bluuebunny/crossref_metadata_2025 huggingface dataset:
Retracted: The PI3K/AKT axis modulates AATF activity in Wilms’ tumor cells
Authors: Jing Peng , Zou Jiaqiong , Weng Kegui , Peng Pei
Published: August 2018

Previous studies have reported excessive expression of apoptosis‐antagonizing transcription factor (AATF) in various tumors, where it reinforces the generation and development of cancers and is linked to the clinical outcome. Nevertheless, the expression and influence of AATF in Wilms’ tumor (WT) is largely unknown. Here, we discovered that AATF expression was markedly increased in WT tissues as compared to the surrounding normal tissues. Elevated levels of AATF expression were related to tumor relapse and pulmonary metastasis, congruent with it being a predictor of clinical outcome in people suffering from WT. Proliferation, invasion, and migration of WT cells were suppressed by knockdown of AATF and promoted by AATF overexpression in vitro. Furthermore, the tumor generation capability of WT cells noticeably decreased after knockout of AATF in vivo. The phosphoinositide‐3‐kinase (PI3K)/AKT pathway modulated the activity of AATF in WT. The findings of our study indicate that AATF expression is increased in WT and can serve as a predictor of clinical outcome; in addition, it may enhance the development of WT via the PI3K/AKT axis and may be a promising marker for WT diagnosis and therapy.
Dosimetric comparison of pencil beam and Monte Carlo algorithms in conformal lung radiotherapy
Authors: Elcim Yelda , Dirican Bahar , Yavas Omer
Published: August 2018

Purpose

In this study, lung radiotherapy target volumes as well as critical organs such as the lungs, spinal cord, esophagus, and heart doses calculated using pencil beam (PB) and Monte Carlo (MC) algorithm‐based treatment planning systems (TPSs) were compared. The main aim was the evaluation of calculated dose differences between the PB and MC algorithms in a highly heterogeneous medium.

Methods

A total of 6 MV photon energy conformal treatment plans were created for a RANDO lung phantom using one PB algorithm‐based Precise Plan Release 2.16 TPS and one MC algorithm‐based Monaco TPS. Thermoluminescence dosimeters (TLDs) were placed into appropriate slices within the RANDO phantom and then irradiated with an Elekta‐Synergy® Linear Accelerator for dose verification. Doses were calculated for the V5, V10, V20, and mean lung doses (MLDs) in bilateral lungs and D50, D98, D2, and mean doses in the target volume (planning target volume, PTV).

Results

The minimum, maximum, and mean doses of the target volumes and critical organs in two treatment plans were compared using dose volume histograms (DVHs). The mean dose difference between the PB and MC algorithms for the PTV was 0.3%, whereas the differences in V5, V10, V20, and MLD were 12.5%, 15.8%, 14.4%, and 9.1%, respectively. The differences in PTV coverage between the two algorithms were 0.9%, 2.7% and 0.7% for D50, D98 and D2, respectively.

Conclusions

A comparison of the dose data acquired in this study reveals that the MC algorithm calculations are closer to the 60 Gy prescribed dose for PTV, while the difference between the PB and MC algorithms was found to be non‐significant. Because of the major difference arising from the dose calculation techniques by TPS that was observed in the MLD with significant medium heterogeneity, we recommend the use of the MC algorithm in such heterogeneous sites.
Fe, Cu‐Coordinated ZIF‐Derived Carbon Framework for Efficient Oxygen Reduction Reaction and Zinc–Air Batteries
Authors: Wang Zhihao , Jin Huihui , Meng Tian , Liao Ke , Meng Wenqian , Yang Jinlong , He Daping , Xiong Yuli , Mu Shichun
Published: August 2018

Zeolitic imidazole frameworks (ZIFs) offer rich platforms for rational design and construction of high‐performance nonprecious‐metal oxygen reduction reaction (ORR) catalysts owing to their flexibility, hierarchical porous structures, and high surface area. Herein, an Fe, Cu‐coordinated ZIF‐derived carbon framework (Cu@Fe‐N‐C) with a well‐defined morphology of truncated rhombic dodecahedron is facilely prepared by introducing Fe2+ and Cu2+ during the growth of ZIF‐8, followed by pyrolysis. The obtained Cu@Fe‐N‐C, with bimetallic active sites, large surface area, high nitrogen doping level, and conductive carbon frameworks, exhibits excellent ORR performance. It displays 50 mV higher half‐wave potential (0.892 V) than that of Pt catalysts in an alkaline medium and comparable performance to Pt catalysts in an acidic medium. In addition, it also has excellent durability and methanol resistance ability in both acidic and alkaline solutions, which makes it one of the best Pt‐free catalysts reported to date for ORR. Impressively, when being employed as a cathode catalyst in zinc–air batteries, Cu@Fe‐N‐C presents a higher peak power density of 92 mW cm−2 than that of Pt/C (74 mW cm−2) as well as excellent durability.
Dynamic Microcapsules with Rapid and Reversible Permeability Switching
Authors: Werner Jörg G. , Deveney Brendan T. , Nawar Saraf , Weitz David A.
Published: August 2018

Dynamic microcapsules are reported that exhibit shell membranes with fast and reversible changes in permeability in response to external stimuli. A hydrophobic anhydride monomer is employed in the thiol–ene polymerization as a disguised precursor for the acid‐containing shells; this enables the direct encapsulation of aqueous cargo in the liquid core using microfluidic fabrication of water‐in‐oil‐in‐water double emulsion drops. The poly(anhydride) shells hydrolyze in their aqueous environment without further chemical treatment, yielding cross‐linked poly(acid) microcapsules that exhibit trigger‐responsive and reversible property changes. The microcapsule shell can actively be switched numerous times between impermeable and permeable due to the exceptional mechanical properties of the thiol–ene network that prevent rupture or failure of the membrane, allowing it to withstand the mechanical stresses imposed on the capsule during the dynamic property changes. The permeability and molecular weight cutoff of the microcapsules can dynamically be controlled with triggers such as pH and ionic environment. The reversibly triggered changes in permeability of the shell exhibit a response time of seconds, enabling actively adjustable release profiles, as well as on‐demand capture, trapping, and release of cargo molecules with molecular selectivity and fast on‐off rates.
Synchronous Tailoring Surface Structure and Chemical Composition of Li‐Rich–Layered Oxide for High‐Energy Lithium‐Ion Batteries
Authors: Wu Bing , Yang Xiukang , Jiang Xia , Zhang Yi , Shu Hongbo , Gao Ping , Liu Li , Wang Xianyou
Published: August 2018

Li‐rich–layered oxide is considered to be one of the most promising cathode materials for high‐energy lithium ion batteries. However, it suffers from poor rate capability, capacity loss, and voltage decay upon cycling that limits its utilization in practical applications. Surface properties of Li‐rich–layered oxide play a critical role in the function of batteries. Herein, a novel and successful strategy for synchronous tailoring surface structure and chemical composition of Li‐rich–layered oxide is proposed. Poor nickel content on the surface of carbonate precursor is initially prepared by a facile treatment of NH3·H2O, which can retain at a certain low amount on the surface in the final lithiated Li‐rich–layered oxide after a solid‐phase reaction process. Moreover, a phase‐gradient outer layer with “layered‐coexisting phase‐spinel” structure toward to the outside surface is self‐induced and formed synchronously based on poor nickel surface of the precursor. Electrochemical tests reveal this unique surface enables excellent cycling stability, improved rate capability, and slight voltage decay of cathodes. The finding here sheds light on a universal principle both for masterly tailoring surface structure and chemical composition at the same time for improving electrochemical performance of electrode materials.
A Thermosetting Oil for Droplet‐Based Real‐Time Monitoring of Digital PCR and Cell Culture
Authors: Wu Wenshuai , Zhou Shufang , Hu Jiumei , Wang Guoping , Ding Xiong , Gou Tong , Sun Jingjing , Zhang Tao , Mu Ying
Published: August 2018

Real‐time observation of small volumes helps to understand phenomena ranging from reaction kinetics to cellular heterogeneity. However, high‐throughput real‐time monitoring systems based on droplets are rarely reported due to droplet motion and coalescence. Herein, a thermosetting oil is developed as a continuous phase to solve these problems through transforming into elastic solid after droplet generation. The thermosetting oil consists of silicon oil, nonionic surfactant, vinyl silicone oil, hydrosilicone oil, and Pt catalyst. Using Pt as the catalyst, the polymerization of this mixture can be accomplished in 72 min and 37 s at 37 and 95 °C, respectively, based on the hydrosilation of vinyl silicone oil and hydrosilicone oil without other inducers (e.g., UV, Ca2+). Droplet‐based real‐time monitoring of digital polymerase chain reaction (PCR) and cell culture is successfully achieved using this thermosetting oil, demonstrating that droplets motion and coalescence can be eliminated by the crosslinking material without the influence on bioreactions. In addition, the PCR products can be totally recovered from microcapsules created by this oil for further analysis. Thus, the newly developed oil allows real‐timely monitoring individual droplets in a high‐throughput manner, as well as has potential for other bioreactions and cell‐based assays.
In Situ Formation of Copper‐Based Hosts Embedded within 3D N‐Doped Hierarchically Porous Carbon Networks for Ultralong Cycle Lithium–Sulfur Batteries
Authors: Yu Qiuhong , Lu Yang , Luo Rongjie , Liu Xianming , Huo Kaifu , Kim Jang‐Kyo , He Jun , Luo Yongsong
Published: August 2018

Lithium–sulfur (Li–S) batteries are promising energy storage systems due to their large theoretical energy density of 2600 Wh kg−1 and cost effectiveness. However, the severe shuttle effect of soluble lithium polysulfide intermediates (LiPSs) and sluggish redox kinetics during the cycling process cause low sulfur utilization, rapid capacity fading, and a low coulombic efficiency. Here, a 3D copper, nitrogen co‐doped hierarchically porous graphitic carbon network developed through a freeze‐drying method (denoted as 3D Cu@NC‐F) is prepared, and it possesses strong chemical absorption and electrocatalytic conversion activity for LiPSs as highly efficient sulfur host materials in Li–S batteries. The porous carbon network consisting of 2D cross‐linked ultrathin carbon nanosheets provides void space to accommodate volumetric expansion upon lithiation, while the Cu, N‐doping effect plays a critical role for the confinement of polysulfides through chemical bonding. In addition, after sulfuration of Cu@NC‐F network, the in situ grown copper sulfide (CuxS) embedded within CuxS@NC/S‐F composite catalyzes LiPSs conversion during reversible cycling, resulting in low polarization and fast redox reaction kinetics. At a current density of 0.1 C, the CuxS@NC/S‐F composites' electrode exhibits an initial capacity of 1432 mAh g−1 and maintains 1169 mAh g−1 after 120 cycles, with a coulombic efficiency of nearly 100%.
A pH‐Mediated Electronic Wound Dressing for Controlled Drug Delivery
Authors: Kiaee Gita , Mostafalu Pooria , Samandari Mohamadmahdi , Sonkusale Sameer
Published: August 2018

Topical administration of drugs in a timely manner according to the physiological need at the wound site can enhance the healing rate of chronic wounds. Herein, an electronic wound dressing that enables active topical drug delivery in response to electrically induced pH change is demonstrated for potential treatment of chronic wounds. In this platform, the pH of the dressing is controlled using an electrical field. This allows precise electrical control over the temporal profile of pH‐mediated drug release. This engineered dressing is comprised of microfabricated electrodes serving as anode and cathode, a pH sensitive hydrogel, and controlled electronic circuitry. The anode is coated with a pH sensitive poly(ethylene glycol)‐diacrylate/Laponite hydrogel layer containing drug loaded chitosan nanoparticles (ChPs). Applying a DC voltage between the electrodes results in a local change in pH near the electrodes. In basic environments found near the anode, the ChPs release their drug due to the dehydration process, while in acidic environments the release profile is negligible. Turning off the DC voltage results in immediate pH recovery and cessation of drug release. The biocompatibility of the dressing has also been confirmed—the pH shift resulting from application of DC voltage does not affect the wound pH significantly.
Control of Domain Structures in Multiferroic Thin Films through Defect Engineering
Authors: Li Linze , Jokisaari Jacob R. , Zhang Yi , Cheng Xiaoxing , Yan Xingxu , Heikes Colin , Lin Qiyin , Gadre Chaitanya , Schlom Darrell G. , Chen Long‐Qing , Pan Xiaoqing
Published: August 2018

Domain walls (DWs) have become an essential component in nanodevices based on ferroic thin films. The domain configuration and DW stability, however, are strongly dependent on the boundary conditions of thin films, which make it difficult to create complex ordered patterns of DWs. Here, it is shown that novel domain structures, that are otherwise unfavorable under the natural boundary conditions, can be realized by utilizing engineered nanosized structural defects as building blocks for reconfiguring DW patterns. It is directly observed that an array of charged defects, which are located within a monolayer thickness, can be intentionally introduced by slightly changing substrate temperature during the growth of multiferroic BiFeO3 thin films. These defects are strongly coupled to the domain structures in the pretemperature‐change portion of the BiFeO3 film and can effectively change the configuration of newly grown domains due to the interaction between the polarization and the defects. Thus, two types of domain patterns are integrated into a single film without breaking the DW periodicity. The potential use of these defects for building complex patterns of conductive DWs is also demonstrated.
Directed Molecular Collection by E‐Jet Printed Microscale Chemical Potential Wells in Hydrogel Films
Authors: Zhang Shiyan , Kieffer Spencer J. , Zhang Chunjie , Alleyne Andrew G. , Braun Paul V.
Published: August 2018

A facile approach to locally concentrate analytes of interest will significantly enhance miniaturized, integrated chemical‐analysis systems. Here, the directed analyte transport and concentration using ≈200 µm‐diameter E‐jet printed chemical potential wells in a polyacrylamide hydrogel is demonstrated. Using a cationic well as the model system, anionic analytes are accumulated into a microscale area with a local concentration enhancement of >50‐fold relative to the surrounding area. By downscaling the diameter of the chemical potential well from a few millimeters to 100s of micrometers, it is found, using both fluorescence and Raman microscopy, that the molecular collection capacity of the well is greatly improved. Additionally, it is shown that molecules can be simultaneously transported and concentrated to arrays of microscale regions using an array of microscale chemical potential wells. This approach enhances many‐fold the limit of detection, enables the formation of microscale potential well arrays with a variety of chemical properties, and provides a novel microscale molecular manipulation technique as an alternative to traditional microfluidic‐based systems.
2D Magnetic Mesocrystals for Bit Patterned Media
Authors: Guo Shanshan , Xu Feng , Wang Baomin , Wang Ning , Yang Huali , Dhanapal Pravarthana , Xue Fei , Wang Junling , Li Run‐Wei
Published: August 2018

Bit patterned media exhibits great potential in satisfying the increasing demand for higher information storage density, but the present media fabrication technique is complicated. Here, a 2D magnetic mesocrystal with monodisperse CoFe2O4 (CFO) nanocrystals is fabricated through a combination of nanoseeds layer growth and oxides self‐assembly method. The monodisperse CFO nanomagnets protrude from the substrate surface with perfect crystal facets, specific crystallographic orientation, and are fully relaxed. Systematic magnetic characterizations, such as dynamic cantilever magnetometry for single CFO nanocrystal, magnetic force microscopy, and superconducting quantum interference device magnetometry for large area, reveal the novel tilted magnetic anisotropy and the switchable single domain state. This work provides a new way to fabricate bit patterned media with controlled material structure simply by a nanoseeds‐mediated self‐assembly method.
Light Emission Properties of 2D Transition Metal Dichalcogenides: Fundamentals and Applications
Authors: Zheng Weihao , Jiang Ying , Hu Xuelu , Li Honglai , Zeng Zhouxiaosong , Wang Xiao , Pan Anlian
Published: August 2018

2D transition metal dichalcogenides (2D TMDs) with energy bandgaps covering the visible and near infrared spectral region have enormous advantages in various photonic and optoelectronic applications, such as light emitting devices, transistors, photovoltaic devices, photodetectors, and nanocavity lasers. Understanding the mechanisms and controlling the optical properties of 2D TMDs is of crucial importance for further applications in integrated photonics. This review focuses on the light emission properties of 2D TMDs and their heterojunctions (HJs), including the fundamentals, tunability, and device applications. The band structures and excitonic properties related to light emission in 2D TMDs are discussed. The approaches to control, tune, and enhance light emission are also discussed. Subsequently, the light emission phenomena in 2D TMD HJs and their mechanisms associated with interlayer exciton, charge transfer, and energy transfer processes are described. Finally, the future potentials and challenges in TMD photonics are presented.
Improving the Stability of an RT‐NaS Battery via In Situ Electrochemical Formation of Protective SEI on a Sulfur–Carbon Composite Cathode
Authors: Lee Hwon‐gi , Lee Jung Tae , Eom KwangSup
Published: August 2018

The room temperature sodium sulfur battery (RT‐NaS) has attracted considerable attention as a next‐generation energy storage system due to its low cost and high specific energy and the abundance of sodium and sulfur. However, the sulfur‐based cathode in RT‐NaS always undergoes dissolution of polysulfides during the cycle, which limits the utilization of active material and the stability of the RT‐NaS. In this study, the authors report an economical and simple method to suppress the dissolution of polysulfides by forming an artificial protective solid electrolyte interphase (SEI) on the cathode surface using an in situ electrochemical treatment with a fluoroethylene carbonate (FEC) electrolyte additive. The artificially formed SEI has a thickness of ≈20 nm and contains fluoride anions that improve electrical conductivity and mechanical stability. The RT‐NaS full cell with the sulfur–carbon cathode and protective SEI exhibits a 0.1 VNa+/Na lower electrochemical polarization for desodiation, and SEI and electrical resistances that are 23% and 45% lower, respectively, than those of untreated NaS. These improvements lead to a capacity increase of ≈120% (270 to 590 mAh g−1 at the 50th cycle) and a high Coloumbic efficiency of 99.5% in the high‐rate cyclability test of the 2 C rate over 200 cycles.
Enhanced CO2/CH4 Separation Performance of a Mixed Matrix Membrane Based on Tailored MOF‐Polymer Formulations
Authors: Liu Yang , Liu Gongping , Zhang Chen , Qiu Wulin , Yi Shouliang , Chernikova Valeriya , Chen Zhijie , Belmabkhout Youssef , Shekhah Osama , Eddaoudi Mohamed , Koros William
Published: August 2018

Membrane‐based separations offer great potential for more sustainable and economical natural gas upgrading. Systematic studies of CO2/CH4 separation over a wide range of temperatures from 65 °C (338 K) to as low as −40 °C (233 K) reveals a favorable separation mechanism toward CO2 by incorporating Y‐fum‐fcu‐MOF as a filler in a 6FDA‐DAM polyimide membrane. Notably, the decrease of the temperature from 308 K down to 233 K affords an extremely high CO2/CH4 selectivity (≈130) for the hybrid Y‐fum‐fcu‐MOF/6FDA‐DAM membrane, about four‐fold enhancement, with an associated CO2 permeability above 1000 barrers. At subambient temperatures, the pronounced CO2/CH4 diffusion selectivity dominates the high permeation selectivity, and the enhanced CO2 solubility promotes high CO2 permeability. The differences in adsorption enthalpy and activation enthalpy for diffusion between CO2 and CH4 produce the observed favorable CO2 permeation versus CH4. Insights into opportunities for using mixed‐matrix membrane‐based natural gas separations at extreme conditions are provided.
Fabrication of Hierarchical Potassium Titanium Phosphate Spheroids: A Host Material for Sodium‐Ion and Potassium‐Ion Storage
Authors: Wei Zhixuan , Wang Dongxue , Li Malin , Gao Yu , Wang Chunzhong , Chen Gang , Du Fei
Published: August 2018

Identifying suitable electrode materials for sodium‐ion and potassium‐ion storage holds the key to the development of earth‐abundant energy‐storage technologies. This study reports an anode material based on self‐assembled hierarchical spheroid‐like KTi2(PO4)3@C nanocomposites synthesized via an electrospray method. Such an architecture synergistically combines the advantages of the conductive carbon network and allows sufficient space for the infiltration of the electrolyte from the porous structure, leading to an impressive electrochemical performance, as reflected by the high reversible capacity (283.7 mA h g−1 for Na‐ion batteries; 292.7 mA h g−1 for K‐ion batteries) and superior rate capability (136.1 mA h g−1 at 10 A g−1 for Na‐ion batteries; 133.1 mA h g−1 at 1 A g−1 for K‐ion batteries) of the resulting material. Moreover, the different ion diffusion behaviors in the two systems are revealed to account for the difference in rate performance. These findings suggest that KTi2(PO4)3@C is a promising candidate as an anode material for sodium‐ion and potassium‐ion batteries. In particular, the present synthetic approach could be extended to other functional electrode materials for energy‐storage materials.
Self‐Assemble and In Situ Formation of Ni1−xFexPS3 Nanomosaic‐Decorated MXene Hybrids for Overall Water Splitting
Authors: Du Cheng‐Feng , Dinh Khang Ngoc , Liang Qinghua , Zheng Yun , Luo Yubo , Zhang Jianli , Yan Qingyu
Published: August 2018

Herein, the authors present the development of novel 0D–2D nanohybrids consisting of a nickel‐based bimetal phosphorus trisulfide (Ni1−xFexPS3) nanomosaic that decorates on the surface of MXene nanosheets (denoted as NFPS@MXene). The nanohybrids are obtained through a facile self‐assemble process of transition metal layered double hydroxide (TMLDH) on MXene surface; followed by a low temperature in situ solid‐state reaction step. By tuning the Ni:Fe ratio, the as‐synthesized NFPS@MXene nanohybrids exhibit excellent activities when tested as electrocatalysts for overall water splitting. Particularly, with the initial Ni:Fe ratio of 7:3, the obtained Ni0.7Fe0.3PS3@MXene nanohybrid reveals low overpotential (282 mV) and Tafel slope (36.5 mV dec−1) for oxygen evolution reaction (OER) in 1 m KOH solution. Meanwhile, the Ni0.9Fe0.1PS3@MXene shows low overpotential (196 mV) for the hydrogen evolution reaction (HER) in 1 m KOH solution. When integrated for overall water splitting, the Ni0.7Fe0.3PS3@MXene || Ni0.9Fe0.1PS3@MXene couple shows a low onset potential of 1.42 V and needs only 1.65 V to reach a current density of 10 mA cm−2, which is better than the all noble metal IrO2 || Pt/C electrocatalyst (1.71 mV@10 mA cm−2). Given the chemical versatility of Ni1−xFexPS3 and the convenient self‐assemble process, the nanohybrids demonstrated in this work are promising for energy conversion applications.
Stinging hair morphology and wall biomineralization across five plant families: Conserved morphology versus divergent cell wall composition
Authors: Mustafa Adeel , Ensikat Hans‐Jürgen , Weigend Maximilian
Published: August 2018

Premise of the Study

Stinging hairs are striking examples of plant microengineering—the plant equivalent of the hypodermic syringe. The requisite mechanical properties are mostly achieved by cell wall mineralization. Stinging hairs of Urtica dioica (Urticaceae) are known to be mineralized with silica and calcium carbonate and those of Loasaceae also with calcium phosphate, but no comparative study has been provided across different taxa with stinging hairs.

Methods

Light microscopy and scanning electron microscopy (SEM) with cryo‐SEM and energy‐dispersive x‐ray spectroscopy were used to analyze morphology and biomineralization of stinging hairs of 43 species from the families Caricaceae, Euphorbiaceae, Loasaceae, Namaceae, and Urticaceae.

Key Results

Stinging hair morphology is similar across the taxa studied, in striking contrast to the divergent patterns of biomineralization. Trichome bases are mostly calcified, sometimes silicified, the shafts are mostly calcified, and the apices silicified (Urticaceae), and contain calcium phosphate (Caricaceae, Namaceae), both silica and calcium phosphate (some Loasaceae), or no minerals (Cnidoscolus, Euphorbiaceae). Some stinging hairs are superficially thinly coated with silica over a cell wall otherwise mineralized with calcium carbonate or calcium phosphate.

Conclusions

Mineralization patterns are surprisingly diverse and involve three different biominerals deposited in different parts of individual trichomes with calcium phosphate a common component. The physical properties of different wall regions of the stinging trichomes are thus fine‐tuned to optimize their function via modulation of wall thickness and differential element deposition. Similar function is apparently achieved through divergent wall compositions.
Femoral‐facial syndrome: A review of the literature and 14 additional patients including a monozygotic discordant twin pair
Authors: Lacarrubba‐Flores Maria Dora Jazmin , Carvalho Daniel Rocha , Ribeiro Erlane Marques , Moreno Carolina Araujo , Esposito Ana Carolina , Marson Fernando Augusto Lima , Loureiro Thereza , Cavalcanti Denise Pontes
Published: August 2018

Femoral‐facial syndrome (FFS, OMIM 134780), also known as femoral hypoplasia‐unusual face syndrome, is a rare sporadic syndrome associated with maternal diabetes, and comprising femoral hypoplasia/agenesis and a distinct facies characterized by micrognathia, cleft palate, and other minor dysmorphisms. The evaluation of 14 unpublished Brazilian patients, prompted us to make an extensive literature review comparing both sets of data. From 120 previously reported individuals with FFS, 66 were excluded due to: not meeting the inclusion criteria (n= 21); not providing sufficient data to ascertain the diagnosis (n= 29); were better assigned to another diagnosis (n= 3); and, being fetuses of the second trimester (n= 13) due to the obvious difficult to confirm a typical facies. Clinical‐radiological and family information from 54 typical patients were collected and compared with the 14 new Brazilian patients. The comparison between the two sets of patients did not show any relevant differences. Femoral involvement was most frequently hypoplasia, observed in 91.2% of patients, and the typical facies was characterized by micrognathia (97%), cleft palate (61.8%), and minor dysmorphisms (frontal bossing 63.6%, short nose 91.7%, long philtrum 94.9%, and thin upper lip 92.3%). Clubfoot (55.9%) was commonly observed. Other observed findings may be part of FFS or may be simply concurrent anomalies since maternal diabetes is a common risk factor. While maternal diabetes was the only common feature observed during pregnancy (50.8%), no evidence for a monogenic basis was found. Moreover, a monozygotic discordant twin pair was described reinforcing the absence of a major genetic factor associated with FFS.
Base‐Promoted Metal‐/Oxidant‐Free Three‐Component Tandem Annulation: A Strategy for the Construction of 2,4,5‐Trisubstituted Thiazoles via C−N Bond Cleavage of Amidines
Authors: Guo Wei , Zhao Mingming , Tan Wen , Zheng Lvyin , Tao Kailiang , Chen Luyan , Wang Mingfeng , Chen Deliang , Fan Xiaolin
Published: August 2018

A base‐promoted and metal‐/oxidant‐free one‐pot three‐component tandem annulation of amidines, aryl/alkyl isothiocyanates, and α‐bromoesters/ketones to 2,4,5‐trisubstituted thiazoles is described. This operationally simple protocol involves a base‐promoted C−N bond cleavage of amidines and features readily available starting materials, excellent functional group tolerance, and high step‐economy. It leads to the preparation of 2,4,5‐trisubstituted thiazoles efficiently and has potential applications in the field of drug screening and modification.
Copper‐Catalyzed Esterification of N‐Heteroaryl Methanes by Oxidative Dehydrogenation
Authors: Chen Xue , Liu Min , Liu Yongping , Chen Yi , Au Chak‐Tong , Yin Shuang‐Feng
Published: August 2018

Copper‐catalyzed cross‐dehydrogenative esterification of readily available N‐heteroaryl methanes with acids has been realized in good to excellent yields of target products. Through simple regulation of acid loading, it is possible to achieve mono‐ or di‐esterification of the methyl group with high chemoselectivity. The protocol is suitable for a wide scope of substrates and exhibits high step efficiency and atom economy. It is envisaged that this radical‐promoted one‐pot dual functionalization of C(sp3)−H bond is a general and facile strategy that would enrich the applications of N‐heteroaryl methanes.
Enzyme‐Mediated, Site‐Specific Protein Coupling Strategies for Surface‐Based Binding Assays
Authors: Ott Wolfgang , Durner Ellis , Gaub Hermann E.
Published: August 2018

Covalent surface immobilization of proteins for binding assays is typically performed non‐specifically via lysine residues. However, receptors that either have lysines near their binding pockets, or whose presence at the sensor surface is electrostatically disfavoured, can be hard to probe. To overcome these limitations and to improve the homogeneity of surface functionalization, we adapted and optimized three different enzymatic coupling strategies (4′‐phosphopantetheinyl transferase, sortase A, and asparaginyl endopeptidase) for biolayer interferometry surface modification. All of these enzymes can be used to site‐specifically and covalently ligate proteins of interest via short recognition sequences. The enzymes function under mild conditions and thus immobilization does not affect the receptors’ functionality. We successfully employed this enzymatic surface functionalization approach to study the binding kinetics of two different receptor–ligand pairs.
Die facettenreiche Reaktivität heterogener Einzelatom‐Katalysatoren
Authors: Mitchell Sharon , Vorobyeva Evgeniya , Pérez‐Ramírez Javier
Published: August 2018

Heterogene Einzelatom‐Katalysatoren (single‐atom heterogeneous catalysts, SACs) finden aufgrund ihrer maximalen Reaktivität pro Metallatom und der einfachen Wiederverwendbarkeit großen Anklang in der akademischen Welt. Jedoch führt der Weg von Nanopartikeln oder Metallclustern zu schließlich einzeln isolierten Atomen zwangsläufig zu Veränderungen in der Reaktivität der Katalysatoren, da die physikalische Struktur der aktiven Zentren verändert wird. Hier bewerten wir durch den Vergleich verschiedenster Anwendungen, ob die katalytische Leistungsfähigkeit durch die Verwendung von SACs verbessert oder verschlechtert wird. Zudem stellen wir fest, dass SACs im Allgemeinen einzigartige katalytische Zyklen aufweisen. Die Wahl des Trägermaterials ist maßgebend, da dieses sowohl die elektronischen als auch die sterischen Eigenschaften des Metallzentrums beeinflusst. Außerdem kann der Träger auch als Cokatalysator wirken. Für die Entwicklung neuer SACs, welche die begehrenswerten Eigenschaften ihrer homogenen oder heterogenen Vorgänger vereinen können, müssen all diese Aspekte berücksichtigt werden. Schließlich könnten SACs auch homogene Metallkomplexe in katalytischen Anwendungen ersetzen, bei denen sich die Heterogenisierung als besonders schwierig erweist.
Site‐Selective, Late‐Stage C−H 18F‐Fluorination on Unprotected Peptides for Positron Emission Tomography Imaging
Authors: Yuan Zheliang , Nodwell Matthew B. , Yang Hua , Malik Noeen , Merkens Helen , Bénard François , Martin Rainer E. , Schaffer Paul , Britton Robert
Published: August 2018

Peptides are often ideal ligands for diagnostic molecular imaging due to their ease of synthesis and tuneable targeting properties. However, labelling unmodified peptides with 18F for positron emission tomography (PET) imaging presents a number of challenges. Here we show the combination of photoactivated sodium decatungstate and [18F]‐N‐fluorobenzenesulfonimide effects site‐selective 18F‐fluorination at the branched position in leucine residues in unprotected and unaltered peptides. This streamlined process provides a means to directly convert native peptides into PET imaging agents under mild aqueous conditions, enabling rapid discovery and development of peptide‐based molecular imaging tools.
Learning from a Mineral Structure toward an Ultra‐Narrow‐Band Blue‐Emitting Silicate Phosphor RbNa3(Li3SiO4)4:Eu2+
Authors: Liao Hongxu , Zhao Ming , Molokeev Maxim S. , Liu Quanlin , Xia Zhiguo
Published: August 2018

Learning from natural mineral structures is an efficient way to develop potential host lattices for applications in phosphor converted (pc)LEDs. A narrow‐band blue‐emitting silicate phosphor, RbNa3(Li3SiO4)4:Eu2+ (RNLSO:Eu2+), was derived from the UCr4C4‐type mineral model. The broad excitation spectrum (320–440 nm) indicates this phosphor can be well matched with the near ultraviolet (n‐UV) LED chip. Owing to the UCr4C4‐type highly condensed and rigid framework, RNLSO:Eu2+ exhibits an extremely small Stokes shift and an unprecedented ultra‐narrow (full‐width at half‐maximum, FWHM=22.4 nm) blue emission band (λem=471 nm) as well as excellent thermal stability (96 %@150 °C of the initial integrated intensity at 25 °C). The color gamut of the as‐fabricated (pc)LEDs is 75 % NTSC for the application in liquid crystal displays from the prototype design of an n‐UV LED chip and the narrow‐band RNLSO:Eu2+ (blue), β‐SiAlON:Eu2+ (green), and K2SiF6:Mn4+ (red) components as RGB emitters.
Syntheses and Structures of Ruthenium Complexes Containing a Ru‐H‐Tl Three‐Center–Two‐Electron Bond
Authors: Bai Wei , Zhang Jing‐Xuan , Fan Ting , Tse Sunny Kai San , Shou Wangge , Sung Herman H. Y. , Williams Ian D. , Lin Zhenyang , Jia Guochen
Published: August 2018

Treatment of CpRuH(PP) (PP=dppm, dppe) with TlPF6 produced [CpRu(H)(Tl)(PP)]PF6. X‐ray diffraction and computational studies suggest that the complexes contain a Ru−H−Tl 3c–2e bond and can be viewed as the first σ‐complexes of period 6 main‐group hydrides [CpRu{η2‐(H−Tl)}(PP)]PF6 or [Tl{η2‐H−RuCp(PP)}]PF6. The complexes can be stored as a solid at room temperature for days without appreciable decomposition, but are unstable in solution and evolved to the trimetallic complexes [{CpRu(PP)}2(μ‐Tl)]PF6.
A Multi‐Component Sensor System for Detection of Amphiphilic Compounds
Authors: Xu Ming , Kelley Steven P. , Glass Timothy E.
Published: August 2018

Many biologically important compounds are amphiphilic in character. Glycolipids, for example, represent a biologically important class of amphiphiles. Receptors and sensors for such compounds must also be amphiphilic making them a challenge to prepare. Here, a cucurbit[8]uril (CB[8])‐based sensor system has been prepared and tested for detection of amphiphilic compounds. This multi‐component system consists: a CB[8], which acts as a hydrophobic lipid receptor, a hydrophilic pyridinium‐based carbohydrate receptor, and a fluorescent indicator. The system self‐assembles in aqueous solution. The pyridinium quenches the fluorescence of the indicator giving a strong turn‐on response when it is displaced by the analyte. The sensor system was characterized by NMR, X‐ray crystallography, and fluorescence titrations.
A Unified Approach to Couple Aromatic Heteronucleophiles to Azines and Pharmaceuticals
Authors: Anderson Ryan G. , Jett Brianna M. , McNally Andrew
Published: August 2018

Coupling aromatic heteronucleophiles to arenes is a common way to assemble drug‐like molecules. Many methods operate via nucleophiles intercepting organometallic intermediates, via Pd‐, Cu‐, and Ni‐catalysis, that facilitate carbon‐heteroatom bond formation and a variety of protocols. We present an alternative, unified strategy where phosphonium salts can replicate the behavior of organometallic intermediates. Under a narrow set of reaction conditions, a variety of aromatic heteronucleophile classes can be coupled to pyridines and diazines that are often problematic in metal‐catalyzed couplings, such as where (pseudo)halide precursors are unavailable in complex structures with multiple polar functional groups.
Two‐Color Valence‐to‐Core X‐ray Emission Spectroscopy Tracks Cofactor Protonation State in a Class I Ribonucleotide Reductase
Authors: Martinie Ryan J. , Blaesi Elizabeth J. , Bollinger J. Martin , Krebs Carsten , Finkelstein Kenneth D. , Pollock Christopher J.
Published: August 2018

Proton transfer reactions are of central importance to a wide variety of biochemical processes, though determining proton location and monitoring proton transfers in biological systems is often extremely challenging. Herein, we use two‐color valence‐to‐core X‐ray emission spectroscopy (VtC XES) to identify protonation events across three oxidation states of the O2‐activating, radical‐initiating manganese–iron heterodinuclear cofactor in a class I‐c ribonucleotide reductase. This is the first application of VtC XES to an enzyme intermediate and the first simultaneous measurement of two‐color VtC spectra. In contrast to more conventional methods of assessing protonation state, VtC XES is a more direct probe applicable to a wide range of metalloenzyme systems. These data, coupled to insight provided by DFT calculations, allow the inorganic cores of the MnIVFeIV and MnIVFeIII states of the enzyme to be assigned as MnIV(μ‐O)2FeIV and MnIV(μ‐O)(μ‐OH)FeIII, respectively.
Lowering Molecular Symmetry To Improve the Morphological Properties of the Hole‐Transport Layer for Stable Perovskite Solar Cells
Authors: Wang Xuchao , Zhang Jing , Yu Shuwen , Yu Wei , Fu Ping , Liu Xuan , Tu Dandan , Guo Xin , Li Can
Published: August 2018

Inspired by the structural feature of the classical hole‐transport material (HTM), Spiro‐OMeTAD, many analogues based on a highly symmetrical spiro‐core were reported for perovskite solar cells (PSCs). However, these HTMs were prone to crystallize because of the high molecular symmetry, forming non‐uniform films, unfavorable for the device stability and large‐area processing. By lowering the symmetry of spiro‐core, we report herein a novel spirobisindane‐based HTM, Spiro‐I, which could form amorphous films with high uniformity and morphological stability. Compared to the Spiro‐OMeTAD‐based PSCs, those containing Spiro‐I exhibit similar efficiencies for small area but higher ones for large area (1 cm2), and especially much higher air stability (retaining 80 % of initial PCE after 2400 h storage without encapsulation). Moreover, the Spiro‐I can be synthesized from a cheap starting material bisphenol A and used with a small amount for the device fabrication.
Scalable Wet Deposition of Zeolite AEI with a High Degree of Preferred Crystal Orientation
Authors: Huang Pei‐Sun , Lam Chon Hei , Su Chien‐You , Chen Yen‐Ru , Lee Wen‐Ya , Wang Da‐Ming , Hua Chi‐Chung , Kang Dun‐Yen
Published: August 2018

Producing zeolite films with controlled preferred orientation on an industrial scale is a long‐standing challenge. Herein we report on a scalable approach to the direct wet deposition of zeolite thin films and membranes while maintaining a high degree of control over the preferred crystal orientation. As a proof of concept, thin films comprising aluminophosphate zeolite AEI were cast on silicon wafer or porous alumina substrates. Electrical properties and separation performance of the zeolite thin films/membranes were engineered through controlling degree of preferred crystal orientation.
Spontaner metallfreier Wasserstofftransfer zwischen Amminboranen und Iminoboranen
Authors: Winner Lena , Ewing William C. , Geetharani K. , Dellermann Theresa , Jouppi Brian , Kupfer Thomas , Schäfer Marius , Braunschweig Holger
Published: August 2018

Wir berichten hier über den ersten spontanen und metallfreien Wasserstofftransfer zwischen Amminboran (NH3BH3) und Iminoboranen bei Raumtemperatur. DFT‐Rechnungen belegen einen konzertierten H+/H−‐Transfer von NH3BH3 mit einer Aktivierungsenergie weit unter der vergleichbarer Wasserstoffübertragungsreaktionen. Zudem konnten durch Umsetzung von Iminoboranen mit Amminboranen neue B,N‐disubstituierte Aminoborane isoliert werden, von denen bisher nur wenige Vertreter bekannt sind. Dieser erfolgreiche Wasserstofftransfer zu einem dehydrierten BN‐System könnte ein Ansatzpunkt für die Entwicklung neuartiger Systeme für Dehydrierungs‐ bzw. Rehydrierungsprozesse sein.
Site‐Selective Remote Radical C−H Functionalization of Unactivated C−H Bonds in Amides Using Sulfone Reagents
Authors: Xia Yong , Wang Lin , Studer Armido
Published: August 2018

A general and practical strategy for remote site‐selective functionalization of unactivated aliphatic C−H bonds in various amides by radical chemistry is introduced. C−H bond functionalization is achieved by using the readily installed N‐allylsulfonyl moiety as an N‐radical precursor. The in situ generated N‐radical engages in intramolecular 1,5‐hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C−H functionalized amides. The generality of the approach is documented by the successful remote C−N3, C−Cl, C−Br, C−SCF3, C−SPh, and C−C bond formation. Unactivated tertiary and secondary C−H bonds, as well as activated primary C−H bonds, can be readily functionalized by this method.
Total Synthesis of Epicolactone
Authors: Kravina Alberto G. , Carreira Erick M.
Published: August 2018

The biologically active and structurally complex secondary metabolite epicolactone is a member of the natural product pool found in cash crop endophytes of the genus Epicoccum. By exploiting inherent reactivity, a total synthesis of this highly oxygenated and polycyclic molecule met chemo‐ and regioselectivity challenges. The key buildup of complexity was accomplished via an intramolecular [2+2] photocycloaddition between a quinone and an electron‐deficient diene followed by a cyclobutane ring expansion. The use of a dioxene as an acyl anion equivalent and an intramolecular carbonyl methenylation furnished the natural product.
Straightforward α‐Amino Nitrile Synthesis Through Mo(CO)6‐Catalyzed Reductive Functionalization of Carboxamides
Authors: Trillo Paz , Slagbrand Tove , Adolfsson Hans
Published: August 2018

The selective reduction of amides into an intermediate hemiaminal catalyzed by Mo(CO)6 together with the inexpensive and easy to handle TMDS (1,1,3,3‐tetramethyldisiloxane) as reducing agent, followed by subsequent trapping of the hemiaminal with a cyanide source, allows for the straightforward synthesis of α‐amino nitriles. The methodology presented here, displays high levels of chemoselectivity allowing for the reduction of amides in the presence of functional groups such as ketones, imines, aldehydes, and acids, which affords a simple route for the synthesis of α‐amino nitriles with a broad scope of functionalities in high yields. Furthermore, the applicability of this methodology is demonstrated by scale up experiments and by derivatization of the target compounds into synthetically interesting products. The selective cyanation is successfully applied in late stage functionalizations of amide containing drugs and prolinol derivatives.
Die lokalen Aktivitäten von Hydroxidionen und Wasser bestimmen die Funktionsweise von auf Silber basierenden Sauerstoffverzehrkathoden
Authors: Botz Alexander , Clausmeyer Jan , Öhl Denis , Tarnev Tsvetan , Franzen David , Turek Thomas , Schuhmann Wolfgang
Published: August 2018

Lokale Änderungen der Ionenaktivitäten an der Oberfläche einer arbeitenden Sauerstoffverzehrkathode (SVK) wurden mittels elektrochemischer Rastermikroskopie gemessen. Während die SVK OH−‐Ionen unter Konsum von H2O durch elektrokatalytische Reduktion von O2 produziert, werden die Änderungen in den Ionenaktivitäten über eine positionierte Pt‐Mikroelektrode bestimmt. Die Empfindlichkeit der Platinelektrode wird durch die pH‐abhängige Reduktion von PtO gewährleistet. Dadurch kann auf eine vorherige Modifikation der Elektrode verzichtet werden. Diese Technik ermöglicht es, Änderungen der Koordination von H2O und OH−‐Ionen darzustellen sowie die lokale katalytische Aktivität zu evaluieren. Damit wird gezeigt, dass die elektrochemische Reaktion an sehr aktiven Katalysatoren einen starken Einfluss auf die Reaktionsumgebung haben kann.
The Crucial Role of Chlorinated Thiophene Orientation in Conjugated Polymers for Photovoltaic Devices
Authors: Wu Yanan , An Cunbin , Shi Lanlan , Yang Liyan , Qin Yunpeng , Liang Ningning , He Chang , Wang Zhaohui , Hou Jianhui
Published: August 2018

Chlorinated conjugated polymers not only show great potential for the realization of highly efficient polymer solar cells (PSCs) but also have simple and high‐yield synthetic routes and low‐cost raw materials available for their preparation. However, the study of the structure–property relationship of chlorinated polymers is lagging. Now two chlorinated conjugated polymers, PCl(3)BDB‐T and PCl(4)BDB‐T are investigated. When the polymers were used to fabricate PSCs with the nonfullerene acceptor (IT‐4F), surprisingly, the PCl(3)BDB‐T:IT‐4F‐based device exhibited a negligible power conversion efficiency (PCE) of 0.18 %, while the PCl(4)BDB‐T:IT‐4F‐based device showed an outstanding PCE of 12.33 %. These results provide new insight for the rational design and synthesis of novel chlorinated polymer donors for further improving the photovoltaic efficiencies of PSCs.
Direct Conversion of Alcohols into Alkenes by Dehydrogenative Coupling with Hydrazine/Hydrazone Catalyzed by Manganese
Authors: Das Uttam Kumar , Chakraborty Subrata , Diskin‐Posner Yael , Milstein David
Published: August 2018

We have developed unprecedented methods for the direct transformation of primary alcohols to alkenes in the presence of hydrazine, and for the synthesis of mixed alkenes by the reaction of alcohols with hydrazones. The reactions are catalyzed by a manganese pincer complex and proceed in absence of added base or hydrogen acceptors, liberating dihydrogen, dinitrogen, and water as the only byproducts. The proposed mechanism, based on preparation of proposed intermediates and control experiments, suggests that the transformation occurs through metal–ligand cooperative N−H activation of a hydrazone intermediate.
An Extremely Simple Method for Protecting Lithium Anodes in Li‐O2 Batteries
Authors: Zhang Xin , Zhang Qinming , Wang Xin‐Gai , Wang Chengyi , Chen Ya‐Nan , Xie Zhaojun , Zhou Zhen
Published: August 2018

Rechargeable Li‐O2 batteries have aroused much attention for their high energy density as a promising battery technology; however, the performance of the batteries is still unsatisfactory. Lithium anodes, as one of the most important part of Li‐O2 batteries, play a vital role in improving the cycle life of the batteries. Now, a very simple method is introduced to produce a protective film on lithium surface via chemical reactions between lithium metals and 1,4‐dioxacyclohexane. The film is mainly composed of ethylene oxide monomers and endows Li‐O2 batteries with enhanced cycling stability. The film could effectually reduce the morphology changes and suppress the parasitic reactions of lithium anodes. This simple approach provides a new strategy to protect lithium anodes in Li‐O2 batteries.