bluuebunny/crossref_metadata_2025 huggingface dataset:
A High‐Efficiency Organic Solar Cell Enabled by the Strong Intramolecular Electron Push–Pull Effect of the Nonfullerene Acceptor
Authors: Li Wanning , Ye Long , Li Sunsun , Yao Huifeng , Ade Harald , Hou Jianhui
Published: March 2018

Besides broadening of the absorption spectrum, modulating molecular energy levels, and other well‐studied properties, a stronger intramolecular electron push–pull effect also affords other advantages in nonfullerene acceptors. A strong push–pull effect improves the dipole moment of the wings in IT‐4F over IT‐M and results in a lower miscibility than IT‐M when blended with PBDB‐TF. This feature leads to higher domain purity in the PBDB‐TF:IT‐4F blend and makes a contribution to the better photovoltaic performance. Moreover, the strong push–pull effect also decreases the vibrational relaxation, which makes IT‐4F more promising than IT‐M in reducing the energetic loss of organic solar cells. Above all, a power conversion efficiency of 13.7% is recorded in PBDB‐TF:IT‐4F‐based devices.
A High‐Capacity O2‐Type Li‐Rich Cathode Material with a Single‐Layer Li2MnO3 Superstructure
Authors: Zuo Yuxuan , Li Biao , Jiang Ning , Chu Wangsheng , Zhang Hao , Zou Ruqiang , Xia Dingguo
Published: March 2018

A high capacity cathode is the key to the realization of high‐energy‐density lithium‐ion batteries. The anionic oxygen redox induced by activation of the Li2MnO3 domain has previously afforded an O3‐type layered Li‐rich material used as the cathode for lithium‐ion batteries with a notably high capacity of 250–300 mAh g−1. However, its practical application in lithium‐ion batteries has been limited due to electrodes made from this material suffering severe voltage fading and capacity decay during cycling. Here, it is shown that an O2‐type Li‐rich material with a single‐layer Li2MnO3 superstructure can deliver an extraordinary reversible capacity of 400 mAh g−1 (energy density: ≈1360 Wh kg−1). The activation of a single‐layer Li2MnO3 enables stable anionic oxygen redox reactions and leads to a highly reversible charge–discharge cycle. Understanding the high performance will further the development of high‐capacity cathode materials that utilize anionic oxygen redox processes.
Design and Fabrication of a Hierarchically Structured Scaffold for Tendon‐to‐Bone Repair
Authors: Zhu Chunlei , Pongkitwitoon Suphannee , Qiu Jichuan , Thomopoulos Stavros , Xia Younan
Published: March 2018

A hierarchically structured scaffold is designed and fabricated for facilitating tendon‐to‐bone repair. The scaffold is composed of three regions with distinct functions: (i) an array of channels to guide the in‐growth of cells and aligned deposition of collagen fibers, as well as integration of the scaffold with the tendon side, (ii) a region with a gradient in mineral composition to facilitate stress transfer between tendon and bone, and (iii) a mineralized inverse opal region to promote the integration of the scaffold with the underlying bone. Cell culture experiments confirm that adipose‐derived stromal cells are able to infiltrate and proliferate through the entire thickness of the scaffold without compromised cell viability. The seeded stem cells exhibit directed differentiation into tenocytes and osteoblasts along the mineral gradient as a response to the gradient in Young's modulus. This novel scaffold holds great promise to promote the formation of a functional tendon‐to‐bone attachment by offering a structurally and compositionally appropriate microenvironment for healing.
3D Nanoporous Gold‐Supported Pt Nanoparticles as Highly Accelerating Catalytic Au‐Pt Micromotors
Authors: Jiang Jin‐Zhi , Ren Ling‐Qing , Huang Yu‐Ping , Li Xiao‐Dong , Wu Shao‐Hua , Sun Jian‐Jun
Published: March 2018

A self‐supported, nanoporous gold microelectrode decorated with various nanoparticles can be used for real‐time electrochemical monitoring, and the high performance of these electrochemical biosensors originates from their unique and seamless solid/porous nanoarchitecture. In this work, new, 3D, nanoporous, gold‐supported Pt nanoparticles are fabricated by Au‐Zn alloying/dealloying and template membrane deposition methods to produce Au‐Pt micromotors with highly accelerated motion. The speed of the micromotors can reach 1025 µm s−1 in a 10% H2O2 solution, which is almost three times faster than unetched Au‐Pt micromotors. Four motion forms (circle, helical, circle and linear alternating, and linear) are demonstrated, and the speed of the circle motion is the fastest motion form. It is envisioned that the new fabrication method and enhanced motion can promote the micromotor efficiency for transport and delivery.
Widening the Temperature Range of Luminescent Thermometers through the Intra‐ and Interconfigurational Transitions of Pr3+
Authors: Brites Carlos D. S. , Fiaczyk Karolina , Ramalho João F. C. B. , Sójka Małgorzata , Carlos Luís D. , Zych Eugeniusz
Published: March 2018

In this study, it is shown how the temperature range of luminescent thermometers can be widened in an unprecedented way by combining the intra‐ and interconfigurational transitions of the Pr3+ ion in a single material. Using Sr2GeO4:Pr3+ crystalline powders as an illustrative example, the implementation of luminescence thermometry is reported in the broadest temperature range up to now (17–600 K) with a remarkable performance: maximum relative sensitivity values of 9.0% · K−1 (at 22 K, cryogenic range), 0.6% · K−1 (at 300 K, physiological range), and 0.5% · K−1 (at 600 K, high‐temperature range) and minimum temperature uncertainty of 0.1 K.
Wavenumber‐Splitting Metasurfaces Achieve Multichannel Diffusive Invisibility
Authors: Xu He‐Xiu , Zhang Lei , Kim Yongjune , Wang Guang‐Ming , Zhang Xiao‐Kuan , Sun Yunming , Ling Xiaohui , Liu Haiwen , Chen Zhining , Qiu Cheng‐Wei
Published: March 2018

The emerging invisibility schemes mainly adopt transformation optics, scattering cancellation, light diffusion, and metasurface‐based phase restoration techniques. However, those aforementioned invisibility achievements natively depend on the predefined curvature, polarization, frequency, and/or angle of the incident wave. Here, an invisibility strategy of using an ultrathin parabolic‐phase metasurface and its applications to achieve diffusive invisibility for dual‐polarization channels and multifrequency channels is reported. Such strategy can intrinsically split the wavenumber of the scattering wave and therein is termed as wavenumber‐splitting metasurface. For verification, two proof‐of‐concept examples are experimentally characterized. The first prototype manifests dual‐polarized near‐isotropic diffusive scattering immune from wide‐angle incidences. The second demonstration exhibits bifunctionality of combined diffusive invisibility and vortex scattering in dual‐polarization channels. In both cases, theoretical, numerical and experimental results agree well, illustrating a well‐separated triple‐band versatile scattering behavior. This approach addresses the fundamental issue of real invisibility under bistatic detection without complex optimization, thanks to the physical essence of numerous splitting wave vectors. Such strategy opens an upstream way to realize invisibility as well as holding the potentials for downstream applications such as stealth and camouflaging devices.
Silver‐Catalyzed Isocyanide Insertion into N−H Bond of Ammonia: [5+1] Annulation to Quinazoline Derivatives
Authors: Zhang Lingjuan , Li Juanjuan , Hu Zhongyan , Dong Jinhuan , Zhang Xian‐Ming , Xu Xianxiu
Published: March 2018

A silver‐catalyzed [5+1] annulation of o‐acylaryl isocyanides with ammonium acetate and hydroxlamine was developed for the efficient and practical synthesis of quinazolines and quinazoline 3‐oxides in good to excellent yields, respectively. The domino process involved an unprecedented isocyanide insertion into the N−H bond of ammonia or hydroxylamine and followed by condensation reaction at ambient conditions.

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Lewis‐acid Promoted Chemoselective Condensation of 2‐Aminobenzimidazoles or 3‐Aminoindazoles with 3‐Ethoxycyclobutanones to Construct Fused Nitrogen heterocycles
Authors: Kong Weiguang , Zhou Yao , Song Qiuling
Published: March 2018

A Lewis‐acid promoted chemoselective condensation of 2‐aminobenzimidazoles or 3‐aminoindazoles with 3‐ethoxycyclobutanones is presented. Diverse fused heterocycles benzo[4,5]‐imidazo[1,2‐a]pyrimidine and pyrimido[1,2‐b]‐indazole derivatives were obtained in moderate to high yields under mild conditions, the reaction mechanism of which was in sharp contrast to previous [3+3] annulation reaction of 3‐ethoxycyclobutanones.

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Recent Advances on Amino Acid Modifications via C–H Functionalization and Decarboxylative Functionalization Strategies
Authors: Mondal Santanu , Chowdhury Sushobhan
Published: March 2018

Over the recent decade tremendous interest has been developed on the synthetic modification of natural as well as non‐proteinogenic amino acids and non‐natural linkages due to their immensely important applications in proteomics, diagnosis, and drug delivery etc. They are synthetically important also. For example, due to the high natural abundance of enantiopure amino acids, they and their derivatives are regularly employed in the development of several interesting synthetic methods, total syntheses of biologically related structures as well as in ligand elaboration. Thus, the synthetic field possesses a direct impact on several basic and applied sciences. But up to date only limited numbers of reviews are available which either appeared almost half a decade earlier or covered very specific areas of this highly expanding topic. Many achievements have already been realized in this field in the meantime which urgently need to be documented. Therefore, to meet the need this review is intended to cover the emerging versatile synthetic methods on the modification of amino acids and related structures over the recent decade with the relevant details of their respective prospects and problems in the best possible systematic and concise manner. Wherever needed relevant mechanistic details are also described.

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Palladium‐Catalyzed Decarboxylative Cross‐Couplings of 1‐Boc‐3‐iodoazetidine: Regioselective Access to 2‐Alkynylazetidines, 3‐Alkynylazetidines and 3‐Vinylazetidines
Authors: Han Shuaijun , Ren Xiaoxiao , Wu Qingsong , Liang Apeng , Li Jingya , Zou Dapeng , Wu Yangjie , Wu Yusheng
Published: March 2018

The first palladium‐catalyzed decarboxylative coupling reactions of alkynyl carboxylic acids or α, β‐unsaturated carboxylic acids with 1‐Boc‐3‐iodoazetidine were described. The strategy could efficiently mediate β‐hydride elimination/migratory insertion sequence and selectively form 2‐alkynylazetidines (10 examples) and 3‐alkynylazetidines (15 examples) with high regioselectivity. The protocol provides convienient access to a variety of useful 3‐vinylazetidines in moderate yields (42%–72%) with good stereoselectivity. Notable advantages of this method include easy operation, mild reaction conditions, and wide substrate scope.

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Divergent Synthesis of Quinoline Derivatives via [5+1] Annulation of 2‐Isocyanochalcones with Nitroalkanes
Authors: Bao Lan , Liu Jinglin , Xu Liang , Hu Zhongyan , Xu Xianxiu
Published: March 2018

An unprecedented substrate‐dependent [5+1] annulation of 2‐isocyanochalcones with nitroalkanes was developed for the efficient synthesis of functionalized quinolines and 3‐nitrodihydroquinolines. This transformation delivers both the aromatic and dihydroquinolines by selectively elimination or retention of the nitro group. Moreover, 3‐nitroquinolines and tricyclic pyrrolo[2,3‐c]quinolines were conveniently constructed from the resulting 3‐nitrodihydroquinolines through a single operation, respectively.

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Additive‐Controlled Switchable Selectivity from Cyanobenzenes to 2‐Alkynylpyridines: Ruthenium(II)‐Catalyzed [2+2+2] Cycloadditions of Diynes and Alkynylnitriles
Authors: Bhatt Divya , Patel Neha , Chowdhury Hrishikesh , Bharatam Prasad V. , Goswami Avijit
Published: March 2018

A highly efficient additive‐dependent chemoselective protocol for the synthesis of fused cyanoarenes and 2‐alkynylpyridines has been developed by the reaction of 1,6‐diynes with alkynylnitriles using chloro(pentamethylcyclopentadienyl) (cyclooctadiyne)ruthenium(II) as catalyst in dimethoxyethane (DME). The course of the reaction can be drastically altered simply by adding a catalytic amount of AgOTf as an additive resulting in a comprehensive shift in product formation from cyanoarenes to 2‐alkynylpyridines. Theoretical studies clearly indicate that the neutral Ru‐complex is responsible for the formation of cyanobenzenes, whereas the in situ generated cationic Ru‐complex plays a crucial role in the 2‐alkynylpyridines formation.

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Trojan‐Horse‐Like Stimuli‐Responsive Microcapsules
Authors: Mou Chuan‐Lin , Wang Wei , Li Zhi‐Lu , Ju Xiao‐Jie , Xie Rui , Deng Nan‐Nan , Wei Jie , Liu Zhuang , Chu Liang‐Yin
Published: March 2018

Multicompartment microcapsules, with each compartment protected by a distinct stimuli‐responsive shell for versatile controlled release, are highly desired for developing new‐generation microcarriers. Although many multicompartmental microcapsules have been created, most cannot combine different release styles to achieve flexible programmed sequential release. Here, one‐step template synthesis of controllable Trojan‐horse‐like stimuli‐responsive microcapsules is reported with capsule‐in‐capsule structures from microfluidic quadruple emulsions for diverse programmed sequential release. The nested inner and outer capsule compartments can separately encapsulate different contents, while their two stimuli‐responsive hydrogel shells can individually control the content release from each capsule compartment for versatile sequential release. This is demonstrated by using three types of Trojan‐horse‐like stimuli‐responsive microcapsules, with different combinations of release styles for flexible programmed sequential release. The proposed microcapsules provide novel advanced candidates for developing new‐generation microcarriers for diverse, efficient applications.
A High‐Speed and Low‐Power Multistate Memory Based on Multiferroic Tunnel Junctions
Authors: Huang Weichuan , Zhao Wenbo , Luo Zhen , Yin Yuewei , Lin Yue , Hou Chuangming , Tian Bobo , Duan Chun‐Gang , Li Xiao‐Guang
Published: March 2018

Ferroic‐order‐based devices are emerging as alternatives to high density, high switching speed, and low‐power memories. Here, multi‐nonvolatile resistive states with a switching speed of 6 ns and a write current density of about 3 × 103 A cm−2 are demonstrated in crossbar‐structured memories based on all‐oxide La0.7Sr0.3MnO3/BaTiO3/La0.7Sr0.3MnO3 multiferroic tunnel junctions. The tunneling resistive switching as a function of voltage pulse duration time, associated with the ferroelectric domain reversal dynamics, is ruled by the Kolmogorov–Avrami–Ishibashi switching model with a Lorentzian distribution of characteristic switching time. It is found that the characteristic resistance switching time decreases with increasing voltage pulse amplitude following Merz's law and the estimated write speed can be less than 6 ns at a relatively higher voltage. These findings highlight the potential application of multiferroic devices in high speed, low power, and high‐density memories.
A Graphene‐Based Filament Transistor with Sub‐10 mVdec−1 Subthreshold Swing
Authors: Tian He , Wang Xuefeng , Zhao Haiming , Mi Wentian , Yang Yi , Chiu Po‐Wen , Ren Tian‐Ling
Published: March 2018

There is a growing trend of developing steep slope transistors with subthreshold swing (SS) below 60 mV dec−1. At present, there are mainly three kinds of steep slope transistors: tunneling transistor, negative capacitance transistor, and nano‐electromechanical relay. Here, a new kind of steep slope transistor named “filament transistor” is proposed with SS down to sub‐10 mV dec−1. Due to the gate E‐filed can penetrate through the graphene, the gate can effectively control the filament formation/rupture inside the 5 nm AlOx with very steep slope. In reverse sweep, the gate can induce the filament formation with SS down to 4.6 mV dec−1. In forward sweep, the gate can break the filament with SS down to 12.2 mV dec−1. Taking the advantages of nanofilament, the filament transistor holds a great potential to scaling down to 5 nm without performance changing.
Interphases in Sodium‐Ion Batteries
Authors: Song Junhua , Xiao Biwei , Lin Yuehe , Xu Kang , Li Xiaolin
Published: March 2018

Sodium‐ion batteries (SIBs) as economical, high energy alternatives to lithium‐ion batteries (LIBs) have received significant attention for large‐scale energy storage in the last few years. While the efforts of developing SIBs have benefited from the knowledge learned in LIBs, thanks to the apparent proximity between Na‐ions and Li‐ions, the unique physical and chemical properties of Na‐ions also distinctly differ themselves from Li‐ions. It is expected that SIBs have drastically different electrode material structure, solvation–desolvation behavior, electrode–electrolyte interphase stabilities, ion transfer properties, and hence electrochemical performance of batteries. In this review, the authors comprehensively summarize the current understanding of the anode solid electrolyte interphase and cathode electrolyte interphase in SIBs, with an emphasis on how the tuning of the stability and ion transfer properties of interphases fundamentally determines the reversibility and efficiency of electrochemical reactions. Through these carefully screened references, the authors intend to reveal the intrinsic correlation between the properties/functionalities of the interphases and the electrochemical performance of batteries.
Thermodynamically Self‐Healing 1D–3D Hybrid Perovskite Solar Cells
Authors: Fan Jiandong , Ma Yunping , Zhang Cuiling , Liu Chong , Li Wenzhe , Schropp Ruud E. I. , Mai Yaohua
Published: March 2018

Thermal degradation in perovskite solar cells is still an unsettled issue that limits its further development. In this study, 2‐(1H‐pyrazol‐1‐yl)pyridine is introduced into lead halide 3D perovskites, which allows 1D–3D hybrid perovskite materials to be obtained. The heterostructural 1D–3D perovskites are proved to be capable of remarkably prolonging the photoluminescence decay lifetime and suppressing charge carrier recombination in comparison to conventional 3D perovskites. The intrinsic properties of thermodynamically stable yet kinetically labile 1D materials allow the system to alleviate the lattice mismatch and passivate the interface traps of heterojunction region of 1D–3D hybrid perovskites that may occur during the crystal growth process. Importantly, the as‐fabricated 1D–3D perovskite solar cells display a thermodynamic self‐healing ability, which is induced through blocking the ion‐migration channels of A‐site ions by the flexible 1D perovskite with less densely close‐packed structure. Particularly, the power conversion efficiency of as‐fabricated unencapsulated 1D–3D perovskite solar cells is demonstrated to be reversible under temperature cycling (25–85 °C) at 55% relative humidity, which largely outperforms the pure 3D perovskite solar cell. The present study provides a facile approach to fabricate 1D–3D perovskite solar cells with high efficiency and long‐term stability.
Exceptionally Enhanced Electrode Activity of (Pr,Ce)O2−δ‐Based Cathodes for Thin‐Film Solid Oxide Fuel Cells
Authors: Seo Han Gil , Choi Yoonseok , Jung WooChul
Published: March 2018

It is shown that an electrochemically‐driven oxide overcoating substantially improves the performance of metal electrodes in high‐temperature electrochemical applications. As a case study, Pt thin films are overcoated with (Pr,Ce)O2−δ (PCO) by means of a cathodic electrochemical deposition process that produces nanostructured oxide layers with a high specific surface area and uniform metal coverage and then the coated films are examined as an O2‐electrode for thin‐film‐based solid oxide fuel cells. The combination of excellent conductivity, reactivity, and durability of PCO dramatically improves the oxygen reduction reaction rate while maintaining the nanoscale architecture of PCO layers and thus the performance of the PCO‐coated Pt thin‐film electrodes at high temperatures. As a result, with an oxide coating step lasting only 5 min, the electrode resistance is successfully reduced by more than 1000 times at 500 °C in air. These observations provide a new direction for the design of high‐performance electrodes for high‐temperature electrochemical cells.
Exceptionally High Performance Anode Material Based on Lattice Structure Decorated Double Perovskite Sr2FeMo2/3Mg1/3O6−δ for Solid Oxide Fuel Cells
Authors: Du Zhihong , Zhao Hailei , Li Shanming , Zhang Yang , Chang Xiwang , Xia Qing , Chen Ning , Gu Lin , Świerczek Konrad , Li Yan , Yang Tianrang , An Ke
Published: March 2018

A novel double perovskite Sr2FeMo2/3Mg1/3O6−δ is prepared and characterized as an anode material for solid oxide fuel cells (SOFCs). X‐ray diffraction refinement reveals that Mg and Mo cations locate separately in two different B sites (B and B′ in A2BB′O6) while Fe occupies both B and B′ sites, forming the lattice structure with the form of Sr2(Mg1/3Fe2/3)(Mo2/3Fe1/3)O6−δ. The inactive element Mg doping not only endows the material with excellent redox structural stability but also triggers the creation of antisite defects in the crystal lattice, which provide the material with excellent electrochemical activity. The anode performance of Sr2FeMo2/3Mg1/3O6−δ is characterized in an La0.8Sr0.2Ga0.8Mg0.2O3−δ electrolyte supported cell with La0.58Sr0.4Fe0.8Co0.2O3−δ cathode. A peak power density of 531, 803, 1038, and 1316 mW cm−2 at 750, 800, 850, and 900 °C, respectively, is achieved in humidified H2. The Sr2FeMo2/3Mg1/3O6−δ shows suitable thermal expansion coefficient (16.9(2) × 10−6 K−1), high electrical conductivity, and good tolerance to carbon deposition and sulfur poisoning. First‐principle computations demonstrate that the presence of FeBOFeB′ bonds can promote the easy formation and fast migration of oxygen vacancies in the lattice, which are the key to affecting the anode reaction kinetics. The excellent overall performance of Sr2FeMo2/3Mg1/3O6−δ compound makes it a promising anode material for SOFCs.
An Ultrafast Rechargeable Hybrid Sodium‐Based Dual‐Ion Capacitor Based on Hard Carbon Cathodes
Authors: Chen Suhua , Wang Jue , Fan Ling , Ma Ruifang , Zhang Erjing , Liu Qian , Lu Bingan
Published: March 2018

Hybrid sodium‐based dual‐ion capacitors (NDICs), which integrate the advantages of supercapacitors and sodium‐ion batteries, have attracted tremendous attention recently. In this work, hybrid sodium‐based dual‐ion capacitors are successfully developed with nitrogen‐doped microporous hard carbon as the cathode and soft carbon as the anode. N‐doping is beneficial to the functional groups, porous structure, and electric conductivity of hard carbon. Hybrid NDICs possess a wide voltage range (0.01–4.7 V), high‐energy density of 245.7 W h kg−1 at a power density of 1626 W kg−1, long cycle life (1000 cycles), and outstanding rate performance.
Controllable fabrication and catalytic performance of nanosheet HZSM‐5 films by vertical secondary growth
Authors: Tian Yajie , Liu Hong , Wang Li , Zhang Xiangwen , Liu Guozhu
Published: March 2018

Significance

Nanosheet HZSM‐5 film vertically grown on the substrate with the tailorable macro‐ and meso‐pores between the layers of nanosheets is hydrothermally synthesized by seed‐assisted secondary growth method. The as‐prepared nanosheet HZSM‐5 film exhibits reaction rate enhancement up to 312% in catalytic cracking of n‐dodecane as well as twice light olefins selectivity, ascribed to the better mass transfer of reactants in the hierarchical porous structure and the ultra‐thin b‐axis pores of nanosheets. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1923–1927, 2018
Nano‐engineered nickel catalysts supported on 4‐channel α‐Al2O3 hollow fibers for dry reforming of methane
Authors: Shang Zeyu , Li Shiguang , Wang Qingfa , Gu Xuehong , Liang Xinhua
Published: March 2018

A nickel (Ni) nanoparticle catalyst, supported on 4‐channel α‐Al2O3 hollow fibers, was synthesized by atomic layer deposition (ALD). Highly dispersed Ni nanoparticles were successfully deposited on the outside surfaces and the inside porous structures of hollow fibers. The catalyst was employed to catalyze the dry reforming of methane (DRM) reaction and showed a methane reforming rate of 2040 Lh−1gNi−1 at 800°C. NiAl2O4 spinel was formed when Ni nanoparticles were deposited on alpha‐alumina substrates by ALD, which enhanced the Ni‐support interaction. Different cycles (two, five, and ten) of Al2O3 ALD films were applied on the Ni/hollow fiber catalysts to further improve the interaction between the Ni nanoparticles and the hollow fiber support. Both the catalyst activity and stability were improved with the deposition of Al2O3 ALD films. Among the Al2O3 ALD coated catalysts, the catalyst with five cycles of Al2O3 ALD showed the best performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2625–2631, 2018
Haploidentical transplantation outcomes for secondary acute myeloid leukemia: Acute Leukemia Working Party (ALWP) of the European Society for Blood and Marrow Transplantation (EBMT) study
Authors: Li Zhuoyan , Labopin Myriam , Ciceri Fabio , Blaise Didier , Tischer Johanna , Ehninger Gerhard , Van Lint MT , Koc Yener , Santarone Stella , Forcade Edouard , Castagna Luca , Polge Emmanuelle , Mailhol Audrey , Ruggeri Annalisa , Mohty Mohamad , Savani Bipin N. , Nagler Arnon
Published: March 2018

Secondary acute myeloid leukemia (sAML) traditionally has inferior outcomes compared to de novo AML. Allogeneic hematopoietic cell transplantation (HCT) is the sole potentially curative therapy. This study analyzes the outcomes for unmanipulated haploidentical HCT (haploHCT) for sAML using the Acute Leukemia Working Party (ALWP) registry of the European Society for Blood and Marrow Transplantation (EBMT). We identified 154 patients with sAML who underwent haploHCT from 2006 to 2016. Median age at HCT was 60 years with time from diagnosis to HCT 5 months. At transplantation, 69 patients were in first CR and 85 had active disease. Fifty‐seven (38.0%) patients underwent myeloablative conditioning and 97 (62.0%) reduced intensity conditioning (RIC) conditioning. Multivariate analysis showed that there was no difference in RI, nonrelapse mortality (NRM), leukemia free survival (LFS), overall survival (OS), or GVHD‐free/relapse free survival (GRFS) for conditioning intensity, age, performance status, or graft source. Active disease was associated with higher RI and inferior LFS, OS, and GRFS compared with patients in CR at time of transplant. T‐cell depletion with anti‐thymoglobulin resulted in higher NRM and inferior LFS, OS, and GRFS compared to post‐transplant cyclophosphamide (PTCy) (HR 2.25, 2.01, 2.16, and 1.73, respectively with P values <.05). Our data shows that haploHCT is a feasible alternative for sAML when matched transplantation is unavailable.
Changes in intracranial volume and cranial shape in modern Koreans over four decades
Authors: Kim Ye Sel , Park In Sung , Kim Hyun Jung , Kim Dasom , Lee Nam Joon , Rhyu Im Joo
Published: March 2018

Objectives

This study investigated whether there was any secular change in cranial vault morphology among Koreans born between the 1930s and 1970s, a period of dramatic shift in Korea's socioeconomic conditions.

Materials and methods

Using three‐dimensional MRI volumetry, we obtained the intracranial volume (ICV) and craniometric measurements of 115 healthy Koreans: 58 individuals (32 males and 26 females) born in the 1930s (1926–1936) and 57 (28 males and 29 females) born in the 1970s (1972–1979).

Results

The intracranial volume of males was 1502.3 ± 110.3 cm3 for the 1930s group and 1594.1 ± 99.5 cm3 for the 1970s group, and for females, it was 1336.0 ± 53.0 cm3 for the 1930s group and 1425.9 ± 79.6 cm3 for the 1970s group. On average, ICV increased by 94 cm3 in males and by 90 cm3 in females. Cranial measurements for the 1970s group were significantly larger than the 1930s group for both sexes except in female cranial length. Each measurement was significantly correlated with ICV [cranial height (R = 0.720), breadth (R = 0.706), and length (R = 0.531)]. The cephalic index decreased from 0.846 to 0.828 in males, indicating the cranium became narrower relative to the cranial length. In females, the cephalic index increased from 0.831 to 0.850. Sex and birthyear were marginally interrelated in cephalic indices.

Discussion

From the 1930s to 1970s, the Korean Peninsula experienced important historical shifts, and we speculate that the consequent shift in socioeconomic status is the most likely factor responsible for Koreans’ cranial vault remodeling.
A High‐Voltage Molecular‐Engineered Organic Sensitizer–Iron Redox Shuttle Pair: 1.4 V DSSC and 3.3 V SSM‐DSSC Devices
Authors: Rodrigues Roberta R. , Cheema Hammad , Delcamp Jared H.
Published: March 2018

The development of high voltage solar cells is an attractive way to use sunlight for solar‐to‐fuel devices, multijunction solar‐to‐electric systems, and to power limited‐area consumer electronics. By designing a low‐oxidation‐potential organic dye (RR9)/redox shuttle (Fe(bpy)33+/2+) pair for dye‐sensitized solar‐cell (DSSC) devices, the highest single device photovoltage (1.42 V) has been realized for a DSSC not relying on doped TiO2. Additionally, Fe(bpy)33+/2+ offers a robust, readily tunable ligand platform for redox potential tuning. RR9 can be regenerated with a low driving force (190 mV), and by utilizing the RR9/Fe(bpy)33+/2+ redox shuttle pair in a subcell for a sequential series multijunction (SSM)‐DSSC system, one of the highest known three subcell photovoltage was attained for any solar‐cell technology (3.34 V, >1.0 V per subcell).
Lithium‐Ion Endohedral Fullerene (Li+@C60) Dopants in Stable Perovskite Solar Cells Induce Instant Doping and Anti‐Oxidation
Authors: Jeon Il , Ueno Hiroshi , Seo Seungju , Aitola Kerttu , Nishikubo Ryosuke , Saeki Akinori , Okada Hiroshi , Boschloo Gerrit , Maruyama Shigeo , Matsuo Yutaka
Published: March 2018

Herein, we report use of [Li+@C60]TFSI− as a dopant for spiro‐MeOTAD in lead halide perovskite solar cells. This approach gave an air stability nearly 10‐fold that of conventional devices using Li+TFSI−. Such high stability is attributed to the hydrophobic nature of [Li+@C60]TFSI− repelling moisture and absorbing intruding oxygen, thereby protecting the perovskite device from degradation. Furthermore, [Li+@C60]TFSI− could oxidize spiro‐MeOTAD without the need for oxygen. The encapsulated devices exhibited outstanding air stability for more than 1000 h while illuminated under ambient conditions.
Isolierbare, neutrale Analoga des [B2H5]−‐Ions als vielseitige und stark bindende η2‐Donorliganden
Authors: Wang Sunewang R. , Prieschl Dominic , Mattock James D. , Arrowsmith Merle , Pranckevicius Conor , Stennett Tom E. , Dewhurst Rian D. , Vargas Alfredo , Braunschweig Holger
Published: March 2018

Zwei isolierbare, neutrale, Basen‐stabilisierte Diborane(5) sind dazu in der Lage, ausschließlich durch ihre B‐B‐Bindung stark an mehrere Kupfer(I)‐Komplexe zu binden. Die resultierenden Komplexe repräsentieren die ersten bekannten Komplexe mit neutralen, ungeschützten σB‐B‐Diboranliganden. Die Einkristall‐Röntgenstrukturanalysen dieser Komplexe zeigen, dass die X‐Cu‐Einheit (X=Cl, OTf, C6F5) gegenüber vom verbrückenden Wasserstoffatom des Diborans liegt und annähernd senkrecht zur B‐B‐Bindung steht. Dabei wechselwirkt diese nahezu gleichermaßen mit beiden Boratomen, woraus eine Verlängerung der B‐B‐Bindung resultiert. DFT‐Studien belegen, dass sowohl σ‐Donor‐ als auch π‐Akzeptor‐Effekte der B‐B‐Bindung für die Bildung dieser Produkte verantwortlich sind. Erstaunlicherweise zeigen sich diese Kupfer‐σB‐B‐Komplexe inert gegen thermisch oder photolytisch induzierten Ligandenaustausch mit Pyridin.
Structural Basis of a Broadly Selective Acyltransferase from the Polyketide Synthase of Splenocin
Authors: Li Yuan , Zhang Wan , Zhang Hui , Tian Wenya , Wu Lian , Wang Shuwen , Zheng Mengmeng , Zhang Jinru , Sun Chenghai , Deng Zixin , Sun Yuhui , Qu Xudong , Zhou Jiahai
Published: March 2018

Polyketides are a large family of pharmaceutically important natural products, and the structural modification of their scaffolds is significant for drug development. Herein, we report high‐resolution X‐ray crystal structures of the broadly selective acyltransferase (AT) from the splenocin polyketide synthase (SpnD‐AT) in the apo form and in complex with benzylmalonyl and pentynylmalonyl extender unit mimics. These structures revealed the molecular basis for the stereoselectivity and substrate specificity of SpnD‐AT, and enabled the engineering of the industrially important Ery‐AT6 to broaden its substrate scope to include three new types of extender units.
Assessing Human Exposure to Organic Pollutants in the Indoor Environment
Authors: Salthammer Tunga , Zhang Yinping , Mo Jinhan , Koch Holger M. , Weschler Charles J.
Published: March 2018

There is an ongoing probing of the role of chemicals in the indoor environment. The majority of potential target substances are so‐called very volatile, volatile, and semi‐volatile organic compounds (VVOCs, VOCs, and SVOCs). Depending on their physical properties and the mass transfer conditions, they are distributed in or between the gas phase, particle phase, settled house dust, surface films, clothing, and other fabrics as well as the exposed skin and hair of the occupants themselves. Therefore, inhalation, ingestion, and dermal uptake all must be considered as relevant pathways for exposure assessment in human habitats. Exposure to VVOCs, VOCs, and SVOCs can be estimated by measuring their concentrations in relevant indoor compartments or by determining the amounts of the target compounds and/or their metabolites in urine and blood. Assessing the various routes of exposure often requires a combination of sophisticated and interdisciplinary theoretical background and experimental techniques. Consequently, close communication and collaboration between chemical and exposure scientists are needed to achieve a better understanding of human exposure to chemical substances in various indoor environments. Embedded in the toxicological context, this is the basis for assessing the corresponding health risks and for determining control strategies or approaches to limit such risks.
Functional Liquid Crystals towards the Next Generation of Materials
Authors: Kato Takashi , Uchida Junya , Ichikawa Takahiro , Sakamoto Takeshi
Published: March 2018

Since the discovery of the liquid‐crystalline state in 1888, liquid crystal science has made great advances through fusion with various technologies and disciplines. Recently, new molecular design strategies and new self‐assembled structures have been developed as a result of the progress made in synthetic procedures and characterization techniques. Since these liquid crystals exhibit new functions and properties derived from their nanostructures and alignment, a variety of new functions for liquid crystals, such as transport for energy applications, separation for environmental applications, chromism, sensing, electrooptical effects, actuation, and templating have been proposed. This Review presents recent advances of liquid crystals that should contribute to the next generation of materials.
Synthesis of Branched‐Chain Sugars with a DHAP‐Dependent Aldolase: Ketones are Electrophile Substrates of Rhamnulose‐1‐phosphate Aldolases
Authors: Laurent Victor , Darii Ekaterina , Aujon Angelina , Debacker Marine , Petit Jean‐Louis , Hélaine Virgil , Liptaj Tibor , Breza Martin , Mariage Aline , Nauton Lionel , Traïkia Mounir , Salanoubat Marcel , Lemaire Marielle , Guérard‐Hélaine Christine , de Berardinis Véronique
Published: March 2018

Dihydroxyacetone phosphate (DHAP)‐dependent rhamnulose aldolases display an unprecedented versatility for ketones as electrophile substrates. We selected and characterized a rhamnulose aldolase from Bacteroides thetaiotaomicron (RhuABthet) to provide a proof of concept. DHAP was added as a nucleophile to several α‐hydroxylated ketones used as electrophiles. This aldol addition was stereoselective and produced branched‐chain monosaccharide adducts with a tertiary alcohol moiety. Several aldols were readily obtained in good to excellent yields (from 76 to 95 %). These results contradict the general view that aldehydes are the only electrophile substrates for DHAP‐dependent aldolases and provide a new C−C bond‐forming enzyme for stereoselective synthesis of tertiary alcohols.
Electrochemical Hydroxylation of Arenes Catalyzed by a Keggin Polyoxometalate with a Cobalt(IV) Heteroatom
Authors: Khenkin Alexander M. , Somekh Miriam , Carmieli Raanan , Neumann Ronny
Published: March 2018

The sustainable, selective direct hydroxylation of arenes, such as benzene to phenol, is an important research challenge. An electrocatalytic transformation using formic acid to oxidize benzene and its halogenated derivatives to selectively yield aryl formates, which are easily hydrolyzed by water to yield the corresponding phenols, is presented. The formylation reaction occurs on a Pt anode in the presence of [CoIIIW12O40]5− as a catalyst and lithium formate as an electrolyte via formation of a formyloxyl radical as the reactive species, which was trapped by a BMPO spin trap and identified by EPR. Hydrogen was formed at the Pt cathode. The sum transformation is ArH+H2O→ArOH+H2. Non‐optimized reaction conditions showed a Faradaic efficiency of 75 % and selective formation of the mono‐oxidized product in a 35 % yield. Decomposition of formic acid into CO2 and H2 is a side‐reaction.
Consecutive Ring Expansion and Contraction for the Synthesis of 1‐Aryl Tetrahydroisoquinolines and Tetrahydrobenzazepines from Readily Available Heterocyclic Precursors
Authors: Hill Jessica E. , Matlock Johnathan V. , Lefebvre Quentin , Cooper Katie G. , Clayden Jonathan
Published: March 2018

Tetrahydroisoquinolines and tetrahydrobenzazepines were prepared by acid‐promoted ring contraction of cyclic ureas, which were themselves formed by ring expansion of indolines and tetrahydroquinolines. The consequent overall one‐carbon insertion reaction gives these 6‐ and 7‐membered heterocyclic scaffolds in three steps from readily available precursors. Other ring sizes may be formed by an alternative elimination reaction of bicyclic structures. Scalability of the method was demonstrated by operating it in a flow system.
Tripalmitin–Sodium Dodecyl Sulfate Emulsion Droplet Liquid vs. Solid State Impacts in vitro Digestive Lipolysis
Authors: Huynh Sally , Wright Amanda J.
Published: March 2018

Questions remain as to the impact of lipid structure, including crystallinity, on digestibility and metabolic response. This study was undertaken to determine the impact of triacylglycerol crystallinity on digestibility using undercooled (liquid emulsion, LE) and crystalline (solid emulsion, SE) particles exposed to an in vitro model simulating upper gastrointestinal tract (GIT) digestive conditions. By hot microfluidization, 10 wt% tripalmitin oil‐in‐water emulsions (D3,2 ~ 0.115 nm) with 0.9 wt% sodium dodecyl sulfate (SDS) were prepared. SE demonstrated complex melting behavior, was predominantly in the beta polymorph, and consisted of a heterogeneous mixture of anisometric particles. In vitro duodenal lipolysis was more extensive for the spherically shaped LE droplets vs. SE (P < 0.05), despite the fact that exposure to simulated gastric conditions (at pH 2, but not at pH 7) induced partial crystallization. Therefore, lipid droplet physical state impacted and was impacted by exposure to gastrointestinal conditions, with differences observed in fatty acid digestive release and implications for lipid absorption.
Use of Essential Oils From Various Plants to Change the Fatty Acids Profiles of Lipids Obtained From Oleaginous Yeasts
Authors: Uprety Bijaya K. , Rakshit Sudip K.
Published: March 2018

We studied the ability of seven essential oils to alter the fatty acid composition of lipids produced by an oleaginous yeast Rhodosporidium toruloides. All of the essential oils, except thyme, significantly increased the stearic acid content of the lipids. The amount of essential oils in the media determined the fatty acid composition obtained. Subsequently, we studied the effect of the major monoterpenes present in these essential oils. When R. toruloides was grown on limonene, a major monoterpene in orange essential oil, the composition of lipid obtained was found to be quite similar to natural orange essential oil. This proved that limonene has a major role in the changes in fatty acid profiles of the lipids. The effect of orange essential oil on another oleaginous yeast, Cryptococcus curvatus, was also carried out. Although the effect of the essential oil on the fatty acid composition and biomass (cell mass) was similar for both these two yeasts, the reduction of the activity of some enzymes involved in the metabolic pathways was quite different. From these results, it can be concluded that the effect of essential oils differs with species and it is possible to produce lipids with alternate fatty acid profiles suitable for different applications and with good market value.
Effects of Vegetable Oil Composition on Epoxidation Kinetics and Physical Properties
Authors: Yan Mengguo , Frank Elizabeth M. , Cochran Eric W.
Published: March 2018

In this article, we investigate the role of triacylglycerol composition on the properties of epoxidized vegetable oils and the kinetics of the epoxidation process under conditions comparable to commercial epoxidation. Commodity soybean oil (24% oleic acid, 50% linoleic acid, and 7% linolenic acid), high‐oleic soybean oil (75% oleic acid, 8% linoleic acid, and 2.5% linolenic acid), and linseed oil (11% oleic acid, 15% linoleic acid, and 64% linolenic acid) were each epoxidized to various extents. Epoxidation rate, viscosity, differential calorimetry, and X‐ray diffraction data are presented for these oils and interpreted in the context of their fatty acid profile (mostly oleic, linoleic, or linolenic). While fully epoxidized soybean oil is widely commercially available and used in an increasing array of industrial applications, information relating to partially epoxidized oils and epoxidized oils of other cultivars is less well known.
Enhanced thermal conductivity of PLA‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid
Authors: Lin Han , Pei Lixia , Zhang Lizhi
Published: March 2018

Enhancing thermal conductivity of polymeric nanocomposites remains a great challenge because of the poor compatibility between nanofillers and the polymeric matrix and the aggregation effect of nanofillers. We report the enhanced thermal conductivity of poly(lactic acid) (PLA)‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid. Graphite nanoplatelets (GNPs) were noncovalently functionalized with tannic acid (TA) by van der Waals forces and π–π interaction without perturbing the conjugated sp2 network, thus preserving the high thermal conductivity of GNPs. PLA‐based nanocomposites with different contents of TA‐functionalized GNPs (TA‐GNPs) were prepared and characterized, and the influences of TA‐GNPs content on the morphologies, mechanical properties, and thermal properties of the composites were investigated in detail. TA‐GNPs remarkably improved the thermal conductivity of PLA up to 0.77 W/(m K), showing its high potential as a thermally conductive filler for polymer‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46397.
Surface modification of UHMWPE/fabric composite membrane via self‐polymerized polydopamine followed by mPEG‐NH2 immobilization
Authors: Liu Rong , Wang Xinwei , Yu Junrong , Wang Yan , Zhu Jing , Hu Zuming
Published: March 2018

In this work, a novel approach to improve the antifouling properties of membrane surfaces was developed. First, a polydopamine layer was attached onto the surface of an ultrahigh molecular weight polyethylene/fabric composite microporous membrane based on dopamine self‐polymerization and adhesive behavior. Then, methoxy polyethylene glycol amine was covalently bonded with the polydopamine layer via a Schiff base reaction. The physicochemical properties of the modified composite membrane surface were investigated, and the results indicated this modification could effectively enhance the membrane surface hydrophilicity. Furthermore, the protein fouling resistance of both dopamine‐coated and methoxy polyethylene glycol amine immobilized composite membranes was evaluated. It was found that a dopamine coating cannot obviously enhance the membrane antifouling properties due to its strong bioadhesion behavior. However, the antifouling properties of the composite membranes were significantly improved after being immobilized with a methoxy polyethylene glycol amine layer. Consequently, a layer‐by‐layer modified composite membrane with excellent antifouling property was obtained. The pure water flux and flux recovery ratio of the resultant membrane were 764 L m−2 h−1 and 83%, respectively. The aim of this paper was to provide an effective approach to optimizing the separation efficiency and antifouling performance of the ultrahigh molecular weight polyethylene/fabric composite membrane. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46428.
Donald Trump as Leader: Psychoanalytic Perspectives
Authors: Rudden Marie , Brandt Stephanie
Published: March 2018

Psychoanalysts who study the internal processes of group formation and functioning have a good deal to offer in understanding Donald Trump's powerful appeal to a segment of American voters. In this paper, we examine how this politician has ignited the fierce loyalty of a dedicated group of followers. We further use group analytic concepts to consider the ways in which his followers in turn exert their influence on Trump himself. Finally, referring to the literature on group leadership, we consider the inevitable impact of a leader whose communications often stray from logic and demonstrable fact and which seem to intentionally promote group regression and fantasy. This analysis pertains to the effect he has on those staunch supporters who say there is little he could do to shake their faith in him.
Cultural Dislocation and Ego Functions: Some Considerations in the Analysis of Bi‐cultural Patients
Authors: Dajani Karim G.
Published: March 2018

Cultural dislocation – the removal of a person from a location organized by a particular set of cultural practices and placing them in another location organized by a substantially different set of cultural practices – can shock and alter the ego. I utilize the cultural anthropologist Pierre Bourdieu's definition of culture or habitus as “a set of durable transposable dispositions” inculcated from a collective in which an individual is embedded to describe the impact of cultural dislocation. Finally, I suggest that difficulty in mourning the loss of a “country” and “set of ideals” that can no longer adequately mediate the immigrant's new world leads to melancholic symptoms, particularly anhedonia (loss of feeling in the body) and a type of self‐loathing that emanates from deeply unconscious sources.