bluuebunny/crossref_metadata_2025 huggingface dataset:
Biluminescence Under Ambient Conditions: Water‐Soluble Organic Emitter in High‐Oxygen‐Barrier Polymer
Authors: Louis Marine , Thomas Heidi , Gmelch Max , Fries Felix , Haft Anna , Lindenthal Jakob , Reineke Sebastian
Published: May 2020

Biluminescent organic systems displaying fluorescence and phosphorescence at room temperature under aerated atmosphere still remain uncommon to date. Especially the utilization of the room temperature phosphorescence (RTP) is limited, as it is effectively quenched by oxygen, rendering it incompatible with many applications for use in ambient conditions. So far, only encapsulation to prevent oxygen penetration into the films or the use of special steroid hosts are known concepts to allow conventional biluminescent emitters to show RTP. Here, the design and synthesis of a novel water‐soluble biluminescent emitter is reported. After dispersion in a host matrix, and using host/guest hydrogen‐bonding interactions, easy‐processable highly phosphorescent transparent thin‐films are realized. Their luminescent properties can be activated at will under aerated atmosphere for several weeks without degradation of the system. The polymer (host) mixture can even be readily used for 3D printing, leading to a large range of accessible phosphorescent objects.
High Stability and Temperature‐Dependent Photoluminescence of Orthorhombic CsPbI3 Perovskite Nanoparticles
Authors: Tang Bing , Ruan Lin Ji , Qin Changyun , Shu Ang , He Huimei , Ma Ying
Published: May 2020

High thermal stability of all‐inorganic perovskite nanocrystals (NCs) offers their potential application in various fields such as solar cells and light‐emitting diodes. However, the cubic cesium lead iodide (α‐CsPbI3) with the most appropriate bandgap for light harvesting is thermodynamically unstable at room temperature and spontaneously transforms into the undesired orthorhombic δ‐CsPbI3. Here, a simple method is demonstrated to synthesize orthorhombic γ‐CsPbI3 NCs using 3‐aminopropyl triethoxysilane molecules as capping ligands. The crystalline structure and morphology of these γ‐CsPbI3 NCs hardly change after exposure to ethanol even though they are capped with fewer ligands. Their high stability is also demonstrated by retaining their photoluminescence (PL) intensity after heating/cooling cycles in the range of 295–375 K, in contrast to a quick destruction of α‐CsPbI3 NCs under the same condition. More importantly, temperature‐dependent PL spectra reveal that the exciton/electron–phonon coupling and exciton recombination process of these γ‐CsPbI3 NCs strongly depend on their particle sizes. This finding may enable versatile design of stable γ‐CsPbI3 NCs with different sizes meeting diverse demands for various applications.
Dielectric Nanoaperture Metasurfaces in Silicon Waveguides for Efficient and Broadband Mode Conversion with an Ultrasmall Footprint
Authors: Yao Chaonan , Wang Yilun , Zhang Jihua , Zhang Xinliang , Zhao Chen , Wang Bin , Singh Subhash C. , Guo Chunlei
Published: May 2020

Efficient and reliable mode converters with broadband operation and small footprint will enable high‐density silicon photonic integrated circuits to build high bitrate optical networks and handheld optical devices. Here, all‐dielectric nanoaperture metasurfaces in the silicon layer of a silicon‐on‐insulator platform are reported for mode‐order conversion with an ultrasmall footprint. Utilizing the advantages of an abrupt width change and metasurface, the mode conversion between TE00 and TE10 modes is realized with a conversion efficiency as high as ≈90% in simulations and 83.1% in experiments at λ = 1.55 µm within an ultrashort conversion length of about 2.42 µm, the shortest ever achieved. The incident TE00 mode is converted to TE10 mode with purity of more than 90% in a broadband (Δλ ≈ 230 nm) wavelength range from 1.42 to 1.65 µm. Moreover, optimizing the number, position, and dimension of nanoapertures, it is further demonstrated that the nanoaperture metasurface design can enable mode conversion between silicon waveguides of different thicknesses and different relative positions, and between TM modes.
Electrothermal Actuators with Ultrafast Response Speed and Large Deformation
Authors: Chen Guinan , Yang Zhonglin , Wang Wenwen , Bi Lili , Chen Liangjun , Peng Yongwu , Ye Changhui
Published: May 2020

The ability to fabricate electrothermal actuators (ETAs) simultaneously featuring ultrafast response speed (within 0.1 s), large deformation (bending for at least 360°), high figure‐of‐merit (FoM, larger than 0.1%), and low driving voltage (smaller than 1 V) in a single device is extremely important and challenging for their applications in artificial muscles, switches, and microsensors for robotics and biomimetic devices. Herein, an ETA composed of a silver nanowire (AgNW) layer and an ultrathin linear low‐density polyethylene (LLDPE) film with all the aforementioned features is designed. Due to the high conductivity of the AgNW layer and the great difference between the coefficients of thermal expansion of AgNW layer and LLDPE film as well as the huge change in the heat transfer coefficient between flat and rolled ETA, the obtained ETA exhibits an ultrafast response speed of 0.08 s for a bending angle of 360° with a FoM of 0.46% at a low driving voltage of 1 V, over one order of magnitude larger than those of reported ETAs. As a proof‐of‐concept application, the as‐prepared ETAs can be used as intelligent mechanical devices with excellent performance.
Multistimuli‐Responsive Insect‐Scale Soft Robotics Based on Anisotropic Super‐Aligned VO2 Nanowire/Carbon Nanotube Bimorph Actuators
Authors: Chen Pengcheng , Shi Run , Shen Nan , Zhang Zhuoqiong , Liang Yuxing , Li Tianran , Wang Jingwei , Kong Dejun , Gan Yichen , Amini Abbas , Wang Ning , Cheng Chun
Published: May 2020

The emerging soft robots have attracted increasing interests and gotten rapidly developed, but it is still challenging to substantially promote their response speed and work density. In addition, the wireless way to conveniently trigger the devices, especially for the centimeter‐scale ones, is highly desired. Herein, the multistimuli‐responsive insect‐scale soft robotics is reported based on a super‐aligned VO2 nanowire arrays (NAs)/carbon nanotube (CNT) bimorph film, comprehensively addressing aforementioned problems. The as‐prepared VO2 NA/CNT bimorph shows improved actuation performance, anisotropic behavior, rapid response to various stimuli (heat, light, and electricity), and multiple movement modes (bending and torsion). Consequently, diverse untethered, insect‐scale soft robots, serving as biomimetic crawler, lifter, gripper, wing of flying robots, torsional robot, and so on are successfully demonstrated. The findings provide an effective strategy to develop high‐performance macroscopic mechanical devices by assembling functional nanostructures.
Integration and reanalysis of transcriptomics and methylomics data derived from blood and testis tissue of men with 47,XXY Klinefelter syndrome indicates the primary involvement of Sertoli cells in the testicular pathogenesis
Authors: Winge Sofia B. , Soraggi Samuele , Schierup Mikkel H. , Rajpert‐De Meyts Ewa , Almstrup Kristian
Published: May 2020

Klinefelter syndrome (KS; 47,XXY) is the most common sex chromosomal anomaly and causes a multitude of symptoms. Often the most noticeable symptom is infertility caused by azoospermia with testicular histology showing hyalinization of tubules, germ cells loss, and Leydig cell hyperplasia. The germ cell loss begins early in life leading to partial hyalinization of the testis at puberty, but the mechanistic drivers behind this remain poorly understood. In this systematic review, we summarize the current knowledge on developmental changes in the cellularity of KS gonads supplemented by a comparative analysis of the fetal and adult gonadal transcriptome, and blood transcriptome and methylome of men with KS. We identified a high fraction of upregulated genes that escape X‐chromosome inactivation, thus supporting previous hypotheses that these are the main drivers of the testicular phenotype in KS. Enrichment analysis showed overrepresentation of genes from the X‐ and Y‐chromosome and testicular transcription factors. Furthermore, by re‐evaluation of recent single cell RNA‐sequencing data originating from adult KS testis, we found novel evidence that the Sertoli cell is the most affected cell type. Our results are consistent with disturbed cross‐talk between somatic and germ cells in the KS testis, and with X‐escapee genes acting as mediators.
Mehr als nur ein Netzwerk: Strukturierung retikulärer Materialien im Nano‐, Meso‐ und Volumenbereich
Authors: Haase Frederik , Hirschle Patrick , Freund Ralph , Furukawa Shuhei , Ji Zhe , Wuttke Stefan
Published: May 2020

Retikuläre Materialien sind von großem Interesse für Anwendungen in der Katalyse und Stofftrennung sowie der Gasspeicherung und gezielten Wirkstoffzufuhr. Diese offenporigen, ausgedehnten Gerüststrukturen können durch Kristallstrukturdesign auf spezifische Anwendungen zugeschnitten werden. Die Implementierung dieser Materialien in Anwendungsumgebungen erfordert jedoch eine Strukturierung über ihr Kristallgitter hinaus, um die Funktionalität auf molekularer Ebene effektiv mit der makroskopischen Welt zu verbinden. Um diese Barriere zu überwinden, werden als nächster Schritt Strategien für die Strukturierung retikulärer Materialien im Nano‐, Meso‐ und Volumenregime benötigt. In diesem Aufsatz geben wir einen Einblick in die jüngsten Fortschritte für die Herstellung von retikulären Materialien über allen Längenskalen, mit dem Fokus auf Selbstorganisationsstrategien und extern kontrollierten Ansätzen. Wir erwarten, dass bedeutende Forschungsfortschritte bei der Anwendung dieser beiden Ansätze in Verbindung mit retikulären Materialien erreicht werden und diese dabei helfen werden, wichtige Bedürfnisse der Gesellschaft zu bewältigen.
A Stable Integrated Photoelectrochemical Reactor for H2 Production from Water Attains a Solar‐to‐Hydrogen Efficiency of 18 % at 15 Suns and 13 % at 207 Suns
Authors: Khan Mohd A. , Al‐Shankiti Ibraheam , Ziani Ahmed , Wehbe Nimer , Idriss Hicham
Published: May 2020

The major challenge in solar water splitting to H2 and O2 is in making a stable and affordable system for large‐scale applications. We have designed, fabricated, and tested a photoelectrochemical reactor characterized as follows: 1) it comprises an integrated device to reduce the balance of the system cost, 2) it utilizes concentrated sunlight to reduce the photoabsorber cost, and 3) it employs and alkaline electrolyte to reduce catalyst cost and eliminate external thermal management needs. The system consists of an III‐V‐based photovoltaic cell integrated with Ni foil as an O2 evolution catalyst that also protects the cell from corrosion. At low light concentration, without the use of optical lenses, the solar‐to‐hydrogen (STH) efficiency was 18.3 %, while at high light concentration (up to 207 suns) with the use of optical lenses, the STH efficiency was 13 %. Catalytic tests conducted for over 100 hours at 100–200 suns showed no sign of degradation nor deviation from product stoichiometry (H2/O2=2). Further tests projected a system stability of years.
The Arachno‐Zintl Ion (Sn5Sb3)3− and the Effects of Element Composition on the Structures of Isoelectronic Clusters: Another Facet of the Pseudo‐Element Concept
Authors: Wilson Robert J. , Weigend Florian , Dehnen Stefanie
Published: May 2020

The pseudo‐element concept, in its most general formulation, states that isoelectronic atoms form equal numbers of bonds. Hence, clusters such as Zintl ions usually retain their structure upon isoelectronic replacement of some or all atoms. Here, a deviation from this common observation is presented, namely the formation of (Sn5Sb3)3− (1), a rare example of an eight‐vertex Zintl ion, and an unprecedented example of a Zintl ion synthesized by solution means that has an arachno‐type structure according to the Wade–Mingos rules. Three structure‐types of interest for (Sn5Sb3)3− were identified by DFT calculations: one that matched the X‐ray diffraction data, and two that that were reminiscent of fragments of known clusters. A study on the isoelectronic series of clusters, (SnxSb8−x)2−x (x=0–8), showed that the relative energies of these three isomers vary significantly with composition (independent of electron count) and that each is the global minimum at least once within the series.
Helical Toroids Self‐Assembled from a Binary System of Polypeptide Homopolymer and its Block Copolymer
Authors: Xu Pengfei , Gao Liang , Cai Chunhua , Lin Jiaping , Wang Liquan , Tian Xiaohui
Published: May 2020

Toroids and helices are fundamental geometrical structures in nature. Polymers can self‐assemble into various nanostructures, including both toroids and helices; however, nanostructures combining toroidal and helical morphologies (that is, helical toroids) are rarely observed. A binary system is reported containing polypeptide homopolymer and its block copolymer, which can hierarchically self‐assemble into uniform helical nanotoroids in solution. The formation of the helical toroids is a successive two‐step process. First, the homopolymers aggregate into fibrils and convolve into toroids, thereby resembling the toroidal condensation of deoxyribonucleic acid (DNA) chains. Second, the block copolymers self‐assemble on the homopolymer toroids and result in helical surface patterns. Additionally, the chirality of the surface helical patterns can be varied by the chirality of the polypeptide block copolymers.
Perylene‐Fused, Aggregation‐Free Polycyclic Aromatic Hydrocarbons for Solution‐Processed Distributed Feedback Lasers
Authors: Zou Ya , Bonal Víctor , Moles Quintero Sergio , Boj Pedro G. , Villalvilla José M. , Quintana José A. , Li Guangwu , Wu Shaofei , Jiang Qing , Ni Yong , Casado Juan , Díaz‐García María A. , Wu Jishan
Published: May 2020

Perylene‐fused, aggregation‐free polycyclic aromatic hydrocarbons with partial zigzag periphery (ZY‐01,ZY‐02, andZY‐03) were synthesized. X‐ray crystallographic analysis reveals that there is no intermolecular π–π stacking in any of the three molecules, and as a result, they show moderate‐to‐high photoluminescence quantum yield in both solution and in the solid state. They also display the characteristic absorption and emission spectra of perylene dyes.ZY‐01andZY‐02with a nearly planar π‐conjugated skeleton exhibit amplified spontaneous emission (ASE) when dispersed in polystyrene thin films. Solution‐processed distributed feedback lasers have been fabricated usingZY‐01andZY‐02as active gain materials, both showing narrow emission linewidth (<0.4 nm) at wavelengths around 515 and 570 nm, respectively. In contrast,ZY‐03did not show ASE and lasing, presumably due to its highly twisted backbone, which facilitates nonradiative internal conversion and intersystem crossing.
Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low‐Dose Photodynamic Therapy
Authors: Wang Zhijia , Huang Ling , Yan Yuxin , El‐Zohry Ahmed M. , Toffoletti Antonio , Zhao Jianzhang , Barbon Antonio , Dick Bernhard , Mohammed Omar F. , Han Gang
Published: May 2020

Intersystem crossing (ISC) of triplet photosensitizers is a vital process for fundamental photochemistry and photodynamic therapy (PDT). Herein, we report the co‐existence of efficient ISC and long triplet excited lifetime in a heavy atom‐free bodipy helicene molecule. Via theoretical computation and time‐resolved EPR spectroscopy, we confirmed that the ISC of the bodipy results from its twisted molecular structure and reduced symmetry. The twisted bodipy shows intense long wavelength absorption (ϵ=1.76×105 m−1 cm−1 at 630 nm), satisfactory triplet quantum yield (ΦT=52 %), and long‐lived triplet state (τT=492 μs), leading to unprecedented performance as a triplet photosensitizer for PDT. Moreover, nanoparticles constructed with such helical bodipy show efficient PDT‐mediated antitumor immunity amplification with an ultra‐low dose (0.25 μg kg−1), which is several hundred times lower than that of the existing PDT reagents.
A Novel Side‐Chain Liquid Crystal Elastomer Exhibiting Anomalous Reversible Shape Change
Authors: Yin Lu , Han Li , Ge Feijie , Tong Xia , Zhang Wei , Soldera Armand , Zhao Yue
Published: May 2020

Liquid crystalline elastomers (LCEs) have been actively investigated as stimuli‐controlled actuators and soft robots. The basis of these applications is the ability of LCEs to undergo a reversible shape change upon a liquid crystalline (LC)‐isotropic phase transition. Herein, we report the synthesis of a novel LCE based on a side‐chain liquid crystalline polymer (SCLCP). In contrast to known LCEs, this LCE exhibits a striking anomalous shape change. Subjecting a mechanically stretched monodomain strip to LC‐disorder phase transition, both the length and width of the strip contract in isotropic phase, and both elongate in LC phase. This thermally induced behaviour is the result of a subtle interplay between the relaxation of polymer main chain oriented along the stretching direction and the disordering of side‐group mesogens oriented perpendicularly to the stretching direction. This finding points out potential design of LCEs of this peculiar type and possible applications to exploit.
Site‐Selective Oxidation of Monolayered Liquid‐Exfoliated WS2 by Shielding the Basal Plane through Adsorption of a Facial Amphiphile
Authors: Grieger Sebastian , Szydłowska Beata M. , Rao Vaishnavi J. , Steinmann Eva , Dodds Marcus , Gholamvand Zahra , Duesberg Georg S. , Zaumseil Jana , Backes Claudia
Published: May 2020

In recent years, various functionalization strategies for transition‐metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS2 with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS2 is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.
Pd supported on graphene modified g‐C3N4 hybrid: a highly efficient catalyst for hydrogenation of nitroarenes
Authors: Zhang Longkang , Zhang Lihong , Cheng Saisai , Zhou Xin , Shang Ningzhao , Gao Shutao , Wang Chun
Published: May 2020

Graphitic carbon nitride (g‐C3N4) and graphene (GO) have been greatly utilized as supports in the field of heterogeneous catalysis. In this work, layered C3N4 polymer/graphene hybrid (CNNS/rGO20) with heterostructure was fabricated by a hydrothermal method followed by loading Pd nanoparticles on the hybrid. The palladium was well dispersed uniformly (1.31 nm) owing to the layered and porous heterostructure of CNNS/rGO20. The obtained catalyst was used for the transfer hydrogenation of a series of nitro‐compounds to give the corresponding aromatic amines with outstanding activity by employing formic acid as hydrogen donor under mild conditions. The catalytic activity of the heterogeneous catalyst showed no significant loss after five continuous use.
Effects of metal centers of complexes supported by S,S′‐bis(2‐pyridylmethyl)‐1,2‐thioethane on catalytic activities for electrochemical‐ and photochemical‐driven hydrogen production
Authors: Liu Wei‐Xia , Xie Zhen‐Lang , Wang Chun‐Li , Zhan Shu‐Zhong , Wu Song‐Ping
Published: May 2020

S,S′‐bis(2‐pyridylmethyl)‐1,2‐thioethane (bpte) reacts with MCl2 (M = Co, Ni, and Fe) to give three complexes, namely, [CoII(bpte)Cl2] (1), [NiII(bpte)Cl2] (2), and [FeII(bpte)Cl2] (3), respectively. They all act as catalysts for proton or water reduction to dihydrogen via electrolysis or photolysis. Under an overpotential of 837.6 mV, the electrolysis of a neutral buffer with complex 1, 2, or 3 can provide 418 (±3), 555 (±3), and 243 (±3) moles of hydrogen per mole of catalyst per hour (mol H2/mol catalyst/h), respectively. Under blue light, together with a photosensitizer and ascorbic acid (H2A) as a sacrificial electron donor, the photolysis of an aqueous solution (pH 4.5) containing complex 1, 2, or 3 can afford 9060 (±5), 24,900 (±5), and 10,630 (±5) moles H2 per mole of catalyst (mol of H2 [mol of cat]−1) during 83‐h irradiation with an average apparent quantum yield of 7.1%, 24%, and 10%, respectively. The results show that the nickel complex [NiII(bpte)Cl2] exhibits a more efficient activity for hydrogen generation than the iron or cobalt species. These findings may offer a new chemical paradigm for the design of efficient catalysts.
Racemic total synthesis and evaluation of the biological activities of the isoquinoline–benzylisoquinoline alkaloid muraricine
Authors: Schütz Ramona , Müller Martin , Gerndt Susanne , Bartel Karin , Bracher Franz
Published: May 2020

The first racemic total synthesis of the isoquinoline–benzylisoquinoline alkaloid muraricine is reported herein. Pharmacological characterization identified muraricine as a moderate inhibitor of P‐glycoprotein, a crucial factor of multidrug resistance in cancer. When combined with vincristine, muraricine partly reversed the chemoresistance of vincristine‐resistant leukemia cells at a nontoxic concentration. Furthermore, no cytotoxic effects on noncancerous human cells in therapeutically relevant concentrations were observed.
Redox Activity of Bromides in Carbon‐Based Electrochemical Capacitors
Authors: Fic Krzysztof , Morimoto Shinya , Frąckowiak Elżbieta , Ishikawa Masashi
Published: May 2020

This paper reports on the electrochemical performance of activated carbon electrodes in aqueous solutions of bromide‐based species and discusses the results in the broader context of redox‐active electrolytes in electrochemical capacitor applications. Operando techniques such as Raman spectroscopy and electrochemical quartz crystal microbalance have been implemented to describe the interactions at the electrode/electrolyte interface. Ex situ experiments, including XPS profiles at different electrode thicknesses, support the discussion by providing insights into surficial and bulk‐related processes. Finally, the electrochemical activity of bromides and their advantages and drawbacks are discussed.
Genetic Causation in Complex Regulatory Systems: An Integrative Dynamic Perspective
Authors: DiFrisco James , Jaeger Johannes
Published: May 2020

The logic of genetic discovery has changed little over time, but the focus of biology is shifting from simple genotype–phenotype relationships to complex metabolic, physiological, developmental, and behavioral traits. In light of this, the traditional reductionist view of individual genes as privileged difference‐making causes of phenotypes is re‐examined. The scope and nature of genetic effects in complex regulatory systems, in which dynamics are driven by regulatory feedback and hierarchical interactions across levels of organization are considered. This review argues that it is appropriate to treat genes as specific actual difference‐makers for the molecular regulation of gene expression. However, they are often neither stable, proportional, nor specific as causes of the overall dynamic behavior of regulatory networks. Dynamical models, properly formulated and validated, provide the tools to probe cause‐and‐effect relationships in complex biological systems, allowing to go beyond the limitations of genetic reductionism to gain an integrative understanding of the causal processes underlying complex phenotypes.
The simultaneous occurrence of lichen planopilaris and alopecia areata: A report of two cases and literature review
Authors: Mohaghegh Fatemeh , Bahrami Bahareh , Saber Mina
Published: May 2020

Although the coexistence of alopecia areata and lichen planopilaris is rare, if alopecic patches appear abruptly, this possible association should be kept in mind.
Excellent Catalytic Activity of a Pd‐Promoted MnOx Catalyst for Purifying Automotive Exhaust Gases
Authors: Hosokawa Saburo , Shibano Takuya , Koga Hiroaki , Matsui Masafuyu , Asakura Hiroyuki , Teramura Kentaro , Okumura Mitsutaka , Tanaka Tsunehiro
Published: May 2020

Currently, there is a strong demand for new automotive catalysts with improved low‐temperature activity and reduced precious metal use. Such catalysts must undergo simultaneous CO/hydrocarbon oxidations and NO reduction. A Pd catalyst supported on Mn‐modified hexagonal YbFeO3 (Pd/Mn‐YFO) exhibited extremely high activity at low temperature via a Mars‐van Krevelen (MvK) mechanism involving lattice oxygen and oxygen vacancy site in the catalyst support. NO reduction proceeded by high CO and C3H6 oxidation activity of Pd/Mn‐YFO, and the catalytic activity of 1.0 wt% Pd/Mn‐YFO was higher than that of 5.0 wt% Pd/Al2O3, despite the lower Pd loading. We clarified that the lattice oxygen in MnOx, which existed on the surface of YFO, consumed by CO and C3H6 oxidation was recovered by NO to form N2 via MvK‐type NO reduction, while the Pd species promoted NO adsorption and dissociation on MnO‐like species.
Bimetallic Nanostructured Catalysts Prepared by Laser Electrodispersion: Structure and Activity in Redox Reactions
Authors: Bryzhin A. A. , Golubina E. V. , Maslakov K. I. , Lokteva E. S. , Tarkhanova I. G. , Gurevich S. A. , Yavsin D. A. , Rostovshchikova T. N.
Published: May 2020

One‐stage size‐selective method of laser electrodispersion (LED) was used to produce nanostructured NiPd, NiMo and NiW coatings on the surface of alumina, HOPG and Sibunit for the catalytic application. The deposition of nanoparticles produced by LED of bimetallic targets from alloyed or pressed metal powders provides the uniform distribution of both metals on the outer support surface; the metal ratio is similar to that in the original target. The catalytic behaviour of produced “core‐shell” catalysts in comparison with monometallic analogues was tested in two model reactions: the CO oxidation with oxygen on NiPd catalysts supported on alumina and Sibunit; and thiophene oxidation with hydrogen peroxide on NiMo and NiW alumina supported catalysts. Novel LED bimetallic catalysts with extremely low metal content (0.005 %) were superior in terms of activity and stability to monometallic ones and the catalysts obtained by “wet” chemistry methods. Improved catalytic properties of bimetallic LED catalysts are related to the high density of single nanoparticles and the formation of active metal‐oxide interfaces on the support surface.
Nanostructure Design Strategies for Aqueous Zinc‐Ion Batteries
Authors: Ling Wei , Wang Panpan , Chen Zhe , Wang Hua , Wang Jiaqi , Ji Zhenyuan , Fei Jinbo , Ma Zhiyuan , He Ning , Huang Yan
Published: May 2020

With reliable safety, environmental friendliness and cost advantage, aqueous rechargeable batteries have attracted great attention in the field of consumer electronics, static energy storage and power cells in recent decades. In particular, aqueous zinc‐ion batteries (AZIBs) possess a high theoretical capacity (820 mAh g−1 and 5855 mAh cm−3) and low anode potential (−0.76 V vs. standard hydrogen electrode), owing to the bivalent ion migration and the high stability of zinc metal in water, resulting in a relatively satisfactory energy density for practical applications. However, AZIBs still face some challenges, such as zinc dendrite growth, narrow voltage window, active materials dissolution, poor zinc ion insertion/extraction kinetics, and so forth, largely impeding the continued progress of AZIBs. Nanostructure design strategies provide a powerful and broad research thought to effectively solve the above problems, owing to unique properties at the nanoscale. Herein, we demonstrate an overview of recent progress in AZIBs from the perspective of nanostructure design, and focus on the nanostructure engineering of cathode materials, zinc anodes and flexible gel electrolytes, giving rise to an excellent electrochemical performances of AZIBs. Finally, a brief summary for nanostructure design strategies applied in AZIBs is presented, and next research directions are proposed to inspire suggestive instructions for further research into AZIBs.
P450Jα: A New, Robust and α‐Selective Fatty Acid Hydroxylase Displaying Unexpected 1‐Alkene Formation
Authors: Armbruster Julia , Steinmassl Mathilde , Müller Bogotá Christina A. , Berg Gabriele , Nidetzky Bernd , Dennig Alexander
Published: May 2020

Oxyfunctionalization of fatty acids (FAs) is a key step in the design of novel synthetic pathways for biobased/biodegradable polymers, surfactants and fuels. Here, we show the isolation and characterization of a robust FA α‐hydroxylase (P450Jα) which catalyses the selective conversion of a broad range of FAs (C6:0‐C16:0) and oleic acid (C18:1) with H2O2 as oxidant. Under optimized reaction conditions P450Jα yields α‐hydroxy acids all with >95 % regioselectivity, high specific activity (up to 15.2 U mg−1) and efficient coupling of oxidant to product (up to 85 %). Lauric acid (C12:0) turned out to be an excellent substrate with respect to productivity (TON=394 min−1). On preparative scale, conversion of C12:0 reached 83 % (0.9 g L−1) when supplementing H2O2 in fed‐batch mode. Under similar conditions P450Jα allowed further the first biocatalytic α‐hydroxylation of oleic acid (88 % conversion on 100 mL scale) at high selectivity and in good yields (1.1 g L−1; 79 % isolated yield). Unexpectedly, P450Jα displayed also 1‐alkene formation from shorter chain FAs (≤C10:0) showing that oxidative decarboxylation is more widely distributed across this enzyme family than reported previously.
Near‐Infrared (>1000 nm) Light‐Harvesters: Design, Synthesis and Applications
Authors: Rao Ravulakollu Srinivasa , Suman  , Singh Surya Prakash
Published: May 2020

Organic molecules can absorb or emit light in UV, visible and infra‐red (IR) region of solar radiation. Fifty percent of energy of solar radiation lies in the IR region of solar spectrum and extended π‐conjugated molecules containing low optical band gap can absorb NIR radiations. Recently IR molecules have grabbed the attention of synthetic chemists. Although only few molecules have been reported so far such as derivative of BODIPY, naphthalimide, porphyrins, perylene, BBT etc., they have shown highest absorbing capacity towards greater than 1100 nm. These compounds have potential applications in different fields, such as for biomedical and optoelectronic applications. In this review, we present different classes of light‐harvesters with harvesting range above 1000 nm.
The Dimeric Form of 1,3‐Diaminoisoquinoline Derivative Rescued the Mis‐splicing of Atp2a1 and Clcn1 Genes in Myotonic Dystrophy Type 1 Mouse Model
Authors: Matsumoto Jun , Nakamori Masayuki , Okamoto Tatsumasa , Murata Asako , Dohno Chikara , Nakatani Kazuhiko
Published: May 2020

Expanded CUG repeat RNA in the dystrophia myotonia protein kinase (DMPK) gene causes myotonic dystrophy type 1 (DM1) and sequesters RNA processing proteins, such as the splicing factor muscleblind‐like 1 protein (MBNL1). Sequestration of splicing factors results in the mis‐splicing of some pre‐mRNAs. Small molecules that rescue the mis‐splicing in the DM1 cells have drawn attention as potential drugs to treat DM1. Herein we report a new molecule JM642 consisted of two 1,3‐diaminoisoquinoline chromophores having an auxiliary aromatic unit at the C5 position. JM642 alternates the splicing pattern of the pre‐mRNA of the Ldb3 gene in the DM1 cell model and Clcn1 and Atp2a1 genes in the DM1 mouse model. In vitro binding analysis by surface plasmon resonance (SPR) assay to the r(CUG) repeat and disruption of ribonuclear foci in the DM1 cell model suggested the binding of JM642 to the expanded r(CUG) repeat in vivo, eventually rescue the mis‐splicing.
Coronenohelicenes with Dynamic Chirality
Authors: Weiss Corinna , Sharapa Dmitry I. , Hirsch Andreas
Published: May 2020

The synthesis of a new type of chiral and dynamic nonplanar aromatics containing a combination of fused perylene‐based coronenes and helicenes is reported. Either one or two helicene moieties were fused to the bay regions of an extended perylene core. The target compounds contain either identical or two different helicene building blocks. The combination with two helicene units leads to six different isomers, including two pairs of enantiomers and twomesoforms. The experimental determination of the isomerization barriers the corresponding double [5]‐helicenes revealed activation energies ofEa=24.81 and 25.38 kcal mol−1, which is slightly above the barrier of the parent [5]‐helicene. Resolution of all possible regio‐ and stereoisomers allowed for the systematic investigation of the chiroptical properties. They revealed remarkable dissymmetry factorsIgabsIof up to 1.2×10−2, which mirror the synergy between the strong absorbing perylenes and the inherent chirality of helicenes.
IrIII‐Catalyzed Selective ortho‐Monoiodination of Benzoic Acids with Unbiased C−H Bonds
Authors: Weis Erik , Johansson Magnus J. , Martín‐Matute Belén
Published: May 2020

An iridium‐catalyzed selective ortho‐monoiodination of benzoic acids with two equivalent C−H bonds is presented. A wide range of electron‐rich and electron‐poor substrates undergo the reaction under mild conditions, with >20:1 mono/di selectivity. Importantly, the C−H iodination occurs selectively ortho to the carboxylic acid moiety in substrates bearing competing coordinating directing groups. The reaction is performed at room temperature and no inert atmosphere or exclusion of moisture is required. Mechanistic investigations revealed a substrate‐dependent reversible C−H activation/protodemetalation step, a substrate‐dependent turnover‐limiting step, and the crucial role of the AgI additive in the deactivation of the iodination product towards further reaction.
The impact of childhood cancer on parental separation, divorce, and family planning in Denmark
Authors: Mader Luzius , Hargreave Marie , Frederiksen Line Elmerdahl , Bidstrup Pernille Envold , Dalton Susanne Oksbjerg , Kjær Susanne K. , Nielsen Thomas Tjørnelund , Kroyer Anja , Winther Jeanette Falck , Erdmann Friederike
Published: May 2020

Background

Childhood cancer is a devastating experience for the family. The objective of the current study was to assess the impact of having a child with cancer on parental separation, divorce, and future family planning among families residing in Denmark.

Methods

The authors conducted a nationwide cohort study using Danish registry data. Parents of children diagnosed with cancer between 1982 and 2014 (7066 children and 12,418 case parents) were matched with 10 comparison parents of cancer‐free children per case parent (69,993 children and 125,014 comparison parents). We used discrete‐time Cox regression models to compare the risk of separation (end of cohabitation) and divorce between case and comparison parents, and to identify risk factors for separation and divorce among case parents only. Descriptive statistics were used to compare family planning between case and comparison parents.

Results

Case parents were found to have a slightly lower risk of separation (hazard ratio, 0.96; 95% confidence interval, 0.93‐0.99) and divorce (hazard ratio, 0.92; 95% confidence interval, 0.87‐0.97) than comparison parents. The authors found that case parents who were aged <45 years, with short education (an International Standard Classification of Education code indicating early childhood education, primary education, and lower secondary education), and who were unemployed were at an increased risk of separation and divorce. Moreover, the parents of children diagnosed with cancer at a young age (aged <15 years) were more likely to separate or divorce. No differences with regard to the total number of children and time to a next child after the cancer diagnosis were observed between case and comparison parents.

Conclusions

Having a child with cancer was not associated with an overall adverse impact on parents' risk of separation or divorce and future family planning. These encouraging findings should be communicated to parents to support them along their child's cancer trajectory.
From Real‐World Patient Data to Individualized Treatment Effects Using Machine Learning: Current and Future Methods to Address Underlying Challenges
Authors: Bica Ioana , Alaa Ahmed M. , Lambert Craig , van der Schaar Mihaela
Published: May 2020

Clinical decision making needs to be supported by evidence that treatments are beneficial to individual patients. Although randomized control trials (RCTs) are the gold standard for testing and introducing new drugs, due to the focus on specific questions with respect to establishing efficacy and safety vs. standard treatment, they do not provide a full characterization of the heterogeneity in the final intended treatment population. Conversely, real‐world observational data, such as electronic health records (EHRs), contain large amounts of clinical information about heterogeneous patients and their response to treatments. In this paper, we introduce the main opportunities and challenges in using observational data for training machine learning methods to estimate individualized treatment effects and make treatment recommendations. We describe the modeling choices of the state‐of‐the‐art machine learning methods for causal inference, developed for estimating treatment effects both in the cross‐section and longitudinal settings. Additionally, we highlight future research directions that could lead to achieving the full potential of leveraging EHRs and machine learning for making individualized treatment recommendations. We also discuss how experimental data from RCTs and Pharmacometric and Quantitative Systems Pharmacology approaches can be used to not only improve machine learning methods, but also provide ways for validating them. These future research directions will require us to collaborate across the scientific disciplines to incorporate models based on RCTs and known disease processes, physiology, and pharmacology into these machine learning models based on EHRs to fully optimize the opportunity these data present.
Plant breeding capacity in U.S. public institutions
Authors: Coe Michael T. , Evans Katherine M. , Gasic Ksenija , Main Dorrie
Published: May 2020

Several studies in recent decades have warned that plant breeding capacity in U.S. institutions may be declining, placing our food system at risk. To further understand the status, trajectory, and needs of these programs, a national survey was conducted in 2018. Public‐sector plant breeding programs (n = 278) in 44 U.S. states responded to questions about staffing levels, budgets, access to needed personnel, and access to technology for selective breeding. Almost half of program leaders were nearing retirement age. Programs reported significantly declining estimates of hours spent on program activities by program leaders and technical support staff. On average, programs reported devoting 2.78 full‐time equivalent (FTE) to plant breeding research in the most recent fiscal year (including all types of personnel); for germplasm enhancement activities and variety development, mean estimated hours per program totaled 1.58 and 2.20 FTE, respectively. The median annual operating budget in the most recent fiscal year was US$150,000; the mean (average) annual operating budget was US$266,562. Budget and FTE means are somewhat skewed toward higher figures because of a few unusually large programs; almost 80% of programs reported annual budgets of US$400,000 or less. Institutional funds, federal competitive grants, and commodity check‐off programs accounted for 67% of program budgets. Many programs reported that budget shortfalls or uncertainty “endangered or severely constrained” or seriously constrained their ability to support key personnel, infrastructure and operations, and access to current technology for collecting, analyzing, and applying knowledge from phenotype and genotype data on plant materials in their programs.
Oxidative Esterification of 5‐Hydroxymethylfurfural with an N‐doped Carbon‐supported CoCu Bimetallic Catalyst
Authors: Liu Huai , Ding Ning , Wei Junnan , Tang Xing , Zeng Xianhai , Sun Yong , Lei Tingzhou , Fang Huayu , Li Tianyuan , Lin Lu
Published: May 2020

The direct fabrication of furan‐2,5‐dimethylcarboxylate (FDMC), a promising renewable monomer, from biomass‐derived 5‐hydroxymethylfurfural (HMF) is a cutting‐edge process. In this contribution, an elaborately designed N‐doped carbon‐supported CoCu bimetallic catalyst (CoxCuy‐NC; x/y=9:1, 7:3, 4:6, which represents the designed molar ratio of Co and Cu in the catalyst), which could offer a desirable FDMC yield of 95 % under mild and base‐free conditions (Co7Cu3‐NC, 2 bar O2, 80 °C, 4 h) is described for the oxidative esterification of HMF. Notably, an FDMC formation rate of 6.1 molFDMC molCo−1 h−1 was achieved over Co7Cu3‐NC, which represents the highest catalytic efficiency so far among Co‐based catalytic systems. It has been demonstrated that Cu‐doping in Co7Cu3‐NC catalyst brings about more active sites (Co‐Nx species) with stronger molecular oxygen activation ability. The increase of surface N content of Co7Cu3‐NC also improves basicity of the catalyst, which favors the hydrogen abstraction process during the HMF oxidative esterification reaction. These findings may pave an efficient and green way for the synthesis of sustainable bio‐based polymer monomers.
Metal–Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al‐SBA‐15
Authors: Shivhare Atal , Hunns James A. , Durndell Lee J. , Parlett Christopher M. A. , Isaacs Mark A. , Lee Adam F. , Wilson Karen
Published: May 2020

Hydrodeoxygenation (HDO) is a promising technology to upgrade fast pyrolysis bio‐oils but it requires active and selective catalysts. Here we explore the synergy between the metal and acid sites in the HDO of anisole, a model pyrolysis bio‐oil compound, over mono‐ and bi‐functional Pt/(Al)‐SBA‐15 catalysts. Ring hydrogenation of anisole to methoxycyclohexane occurs over metal sites and is structure sensitive; it is favored over small (4 nm) Pt nanoparticles, which confer a turnover frequency (TOF) of approximately 2000 h−1 and a methoxycyclohexane selectivity of approximately 90 % at 200 °C and 20 bar H2; in contrast, the formation of benzene and the desired cyclohexane product appears to be structure insensitive. The introduction of acidity to the SBA‐15 support promotes the demethyoxylation of the methoxycyclohexane intermediate, which increases the selectivity to cyclohexane from 15 to 92 % and the cyclohexane productivity by two orders of magnitude (from 15 to 6500 mmol gPt−1 h−1). Optimization of the metal–acid synergy confers an 865‐fold increase in the cyclohexane production per gram of Pt and a 28‐fold reduction in precious metal loading. These findings demonstrate that tuning the metal–acid synergy provides a strategy to direct complex catalytic reaction networks and minimize precious metal use in the production of bio‐fuels.
Coffee and tea consumption in the early adult lifespan and left ventricular function in middle age: the CARDIA study
Authors: Nwabuo Chike C. , Betoko Aisha S. , Reis Jared P. , Moreira Henrique T. , Vasconcellos Henrique D. , Guallar Eliseo , Cox Christopher , Sidney Stephen , Ambale‐Venkatesh Bharath , Lewis Cora E. , Schreiner Pamela J. , Lloyd‐Jones Donald , Kiefe Catarina I. , Gidding Samuel S. , Lima João A.C.
Published: May 2020

Aims

The long‐term impact of coffee or tea consumption on subclinical left ventricular (LV) systolic or diastolic function has not been previously studied. We examined the association between coffee or tea consumption beginning in early adulthood and cardiac function in midlife.

Methods and results

We investigated 2735 Coronary Artery Risk Development in Young Adults (CARDIA) study participants with long‐term total caffeine intake, coffee, and tea consumption data from three visits over a 20 year interval and available echocardiography indices at the CARDIA Year‐25 exam (2010–2011). Linear regression models were used to assess the association between caffeine intake, tea, and coffee consumption (independent variables) and echocardiography outcomes [LV mass, left atrial volume, and global longitudinal strain (GLS), LV ejection fraction (LVEF), and transmitral Doppler early filling velocity to tissue Doppler early diastolic mitral annular velocity (E/e´)]. Models were adjusted for standard cardiovascular risk factors, socioeconomic status, physical activity, alcohol use, and dietary factors (calorie intake, whole and refined grain intake, and fruit and vegetable consumption). Mean (standard deviation) age was 25.2 (3.5) years at the CARDIA Year‐0 exam (1985–1986), 57.4% were women, and 41.9% were African‐American. In adjusted multivariable linear regression models assessing the relationship between coffee consumption and GLS, beta coefficients when comparing coffee drinkers of <1, 1–2, 3–4, and >4 cups/day with non‐coffee drinkers were β = −0.30%, P < 0.05; β = −0.35%, P < 0.05; β = −0.32%, P < 0.05; β = −0.40%, P > 0.05; respectively (more negative values implies better systolic function). In adjusted multivariable linear regression models assessing the relationship between coffee consumption and E/e´, beta coefficients when comparing coffee drinkers of <1, 1–2, 3–4, and >4 cups/day with non‐coffee drinkers were β = −0.29, P < 0.05; β = −0.38, P < 0.01; β = −0.20, P > .05; and β = −0.37, P > 0.05, respectively (more negative values implies better diastolic function). High daily coffee consumption (>4 cups/day) was associated with worse LVEF (β = −1.69, P < 0.05). There were no associations between either tea drinking or total caffeine intake and cardiac function (P > 0.05 for all).

Conclusions

Low‐to‐moderate daily coffee consumption from early adulthood to middle age was associated with better LV systolic and diastolic function in midlife. High daily coffee consumption (>4cups/day) was associated with worse LV function. There was no association between caffeine or tea intake and cardiac function.