bluuebunny/crossref_metadata_2025 huggingface dataset:
Measurement of Texture Gradient in Heavily Cold‐Drawn Pearlitic Wires
Authors: Jamoneau Aurélie , Schmitt Jean‐Hubert , Solas Denis
Published: September 2017

It is well established that cold‐drawing of pearlitic wire develops a strong anisotropy due to a preferential <110> orientation of the ferrite phase parallel to the wire axis. The subsequent wire behavior during torsion, which mainly occurs during assembling of drawn wires, is correlated with the texture and its gradient along the wire radius. Although different attempts were made in the past to measure the texture after drawing, it is still challenging since the final wire diameter is on the order of 0.3 mm. The paper presents a simple and robust method to measure the texture gradient by X‐ray diffraction. First, to overcome the problems of a composite sample made of parallel wires, an isotropic reference sample is prepared by cycles of austenite transformation and quenching. The texture gradient is measured at different thicknesses by dissolving the external surface of the wires. This allows the investigation of the first 40 μm of depth. Finally, the results are compared with EBSD measurements on a longitudinal cross‐section to quantify the influence of the drawing conditions: A flat schedule with constant die angles favors a <110> fiber texture with a weak gradient, while increasing the drawing angle for three dies increases the gradient.
Morphology of a Ternary Blend Solar Cell Based on Small Molecule:Conjugated Polymer:Fullerene Fabricated by Blade Coating
Authors: Wu Xiaomin , Lan Shuqiong , Zhang Guocheng , Chen Qizhen , Chen Huipeng , Guo Tailiang
Published: September 2017

Here, conjugated polymer is added as third component to tune the solution viscosity, morphology, and function of small molecule (SM) based bulk‐heterojunction (BHJ) solar cells, which are fabricated using blade coating. Novel information about the effect of blade coating speed on the nanoscale morphology and function of ternary blend solar cells is provided. The crystal sizes increase with an increase of coating speed for both binary and ternary blends, while the addition of the third component tends to favor smaller SM crystal grains and improves the connectivity of SM crystals. Small angle neutron scattering experiments provide the first clear experimental evidence that the addition of the third component would significantly impact the fullerene phase separation, which is crucial for bimolecular recombination and charge transport. It shows that for both binary and ternary blends, the concentration and sizes of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) aggregates increase with an increase of coating speed, while addition of third component does not affect the volume fraction of PCBM aggregates but impacts the size of PCBM aggregates. It is demonstrated that the judicious selection of blade coating speed and addition of conjugated polymer optimize the morphology of SM‐BHJ, providing guidelines for high performance SM‐BHJs from roll‐to‐roll production.
Hybrid 3D Printing of Soft Electronics
Authors: Valentine Alexander D. , Busbee Travis A. , Boley John William , Raney Jordan R. , Chortos Alex , Kotikian Arda , Berrigan John Daniel , Durstock Michael F. , Lewis Jennifer A.
Published: September 2017

Hybrid 3D printing is a new method for producing soft electronics that combines direct ink writing of conductive and dielectric elastomeric materials with automated pick‐and‐place of surface mount electronic components within an integrated additive manufacturing platform. Using this approach, insulating matrix and conductive electrode inks are directly printed in specific layouts. Passive and active electrical components are then integrated to produce the desired electronic circuitry by using an empty nozzle (in vacuum‐on mode) to pick up individual components, place them onto the substrate, and then deposit them (in vacuum‐off mode) in the desired location. The components are then interconnected via printed conductive traces to yield soft electronic devices that may find potential application in wearable electronics, soft robotics, and biomedical devices.
One‐Pot Enantioselective Synthesis of d‐Phenylglycines from Racemic Mandelic Acids, Styrenes, or Biobased l‐Phenylalanine via Cascade Biocatalysis
Authors: Zhou Yi , Wu Shuke , Li Zhi
Published: September 2017

Enantiopure d‐phenylglycine and its derivatives are an important group of chiral amino acids with broad applications in thepharmaceutical industry. However, the existing synthetic methods for d‐phenylglycine mainly rely on toxic cyanide chemistry and multistep processes. To provide green and safe alternatives, we envisaged cascade biocatalysis for the one‐pot synthesis of d‐phenylglycine from racemic mandelic acid, styrene, and biobased l‐phenylalanine, respectively. Recombinant Escherichia coli (LZ110) was engineered to coexpress four enzymes to catalyze a 3‐step reaction in one pot, transforming mandelic acid (210 mM) to give enantiopure d‐phenylglycine in 29.5 g L−1 (195 mM) with 93% conversion. Using the same whole‐cell catalyst, twelve other d‐phenylglycine derivatives were also produced from the corresponding mandelic acid derivatives in high conversion (58–94%) and very high ee (93–99%). E. coli (LZ116) expressing seven enzymes was constructed for the transformation of styrene to enantiopure d‐phenylglycine in 80% conversion via a one‐pot 6‐step cascade biotransformation. Twelve substituted d‐phenylglycines were also produced from the corresponding styrene derivatives in high conversion (45–90%) and very high ee (92–99%) via the same cascade reactions. A nine‐enzymeexpressing E. coli (LZ143) was engineered to transform biobased l‐phenylalanine to enantiopure d‐phenylglycine in 83% conversion via a one‐pot 8‐step transformation. Preparative biotransformations were also demonstrated. The high‐yielding synthetic methods use cheap and green reagents (ammonia, glucose, and/or oxygen), and E. coli whole‐cell catalysts, thus providing green and useful alternative methods for manufacturing d‐phenylglycine.

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Targeted next‐generation sequencing in myelodysplastic syndromes and prognostic interaction between mutations and IPSS‐R
Authors: Tefferi Ayalew , Lasho Terra L. , Patnaik Mrinal M. , Saeed Lyla , Mudireddy Mythri , Idossa Dame , Finke Christy , Ketterling Rhett P. , Pardanani Animesh , Gangat Naseema
Published: September 2017

A 27‐gene panel was used for next‐generation sequencing (NGS) in 179 patients (median age 73 years) with primary myelodysplastic syndromes (MDS); risk distribution according to the revised International Prognostic Scoring System (IPSS‐R) was 11% very high, 18% high, 17% intermediate, 38% low and 16% very low. At least one mutation/variant was detected in 147 (82%) patients; 23% harbored three or more mutations/variants. The most frequent mutations/variants included ASXL1 (30%), TET2 (25%), SF3B1 (20%), U2AF1 (16%), SRSF2 (16%), TP53 (13%), RUNX1 (11%), and DNMT3A (10%). At a median follow up of 30 months, 148 (83%) deaths and 26 (15%) leukemic transformations were recorded. Multivariable analysis of mutations/variants identified ASXL1 (HR 1.7, 95% CI 1.2‐2.5), SETBP1 (HR 4.1, 95% CI 1.6‐10.2) and TP53 (HR 2.2, 95% CI 1.3‐3.4) as risk factors for overall and SRSF2 (HR 3.9, 95% CI 1.5‐10.2), IDH2 (HR 3.7, 95% CI 1.2‐11.4), and CSF3R (HR 6.0, 95% CI 1.6‐22.6) for leukemia‐free survival. Addition of age to the multivariable model did not affect these results while accounting for IPSS‐R weakened the significance of TP53 mutations/variants (P = .1). An apparently favorable survival impact of SF3B1 mutations was no longer evident after adjustment for IPSS‐R. Approximately 41% and 20% of patients harbored at least one adverse mutation/variant for overall and leukemia‐free survival, respectively. Number of mutations/variants did not provide additional prognostic value. The survival impact of adverse mutations was most evident in IPSS‐R very low/low risk patients. These observations suggest that targeted NGS might assist in treatment decision‐making in lower risk MDS.
Are great apes able to reason from multi‐item samples to populations of food items?
Authors: Eckert Johanna , Rakoczy Hannes , Call Josep
Published: September 2017

Inductive learning from limited observations is a cognitive capacity of fundamental importance. In humans, it is underwritten by our intuitive statistics, the ability to draw systematic inferences from populations to randomly drawn samples and vice versa. According to recent research in cognitive development, human intuitive statistics develops early in infancy. Recent work in comparative psychology has produced first evidence for analogous cognitive capacities in great apes who flexibly drew inferences from populations to samples. In the present study, we investigated whether great apes (Pongo abelii, Pan troglodytes, Pan paniscus, Gorilla gorilla) also draw inductive inferences in the opposite direction, from samples to populations. In two experiments, apes saw an experimenter randomly drawing one multi‐item sample from each of two populations of food items. The populations differed in their proportion of preferred to neutral items (24:6 vs. 6:24) but apes saw only the distribution of food items in the samples that reflected the distribution of the respective populations (e.g., 4:1 vs. 1:4). Based on this observation they were then allowed to choose between the two populations. Results show that apes seemed to make inferences from samples to populations and thus chose the population from which the more favorable (4:1) sample was drawn in Experiment 1. In this experiment, the more attractive sample not only contained proportionally but also absolutely more preferred food items than the less attractive sample. Experiment 2, however, revealed that when absolute and relative frequencies were disentangled, apes performed at chance level. Whether these limitations in apes’ performance reflect true limits of cognitive competence or merely performance limitations due to accessory task demands is still an open question.
Thermal Schrödinger Equation: Efficient Tool for Simulation of Many‐Body Quantum Dynamics at Finite Temperature
Authors: Gelin Maxim F. , Borrelli Raffaele
Published: September 2017

We develop a wave‐function‐based method for the simulation of quantum dynamics of systems with many degrees of freedom at finite temperature. The method is inspired by the ideas of Thermo Field Dynamics (TFD). As TFD, our method is based on the doubling of the system's degrees of freedom and thermal Bogoliubov transformation. As distinct from TFD, our method implements the doubling of thermalized degrees of freedom only, and relies upon the explicitly constructed generalized thermal Bogoliubov transformation, which is not restricted to fermionic and bosonic degrees of freedom. This renders the present approach computationally efficient and applicable to a large variety of systems.
Expanding Anti‐Stokes Shifting in Triplet–Triplet Annihilation Upconversion for In Vivo Anticancer Prodrug Activation
Authors: Huang Ling , Zhao Yang , Zhang He , Huang Kai , Yang Jinyi , Han Gang
Published: September 2017

A strategy to expand anti‐Stokes shifting from the far‐red to deep‐blue region in metal‐free triplet–triplet annihilation upconversion (TTA‐UC) is presented. The method is demonstrated by in vivo titration of the photorelease of an anticancer prodrug. This new TTA system has robust brightness and the longest anti‐Stokes shift of any reported TTA system. TTA core–shell‐structured prodrug delivery capsules that benefit from these properties were developed; they can operate with low‐power density far‐red light‐emitting diode light. These capsules contain mesoporous silica nanoparticles preloaded with TTA molecules as the core, and amphiphilic polymers encapsulating anticancer prodrug molecules as the shell. When stimulated by far‐red light, the intense TTA upconversion blue emission in the system activates the anticancer prodrug molecules and shows effective tumor growth inhibition in vivo. This work paves the way to new organic TTA upconversion techniques that are applicable to in vivo photocontrollable drug release and other biophotonic applications.
Copper‐Catalyzed Synthesis and Applications of Yndiamides
Authors: Mansfield Steven J. , Christensen Kirsten E. , Thompson Amber L. , Ma Kai , Jones Michael W. , Mekareeya Aroonroj , Anderson Edward A.
Published: September 2017

The first synthetic route to yndiamides, a novel class of double aza‐substituted alkyne, has been established by the copper(I)‐catalyzed cross‐coupling of 1,1‐dibromoenamides with nitrogen nucleophiles. The utility of these compounds is demonstrated in a range of transition‐metal‐catalyzed and acid‐catalyzed transformations to afford a wide variety of 1,2‐diamide functionalized products.
Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry
Authors: Buss Joshua A. , Oyala Paul H. , Agapie Theodor
Published: September 2017

A terminal Mo phosphide was prepared through the group transfer of both P and Cl atoms from chloro‐substituted dibenzo‐7λ3‐phosphanorbornadiene. This compound represents the first structurally characterized terminal transition‐metal phosphide with valence d electrons. In the tetragonal ligand field, these electrons populate an orbital of dxy parentage, an electronic configuration that accommodates both metal d electrons and a formal M≡P triple bond. Single‐electron oxidation affords a transient open‐shell terminal phosphide cation with significant spin density on P, as corroborated by continuous wave (CW) and pulse electron paramagnetic resonance (EPR) characterization. Facile P−P bond formation occurs from this species through intermolecular phosphide coupling.
Self‐Assembly of Giant Spherical Liquid‐Crystalline Complexes and Formation of Nanostructured Dynamic Gels that Exhibit Self‐Healing Properties
Authors: Uchida Junya , Yoshio Masafumi , Sato Sota , Yokoyama Hiroyuki , Fujita Makoto , Kato Takashi
Published: September 2017

Supramolecular self‐assembly of 24 forklike mesogenic ligands and 12 transition metal ions led to the formation of giant spherical coordination complexes that exhibit liquid‐crystalline (LC) phases. Self‐healing LC supramolecular gels were also obtained through the introduction of these LC nanostructured supramolecular giant spherical complexes into dynamic covalent networks formed by cross‐linkers and bifunctional polymers. The giant spherical structures of the PdII complexes with 72 rodlike moieties on the periphery were characterized by NMR, diffusion‐ordered NMR spectroscopy, and mass spectrometry. These complexes are stable and exhibit lyotropic LC behavior, while the mesogenic ligands show thermotropic LC properties. The self‐assembled LC structures of the spherical complexes can be tuned by the length of the rodlike moieties.
An NMR Method To Pinpoint Supramolecular Ligand Binding to Basic Residues on Proteins
Authors: Hogeweg Anna , Sowislok Andrea , Schrader Thomas , Beuck Christine
Published: September 2017

Targeting protein surfaces involved in protein–protein interactions by using supramolecular chemistry is a rapidly growing field. NMR spectroscopy is the method of choice to map ligand‐binding sites with single‐residue resolution by amide chemical shift perturbation and line broadening. However, large aromatic ligands affect NMR signals over a greater distance, and the binding site cannot be determined unambiguously by relying on backbone signals only. We herein employed Lys‐ and Arg‐specific H2(C)N NMR experiments to directly observe the side‐chain atoms in close contact with the ligand, for which the largest changes in the NMR signals are expected. The binding of Lys‐ and Arg‐specific supramolecular tweezers and a calixarene to two model proteins was studied. The H2(C)N spectra track the terminal CH2 groups of all Lys and Arg residues, revealing significant differences in their binding kinetics and chemical shift perturbation, and can be used to clearly pinpoint the order of ligand binding.
meta‐Selective C−H Borylation of Benzylamine‐, Phenethylamine‐, and Phenylpropylamine‐Derived Amides Enabled by a Single Anionic Ligand
Authors: Davis Holly J. , Genov Georgi R. , Phipps Robert J.
Published: September 2017

Selective functionalization at the meta position of arenes remains a significant challenge. In this work, we demonstrate that a single anionic bipyridine ligand bearing a remote sulfonate group enables selective iridium‐catalyzed borylation of a range of common amine‐containing aromatic molecules at the arene meta position. We propose that this selectivity is the result of a key hydrogen bonding interaction between the substrate and catalyst. The scope of this meta‐selective borylation is demonstrated on amides derived from benzylamines, phenethylamines and phenylpropylamines; amine‐containing building blocks of great utility in many applications.
Multifunctional triazolylferrocenyl Janus dendron: Nanoparticle stabilizer, smart drug carrier and supramolecular nanoreactor
Authors: Zhao Li , Ling Qiangjun , Liu Xiong , Hang Chaodong , Zhao Qiuxia , Liu Fangfei , Gu Haibin
Published: September 2017

Owing to their unique broken symmetry, amphiphilic Janus dendrimers and dendons provide fascinating properties for material, biological, pharmaceutical and biomedical applications. The integration of various organometallic moieties into these macromolecules will further offer the opportunity to form complex and intelligent architectures and materials. Here, we report a novel, simple and multifunctional Janus dendron containing redox‐reversible hydrophobic ferrocene (Fc) unit, complexing‐effective 1,2,3‐triazole ligand and biocompatible hydrophilic triethylene glycol termini. Silver and gold nanoparticles were firstly successfully prepared by using the Janus dendron as the reducing agent of Au(III) and Ag(I), and the stabilizer of the corresponding nanoparticles. The redox response of the Fc moiety was then employed to trigger the release of model drug, rhodamine B, encapsulated in supramolecular micelles formed by the self‐assembly of the Janus dendron. Finally, the precise and excellent metal‐complexing ability of the triazole group in this dendron was fully utilized to stabilize a water‐soluble Cu(I) catalyst, forming supramolecular nanoreactors for the catalysis of the copper(I)‐catalyzed azide alkyne cycloaddition click reaction in only water. The multifunctional characteristics of this dendron highlight the potential for organometallic Janus dendrimers and dendrons in the fields of functional materials and nanomedicines.
DNA fastening and scission actions of Cu(II), Co(II), Ni(II) and Zn(II) complexes: synthesis, spectral characterization and cytotoxic study
Authors: Kumaravel Ganesan , Utthra Ponnukalai Ponya , Raman Natarajan
Published: September 2017

A heterocyclic compound, 2‐(aminomethyl)benzimidazole dihydrohydrochloride, was treated with nitrobenzaldehyde to form a Schiff base that was made to react with divalent metals. A co‐ligand, either 1,10‐phenanthroline or 2,2′‐bipyridine, was added to this mixture to obtain metal chelators of type [ML(co‐L)2]Cl2. They were in 1:1:2 stoichiometry ratio, which was characterized by various spectroscopic techniques that suggested an octahedral geometry around the central metal ions. These complexes were investigated for their binding affinities with calf thymus (CT) DNA, using various techniques, such as UV–Vis, viscosity, cyclic voltammetry (CV), etc. The binding interaction studies revealed intercalation as the possible binding mode of the complexes with the CT DNA. In addition, these complexes were screened for their antimicrobial potential and DNA denaturing tendencies using gel electrophoretic assay. The antimicrobial screening investigation showed that the complexes behaved as better antimicrobial agents than the ligand, especially, complex 5 shows exceptional activity even in the electrophoretic assay along with the antimicrobial efficacy. Moreover, complex 5 was able to denature the plasmid DNA better than the other compounds. All the compounds were screened for cytotoxic efficacy, and the IC50 values suggest that the compounds possess cytotoxic activity to some extent that is almost the same as the activity of cisplatin.
The Nature of Public Policy Processes in the Pacific Islands
Authors: Aiafi Potoae Roberts
Published: September 2017

What is ‘policy’? Where is it coming from? Who is formulating it and how? What are the characteristics of existing policies? These questions concern the nature of (public) policy processes in any context. This article addresses these questions for the Pacific islands. It draws on empirical evidence from a research to show the nature of the policy processes in Vanuatu, the Solomon Islands, Samoa and key regional intergovernmental organisations. Policy processes have remained heavily top‐down, shaped significantly by political and external interests; society has been the neglected element. In essence, the genesis of public policy has been insufficiently rooted in the context, problems and needs of societies to which policies have been directed. While existing policies were often those transferred from elsewhere, and which do not fit well in the receiving context and culture, the practices were ad hoc, driven by various ideological or social constructions. The implications of these findings for both theory and practice are discussed.
New Zealand's ICT Strategy: The Respective Roles of Senior and Middle Management in Promoting Collaboration and Innovation
Authors: Jones Suzanne , Hooper Tony
Published: September 2017

The global financial crisis of 2007–08 encouraged governments to exploit information and communication technologies. The New Zealand government responded by developing an Information and Technology Strategy to 2017. This investigation surveyed middle managers awareness of the Strategy, the level of collaboration and innovation they engaged in and what they considered the barriers and enablers to be. These data were triangulated with the perceptions of senior public officials. While there was a disconnect between what senior managers expected of middle managers and how middle managers perceived their role and responsibilities, there was agreement among senior and middle managers on the barriers to innovation based on agency responsibilities and priorities. Ingrained corporate behavior has incentivised low risk, stable, reliable and accountable staff, while risk taking and entrepreneurial capabilities have not been rewarded. The Strategy was revised and simplified, and senior manager views gathered again to see if their initial perceptions had changed.
Pseudocontingencies in Consumer Choice: Preference for Prevalent Product Categories Decreases with Decreasing Set Quality
Authors: Vogel Tobias , Kutzner Florian
Published: September 2017

Building on theorizing about contingency inferences, the present research deals with the impact of product category prevalence on consumer choice. We argue that a category's prevalence in the choice set can signal high quality, but the validity depends on the aggregate quality of the choice set. With ever more low‐quality products in the set, high prevalence should increasingly signal poor rather than high quality. When choosing from a poor‐quality set, choices should thus favor products from the rare category. In four experiments, we show that poor‐quality sets increase the proportion of consumers choosing products from a rare category. Furthermore, we show that these effects increase when base rates of a category and quality become more extreme. Finally, Experiment 4 shows that contingency inferences partly mediate the effect of set quality on choice. The results extend previous research on contingency inferences, indicating the adaptive use of base‐rate information in consumer decision making. Copyright © 2017 John Wiley & Sons, Ltd.
Zum Ermüdungsnachweis von druckschwellbeanspruchtem Beton
Authors: Oneschkow Nadja , Lohaus Ludger
Published: September 2017

Für ermüdungsbelastete Bauwerke, insbesondere aus hochfesten Betonen, wird der Ermüdungsnachweis immer häufiger maßgebend für die Bemessung. Gleichzeitig existieren neuere Untersuchungsergebnisse, die zeigen, dass eine Weiterentwicklung des Ermüdungsnachweises sinnvoll und erforderlich ist. Das Sicherheitskonzept des Ermüdungsnachweises ist angelehnt an das Konzept der statischen Bemessung. Hieraus ergeben sich Besonderheiten und Herausforderungen bei der Weiterentwicklung des Nachweiskonzepts. Im Teil 1 dieses Artikels [1] wurde ein Überblick über die Struktur des Ermüdungsnachweises gegeben und die enthaltenen Beiwerte erläutert. In diesem Artikel werden die Wöhlerkurven mit aktuellen Versuchsergebnissen verglichen und der Effekt des Bemessungswerts der Druckfestigkeit von Beton bei Ermüdungsbeanspruchung herausgearbeitet und vor dem Hintergrund sicherheitstheoretischer Überlegungen diskutiert. Das Potenzial für Weiterentwicklungen wird hierauf aufbauend aufgezeigt.
Increased prevalence of celiac disease in idiopathic inflammatory myopathies
Authors: Danielsson Olof , Lindvall Björn , Hallert Claes , Vrethem Magnus , Dahle Charlotte
Published: September 2017

Objectives

Idiopathic inflammatory myopathies (IIM) are often associated with other immune‐mediated diseases or malignancy. Some studies have reported a high frequency of celiac disease in IIM. The aim of this study was to investigate the prevalence of celiac disease, systemic inflammatory diseases, and malignancy in a cohort of IIM patients, and estimate the incidence of IIM in the county of Östergötland, Sweden.

Material and Methods

We reviewed medical records and analyzed sera from 106 patients, fulfilling pathological criteria of inflammatory myopathy, for the presence of IgA antibodies against endomysium and gliadin. Antibody‐positive patients were offered further investigation with small bowel biopsy or investigation for the presence of antibodies against antitissue transglutaminase (t‐TG). The patients were classified according to Bohan and Peter or Griggs criteria. The presence of celiac disease, systemic inflammatory, and malignant diseases was documented.

Results

Four of 88 patients classified as IIM (4.5%) had biopsy‐confirmed celiac disease, which is higher than the prevalence in the general population, detected with a similar screening procedure (0.53%). Thirty‐three patients (38%) had a systemic inflammatory disease and five (5.7%) a malignancy. The incidence of confirmed IIM in the county of Östergötland was 7.3 per million/year.

Conclusions

The results highlight the high frequency of associated inflammatory and malignant diseases and confirm an increased prevalence of celiac disease in IIM.
Reflex‐based grasping, skilled forelimb reaching, and electrodiagnostic evaluation for comprehensive analysis of functional recovery—The 7‐mm rat median nerve gap repair model revisited
Authors: Stößel Maria , Rehra Lena , Haastert‐Talini Kirsten
Published: September 2017

Introduction

The rat median nerve injury and repair model gets increasingly important for research on novel bioartificial nerve grafts. It allows follow‐up evaluation of the recovery of the forepaw functional ability with several sensitive techniques. The reflex‐based grasping test, the skilled forelimb reaching staircase test, as well as electrodiagnostic recordings have been described useful in this context. Currently, no standard values exist, however, for comparison or comprehensive correlation of results obtained in each of the three methods after nerve gap repair in adult rats.

Methods

Here, we bilaterally reconstructed 7‐mm median nerve gaps with autologous nerve grafts (ANG) or autologous muscle‐in‐vein grafts (MVG), respectively. During 8 and 12 weeks of observation, functional recovery of each paw was separately monitored using the grasping test (weekly), the staircase test, and noninvasive electrophysiological recordings from the thenar muscles (both every 4 weeks). Evaluation was completed by histomorphometrical analyses at 8 and 12 weeks postsurgery.

Results

The comprehensive evaluation detected a significant difference in the recovery of forepaw functional motor ability between the ANG and MVG groups. The correlation between the different functional tests evaluated precisely displayed the recovery of distinct levels of forepaw functional ability over time.

Conclusion

Thus, this multimodal evaluation model represents a valuable preclinical model for peripheral nerve reconstruction approaches.
New Cytotoxic Triterpenoid Saponins from the Roots of Albizia gummifera (J.F.Gmel.) C.A.Sm.
Authors: Simo Line Made , Noté Olivier Placide , Mbing Joséphine Ngo , Aouazou Sarah Ali , Guillaume Dominique , Muller Christian Dominique , Pegnyemb Dieudonné Emmanuel , Lobstein Annelise
Published: September 2017

As part of our search for new bioactive saponins from Cameroonian medicinal plants, two new oleanane‐type saponins, named gummiferaosides D and E (1 and 2), along with one known saponin, julibroside J8 (3), were isolated from the roots of Albizia gummifera. Their structures were established on the basis of extensive 1D‐ and 2D‐NMR (1H‐ and 13C‐NMR, DEPT, COSY, TOCSY, NOESY, HSQC, HSQC‐TOCSY, and HMBC) and HR‐ESI‐MS studies, and by chemical evidence. The apoptotic effect of saponins 1 – 3 was evaluated on the A431 human epidermoid cancer cell. Flow cytometric analyses showed that saponins 1 – 3 induced apoptosis of human epidermoid cancer cell (A431) in a dose‐dependent manner.
Effect of Stapling Architecture on Physiochemical Properties and Cell Permeability of Stapled α‐Helical Peptides: A Comparative Study
Authors: Tian Yuan , Jiang Yanhong , Li Jingxu , Wang Dongyuan , Zhao Hui , Li Zigang
Published: September 2017

Stapled peptides have emerged as a new class of targeting molecules with high binding affinity and specificity for intracellular undruggable targets. Their ability to penetrate cell membranes is exceptionally intriguing but remains elusively and controversially discussed. To understand the effect of stapling architectures on their physiochemical properties and to aid in promoting their cell permeability, we report herein a comparative study on the physiochemical properties and cell permeability of stapled α‐helical peptides with different types of crosslinks. We highlight the decisive impact of the intrinsic properties of the crosslinks on cell permeability rather than the helical contents of the peptides in model amphipathic sequences targeting estrogen receptor–coactivator interaction. We envision this finding to shed further light on the chemical optimization of stapled α‐helical peptides or macrocyclic cell‐penetrating peptides for enhanced cell penetration.
Exosomes secreted from mutant‐HIF‐1α‐modified bone‐marrow‐derived mesenchymal stem cells attenuate early steroid‐induced avascular necrosis of femoral head in rabbit
Authors: Li Haile , Liu Danping , Li Chen , Zhou Shanjian , Tian Dachuan , Xiao Dawei , Zhang Huan , Gao Feng , Huang Jianhua
Published: September 2017

Mesenchymal stem cells (MSCs)‐derived exosomes exhibit protective effects on damaged or diseased tissues. Hypoxia‐inducible factor 1α (HIF‐1α) plays a critical role in bone development. However, HIF‐1α is easily biodegradable under normoxic conditions. The bone‐marrow‐derived mesenchymal stem cells (BMSCs) were transfected with adenovirus carrying triple point‐mutations (amino acids 402, 564, and 803) in the HIF‐1α coding sequence (CDS). The mutant HIF‐1α can efficiently express functional proteins under normoxic conditions. To date, no study has reported the role of exosomes secreted by mutant HIF‐1α modified BMSCs in the recovery of the early steroid‐induced avascular necrosis of femoral head (SANFH). In this study, we firstly analyzed exosomes derived from BMSCs modified by mutant (BMSC‐ExosMU) or wild‐type HIF‐1α (BMSC‐ExosWT). In vitro, we investigated the osteogenic differentiation capacity of BMSCs modified by BMSC‐ExosMU or BMSC‐ExosWT, and the angiogenesis effects of BMSC‐ExosMU and BMSC‐ExosWT on human umbilical vein endothelial cells (HUVECs). Besides, the healing of the femoral head was also assessed in vivo. We found that the potential of osteogenic differentiation of BMSCs treated with BMSC‐ExosMU was higher than the wild‐type group in vitro. In addition, BMSC‐ExosMU stimulated the proliferation, migration, and tube formation of HUVECs in a dose‐dependent manner. Compared with the BMSC‐ExosWT or PBS control group, the injection of BMSC‐ExosMU into the necrosis region markedly accelerated the bone regeneration and angiogenesis, which were indicated by the increased trabecular reconstruction and microvascular density. Taken together, our data suggest that BMSC‐ExosMU facilitates the repair of SANFH by enhancing osteogenesis and angiogenesis.
An Imide‐Based Pentacyclic Building Block for n‐Type Organic Semiconductors
Authors: Wu Fu‐Peng , Un Hio‐Ieng , Li Yongxi , Hu Hailiang , Yuan Yi , Yang Bin , Xiao Kai , Chen Wei , Wang Jie‐Yu , Jiang Zuo‐Quan , Pei Jian , Liao Liang‐Sheng
Published: September 2017

A new electron‐deficient unit with a fused 5‐membered heterocyclic ring was developed by replacing a cyclopenta‐1,3‐diene from electron‐rich donor indacenodithiophene (IDT) with a cyclohepta‐4,6‐diene‐1,3‐diimde unit. The imide bridge endows dithienylbenzenebisimide (BBI) with a fixed planar configuration and low energy levels for both the highest occupied molecular orbital (HOMO; −6.24 eV) and the lowest unoccupied molecular orbit (LUMO; −2.57 eV). Organic field‐effect transistors (OFETs) based on BBI polymers exhibit electron mobility up to 0.34 cm2 V−1 s−1, which indicates that the BBI is a promising n‐type building block for optoelectronics.
Silver–Sulfur Hybrid Supertetrahedral Clusters: The Hitherto Missing Members in the Metal–Chalcogenide Tetrahedral Clusters
Authors: Luo Geng‐Geng , Su Hai‐Feng , Xiao An , Wang Zhi , Zhao Yang , Wu Qiao‐Yu , Wu Ji‐Huai , Sun Di , Zheng Lan‐Sun
Published: September 2017

The synthesis of Group 11 metal chalcogenide supertetrahedral clusters (SCs) still remains a great challenge mainly due to the high tendency of metal aggregation through metallophilicity and global charge balance. Demonstrated herein are the preparation, crystallographic characterization, and optical properties of two stable silver–sulfur SCs through ligand‐control; one as a discrete zero‐dimensional (0D) V3,4‐type cluster and the other as a one‐dimensional (1D) zigzag chain extended by alternating V3,2‐type clusters. The notation Vn,m (where n is the number of metal layers, and m is the number of vacant corners) is used to describe a new series of vacant‐corner SCs, which can be derived from the regular Tn clusters. The existence of vacant‐corner‐type SCs may be ascribed to the low valence and tri‐coordinated environment of silver ions. These are the first representatives of structurally determined silver–sulfur tetrahedral clusters thus far. This work enriches the coinage‐metal chalcogenide tetrahedral cluster portfolio, discovers vacant‐corner SCs present in silver–sulfur hybrid tetrahedral clusters, and provides effective means for further development of Group 11 coinage‐metal chalcogenide SCs.
Concise Total Synthesis of (−)‐Affinisine Oxindole, (+)‐Isoalstonisine, (+)‐Alstofoline, (−)‐Macrogentine, (+)‐Na‐Demethylalstonisine, (−)‐Alstonoxine A, and (+)‐Alstonisine
Authors: Stephen Michael Rajesh , Rahman M. Toufiqur , Tiruveedhula V. V. N. Phani Babu , Fonseca German O. , Deschamps Jeffrey R. , Cook James M.
Published: September 2017

A highly enantio‐ and diastereoselective strategy to access any member of the sarpagine/macroline family of oxindole alkaloids via internal asymmetric induction was developed from readily available d‐(+)‐tryptophan. At the center of this approach was the diastereospecific generation of the spiro[pyrrolidine‐3,3′‐oxindole] moiety at an early stage via a tert‐butyl hypochlorite‐promoted oxidative rearrangement of a chiral tetrahydro‐β‐carboline derivative. This key branching point determined the spatial configuration at the C‐7 spiro center to be entirely 7R or 7S. Other key stereospecific processes were the asymmetric Pictet–Spengler reaction and Dieckmann cyclization, which were scalable to the 600 and 150 gram levels, respectively. Execution of this approach resulted in first enantiospecific total synthesis of (+)‐isoalstonisine and (−)‐macrogentine from the chitosenine series (7R), as well as (+)‐alstonisine, (+)‐alstofoline, (−)‐alstonoxine A and (+)‐Na‐demethylalstonisine from the alstonisine series (7S).
Size makes a difference: Chiral recognition in complexes of fenchone with cyclodextrins studied by means of NMR titration
Authors: Dudzik Karolina , Wojcik Jacek , Ejchart Andrzej , Nowakowski Michał
Published: September 2017

Gibbs energies of complex formation between enantiomers of bicyclic terpenoid, fenchone, and naturally occurring cyclodextrins, βCD and γCD, were determined by means of13C and1H nuclear magnetic resonance (NMR) titration data. These results were compared with the corresponding data obtained previously for the diastereomeric fenchone/αCD complexes. The size of the inner cavity of host molecules significantly influences stoichiometry, association constants, and enantiomeric differentiation of the studied complexes. These complementary data allow us to discuss qualitatively the influence of the host size on the guest–host interactions. A method of the simultaneous use of titration data collected for several resonances of different isotopes in the determination of association constants was worked out and thoroughly analyzed. Comparison of the results of global data analyses with weighted means of individual ones revealed that both these approaches are equally trustworthy.
Structure and development of the subesophageal zone of the Drosophila brain. II. Sensory compartments
Authors: Kendroud Sarah , Bohra Ali A. , Kuert Philipp A. , Nguyen Bao , Guillermin Oriane , Sprecher Simon G. , Reichert Heinrich , VijayRaghavan Krishnaswamy , Hartenstein Volker
Published: September 2017

The subesophageal zone (SEZ) of the Drosophila brain processes mechanosensory and gustatory sensory input from sensilla located on the head, mouth cavity and trunk. Motor output from the SEZ directly controls the movements involved in feeding behavior. In an accompanying paper (Hartenstein et al., ), we analyzed the systems of fiber tracts and secondary lineages to establish reliable criteria for defining boundaries between the four neuromeres of the SEZ, as well as discrete longitudinal neuropil domains within each SEZ neuromere. Here we use this anatomical framework to systematically map the sensory projections entering the SEZ throughout development. Our findings show continuity between larval and adult sensory neuropils. Gustatory axons from internal and external taste sensilla of the larva and adult form two closely related sensory projections, (a) the anterior central sensory center located deep in the ventromedial neuropil of the tritocerebrum and mandibular neuromere, and (b) the anterior ventral sensory center (AVSC), occupying a superficial layer within the ventromedial tritocerebrum. Additional, presumed mechanosensory terminal axons entering via the labial nerve define the ventromedial sensory center (VMSC) in the maxilla and labium. Mechanosensory afferents of the massive array of chordotonal organs (Johnston's organ) of the adult antenna project into the centrolateral neuropil column of the anterior SEZ, creating the antenno‐mechanosensory and motor center (AMMC). Dendritic projections of dye back‐filled motor neurons extend throughout a ventral layer of the SEZ, overlapping widely with the AVSC and VMSC. Our findings elucidate fundamental structural aspects of the developing sensory systems in Drosophila.
The physiological motor patterns produced by neurons in the nucleus retroambiguus in the rat and their modulation by vagal, peripheral chemosensory, and nociceptive stimulation
Authors: Subramanian Hari H. , Huang Zheng‐Gui , Silburn Peter A. , Balnave Ron J. , Holstege Gert
Published: September 2017

The nucleus retroambiguus (NRA) is a neuronal cell group in the medullary ventrolateral tegmentum, rostrocaudally between the obex and the first cervical spinal segment. NRA neurons are premotor interneurons with direct projections to the motoneurons of soft palate, pharynx, and larynx in the nucleus ambiguus in the lateral medulla as well as to the motoneurons in the spinal cord innervating diaphragm, abdominal, and pelvic floor muscles and the lumbosacral motoneurons generating sexual posture. These NRA premotor interneurons receive very strong projections from the periaqueductal gray (PAG) in the context of basic survival mechanisms as fight, flight, freezing, sound production, and sexual behavior. In the present study in rat we investigated the physiological motor patterns generated by NRA neurons, as the result of vagal, peripheral chemosensory, and nociceptive stimulation. The results show that the NRA contains phasic respiratory modulated neurons, as well as nonphasic tonically modulated neurons. Stimulation in the various rostrocaudal levels of the NRA generates site‐specific laryngeal, respiratory, abdominal, and pelvic floor motor activities. Vagal and peripheral chemosensory stimulation induces both excitatory and inhibitory modulation of phasic NRA‐neurons, while peripheral chemosensory and nociceptive stimulation causes excitation and inhibition of nonphasic NRA‐neurons. These results are in agreement with the concept that the NRA represents a multifunctional group of neurons involved in the output of the emotional motor system, such as vomiting, vocalization, mating, and changes in respiration.
Thorny ganglion cells in marmoset retina: Morphological and neurochemical characterization with antibodies against calretinin
Authors: Chandra Ashleigh J. , Lee Sammy C. S. , Grünert Ulrike
Published: September 2017

In primates, over 17 morphological types of retinal ganglion cell have been distinguished by their dendritic morphology and stratification, but reliable markers for specific ganglion cell populations are still rare. The calcium binding protein calretinin is known to be expressed in the inner nuclear and the ganglion cell layer of marmoset retina, however, the specific cell type(s) expressing calretinin in the ganglion cell layer are yet to be determined. Here, we identified calretinin positive retinal ganglion cells in the common marmoset Callithrix jacchus. Double labeling with the ganglion cell marker RBPMS demonstrated that the large majority (80%) of the calretinin positive cells in the ganglion cell layer are ganglion cells, and 20% are displaced amacrine cells. The calretinin positive ganglion cells made up on average 12% of the total ganglion cell population outside of the foveal region and their proportion increased with eccentricity. Prelabeling with antibodies against calretinin and subsequent intracellular injection with DiI revealed that the large majority of the injected cells (n = 74) were either narrow thorny or broad thorny ganglion cells, 14 cells were displaced amacrine cells. Narrow thorny cells were further distinguished into outer and inner stratifying cells. In addition, weakly labeled cells with a large soma were identified as parasol ganglion cells. Our results show that three types of thorny ganglion cells in marmoset retina can be identified with antibodies against calretinin. Our findings are also consistent with the idea that the proportion of wide‐field ganglion cell types increases in peripheral retina.
Quantum Chemical Modeling of Homogeneous Water Oxidation Catalysis
Authors: Liao Rong‐Zhen , Siegbahn Per E. M.
Published: September 2017

The design of efficient and robust water oxidation catalysts has proven challenging in the development of artificial photosynthetic systems for solar energy harnessing and storage. Tremendous progress has been made in the development of homogeneous transition‐metal complexes capable of mediating water oxidation. To improve the efficiency of the catalyst and to design new catalysts, a detailed mechanistic understanding is necessary. Quantum chemical modeling calculations have been successfully used to complement the experimental techniques to suggest a catalytic mechanism and identify all stationary points, including transition states for both O−O bond formation and O2 release. In this review, recent progress in the applications of quantum chemical methods for the modeling of homogeneous water oxidation catalysis, covering various transition metals, including manganese, iron, cobalt, nickel, copper, ruthenium, and iridium, is discussed.
Optimization of Photoanodes for Photocatalytic Water Oxidation by Combining a Heterogenized Iridium Water‐Oxidation Catalyst with a High‐Potential Porphyrin Photosensitizer
Authors: Materna Kelly L. , Jiang Jianbing , Regan Kevin P. , Schmuttenmaer Charles A. , Crabtree Robert H. , Brudvig Gary W.
Published: September 2017

The development of water‐splitting dye‐sensitized photoelectrochemical cells has gained interest owing to their ability to generate renewable fuels from solar energy. In this study, photoanodes were assembled from a SnO2 film sensitized with a combination of a high‐potential CF3‐substituted porphyrin dye with a tetrahydropyranyl‐protected hydroxamic acid surface‐anchoring group and a Cp*Ir (Cp*=pentamethylcyclopentadienyl) water‐oxidation catalyst containing a silatrane anchoring group. The dye/catalyst ratios were varied from 2:1 to 32:1 to optimize the photocatalytic water oxidation. Photoelectrochemical measurements showed not only more stable and reproducible photocurrents for lower dye/catalyst ratios but also improved photostability. O2 production was confirmed in real time over a 20 h period with a Clark electrode. Photoanodes prepared from 2:1 and 8:1 dye/catalyst sensitization solutions provided the most active electrodes for photocatalytic water oxidation and performed approximately 30–35 turnovers in 20 h.
67‐90 GHz broadband power detector with 3 GHz output bandwidth for on‐chip test of millimeter‐wave circuits
Authors: del Rio David , Gurutzeaga Iñaki , Rezola Ainhoa , Velez Igone , Berenguer Roc
Published: September 2017

This paper presents the design of a compact and wide bandwidth millimeter‐wave power detector, integrated at the output of an E‐band power amplifier and implemented in a 55‐nm SiGe BiCMOS process. It is based on a nonlinear PMOS detector core, and its measured output voltage tracks the output power of the PA from 67 to 90 GHz. It provides an insertion loss lower than 0.2 dB, and its responsivity can be tuned between 8 and 17 V/W. The output bandwidth is bigger than 3 GHz, which allows built‐in self‐test when transmitting multigigabit millimeter‐wave signals.
A new mouse line for cell ablation by diphtheria toxin subunit A controlled by a Cre‐dependent FLEx switch
Authors: Plummer Nicholas W. , Ungewitter Erica K. , Smith Kathleen G. , Yao Humphrey H.‐C. , Jensen Patricia
Published: September 2017

Recombinase responsive mouse lines expressing diphtheria toxin subunit A (DTA) are well established tools for targeted ablation of genetically defined cell populations. Here we describe a new knock‐in allele at the Gt(Rosa)26Sor locus that retains the best features of previously described DTA alleles—including a CAG promoter, attenuated mutant DTA cDNA, and ubiquitous EGFP labeling—with the addition of a Cre‐dependent FLEx switch for tight control of expression. The FLEx switch consists of two pairs of antiparallel lox sites requiring Cre‐mediated recombination for inversion of the DTA to the proper orientation for transcription. We demonstrate its utility by Cre‐dependent ablation of both a broad domain in the embryonic nervous system and a discrete population of cells in the fetal gonads. We conclude that this new DTA line is useful for targeted ablation of genetically‐defined cell populations.