bluuebunny/crossref_metadata_2025 huggingface dataset:
Significant differentiation in the apolipoprotein(a)/lipoprotein(a) trait between chimpanzees from Western and Central Africa
Authors: Noureen Asma , Ronke Claudius , Khalifa Mahmoud , Halbwax Michel , Fischer Anne , André Claudine , Atencia Rebeca , Garriga Rosa , Mugisha Lawrence , Ceglarek Uta , Thiery Joachim , Utermann Gerd , Schmidt Konrad
Published: July 2017

Elevated Lipoprotein(a) (Lp(a)) plasma concentrations are a risk factor for cardiovascular disease in humans, largely controlled by the LPA gene encoding apolipoprotein(a) (apo(a)). Lp(a) is composed of low‐density lipoprotein (LDL) and apo(a) and restricted to Catarrhini. A variable number of kringle IV (KIV) domains in LPA lead to a size polymorphism of apo(a) that is inversely correlated with Lp(a) concentrations. Smaller apo(a) isoforms and higher Lp(a) levels in central chimpanzees (Pan troglodytes troglodytes [PTT]) compared to humans from Europe had been reported. We studied apo(a) isoforms and Lp(a) concentrations in 75 western (Pan troglodytes verus [PTV]) and 112 central chimpanzees, and 12 bonobos (Pan paniscus [PPA]), all wild born and living in sanctuaries in Sierra Leone, Republic of the Congo, and DR Congo, respectively, and 116 humans from Gabon. Lp(a) levels were severalfold higher in western than in central chimpanzees (181.0 ± 6.7 mg/dl vs. 56.5 ± 4.3 mg/dl), whereas bonobos showed intermediate levels (134.8 ± 33.4 mg/dl). Apo(a) isoform sizes differed significantly between subspecies (means 20.9 ± 2.2, 22.9 ± 4.4, and 23.8 ± 3.8 KIV repeats in PTV, PTT, and PPA, respectively). However, far higher isoform‐associated Lp(a) concentrations for all isoform sizes in western chimpanzees offered the main explanation for the higher overall Lp(a) levels in this subspecies. Human Lp(a) concentrations (mean 47.9 ± 2.8 mg/dl) were similar to those in central chimpanzees despite larger isoforms (mean 27.1 ± 4.9 KIV). Lp(a) and LDL, apoB‐100, and total cholesterol levels only correlated in PTV. This remarkable differentiation between chimpanzees from different African habitats and the trait's similarity in humans and chimpanzees from Central Africa poses the question of a possible impact of an environmental factor that has shaped the genetic architecture of LPA. Overall, studies on the cholesterol‐containing particles of Lp(a) and LDL in chimpanzees should consider differentiation between subspecies.
Realization of Absolute‐Phase Unwrapping and Speckle Suppression in Laser Digital Holography
Authors: Wang Mingqing , Li Fang , Zheng Ming , Lu Wei , Jia Yan , Yu Qingnan , Zhao Sufen , Wu Jian
Published: July 2017

In this paper, an absolute‐phase unwrapping and speckle suppression approach to reconstruct a three‐dimensional (3‐D) image of an object with laser digital holography is described. This method offers three advantages to enhance the performance of the phase reconstruction technique. First, both speckle suppression and phase unwrapping are processed in the complex amplitude domain rather than in the single phase or amplitude domain. With this approach, the phase details of the object are better preserved upon phase reconstruction. Second, the proposed algorithm requires no threshold determination and thus achieves self‐adaptive speckle suppression and robust phase unwrapping, in contrast to other methods. Finally, an improved dual‐domain image denoising method is applied to further remove speckle‐remnant‐induced phase distortion. Ideal 3‐D phase reconstruction results are obtained both theoretically and experimentally for the first time.
Dimensional Confinement in Carbon‐based Structures – From 3D to 1D
Authors: Richter Nils , Chen Zongping , Braatz Marie‐Luise , Musseau Fabienne , Weber Nils‐Eike , Narita Akimitsu , Müllen Klaus , Kläui Mathias
Published: July 2017

We present an overview of charge transport in selected one‐, two‐ and three‐dimensional carbon‐based materials with exciting properties. The systems are atomically defined bottom‐up synthesized graphene nanoribbons, doped graphene and turbostratic graphene micro‐disks, where up to 100 graphene layers are rotationally stacked. For turbostratic graphene we show how this system lends itself to spintronic applications. This follows from the inner graphene layers where charge carriers are protected and thus highly mobile. Doped graphene and graphene nanoribbons offer the possibility to tailor the electronic properties of graphene either by introducing heteroatoms or by confining the system geometrically. Herein, we describe the most recent developments of charge transports in these carbon systems.
Redox‐Driven Migration of Copper Ions in the Cu‐CHA Zeolite as Shown by the In Situ PXRD/XANES Technique
Authors: Andersen Casper Welzel , Borfecchia Elisa , Bremholm Martin , Jørgensen Mads Ry Vogel , Vennestrøm Peter Nicolai Ravnborg , Lamberti Carlo , Lundegaard Lars Fahl , Iversen Bo Brummerstedt
Published: July 2017

Using quasi‐simultaneous in situ PXRD and XANES, the direct correlation between the oxidation state of Cu ions in the commercially relevant deNOx NH3‐SCR zeolite catalyst Cu‐CHA and the Cu ion migration in the zeolitic pores was revealed during catalytic activation experiments. A comparison with recent reports further reveals the high sensitivity of the redox‐active centers concerning heating rates, temperature, and gas environment during catalytic activation. Previously, Cu+ was confirmed present only in the 6R. Results verify a novel 8R monovalent Cu site, an eventually large Cu+ presence upon heating to high temperatures in oxidative conditions, and demonstrate the unique potential in combining in situ PXRD and XANES techniques, with which both oxidation state and structural location of the redox‐active centers in the zeolite framework could be tracked.
Phosphorene Co‐catalyst Advancing Highly Efficient Visible‐Light Photocatalytic Hydrogen Production
Authors: Ran Jingrun , Zhu Bicheng , Qiao Shi‐Zhang
Published: July 2017

Transitional metals are widely used as co‐catalysts boosting photocatalytic H2 production. However, metal‐based co‐catalysts suffer from high cost, limited abundance and detrimental environment impact. To date, metal‐free co‐catalyst is rarely reported. Here we for the first time utilized density functional calculations to guide the application of phosphorene as a high‐efficiency metal‐free co‐catalyst for CdS, Zn0.8Cd0.2S or ZnS. Particularly, phosphorene modified CdS shows a high apparent quantum yield of 34.7 % at 420 nm. This outstanding activity arises from the strong electronic coupling between phosphorene and CdS, as well as the favorable band structure, high charge mobility and massive active sites of phosphorene, supported by computations and advanced characterizations, for example, synchrotron‐based X‐ray absorption near edge spectroscopy. This work brings new opportunities to prepare highly‐active, cheap and green photocatalysts.
Enantioselective Oxidative (4+3) Cycloadditions between Allenamides and Furans through Bifunctional Hydrogen‐Bonding/Ion‐Pairing Interactions
Authors: Villar Laura , Uria Uxue , Martínez Jose I. , Prieto Liher , Reyes Efraim , Carrillo Luisa , Vicario Jose L.
Published: July 2017

BINOL‐based N‐trifluoromethanesulfonyl phosphoramides catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. The chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative hydrogen‐bonding and ion‐pairing interactions, enabling an efficient chirality transfer that provide the final adducts with high diastereo‐ and enantioselectivities. Remarkably, the reaction shows a wide substrate scope that includes a variety of substituted allenamides and furans.
Hydroformylation of Alkenes in a Planetary Ball Mill: From Additive‐Controlled Reactivity to Supramolecular Control of Regioselectivity
Authors: Cousin Kévin , Menuel Stéphane , Monflier Eric , Hapiot Frédéric
Published: July 2017

The Rh‐catalyzed hydroformylation of aromatic‐substituted alkenes is performed in a planetary ball mill under CO/H2 pressure. The dispersion of the substrate molecules and the Rh‐catalyst into the grinding jar is ensured by saccharides: methyl‐α‐d‐glucopyranoside, acyclic dextrins, or cyclodextrins (CDs, cyclic oligosaccharides). The reaction affords the exclusive formation of aldehydes whatever the saccharide. Acyclic saccharides disperse the components within the solid mixture leading to high conversions of alkenes. However, they showed typical selectivity for α‐aldehyde products. If CDs are the dispersing additive, the steric hindrance exerted by the CDs on the primary coordination sphere of the metal modifies the selectivity so that the β‐aldehydes were also formed in non‐negligible proportions. Such through‐space control via hydrophobic effects over reactivity and regioselectivity reveals the potential of such solventless process for catalysis in solid state.
Nuclear Spin Isomers: Engineering a Et4N[DyPc2] Spin Qudit
Authors: Moreno‐Pineda Eufemio , Damjanović Marko , Fuhr Olaf , Wernsdorfer Wolfgang , Ruben Mario
Published: July 2017

Two dysprosium isotopic isomers were synthesized: Et4N[163DyPc2] (1) with I=5/2 and Et4N[164DyPc2] (2) with I=0 (where Pc=phthalocyaninato). Both isotopologues are single‐molecule magnets (SMMs); however, their relaxation times as well as their magnetic hystereses differ considerably. Quantum tunneling of the magnetization (QTM) at the energy level crossings is found for both systems via ac‐susceptibility and μ‐SQUID measurements. μ‐SQUID studies of 1(I=5/2) reveal several nuclear‐spin‐driven QTM events; hence determination of the hyperfine coupling and the nuclear quadrupole splitting is possible. Compound 2(I=0) shows only strongly reduced QTM at zero magnetic field. 1(I=5/2) could be used as a multilevel nuclear spin qubit, namely qudit (d=6), for quantum information processing (QIP) schemes and provides an example of novel coordination‐chemistry‐discriminating nuclear spin isotopes. Our results show that the nuclear spin of the lanthanide must be included in the design principles of molecular qubits and SMMs.
Highly Bent 1,3‐Digerma‐2‐silaallene
Authors: Sugahara Tomohiro , Sasamori Takahiro , Tokitoh Norihiro
Published: July 2017

A 1,3‐digerma‐2‐silacyclopenta‐1,2‐diene, that is, a 1,3‐digerma‐2‐silaallene incorporated into a five‐membered ring system, was synthesized and obtained as a stable orange solid. Owing to incorporation into a cyclic framework, the 1,3‐digerma‐2‐silaallene moiety is highly bent, exhibiting a Si0 character for the central silicon moiety.
A Stimuli‐Responsive Zirconium Metal–Organic Framework Based on Supermolecular Design
Authors: Krause Simon , Bon Volodymyr , Stoeck Ulrich , Senkovska Irena , Többens Daniel M. , Wallacher Dirk , Kaskel Stefan
Published: July 2017

A flexible, yet very stable metal–organic framework (DUT‐98, Zr6O4(OH)4(CPCDC)4(H2O)4, CPCDC=9‐(4‐carboxyphenyl)‐9H‐carbazole‐3,6‐dicarboxylate) was synthesized using a rational supermolecular building block approach based on molecular modelling of metal–organic chains and subsequent virtual interlinking into a 3D MOF. Structural characterization via synchrotron single‐crystal X‐ray diffraction (SCXRD) revealed the one‐dimensional pore architecture of DUT‐98, envisioned in silico. After supercritical solvent extraction, distinctive responses towards various gases stimulated reversible structural transformations, as detected using coupled synchrotron diffraction and physisorption techniques. DUT‐98 shows a surprisingly low water uptake but a high selectivity for pore opening towards specific gases and vapors (N2, CO2, n‐butane, alcohols) at characteristic pressure resulting in multiple steps in the adsorption isotherm and hysteretic behavior upon desorption.
Cyanide‐Free and Broadly Applicable Enantioselective Synthetic Platform for Chiral Nitriles through a Biocatalytic Approach
Authors: Betke Tobias , Rommelmann Philipp , Oike Keiko , Asano Yasuhisa , Gröger Harald
Published: July 2017

A cyanide‐free platform technology for the synthesis of chiral nitriles by biocatalytic enantioselective dehydration of a wide range of aldoximes is reported. The nitriles were obtained with high enantiomeric excess of >90 % ee (and up to 99 % ee) in many cases, and a “privileged substrate structure” with respect to high enantioselectivity was identified. Furthermore, a surprising phenomenon was observed for the enantiospecificity that is usually not observed in enzyme catalysis. Depending on whether the E or Z isomer of the racemic aldoxime substrate was employed, one or the other enantiomer of the corresponding nitrile was formed preferentially with the same enzyme.
Resonant Formation of Strand Breaks in Sensitized Oligonucleotides Induced by Low‐Energy Electrons (0.5–9 eV)
Authors: Schürmann Robin , Tsering Thupten , Tanzer Katrin , Denifl Stephan , Kumar S. V. K. , Bald Ilko
Published: July 2017

Halogenated nucleobases are used as radiosensitizers in cancer radiation therapy, enhancing the reactivity of DNA to secondary low‐energy electrons (LEEs). LEEs induce DNA strand breaks at specific energies (resonances) by dissociative electron attachment (DEA). Although halogenated nucleobases show intense DEA resonances at various electron energies in the gas phase, it is inherently difficult to investigate the influence of halogenated nucleobases on the actual DNA strand breakage over the broad range of electron energies at which DEA can take place (<12 eV). By using DNA origami nanostructures, we determined the energy dependence of the strand break cross‐section for oligonucleotides modified with 8‐bromoadenine (8BrA). These results were evaluated against DEA measurements with isolated 8BrA in the gas phase. Contrary to expectations, the major contribution to strand breaks is from resonances at around 7 eV while resonances at very low energy (<2 eV) have little influence on strand breaks.
Direct Alkylation of Amines with Primary and Secondary Alcohols through Biocatalytic Hydrogen Borrowing
Authors: Montgomery Sarah L. , Mangas‐Sanchez Juan , Thompson Matthew P. , Aleku Godwin A. , Dominguez Beatriz , Turner Nicholas J.
Published: July 2017

The reductive aminase from Aspergillus oryzae (AspRedAm) was combined with a single alcohol dehydrogenase (either metagenomic ADH‐150, an ADH from Sphingobium yanoikuyae (SyADH), or a variant of the ADH from Thermoanaerobacter ethanolicus (TeSADH W110A)) in a redox‐neutral cascade for the biocatalytic alkylation of amines using primary and secondary alcohols. Aliphatic and aromatic secondary amines were obtained in up to 99 % conversion, as well as chiral amines directly from the racemic alcohol precursors in up to >97 % ee, releasing water as the only byproduct.
Terminal Iron Carbyne Complexes Derived from Arrested CO2 Reductive Disproportionation
Authors: Mokhtarzadeh Charles C. , Moore Curtis E. , Rheingold Arnold L. , Figueroa Joshua S.
Published: July 2017

The encumbered tetraisocyanide dianion Na2[Fe(CNAr
)4] reacts with two molecules of CO2 to effect reductive disproportionation to CO and carbonate ([CO3]2−). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested by silylative esterification of a mono‐CO2 adduct. This results in the formation of four‐coordinate terminal iron carbynes possessing an aryl carbamate substituent owing to the direct attachment of an C(O)OSiR3 group to an isocyanide nitrogen atom. Crystallographic, spectroscopic, and computational analyses of these iron–carbon multiply bonded species reveal electronic structure properties indicative of a conformationally locked iron carbyne unit.
Curing kinetics and curing process of phenolic impregnated carbon ablator
Authors: Tian Ye , Huang Haiming , Xu Xiaoliang
Published: July 2017

Phenolic impregnated carbon ablator (PICA), which is composed of the phenolic resin (PR) and carbon fiber, is of particular interest to researchers in the aerospace field. In this work, PICA was prepared by the double‐stage isothermal heating curing. Then, the curing kinetics of boron‐modified phenolic resin (BPR) was investigated by non‐isothermal differential scanning calorimetry method in order to optimize the curing temperature of BPR. Further, the effect of the heating rate during curing process on the compressive strength of PICA was discussed in detail. The experimental data show that the curing of BPR needs more energy so that the curing temperature of BPR under different condition is higher than that of virgin PR. Notably, with the increasing heating rate during the curing process, the micro‐cracks increase and the compressive strength of PICA decreases. Once the heating rate exceeds a critical value, the micro‐cracks no longer increase and the heating rate has insignificant effect on the compressive strength. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45434.
Effect of methyl position on the dynamic mechanical and shape‐memory properties of cresol‐based polybenzoxazines
Authors: Liu Yanfang , Song Shuning , Su Xuehui , Wang Aiqing , Shen Shanshan , Li Cuiyun
Published: July 2017

Three difunctional benzoxazines were synthesized from cresol isomers (o‐, m‐, and p‐methylphenols), 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetramethyldisiloxane, and formaldehyde. The ring‐opening polymerization temperature decreases in the order of ortho‐, para‐, and meta‐positions of methyl group for the benzoxazine monomers, whereas the glass transition temperature increases in the order of ortho‐, para‐, and meta‐positions of methyl group for the resultant polybenzoxazines. In addition, the polybenzoxazines exhibit one‐way dual‐shape‐memory behavior in response to changes in temperature, and the shape‐memory effects are evaluated by tensile and bending tests with a temperature program based on glass transition temperature. The o‐ and p‐cresol‐based polybenzoxazines exhibit higher shape‐memory performance than their m‐cresol‐based analogue/counterpart. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45443.
Mendeley readership as a filtering tool to identify highly cited publications
Authors: Zahedi Zohreh , Costas Rodrigo , Wouters Paul
Published: July 2017

This study presents a large‐scale analysis of the distribution and presence of Mendeley readership scores over time and across disciplines. We study whether Mendeley readership scores (RS) can identify highly cited publications more effectively than journal citation scores (JCS). Web of Science (WoS) publications with digital object identifiers (DOIs) published during the period 2004–2013 and across five major scientific fields were analyzed. The main result of this study shows that RS are more effective (in terms of precision/recall values) than JCS to identify highly cited publications across all fields of science and publication years. The findings also show that 86.5% of all the publications are covered by Mendeley and have at least one reader. Also, the share of publications with Mendeley RS is increasing from 84% in 2004 to 89% in 2009, and decreasing from 88% in 2010 to 82% in 2013. However, it is noted that publications from 2010 onwards exhibit on average a higher density of readership versus citation scores. This indicates that compared to citation scores, RS are more prevalent for recent publications and hence they could work as an early indicator of research impact. These findings highlight the potential and value of Mendeley as a tool for scientometric purposes and particularly as a relevant tool to identify highly cited publications.
Clinical assessment of the lag‐time and tmax of pellets with controlled release of glucose: in vitro/in vivo comparison using 13C–breath test
Authors: Neumann David , Muselík Jan , Sabadková Dana , Pavloková Sylvie , Špirková Jana , Franc Aleš
Published: July 2017

Maintaining a stable glycaemia in diabetes mellitus type 1 requires flexible insulin administration and carbohydrate intake to affected individuals. In real life, there might be some situations limiting the insulin–sugar balance control, e.g. night sleep or prolonged sporting activities. Glucose pellets with a pre‐determined time lag between the pellet administration and glucose release were developed to mimic a ‘snack eaten in advance’. In this article, a 13C–glucose breath test was introduced to translate laboratory dissolution testing to clinical confirmation of the glucose release pattern using 5% δ abundance to differentiate the appearance of in 13C exhaled breath. An independent two‐sample t‐test (p = 0.20) confirmed an average clinical lag time of 300 min and an in vitro time of 338 min to be identical at a level of significance of α = 0.05. Moreover, using the same statistical method, the clinical tmax (564 min) and the in vitro t50 (594 min) were also considered identical (p = 0.34). It was concluded that dissolution testing is a relevant method to determine the time lags of dosage forms with controlled release of glucose and that the 13C–glucose breath test is a suitable clinical tool for lag time verification in clinical studies.
Giving, Fast and Slow: Reflection Increases Costly (but Not Uncostly) Charitable Giving
Authors: Mrkva Kellen
Published: July 2017

Are people intuitively generous or stingy? Does reflection make people more willing to give generous amounts to charity? Findings across the literature are mixed, with many studies finding no clear relationship between reflection and charitable giving (e.g., Hauge, Brekke, Johansson, Johansson‐Stenman, & Svedsäter, ; Tinghög et al., ), while others find that reflection negatively affects giving (e.g., Small, Loewenstein, & Slovic, ), and still others find that reflection is positively associated with giving (e.g., Lohse, Goeschl, & Diederich, ). I demonstrate that reflection consistently increases costly giving to charity. In Study 1, people were initially reluctant to give costly amounts of money to charity, but those who reflected about the decision were more willing to give. In Studies 2–3, I isolated the role of costly stakes by randomly assigning people to either an uncostly donation ($0.40) or costly donation condition (e.g., $100), and randomly assigning them to decide under time pressure or after reflecting. Reflection increased their willingness to give costly amounts, but did not influence their willingness to give uncostly amounts. Similarly, the relationship between decision time and giving was positive when the stakes were costly but was relatively flat when the stakes were uncostly (Study 4). Copyright © 2017 John Wiley & Sons, Ltd.
Synthetic alienation of microbial organisms by using genetic code engineering: Why and how?
Authors: Kubyshkin Vladimir , Budisa Nediljko
Published: July 2017

The main goal of synthetic biology (SB) is the creation of biodiversity applicable for biotechnological needs, while xenobiology (XB) aims to expand the framework of natural chemistries with the non‐natural building blocks in living cells to accomplish artificial biodiversity. Protein and proteome engineering, which overcome limitation of the canonical amino acid repertoire of 20 (+2) prescribed by the genetic code by using non‐canonic amino acids (ncAAs), is one of the main focuses of XB research. Ideally, estranging the genetic code from its current form via systematic introduction of ncAAs should enable the development of bio‐containment mechanisms in synthetic cells potentially endowing them with a “genetic firewall” i.e. orthogonality which prevents genetic information transfer to natural systems. Despite rapid progress over the past two decades, it is not yet possible to completely alienate an organism that would use and maintain different genetic code associations permanently. In order to engineer robust bio‐contained life forms, the chemical logic behind the amino acid repertoire establishment should be considered. Starting from recent proposal of Hartman and Smith about the genetic code establishment in the RNA world, here the authors mapped possible biotechnological invasion points for engineering of bio‐contained synthetic cells equipped with non‐canonical functionalities.
Small cause, large effect: Structural characterization of cutinases from Thermobifida cellulosilytica
Authors: Ribitsch Doris , Hromic Altijana , Zitzenbacher Sabine , Zartl Barbara , Gamerith Caroline , Pellis Alessandro , Jungbauer Alois , Łyskowski Andrzej , Steinkellner Georg , Gruber Karl , Tscheliessnig Rupert , Herrero Acero Enrique , Guebitz Georg M.
Published: July 2017

We have investigated the structures of two native cutinases from Thermobifida cellulosilytica, namely Thc_Cut1 and Thc_Cut2 as well as of two variants, Thc_Cut2_DM (Thc_Cut2_ Arg29Asn_Ala30Val) and Thc_Cut2_TM (Thc_Cut2_Arg19Ser_Arg29Asn_Ala30Val). The four enzymes showed different activities towards the aliphatic polyester poly(lactic acid) (PLLA). The crystal structures of the four enzymes were successfully solved and in combination with Small Angle X‐Ray Scattering (SAXS) the structural features responsible for the selectivity difference were elucidated. Analysis of the crystal structures did not indicate significant conformational differences among the different cutinases. However, the distinctive SAXS scattering data collected from the enzymes in solution indicated a remarkable surface charge difference. The difference in the electrostatic and hydrophobic surface properties could explain potential alternative binding modes of the four cutinases on PLLA explaining their distinct activities. Biotechnol. Bioeng. 2017;114: 2481–2488. © 2017 Wiley Periodicals, Inc.
Determination of silodosin and its active glucuronide metabolite KMD‐3213G in human plasma by LC–MS/MS for a bioequivalence study
Authors: Shah Priyanka A. , Shrivastav Pranav S.
Published: July 2017

A sensitive and selective liquid chromatography–tandem mass spectrometry (LC–MS/MS) method is described for the simultaneous determination of silodosin (SLD) and its active metabolite silodosin β‐d‐glucuronide (KMD‐3213G) in human plasma. Liquid–liquid extraction of plasma samples was carried out with ethyl acetate and methyl tert‐butyl ether solvent mixture using deuterated analogs as internal standards. The extraction recoveries of SLD and KMD‐3213G were in the ranges 90.8–93.4 and 87.6–89.9%, respectively. The extracts were analyzed on a Symmetry C18 (50 × 4.6 mm, 5 μm) column under gradient conditions using 10 mm ammonium formate in water and methanol–acetonitrile (40:60, v/v), within 6.0 min. For MS/MS measurements, ionization of the analytes was carried out in the positive ionization mode and the transitions monitored were m/z 496.1 → 261.2 for SLD and m/z 670.2 → 494.1 for KMD‐3213G. The method showed good linearity, accuracy, precision and stability in the range 0.10–80.0 ng/mL for SLD and KMD‐3213G. The IS‐normalized matrix factors obtained were highly consistent, ranging from 0.962 to 1.023 for both analytes. The method was used to support a bioequivalence study of SLD and its metabolite in healthy volunteers after oral administration of 8 mg silodosin capsules.
Community Protection versus Individual Healing: Two Traditions in Community Mental Health
Authors: Yanos Philip T. , Knight Edward L. , Vayshenker Beth , Gonzales Lauren , DeLuca Joseph S.
Published: July 2017

This article identifies two major traditions that drive the mandate for a community mental health care system—community protection and individual healing. It discusses the historical antecedents of these two traditions and how these traditions relate to different visions of what the “common good” means. It then discusses how they both operate in the current US‐based system, creating inherent conflicts and tensions, and gives specific examples from the personal and professional experiences of the authors. The article proposes ways to reduce the tension and discusses what sacrifices and compromises this resolution would entail for the US community mental health system. Copyright © 2017 John Wiley & Sons, Ltd.
A Novel Blending Adhesive in the Fabrication of the Composite Cathode for Lithium‐Ion Batteries
Authors: Zhu Zhengbao , Lu Zhongpei , Ding Jingjing , Yang Gang , Li Weili , Ji Hongmei
Published: July 2017

In this paper, a novel adhesive prepared by blending lithium‐ion functionalized epoxy resin (ionized oligomer) with poly(vinylidenedifluoride) (PVdF) is used to fabricate the cathode electrode of LiCoO2. The properties of the blending adhesive are studied by Fourier transform infrared spectroscopy, differential scanning calorimeter, and thermogravimetric analysis, and the morphology and performance of the composite cathodes are characterized by using X‐ray photoelectron spectroscopy (XPS), scanning and transmission electron microscopy, electrochemical impedance spectroscopy, and galvanostatic charge‐discharge. With the blended ionized oligomer, the crystallinity behavior of PVdF is decreased effectively, which will be beneficial to the movement of conducting ions. An appropriate amount of ionized oligomer effectively improves the conductivity and charge‐transfer capability of the cathode material. When the amount of ionized oligomer to the PVdF binder is 10 wt%, the LiCoO2‐based composite cathode delivers the highest charge−discharge capacity (178 mAh g−1) and the capacity retention is up to 82.2 % after 100 cycles.
Small “Yaw” Angles, Large “Bite” Angles and an Electron‐Rich Metal: Revealing a Stereoelectronic Synergy To Enhance Hydride‐Transfer Activity
Authors: Semwal Shrivats , Mukkatt Indulekha , Thenarukandiyil Ranjeesh , Choudhury Joyanta
Published: July 2017

Cyclometalated complexes are an important class of (pre)catalysts in many reactions including hydride transfer. The ring size of such complexes could therefore be a relevant aspect to consider while modulating their catalytic activity. However, any correlation between the cyclometalating ring size and the catalytic activity should be drawn by careful assessment of the pertinent geometrical parameters, and overall electronic effects thereof. In this study, we investigated the vital role of key stereoelectronic functions of two classes of iridacyclic complexes—five‐membered and six‐membered cycles—in manupulating the catalytic efficiency in a model hydride‐transfer reaction. Our investigation revealed that there exists an interesting multidimensional synergy among all the relevant stereoelectronic factors—yaw angle, bite angle, and the electronic properties of both the ligand and the metal center—that governs the hydride donor ability (hydricity) of the complexes during catalysis. Thus the six‐membered chelate complexes with small yaw and large bite angles, strong donor ligand, and electron‐rich metal were found to be better catalysts than their five‐membered analogues. A frontier molecular orbital analysis supported the significant role of the above stereoelectronic synergistic effect associated with the chelate ring to control the hydride donor ability of the complexes.
Photocaged Competitor Guests: A General Approach Toward Light‐Activated Cargo Release From Cucurbiturils
Authors: Romero Miguel A. , Basílio Nuno , Moro Artur J. , Domingues Mara , González‐Delgado José A. , Arteaga Jesús F. , Pischel Uwe
Published: July 2017

A general approach toward the light‐induced guest release from cucurbit[7]uril by means of a photoactivatable competitor was devised. An o‐nitrobenzyl‐caged competitor is photolyzed to generate a competitive guest that can displace cargo from the host macrocycle solely based on considerations of chemical equilibrium. With this method the release of terpene guests from inclusion complexes with cucurbit[7]uril was demonstrated. The binding of the herein investigated terpenes, all being lead fragrant components in essential oils, has been characterized for the first time. They feature binding constants of up to 108 L mol−1 and a high differential binding selectivity (spanning four orders of magnitude for the binding constants for the particular set of terpenes). By fine‐tuning the photoactivatable competitor guest, selective and also sequential release of the terpenes was achieved.
Mechanistic Characterization of Two Chimeric Sesterterpene Synthases from Penicillium
Authors: Mitsuhashi Takaaki , Rinkel Jan , Okada Masahiro , Abe Ikuro , Dickschat Jeroen S.
Published: July 2017

The products of two bifunctional fungal sesterterpene synthases (StTPS), with prenyl transferase (PT) and terpene synthase (TPS) domains from Penicillium, were structurally characterized and their mechanisms studied in detail by labeling experiments. A phylogenetic analysis of the TPS domains of the new and previously characterized enzymes revealed six distinct clades. Enzymes from the same clade catalyze a common initial cyclization step, which suggests the potential for structural predictions from amino acid sequences.
Multiple Magnetic Relaxation Pathways and Dual‐Emission Modulated by a Heterometallic Tb‐Pt Bonding Environment
Authors: Yoshida Takefumi , Izougu David Chukwuma , Iwasawa Daichi , Ogata Shuhei , Hasegawa Miki , Breedlove Brian K. , Cosquer Goulven , Wernsdorfer Wolfgang , Yamashita Masahiro
Published: July 2017

A heterometallic Tb‐Pt complex, [Tb2Pt3(SAc)12(H2O)2] (SAc=thioacetate), was synthesized. Dual emission was modulated by the presence of a heterometallic Tb–Pt bonding environment. The heterometallic Tb–Pt bond lowers the symmetry of the Tb ion and enhanced the emission efficiency. In addition, the Tb–Pt complex shows field‐induced multiple magnetic relaxation pathways. Furthermore, it served as an antenna for the observed dual emission. In other words, the heterometallic Tb–Pt bond has a significant effect on the luminescence and magnetic properties of the complex.
Bleaching Earths as Powerful Additives for Ru‐Catalyzed Self‐Metathesis of Non‐Refined Methyl Oleate at Pilot Scale
Authors: Allard Jessica , Curbet Idriss , Chollet Guillaume , Tripoteau Fabien , Sambou Sophie , Caijo Frédéric , Raoul Yann , Crévisy Christophe , Baslé Olivier , Mauduit Marc
Published: July 2017

A practical and cost‐effective ruthenium‐catalyzed self‐metathesis of non‐refined methyl oleate (85 %) derived from very high oleic sunflower oils was demonstrated at pilot scale using a robust and kg‐scale commercially available SIPr‐M71 pre‐catalyst. The simple addition of 1 wt % bleaching earths (Tonsil 110FF) to a thermally pretreated oil could efficiently prevent catalyst deactivation. Remarkably, without the need for filtration, the catalytic system was able to achieve a turnover number (TON) of more than 744 000 at a catalyst loading of only 1 ppm. At large scale (up to 200 kg), the equilibrium of the self‐metathesis reaction was reached within 1 hour at 50 °C under neat conditions at a very low 5 ppm catalyst loading to produce the expected primary metathesis products (PMP), that is, 9‐octadecene and dimethyl‐9‐octadecenoate, with a productive TON of 94900.
Selective neuronal expression of the SoxE factor, Sox8, in direct pathway striatal projection neurons of the developing mouse brain
Authors: Merchan‐Sala Paloma , Nardini Diana , Waclaw Ronald R. , Campbell Kenneth
Published: July 2017

The striatum is the major component of the basal ganglia and is well known to play a key role in the control of motor function via balanced output from the indirect (iSPNs) and direct pathway striatal projection neurons (dSPNs). Little is known, however, about the molecular genetic mechanisms that control the formation of the iSPNs versus dSPNs. We show here that the SoxE family member, Sox8, is co‐expressed with the dSPN markers, Isl1 and Ebf1, in the developing striatum. Moreover, dSPNs, as marked by Isl1‐cre fate map, express Sox8 in the embryonic striatum and Sox8‐EGFP BAC transgenic mice specifically reveal the direct pathway axons during development. These EGFP+ axons are first observed to reach their midbrain target, the substantia nigra pars reticulata (SNr), at E14 in the mouse with a robust connection observed already at birth. The selective expression of EGFP in dSPNs of Sox8‐EGFP BAC mice is maintained at postnatal timepoints. Sox8 is known to be expressed in oligodendrocyte precursor cells (OPCs) together with other SoxE factors and we show here that the EGFP signal co‐localizes with the OPC markers throughout the brain. Finally, we show that Sox8‐EGFP BAC mice can be used to interrogate the altered dSPN development in Isl1 conditional mutants including aberrant axonal projections detected already at embryonic timepoints. Thus, Sox8 represents an early and specific marker of embryonic dSPNs and the Sox8‐EGFP BAC transgenic mice are an excellent tool to study the development of basal ganglia circuitry.
Monitoring Complex Formation by Relaxation‐Induced Pulse Electron Paramagnetic Resonance Distance Measurements
Authors: Giannoulis Angeliki , Oranges Maria , Bode Bela E.
Published: July 2017

Biomolecular complexes are often multimers fueling the demand for methods that allow unraveling their composition and geometric arrangement. Pulse electron paramagnetic resonance (EPR) spectroscopy is increasingly applied for retrieving geometric information on the nanometer scale. The emerging RIDME (relaxation‐induced dipolar modulation enhancement) technique offers improved sensitivity in distance experiments involving metal centers (e.g. on metalloproteins or proteins labelled with metal ions). Here, a mixture of a spin labelled ligand with increasing amounts of paramagnetic CuII ions allowed accurate quantification of ligand‐metal binding in the model complex formed. The distance measurement was highly accurate and critical aspects for identifying multimerization could be identified. The potential to quantify binding in addition to the high‐precision distance measurement will further increase the scope of EPR applications.
Genetic sampling for estimating density of common species
Authors: Cheng Ellen , Hodges Karen E. , Sollmann Rahel , Mills L. Scott
Published: July 2017

Understanding population dynamics requires reliable estimates of population density, yet this basic information is often surprisingly difficult to obtain. With rare or difficult‐to‐capture species, genetic surveys from noninvasive collection of hair or scat has proved cost‐efficient for estimating densities. Here, we explored whether noninvasive genetic sampling (NGS) also offers promise for sampling a relatively common species, the snowshoe hare (Lepus americanusErxleben, 1777), in comparison with traditional live trapping. We optimized a protocol for single‐sessionNGSsampling of hares. We compared spatial capture–recapture population estimates from live trapping to estimates derived fromNGS, and assessedNGScosts.NGSprovided population estimates similar to those derived from live trapping, but a higher density of sampling plots was required forNGS. The optimalNGSprotocol for our study entailed deploying 160 sampling plots for 4 days and genotyping one pellet per plot.NGSlaboratory costs ranged from approximately $670 to $3000USDper field site. While live trapping does not incur laboratory costs, its field costs can be considerably higher than forNGS, especially when study sites are difficult to access. We conclude thatNGScan work for common species, but that it will require field and laboratory pilot testing to develop cost‐effective sampling protocols.
Influence of olfactory and visual cover on nest site selection and nest success for grassland‐nesting birds
Authors: Fogarty Dillon T. , Elmore R. Dwayne , Fuhlendorf Samuel D. , Loss Scott R.
Published: July 2017

Habitat selection by animals is influenced by and mitigates the effects of predation and environmental extremes. For birds, nest site selection is crucial to offspring production because nests are exposed to extreme weather and predation pressure. Predators that forage using olfaction often dominate nest predator communities; therefore, factors that influence olfactory detection (e.g., airflow and weather variables, including turbulence and moisture) should influence nest site selection and survival. However, few studies have assessed the importance of olfactory cover for habitat selection and survival. We assessed whether ground‐nesting birds select nest sites based on visual and/or olfactory cover. Additionally, we assessed the importance of visual cover and airflow and weather variables associated with olfactory cover in influencing nest survival. In managed grasslands in Oklahoma, USA, we monitored nests of Northern Bobwhite (Colinus virginianus), Eastern Meadowlark (Sturnella magna), and Grasshopper Sparrow (Ammodramus savannarum) during 2015 and 2016. To assess nest site selection, we compared cover variables between nests and random points. To assess factors influencing nest survival, we used visual cover and olfactory‐related measurements (i.e., airflow and weather variables) to model daily nest survival. For nest site selection, nest sites had greater overhead visual cover than random points, but no other significant differences were found. Weather variables hypothesized to influence olfactory detection, specifically precipitation and relative humidity, were the best predictors of and were positively related to daily nest survival. Selection for overhead cover likely contributed to mitigation of thermal extremes and possibly reduced detectability of nests. For daily nest survival, we hypothesize that major nest predators focused on prey other than the monitored species’ nests during high moisture conditions, thus increasing nest survival on these days. Our study highlights how mechanistic approaches to studying cover informs which dimensions are perceived and selected by animals and which dimensions confer fitness‐related benefits.
Habitat predictors of genetic diversity for two sympatric wetland‐breeding amphibian species
Authors: McKee Anna M. , Maerz John C. , Smith Lora L. , Glenn Travis C.
Published: July 2017

Population genetic diversity is widely accepted as important to the conservation and management of wildlife. However, habitat features may differentially affect evolutionary processes that facilitate population genetic diversity among sympatric species. We measured genetic diversity for two pond‐breeding amphibian species (Dwarf salamanders, Eurycea quadridigitata; and Southern Leopard frogs, Lithobates sphenocephalus) to understand how habitat characteristics and spatial scale affect genetic diversity across a landscape. Samples were collected from wetlands on a longleaf pine reserve in Georgia. We genotyped microsatellite loci for both species to assess population structures and determine which habitat features were most closely associated with observed heterozygosity and rarefied allelic richness. Both species exhibited significant population genetic structure; however, structure in Southern Leopard frogs was driven primarily by one outlier site. Dwarf salamander allelic richness was greater at sites with less surrounding road area within 0.5 km and more wetland area within 1.0 and 2.5 km, and heterozygosity was greater at sites with more wetland area within 0.5 km. In contrast, neither measure of Southern Leopard frog genetic diversity was associated with any habitat features at any scale we evaluated. Genetic diversity in the Dwarf salamander was strongly associated with land cover variables up to 2.5 km away from breeding wetlands, and/or results suggest that minimizing roads in wetland buffers may be beneficial to the maintenance of population genetic diversity. This study suggests that patterns of genetic differentiation and genetic diversity have associations with different habitat features across different spatial scales for two syntopic pond‐breeding amphibian species.
Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes
Authors: Díez‐Poza Carlos , Barbero Asunción
Published: July 2017

Prins cyclization has emerged as one of the most valuable methods for the construction of heterocycles. It proceeds through intramolecular addition of a π‐nucleophile to an oxocarbenium or related ion. The use of electron‐rich alkenes, such as allylsilanes (so‐called silyl‐Prins cyclization) offers the benefit of allowing more selective reactions. The regio‐ and stereochemical outcomes of these transformations are explained by well‐stablished transition states. This review presents the most important contributions involving silyl‐Prins cyclization to the stereoselective preparation of oxygen and nitrogen heterocycles. The influence of different structural variants in the selectivity of the cyclization is discussed. These reactions have frequently been used as key steps in the synthesis of a wide variety of natural products.
A Mechanochemical‐Assisted Oxidation of Amines to Carbonyl Compounds and Nitriles
Authors: Gaspa Silvia , Porcheddu Andrea , Valentoni Antonio , Garroni Sebastiano , Enzo Stefano , De Luca Lidia
Published: July 2017

A mild, efficient, metal‐ and solvent‐free oxidation of primary amines to aldehydes, ketones, and nitriles under ball‐milling conditions is presented. This method has proved to be compatible with various functional groups and only requires easily accessible starting materials. Simple purification of the reaction mixtures by short‐column chromatography afforded pure aldehydes, ketones, and nitriles as products.
Modular De novo Synthesis of Unsymmetrical BODIPY Dyes Possessing Four Different Aryl Substituents
Authors: Netz Natalie , Díez‐Poza Carlos , Barbero Asunción , Opatz Till
Published: July 2017

A modular synthesis of unsymmetrical BODIPY dyes based on a [6π] electrocyclization to construct both pyrrole rings is presented. The products carry four aryl moieties in positions 1, 3, 5, and 7, which can be freely selected, as well as optional substitution in positions 2 and 8. The method employs acetophenones, benzaldehydes as well as glycine nitrile or glycine ethyl ester as the key building blocks.
Acid Fluorides as Acyl Electrophiles in Suzuki–Miyaura Coupling
Authors: Ogiwara Yohei , Sakino Daisuke , Sakurai Yuka , Sakai Norio
Published: July 2017

The first palladium‐catalyzed construction of ketones through Suzuki–Miyaura reaction by using acid fluorides is described. In contrast to typical acyl electrophiles such as acid chlorides, acid fluorides are uncommon acyl electrophiles to use in boron‐based coupling reactions, probably due to a high level of stability toward nucleophiles. This first attempt to use acid fluorides as a coupling partner with boronic acids allowed highly functional group tolerance and a wide substrate scope while affording various ketones in effective yields.