bluuebunny/crossref_metadata_2025 huggingface dataset:
Curriculum Model for Indonesian Major at Busan University of Foreign Studies
Authors: Jin Ryeo Park , Emzir - , Lustyantie Ninuk
Published: July 2018

Indonesian Major at Busan University of Foreign Studies has no standardize curriculum in the program. Since the program was established in 1982, teaching process is given based on lecture’s lesson plans. This method berings to inconsistency in grading the language competence. This affect the language skill of the students in the working fields. The goal of the study is to develop a curriculum model that will relate the standard of competence, syllabus, and lesson plans with cross-cultural understanding, namely culture-based curriculum. The materials of the curriculum are compiled from selected cultural elements. Cultural aspects that can be utilized in the preparation of teaching materials are (1) a system of life equipment and supplies; (2) The livelihood system; (3) the social system; (4) language, (5) the arts; (6) the knowledge system; and (7) the religious system.
A Cognitive Approach to EkeGusii Pop Songs
Authors: Ntabo Victor Ondara , Gathigia Moses Gatambuki , Nyarigoti Naom Moraa
Published: July 2018

A review of literature on pop songs reveals that composers use metaphors to communicate their feelings. In particular, the meaning of the metaphors in EkeGusii pop songs needs to be interpreted to reveal the message of the composers. The EkeGusii pop singer Christopher Mosioma’s (Embarambamba) songs have gained fame in Kenya because of their richness in the usage of metaphors. One of Christopher Mosioma’s songs, amasomo (education) which was launched in 2015 has gained acclaim from Kenyans. The song amasomo (education) is basically presented as a piece of advice to students to embrace education in order to optimally reap from its benefits. The study identified 10 metaphors in the song amasomo (education) through the Metaphor Identification Procedure Vrije Universiteit. In order to interpret the metaphors in the EkeGusii pop song amasomo (education), the Conceptual Metaphor Theory complemented by the folk conception of the generic Great Chain of Being Metaphor were employed. The study employed four coders (including the researchers) in the identification of the metaphors. The study found that, inter alia, animal, plant and object metaphors are used in the song amasomo (education). The study concludes that the metaphors in the EkeGusii pop songs belong inherently to different levels of the generic Great Chain of Being Metaphor.
Good EFL Learner’s Strategy In Enhancing English Mastery: A Case Study at Indonesian College Students
Authors: Syawal - , Patahuddin - , AS Nasrullah , Wira Rahman Ali
Published: July 2018

EFL learner strategy has become a popular issue since English considered as an International language which goes through with international public communication tools. In this study, the researcher focused on verifying learner strategy in enhancing English mastery inside classroom context of Indonesian college student. This study was qualitative research applied case study approach, which involves grounded theory method. The subject of this study was a learner which was considered as good EFL learner. Findings indicated that; a) Good EFL learner acts to obey a rule of learners (discipline). b) Good EFL learner tends to be relaxed and not easily upset (easy going). c) Good EFL learner has an eager to learn or to know something (curiosity). d) Good EFL learner dare to be different or prefers to act differently. In addition, e) Good EFL learner usually determined to follow a particular plan of action and sometimes using words in a clever and funny way (serious and witty).
The Illusion of Magic Realism as a Stratagem in the Hound of the Baskervilles
Authors: Ahmadi Moslem , Ahmadi Mosleh
Published: July 2018

The focus of the current research is on the relationship between detective fiction and the art of magic. Such a study is important in order to bring into surface a hidden aspect in one of the most popular novels of detective fiction, i.e., The Hound of the Baskervilles and to reconsider this novel from a new and different point of view. The research approach adopted in this paper includes reconsidering the antagonist of the novel as a professional illusionist rather than a mere villain. The findings from this research provide evidence that adopting an illusionist’s position can provide the antagonist of the novel with concealment and more freedom of action. The main conclusion drawn from this study is that resort to the art of magic on the antagonist’s part can become a great challenge to a detective in a detective novel. This paper recommends that all the antagonists of detective fiction assume hidden roles for achieving their goals not yet known by the readers.
ʿĀʾisha al-Kaʿbī’s “The Ladies’ Fitting Room”: Translation with an Introduction
Authors: Tijani O. Ishaq , Nsiri Imed
Published: July 2018

This article features a translation of “Ghurfat al-qiyās” (2007, The Ladies’ Fitting Room), a short story by the emerging Emirati female writer ʿĀʾisha al-Kaʿbī (1973-). The Introduction provides some brief comments on the content of the story in order to show how, while foregrounding the portrayal of some women’s obsession with their looks, the narrative reflects some of the socio-cultural issues that concern women and gender in contemporary Emirati and Arabian Gulf societies. The story is very minimalistic in the exploration of its subject-matters, but it is this narrative technique that makes its content—especially the sub-text, or the un-said aspects of the story—much more intriguing than its form.
Translation of Arabic Ecological Terms: An Eco-Cultural Approach
Authors: Mustafa Halimah Ahmad
Published: July 2018

Unlike most translations which are carried out within the Indo-European language-family and culture, the translation of Arabic language and culture into English language and culture tends to cause serious problems for translators. This paper is an attempt to examine the problems and difficulties in translating Arabic ecological terms of literary and religious texts using Peter Newmark’s (1988) ecological categorizations of ‘Fauna’, Flora’, and other ‘Geographical features’ in conceptualised and contextualised examples as parameters for discussion and analysis. Results of the discussion and analysis of the samples used in this paper have highlighted the importance of attending to ecological issues in translation and the need for an eco-cultural approach to be used for solving such problems. Some suggestions and recommendations have been made to help translators adjust their translation methods to fit the Arabic eco-cultural context as well as those who are interested in carrying out further research in this field.
The Postcoloniality of Poor African Leadership in Achebe’s Fiction: A Close Reading of Arrow of God and A Man of the People
Authors: Gbolo Sanka Confidence , Gustafson-Asamoah Patricia , Azumi Issaka Charity
Published: July 2018

The paper aims at tracing the genesis of abuse of power and the irresponsibility that goes with it to its full blossoming in Achebe’s fiction through a close reading of Arrow of God and A Man of the People. Disenchantment with leadership in Africa, especially after independence, is not new on the African literary scene. But to Achebe, the problems associated with poor leadership in Africa did not start after independence. Failure in leadership only worsened in most African countries after independence due to the perpetuation of colonial vestiges. By doing a close reading of the two novels and by using the theory of postcoloniality, the researchers compare the traditional world of Ezeulu in Arrow of God to the post-independence setting of Chief Nanga in A Man of the People. The paper concludes that Africa has gone beyond the politics of post-colonialism and is now at the postcoloniality stage. In order for Africans to truly overcome the perennial problem of poor leadership, there is the need for us to first accept our role as a continent in contributing towards the failure of leadership in Africa. There is also the urgency to encourage grass root participation and understanding of modern democracy, to build stronger institutions and to put in place heavier punishments for those who abuse power.
Análisis de metáforas conceptuales sobre la imagen social del profesorado en estudiantes de pedagogía
Authors:   Universidad de Concepción (Chile), Alarcón Paola , Díaz Claudio ,   Universidad de Concepción (Chile), Vergara Jorge ,   Universidad de Concepción (Chile), Vásquez Víctor ,   Universidad de Concepción (Chile), Torres Claudio ,   Universidad de Concepción (Chile)
Published: July 2018

Se presenta un análisis de metáforas conceptuales sobre la imagen social de los docentes en un grupo de estudiantes de pedagogía de una universidad chilena. El marco teórico se basa en la metáfora conceptual. Los objetivos del estudio son describir las categorías metafóricas por cohorte; establecer similitudes y diferencias entre las cohortes, y determinar la estabilidad de las categorías metafóricas obtenidas. Desde 2012 a 2014 se aplicó un instrumento de entrada escrita a estudiantes de 1.er año. En 2014 se aplicó también a estudiantes de 5.º año, con quienes se realizó además un grupo focal para profundizar la información obtenida en el instrumento de entrada escrita; luego se les aplicó una escala para clasificar las categorías metafóricas según su nivel de representatividad. Los resultados muestran que los factores del contexto social y profesional inciden en la configuración de los conceptos con que los sujetos creen que el profesorado es representado por la sociedad.
Occurrences of formulaic sequences in personal descriptions
Authors:   Universidad de Talca (Chile), Gómez Burgos Eric
Published: July 2018

Formulaic sequences are extremely necessary components of language production as they play a crucial role in building genres, not only in spoken discourse, but also in written production. Bearing in mind this consideration, the present article aims to investigate the frequency and occurrences of formulaic sequences in 27 personal descriptions written by 27 students of an English for medical purposes course from a university in the south of Chile. The procedure adopted two phases: first, the most common formulaic sequences used by the participants were identified and categorised, and, second, some examples of the inclusion of formulaic sequences in the genre of personal descriptions were made available. The findings reveal that the participants’ selection of formulaic sequences is very similar among them, and their occurrences in personal descriptions are related to the number of words of the text. Furthermore, the investigation reasserts that each genre has its own phraseology; for this reason, 15 formulaic sequences identified in the study seem to be specific features of the genre of personal descriptions.
The signal metabolite trehalose‐6‐phosphate inhibits the sucrolytic activity of sucrose synthase from developing castor beans
Authors: Fedosejevs Eric T. , Feil Regina , Lunn John E. , Plaxton William C.
Published: July 2018

In plants, trehalose 6‐phosphate (T6P) is a key signaling metabolite that functions as both a signal and negative feedback regulator of sucrose levels. The mode of action by which T6P senses and regulates sucrose is not fully understood. Here, we demonstrate that the sucrolytic activity of RcSUS1, the dominant sucrose synthase isozyme expressed in developing castor beans, is allosterically inhibited by T6P. The feedback inhibition of SUS by T6P may contribute to the control of sink strength and sucrolytic flux in heterotrophic plant tissues.
Shear Containment of BDNF within Molecular Hydrogels Promotes Human Stem Cell Engraftment and Postinfarction Remodeling in Stroke
Authors: Nisbet D. R. , Wang T. Y. , Bruggeman K. F. , Niclis J. C. , Somaa F. A. , Penna V. , Hunt C. P. J. , Wang Y. , Kauhausen J. A. , Williams R. J. , Thompson L. H. , Parish C. L.
Published: July 2018

Improved control over spatiotemporal delivery of growth factors is needed to enhance tissue repair. Current methods are limited–requiring invasive procedures, poor tissue targeting, and/or limited control over dosage and duration. Incorporation into implantable biomaterials enables stabilized delivery and avoids burst release/fluctuating doses. Here, the physical forces of fibrils formed by self‐assembly of epitope‐containing peptides are exploited. This biomimetic hydrogel is loaded with neurotrophic factor BDNF via a shear‐induced gel–solution transition, unique to noncovalent hydrogels. This results in a biomaterial with three desirable features: a nanofibrillar scaffold, presentation of a laminin epitope, and slow release of BDNF. In a stroke‐injury model, synergistic actions of this trimodal strategy on the integration of transplanted human neural progenitor cells, and protection of peri‐infarct tissue are identified. These BDNF‐functionalized hydrogels promote the integration of transplanted human embryonic stem cell–derived neural progenitors–resulting in larger grafts with greater cortical differentiation, appropriate for neuronal replacement. Furthermore, BDNF promotes the infiltration of host endothelial cells into the graft to augment vascularization of the graft, and adjacent penumbra tissue. These findings demonstrate the benefits of multifaceted tissue‐specific hydrogels to provide biomimetics of the host tissue, while sustain protein delivery, to promote endogenous and graft‐derived tissue repair.
Strong Graphene 3D Assemblies with High Elastic Recovery and Hardness
Authors: Jin Huile , Bu Yongfeng , Li Jun , Liu Jianping , Fen Xing , Dai Liming , Wang Jichang , Lu Jun , Wang Shun
Published: July 2018

The rational design and construction of 3D graphene assemblies is a crucial step to extend the graphene properties for practical applications. Here, a novel interfacially reactive self‐assembling process is reported to prepare well‐organized 3D honeycomb‐like graphene assemblies with unique polygonal nanopores interconnected by silicon‐oxygen chemical bonds. The newly developed silicate‐bridged graphene assembly (SGA) exhibits an exceptionally high hardness of 13.09 GPa, outperforming all existing 3D graphene materials, while maintains high Young's modulus (162.96 GPa), elastic recovery (75.27%), and superb thermal stability (600 °C in air). The observed unusual merits are resulted from unique pore structure combining the mechanical stability of the trihedral‐nanopore structure and the deformability of the other polygonal nanopores. As a filling material, a merely 0.05% (w/w) addition of SGA could double the impact resistance of unsaturated resins (e.g., polyester). While SGA is attractive for various applications, including body armors, wearable electronics, space elevators, and multifunctional reinforcement fibers for automobiles, and aerospace vehicles, the novel liquid sodium–water interfacial reactive self‐assembling developed in this study could open avenues for further development of various well‐defined 3D assemblies from graphene and many other materials.
Amplifying Strength, Toughness, and Auxeticity via Wavy Sutural Tessellation in Plant Seedcoats
Authors: Gao Chao , Hasseldine Benjamin P. J. , Li Ling , Weaver James C. , Li Yaning
Published: July 2018

Protective armors are widespread in nature and often consist of periodic arrays of tile‐like building blocks that articulate with each other through undulating interfaces. To investigate the mechanical consequences of these wavy tessellations, especially in instances where the amplitude of the undulations is near the scale of the constituent tiles as is found in the seedcoats of many plant species, an approach that integrates parametric modeling and finite element simulations with direct mechanical testing on their 3D‐printed multi‐material structural analogues is presented. Results from these studies demonstrate that these tiled arrays of largely isotropic star‐like unit cells exhibit an unusual combination of mechanical properties including auxeticity and mutually amplified strength and toughness which can be systematically tuned by varying the waviness of the sutural tessellation.
Scanning Nanowelding Lithography for Rewritable One‐Step Patterning of Sub‐50 nm High‐Aspect‐Ratio Metal Nanostructures
Authors: Liu Guoqiang , Chen Lina , Liu Jin , Qiu Meng , Xie Zhuang , Chang Jian , Zhang Yaokang , Li Peng , Lei Dang Yuan , Zheng Zijian
Published: July 2018

The development of a new nanolithographic strategy, named scanning nanowelding lithography (SNWL), for the one‐step fabrication of arbitrary high‐aspect‐ratio nanostructures of metal is reported in this study. Different from conventional pattern transfer and additive printing strategies which require subtraction or addition of materials, SNWL makes use of a sharp scanning tip to reshape metal thin films or existing nanostructures into desirable high‐aspect‐ratio patterns, through a cold‐welding effect of metal at the nanoscale. As a consequence, SNWL can easily fabricate, in one step and at ambient conditions, sub‐50 nm metal nanowalls with remarkable aspect ratio >5, which are found to be strong waveguide of light. More importantly, SNWL outweighs the existing strategies in terms of the unique ability to erase the as‐made nanostructures and rewrite them into other shapes and orientations on‐demand. Taking advantages of the serial and rewriting capabilities of SNWL, the smart information storage–erasure of Morse codes is demonstrated. SNWL is a promising method to construct arbitrary high‐aspect‐ratio nanostructure arrays that are highly desirable for biological, medical, optical, electronic, and information applications.
A Novel Top‐Down Synthesis of Ultrathin 2D Boron Nanosheets for Multimodal Imaging‐Guided Cancer Therapy
Authors: Ji Xiaoyuan , Kong Na , Wang Junqing , Li Wenliang , Xiao Yuling , Gan Silvia Tian , Zhang Ye , Li Yujing , Song Xiangrong , Xiong Qingqing , Shi Sanjun , Li Zhongjun , Tao Wei , Zhang Han , Mei Lin , Shi Jinjun
Published: July 2018

Single atom nonmetal 2D nanomaterials have shown considerable potential in cancer nanomedicines, owing to their intriguing properties and biocompatibility. Herein, ultrathin boron nanosheets (B NSs) are prepared through a novel top‐down approach by coupling thermal oxidation etching and liquid exfoliation technologies, with controlled nanoscale thickness. Based on the PEGylated B NSs, a new photonic drug delivery platform is developed, which exhibits multiple promising features for cancer therapy and imaging, including: i) efficient NIR‐light‐to‐heat conversion with a high photothermal conversion efficiency of 42.5%, ii) high drug‐loading capacity and triggered drug release by NIR light and moderate acidic pH, iii) strong accumulation at tumor sites, iv) multimodal imaging properties (photoacoustic, photothermal, and fluorescence imaging), and v) complete tumor ablation and excellent biocompatibility. As far as it is known, this is the first report on the top‐down fabrication of ultrathin 2D B NSs by the combined thermal oxidation etching and liquid exfoliation, as well as their application as a multimodal imaging‐guided drug delivery platform. The newly prepared B NSs are also expected to provide a robust and useful 2D nanoplatform for various biomedical applications.
Iron Vacancies Induced Bifunctionality in Ultrathin Feroxyhyte Nanosheets for Overall Water Splitting
Authors: Liu Bin , Wang Yun , Peng Hui‐Qing , Yang Ruoou , Jiang Zheng , Zhou Xingtai , Lee Chun‐Sing , Zhao Huijun , Zhang Wenjun
Published: July 2018

Exploring of new catalyst activation principle holds a key to unlock catalytic powers of cheap and earth‐abundant materials for large‐scale applications. In this regard, the vacancy defects have been proven to be effective to initiate catalytic active sites and endow high electrocatalytic activities. However, such electrocatalytically active defects reported to date have been mostly formed by anion vacancies. Herein, it is demonstrated for the first time that iron cation vacancies induce superb water splitting bifunctionality in alkaline media. A simple wet‐chemistry method is developed to grow ultrathin feroxyhyte (δ‐FeOOH) nanosheets with rich Fe vacancies on Ni foam substrate. The theoretical and experimental results confirm that, in contrast to anion vacancies, the formation of rich second neighboring Fe to Fe vacancies in δ‐FeOOH nanosheets can create catalytic active centers for both hydrogen and oxygen evolution reactions. The atomic level insight into the new catalyst activation principle based on metal vacancies is adaptable for developing other transition metal electrocatalysts, including Fe‐based ones.
Mechanically Robust Atomic Oxygen‐Resistant Coatings Capable of Autonomously Healing Damage in Low Earth Orbit Space Environment
Authors: Wang Xiaohan , Li Yixuan , Qian Yuhai , Qi Hong , Li Jian , Sun Junqi
Published: July 2018

Polymeric materials used in spacecraft require to be protected with an atomic oxygen (AO)‐resistant layer because AO can degrade these polymers when spacecraft serves in low earth orbit (LEO) environment. However, mechanical damage on AO‐resistant coatings can expose the underlying polymers to AO erosion, shortening their service life. In this study, the fabrication of durable AO‐resistant coatings that are capable of autonomously healing mechanical damage under LEO environment is presented. The self‐healing AO‐resistant coatings are comprised of 2‐ureido‐4[1H]‐pyrimidinone (UPy)‐functionalized polyhedral oligomeric silsesquioxane (POSS) (denoted as UPy‐POSS) that forms hydrogen‐bonded three‐dimensional supramolecular polymers. The UPy‐POSS supramolecular polymers can be conveniently deposited on polyimides by a hot pressing process. The UPy‐POSS polymeric coatings are mechanically robust, thermally stable, and transparent and have a strong adhesion toward polyimides to endure repeated bending/unbending treatments and thermal cycling. The UPy‐POSS polymeric coatings exhibit excellent AO attack resistance because of the formation of epidermal SiO2 layer after AO exposure. Due to the reversibility of the quadruple hydrogen bonds between UPy motifs, the UPy‐POSS polymeric coatings can rapidly heal mechanical damage such as cracks at 80 °C or under LEO environment to restore their original AO‐resistant function.
Self‐Healing Asphalt Review: From Idea to Practice
Authors: Xu Shi , García Alvaro , Su Junfeng , Liu Quantao , Tabaković Amir , Schlangen Erik
Published: July 2018

In recent decades, researchers have revealed the great healing potential of asphalt and proposed various novel methods to inspire and improve the self‐healing capacity of asphalt aimed to prolong the service life of asphalt pavement. In this review, up to date research progresses in induction healing and embedded rejuvenator encapsulation are presented, respectively. Meanwhile, the trial section applications of induction healing and capsule healing are highlighted, which show promising results. Finally, some recommendations for the future development of self‐healing asphalt are proposed.
2D Material Microcavity Light Emitters: To Lase or Not to Lase?
Authors: Reeves Lewis , Wang Yue , Krauss Thomas F.
Published: July 2018

Atomically thin layers of transition metal dichalcogenides (TMDs) are of great interest to the photonics community because of their unique optical properties. For example, in conjunction with microring or photonic crystal microresonators, they readily form microcavity light emitters. A number of configurations are now presented that apparently meet the conditions for lasing, yet there is considerable debate in the community as to whether lasing is actually achieved. By employing a very comprehensive set of assessment criteria, herein is shown that none of the TMD devices meet all the conditions for lasing, despite some very convincing data being presented. These findings are examined in the context of microcavity lasers based on III–V gain materials. Applications of TMD light emitters in the areas of quantum information and biosensing are also discussed to highlight areas where lasing action is not necessarily required.
Dopant/Semiconductor/Electret Trilayer Architecture for High‐Performance Organic Field‐Effect Transistors
Authors: Wei Peng , Hu Yupeng , Zhu Yuanwei , Jiang Yihang , Feng Xiaoshan , Li Shengtao , Bu Laju , Yang Xiaoniu , Lu Guanghao
Published: July 2018

Polycrystalline organic semiconductors are widely used for thin‐film organic electronics; however, such films are usually featured with charge traps due to various crystalline defects and domain boundaries. Chemical doping and applying external electric field are two representative methods to fill traps and induce free charges to modulate charge transport behaviors. However, for organic field‐effect transistors (OFETs) with high threshold voltages usually induced by charge traps, increasing doping concentration and electric field are frequently inaccessible, energy‐consuming, or even deteriorative to device performance. In this work, using the organic semiconductor 2,7‐dialkyl[1]benzothieno[3,2‐b][1]benzothiophene, a combined approach is proposed to synergistically utilize chemical doping and electret induced electric potential for OFET applications, via constructing dopant/semiconductor/electret trilayer architecture. Charges induced by dopant are mainly confined near the dopant/semicondcutor interface, while electrostatic field provided by electret accumulates/depletes charges near semiconductor/electret interface. Although both of doping concentration and charge density in electret are relatively low, which is crucial to warrant high‐performance stable device, the performance of the OFETs is greatly modulated. Moreover, the dopant/semiconductor/electret trilayer structure is optically transparent. Using this method, high‐performance OFETs with field‐effect mobility of ≈6 cm2 V−1 s−1, subthreshold‐swing of 0.3 V decade−1, on–off ratio exceeding 106, and tunable threshold voltages are realized.
Effect of bevacizumab plus XELOX (CapeOX) chemotherapy on liver natural killer cell activity in colorectal cancer with resectable liver metastasis
Authors: Hirata Fumihiro , Ishiyama Kohei , Tanaka Yuka , Kobayashi Tsuyoshi , Hashimoto Masakazu , Saeki Yoshihiro , Ishida Nobuki , Taguchi Kazuhiro , Tanaka Junko , Arihiro Koji , Ohdan Hideki ,   Hiroshima Surgical Study Group of Clinical Oncology (HiSCO)
Published: July 2018

Aim

We investigated the chemotherapy effect of resectable colorectal cancer with liver metastasis (CRLM) on the function of intrahepatic immune cells.

Methods

We classified patients into adjuvant chemotherapy (bevacizumab+CapeOX) after hepatectomy group (group A) and neoadjuvant chemotherapy followed by hepatectomy group (group B), and collected peripheral blood mononuclear cells (PBMC) and liver mononuclear cells (LMNC) to ascertain phenotypic and functional differences.

Results

There were no significant differences in lymphocyte fractions of either PBMC or LMNC between groups, except for the significantly lower percentage of natural killer (NK) cells in LMNC in group B than in group A. Significantly higher percentage of natural‐killer group 2, member D (NKG2D)‐ positive NK cells in PBMC and percentage of tumor necrosis factor‐related apoptosis‐inducing ligand (TRAIL)‐, NKp30‐, and signal regulatory protein β (SIRPβ)‐positive NK cells in LMNC were found in group B. Furthermore, significantly higher expressions of NKG2D and SIRPβ in peripheral blood NK cells and of NKp46 and CD122 in liver NK cells were found in group B. When LMNC were incubated with interleukin (IL)‐2 in vitro, no difference was observed in the expression of these molecules in NK cells between groups. Consistently, there was no difference in the cytotoxic activity of those LMNC against a colon adenocarcinoma cell line between groups.

Conclusion

Colorectal cancer with liver metastasis patients treated with neoadjuvant chemotherapy showed enhanced expression of activation markers on peripheral blood and liver NK cells in comparison with patients who did not receive therapy; however, the difference in those function remains unclear. These results suggest that neoadjuvant chemotherapy does not have a negative impact on intrahepatic immune cells in resectable CRLM patients.
Sooty mangabeys scavenge on nuts cracked by chimpanzees and red river hogs—An investigation of inter‐specific interactions around tropical nut trees
Authors: van Pinxteren Bryndan O.C.M. , Sirianni Giulia , Gratton Paolo , Després‐Einspenner Marie‐Lyne , Egas Martijn , Kühl Hjalmar , Lapuente Juan , Meier Amelia C. , Janmaat Karline R.L.
Published: July 2018

Carrion scavenging is a well‐studied phenomenon, but virtually nothing is known about scavenging on plant material, especially on remnants of cracked nuts. Just like meat, the insides of hard‐shelled nuts are high in energetic value, and both foods are difficult to acquire. In the Taï forest, chimpanzees (Pan troglodytes) and red river hogs (Potamochoerus porcus) crack nuts by using tools or strong jaws, respectively. In this study, previously collected non‐invasive camera trap data were used to investigate scavenging by sooty mangabeys (Cercocebus atys), two species of Guinea fowl (Agelestres meleagrides; Guttera verreauxi), and squirrels (Scrunidaespp.) on the nut remnants cracked by chimpanzees and red river hogs. We investigated how scavengers located nut remnants, by analyzing their visiting behavior in relation to known nut‐cracking events. Furthermore, since mangabeys are infrequently preyed upon by chimpanzees, we investigated whether they perceive an increase in predation risk when approaching nut remnants. In total, 190 nut‐cracking events were observed in four different areas of Taï National Park, Ivory Coast. We could confirm that mangabeys scavenged on the nuts cracked by chimpanzees and hogs and that this enabled them to access food source that would not be accessible otherwise. We furthermore found that mangabeys, but not the other species, were more likely to visit nut‐cracking sites after nut‐cracking activities than before, and discuss the potential strategies that the monkeys could have used to locate nut remnants. In addition, mangabeys showed elevated levels of vigilance at the chimpanzee nut‐cracking sites compared with other foraging sites, suggesting that they perceived elevated danger at these sites. Scavenging on remnants of cracked nuts is a hitherto understudied type of foraging behavior that could be widespread in nature and increases the complexity of community ecology in tropical rainforests.
Pressure‐Tuneable Visible‐Range Band Gap in the Ionic Spinel Tin Nitride
Authors: Kearney John S. C. , Graužinytė Miglė , Smith Dean , Sneed Daniel , Childs Christian , Hinton Jasmine , Park Changyong , Smith Jesse S. , Kim Eunja , Fitch Samuel D. S. , Hector Andrew L. , Pickard Chris J. , Flores‐Livas José A. , Salamat Ashkan
Published: July 2018

The application of pressure allows systematic tuning of the charge density of a material cleanly, that is, without changes to the chemical composition via dopants, and exploratory high‐pressure experiments can inform the design of bulk syntheses of materials that benefit from their properties under compression. The electronic and structural response of semiconducting tin nitride Sn3N4 under compression is now reported. A continuous opening of the optical band gap was observed from 1.3 eV to 3.0 eV over a range of 100 GPa, a 540 nm blue‐shift spanning the entire visible spectrum. The pressure‐mediated band gap opening is general to this material across numerous high‐density polymorphs, implicating the predominant ionic bonding in the material as the cause. The rate of decompression to ambient conditions permits access to recoverable metastable states with varying band gaps energies, opening the possibility of pressure‐tuneable electronic properties for future applications.
Genome‐Based Identification of a Plant‐Associated Marine Bacterium as a Rich Natural Product Source
Authors: Ueoka Reiko , Bhushan Agneya , Probst Silke I. , Bray Walter M. , Lokey R. Scott , Linington Roger G. , Piel Jörn
Published: July 2018

The large number of sequenced bacterial genomes provides the opportunity to bioinformatically identify rich natural product sources among previously neglected microbial groups. Testing this discovery strategy, unusually high biosynthetic potential was suggested for the Oceanospirillales member Gynuella sunshinyii, a Gram‐negative marine bacterium from the rhizosphere of the halophilic plant Carex scabrifolia. Its genome contains numerous unusual biosynthetic gene clusters for diverse types of metabolites. Genome‐guided isolation yielded representatives of four different natural product classes, of which only alteramide A was known. Cytotoxic lacunalides were identified as products of a giant trans‐acyltransferase polyketide synthase gene cluster, one of six present in this strain. Cytological profiling against HeLa cells suggested that lacunalide A disrupts CDK signaling in the cell cycle. In addition, chemical studies on model compounds were conducted, suggesting the structurally unusual ergoynes as products of a conjugated diyne–thiourea cyclization reaction.
A Photoactivatable BODIPY Probe for Localization‐Based Super‐Resolution Cellular Imaging
Authors: Wijesooriya Chamari S. , Peterson Julie A. , Shrestha Pradeep , Gehrmann Elizabeth J. , Winter Arthur H. , Smith Emily A.
Published: July 2018

The synthesis and application of a photoactivatable boron‐alkylated BODIPY probe for localization‐based super‐resolution microscopy is reported. Photoactivation and excitation of the probe is achieved by a previously unknown boron‐photodealkylation reaction with a single low‐power visible laser and without requiring the addition of reducing agents or oxygen scavengers in the imaging buffer. These features lead to a versatile probe for localization‐based microscopy of biological systems. The probe can be easily linked to nucleophile‐containing molecules to target specific cellular organelles. By attaching paclitaxel to the photoactivatable BODIPY, in vitro and in vivo super‐resolution imaging of microtubules is demonstrated. This is the first example of single‐molecule localization‐based super‐resolution microscopy using a visible‐light‐activated BODIPY compound as a fluorescent probe.
One‐Dimensional Arsenic Allotropes: Polymerization of Yellow Arsenic Inside Single‐Wall Carbon Nanotubes
Authors: Hart Martin , Chen Ji , Michaelides Angelos , Sella Andrea , Shaffer Milo S. P. , Salzmann Christoph G.
Published: July 2018

The pnictogen nanomaterials, including phosphorene and arsenene, display remarkable electronic and chemical properties. Yet, the structural diversity of these main group elements is still poorly explored. Here we fill single‐wall carbon nanotubes with elemental arsenic from the vapor phase. Using electron microscopy, we find chains of highly reactive As4 molecules as well as two new one‐dimensional allotropes of arsenic: a single‐stranded zig‐zag chain and a double‐stranded zig‐zag ladder. These linear structures are important intermediates between the gas‐phase clusters of arsenic and the extended sheets of arsenene. Raman spectroscopy indicates weak electronic interaction between the arsenic and the nanotubes which implies that the formation of the new allotropes is driven primarily by the geometry of the confinement. The relative stabilities of the new arsenic structures are estimated computationally. Band‐gap calculations predict that the insulating As4 chains become semiconducting, once converted to the zig‐zag ladder, and form a fully metallic allotrope of arsenic as the zig‐zag chain.
Rationally Designed Semisynthetic Natural Product Analogues for Stabilization of 14‐3‐3 Protein–Protein Interactions
Authors: Andrei Sebastian A. , de Vink Pim , Sijbesma Eline , Han Ling , Brunsveld Luc , Kato Nobuo , Ottmann Christian , Higuchi Yusuke
Published: July 2018

The natural product family of fusicoccanes are stabilizers of 14‐3‐3 mediated protein–protein interactions (PPIs), some of which possess antitumor activity. In this study, the first use of molecular dynamics (MD) to rationally design PPI stabilizers with increased potency is presented. Synthesis of a focused library, with subsequent characterization by fluorescence polarization, mutational studies, and X‐ray crystallography confirmed the power of the MD‐based design approach, revealing the potential for an additional hydrogen bond with the 14‐3‐3 protein to lead to significantly increased potency. Additionally, these compounds exert their action in a cellular environment with increased potency. The newly found polar interaction could provide an anchoring point for new small‐molecule PPI stabilizers. These results facilitate the development of fusicoccanes towards drugs or tool compounds, as well as allowing the study of the fundamental principles behind PPI stabilization.
Totalsynthese der Keramamide A und L aus einer gemeinsamen Vorstufe durch späte Indolsynthese und Revision ihrer Konfiguration
Authors: Junk Lukas , Kazmaier Uli
Published: July 2018

Die marinen Naturstoffe Keramamid A und L, Vertreter der Klasse der Anabaenopeptin‐artigen Peptide, wurden zum ersten Mal mittels einer konvergenten und flexiblen Route synthetisiert. Der Aufbau der substituierten Tryptophan‐Einheiten erfolgte hierbei ganz am Ende der Synthese am cyclischen Peptid, was die Herstellung beider Naturstoffe aus einer gemeinsamen Vorstufe ermöglichte. Durch die Synthese verschiedener Epimere konnte festgestellt werden, dass die ursprünglich postulierte relative Konfiguration beider Naturstoffe nicht der tatsächlichen entspricht.
Copper‐Catalyzed Tandem Hydrocupration and Diastereo‐ and Enantioselective Borylalkyl Addition to Aldehydes
Authors: Jang Won Jun , Yun Jaesook
Published: July 2018

We report the copper‐catalyzed stereoselective addition of in situ generated chiral boron‐α‐alkyl intermediates to various aldehydes including α,β‐unsaturated aldehydes under mild conditions. This tandem and multicomponent method facilitated the synthesis of enantiomerically enriched 1,2‐hydroxyboronates bearing contiguous stereocenters in good yield with high diastereo‐ and enantioselectivity up to a ratio greater than 98:2. In particular, α,β‐unsaturated aldehydes were successfully used as electrophiles in Cu−H catalysis through 1,2‐addition without significant reduction. The resulting 1,2‐hydroxyboronates were used in various transformations.
Combining Electrodeposition and Optical Microscopy for Probing Size‐Dependent Single‐Nanoparticle Electrochemistry
Authors: Lemineur Jean‐François , Noël Jean‐Marc , Ausserré Dominique , Combellas Catherine , Kanoufi Frédéric
Published: July 2018

Electrodeposition of nanoparticles (NPs) is a promising route for the preparation of highly electroactive nanostructured electrodes. By taking advantage of progressive electrodeposition, disordered arrays with a wide size distribution of Ag NPs are produced. Combined with surface‐reaction monitoring by using highly sensitive backside absorbing‐layer optical microscopy (BALM), such arrays offer a platform for screening size‐dependent electrochemistry at the single NP level. In particular, this strategy allows rationalizing the electrodeposition dynamics at the single‐NP level (>10 nm), up to the point of quantifying the presence of metal nanoclusters (<2 nm), and probing easier NP oxidation with size decrease, either through electrochemical or galvanic reactions.
Domino Pd0‐Catalyzed C(sp3)–H Arylation/Electrocyclic Reactions via Benzazetidine Intermediates
Authors: Rocaboy Ronan , Dailler David , Zellweger Florian , Neuburger Markus , Salomé Christophe , Clot Eric , Baudoin Olivier
Published: July 2018

The Pd0‐catalyzed C(sp3)‐H arylation of 2‐bromo‐N‐methylanilides leads to unstable benzazetidine intermediates that rearrange to benzoxazines through 4π electrocyclic ring‐opening and 6π electrocyclization. The introduction of a bulky, non‐activatable amide group on the nitrogen atom was key to favor the challenging reductive elimination step and disfavor undesired reaction pathways.
A Practical and General Amidation Method from Isocyanates Enabled by Flow Technology
Authors: Williams Jason D. , Kerr William J. , Leach Stuart G. , Lindsay David M.
Published: July 2018

The addition of carbon nucleophiles to isocyanates represents a conceptually flexible and efficient approach to the preparation of amides. This general synthetic strategy has, however, been relatively underutilized owing to narrow substrate tolerance and the requirement for less favourable reaction conditions. Herein, we disclose a high‐yielding, mass‐efficient, and scalable method with appreciable functional group tolerance for the formation of amides by reaction of Grignard reagents with isocyanates. Through the application of flow chemistry and the use of substoichiometric amounts of CuBr2, this process has been developed to encompass a broad range of substrates, including reactants found to be incompatible with previously published procedures.
A Multifunctional Dye‐doped Liquid Crystal Polymer Actuator: Light‐Guided Transportation, Turning in Locomotion, and Autonomous Motion
Authors: Ge Feijie , Yang Rong , Tong Xia , Camerel Franck , Zhao Yue
Published: July 2018

A strip of a liquid crystal elastomer doped with a near‐infrared dye with one side crosslinked monodomain and the other crosslinked polydomain along the thickness behaves like a multifunctional photoactuator without the need for a support. A flat strip with two ends fixed on substrate surface forms a moving bump under laser scanning, which can be used as light‐fueled conveyor to transport an object. Cutting off and laser scanning the bump with two free ends makes a soft and flexible millimeter‐scale crawler that can not only move straight and climb an inclined surface, but also undergo light‐guided turning to right or left as a result of combined out‐of‐plane and in‐plane actuation. Based on the self‐shadowing mechanism, with one end of the strip fixed on substrate surface, it can execute a variety of autonomous arm‐like movements under constant laser illumination, such as bending–unbending and twisting, depending on the laser incident angles with respect to the strip actuator.
Ion Hydration and Ion Pairing as Probed by THz Spectroscopy
Authors: Schwaab Gerhard , Sebastiani Federico , Havenith Martina
Published: July 2018

Ion hydration is of pivotal importance for many fundamental processes. Various spectroscopic methods are used to study the retardation of the hydration bond dynamics in the vicinity of anions and cations. Here we introduce THz‐FTIR spectroscopy as a powerful method to answer the open questions. We show through dissection of THz spectra that we can pinpoint characteristic absorption features that can be attributed to the rattling modes of strongly hydrating ions within their hydration cages as well as vibrationally induced charge fluctuations in the case of weakly hydrating ions. Further analysis yields information on anion–cation cooperativity, the size of the dynamic hydration shell, as well as the lifetimes of these collective ion‐hydration water modes and their connecting thermal bath states. Our study provides evidence for a non‐additive behavior, thus questioning the simplified Hofmeister model. THz spectroscopy enables ion pairing to be observed and quantified at a high salt concentration.
Arylfluorosulfate‐Based Electrophiles for Covalent Protein Labeling: A New Addition to the Arsenal
Authors: Martín‐Gago Pablo , Olsen Christian A.
Published: July 2018

Selective covalent modification of a targeted protein is a powerful tool in chemical biology and drug discovery, with applications ranging from identification and characterization of proteins and their functions to the development of targeted covalent inhibitors. Most covalent ligands contain an affinity motif and an electrophilic warhead that reacts with a nucleophilic residue of the targeted protein. Because the electrophilic warhead is prone to react and modify off‐target nucleophiles, its reactivity should be balanced carefully to maximize target selectivity. Arylfluorosulfates have recently emerged as latent electrophiles for selective labeling of context‐specific tyrosine and lysine residues in protein pockets. Here, we review the recent but intense introduction of arylfluorosulfates into the arsenal of available warheads for selective covalent modification of proteins. We highlight the untapped potential of this functional group for use in chemical biology and drug discovery.
Carbon Nitride Materials for Water Splitting Photoelectrochemical Cells
Authors: Volokh Michael , Peng Guiming , Barrio Jesús , Shalom Menny
Published: July 2018

Graphitic carbon nitride materials (CNs) have emerged as suitable photocatalysts and heterogeneous catalysts for various reactions thanks to their tunable band gap, suitable energy‐band position, high stability under harsh chemical conditions, and low cost. However, the utilization of CN in photoelectrochemical (PEC) and photoelectronic devices is still at an early stage owing to the difficulties in depositing high‐quality and homogenous CN layer on substrates, its wide band gap, poor charge‐separation efficiency, and low electronic conductivity. In this Minireview, we discuss the synthetic pathways for the preparation of various structures of CN on substrates and their underlying photophysical properties and current photoelectrochemical performance. The main challenges for CN incorporation into PEC cell are described, together with possible routes to overcome the standing limitations toward the integration of CN materials in PEC and other photoelectronic devices.
Total Synthesis of Keramamides A and L from a Common Precursor by Late‐Stage Indole Synthesis and Configurational Revision
Authors: Junk Lukas , Kazmaier Uli
Published: July 2018

The marine natural products keramamide A and L, members of the class of anabaenopeptin‐type peptides, were synthesized for the first time by a convergent and flexible route. The installation of the substituted tryptophan moieties was accomplished at the very end of the synthesis on the cyclic peptides, and thus enabled the synthesis of both natural products from one common precursor. The preparation of several epimers clearly indicates that the originally proposed relative configurations of both Keramamides A and L were not correct.
Visible Light Mediated Aryl Migration by Homolytic C−N Cleavage of Aryl Amines
Authors: Alpers Dirk , Cole Kevin P. , Stephenson Corey R. J.
Published: July 2018

The photocatalytic preparation of aminoalkylated heteroarenes from haloalkylamides via a 1,4‐aryl migration from nitrogen to carbon, conceptually analogous to a radical Smiles rearrangement, is reported. This method enables the substitution of amino groups in heteroaromatic compounds with aminoalkyl motifs under mild, iridium(III)‐mediated photoredox conditions. It provides rapid access to thienoazepinone, a pharmacophore present in multiple drug candidates for potential treatment of different conditions, including inflammation and psychotic disorders.
A Continuously Regenerable Chiral Ammonia Borane for Asymmetric Transfer Hydrogenations
Authors: Zhou Qiwen , Meng Wei , Yang Jing , Du Haifeng
Published: July 2018

A novel chiral ammonia borane was designed and developed through the dehydrogenation of ammonia borane with a chiral phosphoric acid, which was highly effective for the asymmetric transfer hydrogenation of imines and β‐enamino esters to afford high levels of reactivities and enantioselectivities. Significantly, this chiral ammonia borane can be continuously regenerated during the transfer hydrogenation with the assistance of water and ammonia borane, which made it possible to obtain satisfactory results using only 0.1 mol % of the chiral phosphoric acid. Notably, the role of chiral phosphoric acid is to produce the chiral ammonia borane.