bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractThe 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

ABSTRACTPhenolic 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

ABSTRACTThree 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.
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

AbstractMaintaining 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

AbstractAre 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

AbstractThe 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

ABSTRACTWe 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

AbstractA 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.
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

AbstractIn 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

AbstractCyclometalated 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

AbstractA 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

AbstractThe 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

AbstractA 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

AbstractA 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

AbstractThe 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

AbstractBiomolecular 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

AbstractUnderstanding 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.