bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractThe 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

AbstractToroids 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

AbstractPerylene‐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

AbstractIntersystem 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

AbstractLiquid 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

AbstractIn 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.
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

AbstractThe 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

AbstractThis 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

AbstractThe 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

AbstractAlthough 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

AbstractCurrently, 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

AbstractOne‐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

AbstractWith 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

AbstractOxyfunctionalization 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

AbstractOrganic 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

AbstractExpanded 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

AbstractThe 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

AbstractAn 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

BackgroundChildhood 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.MethodsThe 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.ResultsCase 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.ConclusionsHaving 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.