bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractA 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

AbstractThe 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

AbstractA 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

AbstractSupramolecular 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

AbstractTargeting 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

AbstractSelective 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.
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

AbstractA 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

AbstractWhat 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

AbstractThe 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

AbstractBuilding 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

AbstractFür 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

AbstractObjectivesIdiopathic 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 MethodsWe 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.ResultsFour 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.ConclusionsThe 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

AbstractIntroductionThe 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.MethodsHere, 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.ResultsThe 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.ConclusionThus, 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

AbstractStapled 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

AbstractMesenchymal 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

AbstractA 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

AbstractThe 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

AbstractA 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).