the conformational analysis of the organocatalyst studied by a combination of nuclear Overhauser effect (NOE) and residual dipolar coupling (RDC)‐based methods that resulted in an ensemble of four final conformers. To corroborate the proposed mechanism, we also investigated the catalyst in mixtures with both trans‐cyclohexane‐1,2‐diol enantiomers separately, using advanced NMR methods such as T1 relaxation time and diffusion‐ordered spectroscopy (DOSY) measurements to probe molecular aggregation. We determined intramolecular distance changes within the catalyst after diol addition from quantitative NOE data. Finally, we developed a pure shift EASY ROESY experiment using PSYCHE homodecoupling to directly observe intermolecular NOE contacts between the trans‐1,2‐diol and the cyclohexyl moiety of the catalyst hidden by spectral overlap in conventional spectra. All experimental NMR data support the results proposed by earlier computations including the proposed key role of dispersion interaction.
Cassava starch‐based nanocomposites reinforced with cellulose nanofibers extracted from sisal
Authors: Santana Jamille Santos , do Rosário Jamile Marques , Pola Cícero Cardoso , Otoni Caio Gomide , de Fátima FerreiraSoares Nilda , Camilloto Geany Peruch , Cruz Renato Souza 
Published: November 2016

ABSTRACTCellulose nanofibers were extracted from sisal and incorporated at different concentrations (0–5%) into cassava starch to produce nanocomposites. Films' morphology, thickness, transparency, swelling degree in water, water vapor permeability (WVP) as well as thermal and mechanical properties were studied. Cellulose nanofiber addition affected neither thickness (56.637 ± 2.939 µm) nor transparency (2.97 ± 1.07 mm−1). WVP was reduced until a cellulose nanofiber content of 3.44%. Tensile force was increased up to a nanocellulose concentration of 3.25%. Elongation was decreased linearly upon cellulose nanofiber addition. Among all films, the greatest Young's modulus was 2.2 GPa. Cellulose nanofibers were found to reduce the onset temperature of thermal degradation, although melting temperature and enthalpy were higher for the nanocomposites. Because cellulose nanofibers were able to improve key properties of the films, the results obtained here can pave the route for the development and large‐scale production of novel biodegradable packaging materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44637.
Electrospinning of in situ and ex situ synthesized polyimide composites reinforced by titanate nanotubes
Authors: Harito Christian , Porras Ruben , Bavykin Dmitry V. , Walsh Frank C. 
Published: November 2016

ABSTRACTA colloidal dispersion of titanate nanotubes (TiNT) and polyamic acid (PAA) in dimethylformamide (DMF) was electrospun and chemically converted to polyimide (PI)–titanate nanotube (PI‐TiNT) composite nanofibers of 500–1000 nm diameter. The dispersion of nanotubes in the polymer was addressed by two different approaches, namely an in situ method (when TiNT was coated with one of the monomers) and an ex situ one (when TiNT reacted directly with PAA). SEM images showed bead formation on samples from the in situ approach, while ex situ samples showed the absence of such features. Good distribution and some alignment of TiNT within the polymer fibers from in situ or ex situ approaches were observed by TEM imaging. Addition of titanate nanotubes into the polyimide significantly decreased the viscosity of polyamic acid solution and increased the glass transition temperature of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44641.
Estimating the required logistical resources to support the development of a sustainable corn stover bioeconomy in the USA
Authors: Ebadian Mahmood , Sokhansanj Shahab , Webb Erin 
Published: November 2016

AbstractIn this study, the logistical resources required to develop a bioeconomy based on corn stover in the USA are quantified, including field equipment, storage sites, transportation and handling equipment, workforce, corn growers, and corn lands. These resources are essential to mobilize large quantities of corn stover from corn fields to biorefineries. The logistical resources are estimated over the lifetime of the biorefineries. Seventeen corn‐growing states are considered for the logistical resource assessment. Over 6.8 billion gallons of cellulosic ethanol can be produced annually from 108 million dry tons of corn stover in these states. The maximum number of required field equipment (i.e., choppers, balers, collectors, loaders, and tractors) is estimated to be 194 110 units with a total economic value of about $26 billion. In addition, 40 780 trucks and flatbed trailers would be required to transport bales from corn fields and storage sites to biorefineries with a total economic value of $4.0 billion. About 88 899 corn growers need to be contracted with an annual net income of over $2.1 billion. About 1903 storage sites would be required to hold 53.1 million dry tons of inventory after the harvest season. These storage sites would take up about 35 320.2 acres and 4077 loaders with an economic value of $0.4 billion would handle this inventory. The total required workforce to run the logistics operations is estimated to be 50 567. The magnitude of the estimated logistical resources demonstrates the economic and social significance of the corn stover bioeconomy in rural areas in the USA. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Randomized clinical trial of preoperative skin antisepsis with chlorhexidine gluconate or povidone–iodine
Authors: Park H M , Han S-S , Lee E C , Lee S D , Yoon H M , Eom B W , Kim S H , Ryu K W , Park S-J , Kim Y W , Park B 
Published: November 2016

Abstract

Background
Skin antiseptic agents are used to prevent surgical-site infection (SSI); few trials have reported the superiority of any specific agent in clean-contaminated abdominal surgery. This RCT was designed to compare the effectiveness of chlorhexidine gluconate and povidone–iodine.

Methods
Consecutive patients who underwent clean-contaminated upper gastrointestinal or hepatobiliary–pancreatic open surgery between 2011 and 2014 were assigned randomly to either chlorhexidine gluconate or povidone–iodine. The primary endpoint was the occurrence of SSI within 30 days of surgery. Secondary endpoints included causative organisms and risk factors for SSI.

Results
A total of 534 patients were randomized; 31 (5·8 per cent) developed an SSI. There was no difference in the overall SSI rate in the chlorhexidine gluconate and povidone–iodine groups: 15 of 267 (5·6 per cent) and 16 of 267 (6·0 per cent) respectively (P = 0·853). The most common causative organism was Enterococcus faecalis. In subgroup analysis, biliary–pancreatic surgery had a higher SSI rate (26 of 127, 20·5 per cent) than upper gastrointestinal (2 of 204, 1·0 per cent) and hepatic (3 of 203, 1·5 per cent) resection. Both age (60 years and over) and type of incision were associated with the risk of SSI.

Conclusion
No difference was detected between chlorhexidine gluconate and povidone–iodine antiseptics for prevention of SSI. Registration number: NCT01495117 (http://www.clinicaltrials.gov).
Lithium Deposition from a Piperidinium–based Ionic Liquid: Rapping Dendrites on the Knuckles
Authors: Berger Claudia A. , Ceblin Maximilian U. , Jacob Timo 
Published: November 2016

AbstractUsing cyclic voltammetry (CV), in‐situ scanning tunneling microscopy (STM) and electrochemical quartz crystal microbalance (EQCM) the initial stages of lithium deposition on Au(111) from a solution of lithium bis(trifluoromethylsulfonyl)imide in the commercially available ionic liquid 1‐methyl‐1‐propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPipTFSI) were investigated. We could identify three distinct cathodic peaks in the potential range from 0 to −2.5 V (vs. Pt quasi‐reference electrode), corresponding to different lithium deposition modes. While in the potential region of the under‐potential deposition (UPD) (−1.2 to −1.8 V) the growth of monoatomic high islands (300–370 pm) takes place, Li bulk deposition occurs at potentials <−2.3 V. Finally, the third peak at 0 V, which only appears after a previous bulk deposition, is connected to a strand‐like growth of lithium at (111) terraces with a uniform orientation over the whole substrate. Interestingly, once reaching a step‐edge, the one‐dimensional growth continues into the electrolyte, indicating the initial stages of Li dendrite formation.
Structural Tuning of Anion‐Templated Motifs with External Stimuli through Crystal‐to‐Crystal Transformation
Authors: Singh Ashutosh S. , Tiwari Ranjay K. , Lee Mandy M. , Behera Jogendra N. , Sun Shih‐Sheng , Chandrasekhar V. 
Published: November 2016

AbstractProtonation of trans‐1,2‐bis(4‐pyridyl)ethylene (4,4′‐bpe) with dilute sulfuric acid (33 %) afforded a protonated adduct [{4,4′‐bpe⋅2 H+}2{HSO4}−2{SO4}−2{H2O}2] (1). The neighboring olefinic bond in 1 is in a suitable range (3.931–4.064 Å) to undergo a photochemical [2+2] cycloaddition reaction. Upon irradiation with UV light (365 nm), 1 undergoes a molecular sliding involving the 4,4′‐bpe⋅2 H+ units, affording 2, stabilized through OSO4⋅⋅⋅π interactions. Heating 1 to 50° C leads to a 3D hydrogen‐bonded organic framework (HOF) (3). This process occurs through thermal dissociation of the bisulfate anion. Diffusion of iodine through the crystal lattice of 1 and 3 enables the reduction of sulfate to bisulfate, affording a 1D hydrogen‐bonded chain (4). Solid‐state 13C CPMAS NMR, IR, DSC, and powder XRD studies further support stimuli‐responsive structural tuning through crystal‐to‐crystal transformation. All these conversions occur with significant translational and rotational movements along with a series of bond‐breaking and bond‐forming processes.
Immobilizing Molecular Metal Dithiolene–Diamine Complexes on 2D Metal–Organic Frameworks for Electrocatalytic H2 Production
Authors: Dong Renhao , Zheng Zhikun , Tranca Diana C. , Zhang Jian , Chandrasekhar Naisa , Liu Shaohua , Zhuang Xiaodong , Seifert Gotthard , Feng Xinliang 
Published: November 2016

AbstractCarbon electrocatalysts consisting of metal complexes such as MNx or MSx are promising alternatives to high‐cost Pt catalysts for the hydrogen evolution reaction (HER). However, the exact HER active sites remain elusive. Here, molecular metal dithiolene‐diamine (MS2N2, M=Co and Ni), metal bis(dithiolene) (MS4), and metal bis(diamine) (MN4) complexes were selectively incorporated into carbon‐rich 2D metal–organic frameworks (2D MOFs) as model carbon electrocatalysts. The 2D MOF single layers, powders, and composites with graphene were thus prepared and showed definite active sites for H2 generation. The electrocatalytic HER activity of the 2D MOF‐based catalysts with different metal complexes follow the order of MS2N2>MN4>MS4. Moreover, the protonation preferentially occurred on the metal atoms, and the concomitant heterolytic elimination of H2 was favored on the M–N units in the MS2N2 active centers. The results provide an in‐depth understanding of the catalytic active sites, thus making way for the future development of metal complexes in carbon‐rich electrode materials for energy generation.
Synthesis of Monoalkyl Glyceryl Ethers by Ring Opening of Glycidol with Alcohols in the Presence of Lewis Acids
Authors: Cucciniello Raffaele , Ricciardi Maria , Vitiello Rosa , Di Serio Martino , Proto Antonio , Capacchione Carmine 
Published: November 2016

AbstractThe present work deals with the production of monoalkyl glyceryl ethers (MAGEs) through a new reaction pathway based on the reaction of glycidol and alcohols catalyzed by Lewis acid‐based catalysts. Glycidol is quantitatively converted with high selectivity (99 %) into MAGEs under very mild reaction conditions (80 °C and 0.01 mol % catalyst loading) in only 1 h using Al(OTf)3 or Bi(OTf)3 as catalyst. The proposed method enhances the choice of possible green synthetic approaches for the production of value‐added products such as MAGEs.
Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin
Authors: Ohta Yukari , Hasegawa Ryoichi , Kurosawa Kanako , Maeda Allyn H. , Koizumi Toshio , Nishimura Hiroshi , Okada Hitomi , Qu Chen , Saito Kaori , Watanabe Takashi , Hatada Yuji 
Published: November 2016

AbstractEnzymatic catalysis is an ecofriendly strategy for the production of high‐value low‐molecular‐weight aromatic compounds from lignin. Although well‐definable aromatic monomers have been obtained from synthetic lignin‐model dimers, enzymatic‐selective synthesis of platform monomers from natural lignin has not been accomplished. In this study, we successfully achieved highly specific synthesis of aromatic monomers with a phenylpropane structure directly from natural lignin using a cascade reaction of β‐O‐4‐cleaving bacterial enzymes in one pot. Guaiacylhydroxylpropanone (GHP) and the GHP/syringylhydroxylpropanone (SHP) mixture are exclusive monomers from lignin isolated from softwood (Cryptomeria japonica) and hardwood (Eucalyptus globulus). The intermediate products in the enzymatic reactions show the capacity to accommodate highly heterologous substrates at the substrate‐binding sites of the enzymes. To demonstrate the applicability of GHP as a platform chemical for bio‐based industries, we chemically generate value‐added GHP derivatives for bio‐based polymers. Together with these chemical conversions for the valorization of lignin‐derived phenylpropanone monomers, the specific and enzymatic production of the monomers directly from natural lignin is expected to provide a new stream in “white biotechnology” for sustainable biorefineries.
Three‐Phase Current Control by Dynamic Reconstruction of Undetected Currents for AC Motor Drives
Authors: SHINNAKA SHINJI , ISHIDUKA TAKUMI 
Published: November 2016

SUMMARYThis paper proposes new three‐phase current control methods for AC motor drives, which detects only a phase current from among three‐phase currents. The first proposed method first detects a phase current, and then estimates the two‐phase current in the stationary reference frame using the detected single phase current. The second proposed method first detects a phase current, then synthesizes the two‐phase quasi‐current in the dq rotating reference frame, and finally produces two‐phase current estimates by extracting the positive‐phase component from the quasi‐current. The third proposed method produces two‐phase current estimates by filtering out the negative‐phase component from the quasi‐current. This paper presents the principles and detailed characteristic analyses of the proposed methods and validates them on the basis of extensive experiments.
Highly Efficient dc–dc Transformer Based on Multicell Converter Topology for Next Generation dc Distribution System
Authors: HAYASHI YUSUKE , TAKAI DAIKI , MATSUMOTO AKIRA , ISE TOSHIFUMI 
Published: November 2016

SUMMARYA multicell dc–dc transformer (DCX) with an efficiency of 98.0% is developed for a next generation dc distribution system. Input series output parallel (ISOP) and input parallel output series (IPOS) connection topologies of highly efficient dc–dc cell converters have been applied to realize DCXs that have arbitrary I/O voltages and a high transfer factor. The behavior of a DCX based on multicell topology using nonregulated dc–dc converters is analyzed, and the voltage stress in each cell converter is discussed quantitatively considering the variation in converter circuit parameters. Further, the availability of the applied topology and the validity of the analysis are confirmed by fabricating a prototype of a 384 V to 12 V 2400 W DCX. The multicell topology contributes to realizing a low‐carbon society pushing the promotion of highly efficient, space‐saving, and low cost dc power supplies with standardized, highly efficient cell converter modules.