bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multifunctional Compounds for Activation of the p53‐Y220C Mutant in Cancer
Authors: Miller Jessica J. , Orvain Christophe , Jozi Shireen , Clarke Ryan M. , Smith Jason R. , Blanchet Anaïs , Gaiddon Christian , Warren Jeffrey J. , Storr Tim 
Published: September 2018

AbstractThe p53 protein plays a major role in cancer prevention, and over 50 % of cancer diagnoses can be attributed to p53 malfunction. The common p53 mutation Y220C causes local protein unfolding, aggregation, and can result in a loss of Zn in the DNA‐binding domain. Structural analysis has shown that this mutant creates a surface site that can be stabilized using small molecules, and herein a multifunctional approach to restore function to p53‐Y220C is reported. A series of compounds has been designed that contain iodinated phenols aimed for interaction and stabilization of the p53‐Y220C surface cavity, and Zn‐binding fragments for metallochaperone activity. Their Zn‐binding affinity was characterized using spectroscopic methods and demonstrate the ability of compounds L4 and L5 to increase intracellular levels of Zn2+ in a p53‐Y220C‐mutant cell line. The in vitro cytotoxicity of our compounds was initially screened by the National Cancer Institute (NCI‐60), followed by testing in three stomach cancer cell lines with varying p53 status’, including AGS (WTp53), MKN1 (V143A), and NUGC3 (Y220C). Our most promising ligand, L5, is nearly 3‐fold more cytotoxic than cisplatin in a large number of cell lines. The impressive cytotoxicity of L5 is further maintained in a NUGC3 3D spheroid model. L5 also induces Y220C‐specific apoptosis in a cleaved caspase‐3 assay, reduces levels of unfolded mutant p53, and recovers p53 transcriptional function in the NUGC3 cell line. These results show that these multifunctional scaffolds have the potential to restore wild‐type function in mutant p53‐Y220C.
Azolate Anions in Ionic Liquids: Promising and Under‐Utilized Components of the Ionic Liquid Toolbox
Authors: Easton Max E. , Choudhary Hemant , Rogers Robin D. 
Published: September 2018

AbstractOwing to their ease of synthesis, diffuse positive charge, and chemical stability, 1‐alkyl‐3‐methylimidazolium cations (i.e., [Cnmim]+) are one of the most routinely utilized and historically important components in ionic liquid (IL) chemistry. However, while this is a routinely encountered member of the IL family as cations, relatively few workers have explored the versatile chemistry of azoles to allow their use as an anionic component in ILs, as azolates. Azolate anions possess many of the desired properties for IL formation, including a diffuse ionic charge, tailorable asymmetry, and synthetic flexibility, with the added advantages of not relying on halogen atoms for electron‐withdrawing effects, as is commonly encountered with IL anions such as hexafluorophosphate. This review explores the 122 azolate‐containing ILs known in the literature (prepared from only 39 disparate azolate anions), with a view to highlighting not only their demonstrated utility as an IL component, but the ways in which the larger scientific community may utilize their advantageous properties for new tailored materials.
Ruthenium Complexes Bearing Thiophene‐Based Unsymmetrical N‐Heterocyclic Carbene Ligands as Selective Catalysts for Olefin Metathesis in Toluene and Environmentally Friendly 2‐Methyltetrahydrofuran
Authors: Smoleń Michał , Kośnik Wioletta , Gajda Roman , Woźniak Krzysztof , Skoczeń Aleksandra , Kajetanowicz Anna , Grela Karol 
Published: September 2018

AbstractThree mono‐N‐heterocyclic carbene (NHC) ruthenium 2‐isopropoxybenzylidene (10 a–c) and one bis(NHC) indenylidene complex (8) bearing an unsymmetrical N‐heterocyclic carbene ligand were synthesized and structurally characterized by single‐crystal X‐ray diffraction. The catalytic activity of the newly obtained complexes were evaluated in ring‐closing metathesis (RCM) and ene–yne (RCEYM) reactions in toluene and environmentally friendly 2‐MeTHF under air. The results confirmed that although all tested reactions can be successfully mediated by catalysts 10 a–c, their general reactivity is lower than the benchmark all‐purpose Ru catalysts with symmetrical NHC ligands. However, the latter cannot compete with specialized ruthenium complex 10 a in industrially relevant self‐CM of terminal olefins in neat conditions.
Corroles at the Real Solid–Liquid Interface: In Situ STM Investigation of a Water‐Soluble Corrole Layer Deposited onto Au(111)
Authors: Bonanni Beatrice , Fazi Laura , Fanfoni Massimo , Sgarlata Anna , Caroleo Fabrizio , Pomarico Giuseppe , Galloni Pierluca , Sabuzi Federica , Persichetti Luca , Paolesse Roberto , Goletti Claudio 
Published: September 2018

AbstractCorrole derivatives have been recently employed in many applications at the solid–liquid interface. Therefore, the structural arrangement of the molecular layers in direct contact with the liquid is of fundamental interest. We investigated in solution the deposition of molecular layers of the previously prepared water‐soluble phosphorus complex of a 2‐sulfonato‐10‐(4‐sulfonatophenyl)‐5,15‐dimesitylcorrole [see synthesis in our previous paper, M. Naitana et al., Chem. Eur. J. 2017, 23, 905–916]. The layer formation of P corroles onto the Au(111) surface was monitored by STM in situ, that is, with the substrate immersed in the solution. Marked differences in the morphology between the organic layer formed on the substrate and that deposited after solvent evaporation (drop casting) are reported. In particular, the coating of gold was more effective and stable in the presence of liquid. Preservation of functionality of the corrole molecules after adsorption was verified. This result validates the relevance of corrole layers at the solid–liquid interface to exploit the peculiar properties of these molecules in real‐world applications.
First Micelle‐Free Photoredox Catalytic Access to Hydrated Electrons for Syntheses and Remediations with a Visible LED or even Sunlight
Authors: Naumann Robert , Goez Martin 
Published: September 2018

AbstractHydrated electrons are super‐reductants, yet can be generated with visible light when two photons are pooled, most efficiently through storing the energy of the first photon in a radical pair formed by the reduction of an excited catalyst by a sacrificial donor. All previous such systems for producing synthetically useable amounts of hydrated electrons with an LED in the visible range had to resort to compartmentalization by SDS micelles to curb the performance‐limiting recombination of the pair. To overcome micelle‐imposed constraints on sustainability and applications, we have instead attached carboxylate groups to a ruthenium (tris)bipyridyl catalyst such that its pentaanionic radical strongly repels the dianionic radical of the bioavailable donor urate. We have explored the influence of the Coulombic interactions on the electron generation by a time‐resolved study from microseconds to hours, including for comparison the unsubstituted complex, which forms a monocationic radical, with and without SDS micelles. The new homogeneous electron source is best with regard to stability and total electron output; it has a broader synthetic scope because it does not entail micellar shielding of less hydrophilic compounds, which particularly facilitates cross‐couplings; and it tolerates supramolecular containers as carriers of water‐insoluble substrates or products. As an application in the field, we demonstrate the solar remediation of a recalcitrant chloro‐organic bulk chemical.
Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives
Authors: Morales‐Cerrada Roberto , Fliedel Christophe , Daran Jean‐Claude , Gayet Florence , Ladmiral Vincent , Améduri Bruno , Poli Rinaldo 
Published: September 2018

AbstractThermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single‐crystal X‐ray diffraction studies. The solution‐phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq‐13CO)(RF)] and [Mn(12CO)4(ax‐13CO)(RF)] isotopomers and a ranking of the RFdonor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RFbond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RFradicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠and ΔS≠that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem.2018,864, 12–18). The ability of these complexes to undergo homolytic Mn−RFbond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RFbond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.
Insight into the Mechanochemical Synthesis and Structural Evolution of Hybrid Organic–Inorganic Guanidinium Lead(II) Iodides
Authors: Wilke Manuel , Casati Nicola 
Published: September 2018

AbstractThe in situ investigations of the mechanochemical synthesis of four hybrid organic–inorganic lead(II) iodides with the formula (C(NH2)3)nPbI2+n (n=1, 2, 3, and 4) are presented. Synchrotron X‐ray diffraction data show that the four guanidinium lead(II) iodides easily convert into each other. Although the end product is dictated by the initial stoichiometry, complex pathways were found with different behaviors of the compounds in terms of nucleation, growth, and intermediate formation. This appears to be linked to the respective structural features of the different compounds, especially the connectivity of the inorganic framework and the strength of ionic interactions. High‐temperature studies were conducted on compounds 1, 3, and 4 to reveal the new phases 1‐II, 3‐II, and 3‐III. Unknown structures were solved from single‐crystal analysis and powder X‐ray diffraction.
Molecular Networks in Dynamic Multilevel Systems
Authors: Orrillo A. Gastón , Escalante Andrea M. , Martinez‐Amezaga Maitena , Cabezudo Ignacio , Furlan Ricardo L. E. 
Published: September 2018

AbstractDynamic multilevel systems can be assembled from molecular building blocks through two or more reversible reactions that form covalent bonds. Molecular networks of dynamic multilevel systems can exhibit different connectivities between nodes. The design and creation of molecular networks in multilevel systems require control of the crossed reactivity of the functional groups (how to connect nodes) and the conditions of the reactions (when to connect nodes). In recent years, the combination of orthogonal and communicating reactions, which can be simultaneous or individually activated, has produced a variety of systems that have given rise to macrocycles and cages, as well as molecular motors and multicomponent architectures on surfaces. A given set of reactions can lead to systems with unique responsiveness, compositions, and functions as a result of the relative reactivities. In this Concept article, different molecular networks from synthetic systems that can be produced by combinations of different reaction types are discussed. Moreover, applications of this chemistry are highlighted, and future perspectives are envisioned.
A Facile Synthesis of Ternary Nickel Iron Sulfide Nanospheres as Counter Electrode in Dye‐Sensitized Solar Cells
Authors: Wei Pengkun , Li Xuemin , Li Jing , Bai Jinwu , Jiang Chuanjia , Liu Lu 
Published: September 2018

AbstractThe incorporation of a foreign metal into a material may adjust the surface electronic structure and promote charge transfer, which then ultimately improves electrical conductivity and electrocatalytic performance because of the possible charge delocalization between the metal cations. As a result, for the first time, ternary nickel iron sulfide nanospheres have been successfully fabricated through a two‐step solvothermal approach with the help of glucose (Ni0.5Fe0.5S2/C). Subsequently, the electrochemical performance and electrocatalytic activity of Ni0.5Fe0.5S2/C were evaluated by electrochemical impedance spectroscopy, Tafel polarization and cyclic voltammetry, indicating high electrical conductivity and great electrocatalytic activity. Ni0.5Fe0.5S2/C was employed as a counter electrode for dye‐sensitized solar cells, and exhibited higher power conversion efficiency (6.79 %) than the device with Pt CE (6.31 %) under full sunlight illumination (100 mW cm−2, AM 1.5G).
Long‐Persistent Circularly Polarized Phosphorescence from Chiral Organic Ionic Crystals
Authors: Chen Wenjie , Tian Zimin , Li Yuangang , Jiang Yuqian , Liu Minghua , Duan Pengfei 
Published: September 2018

AbstractLong‐persistent circularly polarized phosphorescence (LPCPP) is achieved for the first time in chiral organic ionic crystals at room temperature. The co‐crystal composed of terephtalic acid (TPA) and chiral α‐phenylethyamines (PEAs) gave rise to LPCPP with lifetimes up to 862 ms and large dissymmetric factor (glum). The hybridization of TPA with chiral PEAs allows circular polarization of the generated long‐persistent phosphorescence. The observed mirror‐image twisted molecular structures in the rigid lattices were responsible for the chiroptical activation of the generated long‐persistent phosphorescence.
Pillararene‐Based Two‐Component Thixotropic Supramolecular Organogels: Complementarity and Multivalency as Prominent Motifs
Authors: Zafrani Yossi , Kaizerman Dana , Hadar Maya , Bigan Nitzan , Granot Eran , Ghosh Moumita , Adler‐Abramovich Lihi , Patolsky Fernando , Cohen Yoram 
Published: September 2018

AbstractInvited for the cover of this issue is the group of Yossi Zafrani and Yoram Cohen at the Tel Aviv University. The image depicts an artistic rendition of the supramolecular organogel with nanotubular molecular core structure. Read the full text of the article at 10.1002/chem.201801418.
Alternation of Metal‐Bridged Metallacycle Skeletons: From Ruthenapentalyne to Ruthenapentalene and Ruthenaindene Derivative
Authors: Li Jinhua , Kang Huijun , Zhuo Kaiyue , Zhuo Qingde , Zhang Hong , Lin Yu‐Mei , Xia Haiping 
Published: September 2018

AbstractThe reaction of ruthenapentalyne with one equivalent of isocyanide led to the formation of a rare ruthenapentalene complex by nucleophilic addition. When excess isocyanides were used, the metal‐bridged ruthenaindene derivatives can be isolated and were formed by one carbon of isocyanide insertion into the ruthenacycle. Complexes 3 represent the first metallaindene derivatives with a second‐row transition metal at the bridge‐head position. The transformations from ruthenapentalyne via ruthenapentalene to ruthenaindene derivatives are of interest and can be extended to the syntheses of other polycyclic ruthenacycles. These unique metallacycles exhibit considerable stability and broad spectral absorption spanning the visible spectrum, enabling their potential applications in photoelectric materials.
Promoting resilience in adolescents and young adults with cancer: Results from the PRISM randomized controlled trial
Authors: Rosenberg Abby R. , Bradford Miranda C. , McCauley Elizabeth , Curtis J. Randall , Wolfe Joanne , Baker K. Scott , Yi‐Frazier Joyce P. 
Published: September 2018

AbstractBackgroundAdolescents and young adults (AYAs) with cancer are at risk for poor psychosocial outcomes. This study aimed to determine whether a novel intervention targeting resilience resources would improve patient‐reported resilience, quality of life, and psychological distress.MethodsIn this parallel, phase 2 randomized controlled trial, English‐speaking AYAs (12‐25 years old) with cancer were randomized to the Promoting Resilience in Stress Management (PRISM) intervention or usual care (UC). PRISM is a brief, skills‐based intervention targeting stress management, goal setting, cognitive reframing, and meaning making. Participants completed surveys at enrollment and 6 months. Mixed effects regression models evaluated associations between PRISM and the primary outcome (10‐item Connor‐Davidson Resilience Scale scores) and secondary outcomes (generic and cancer‐related quality of life [Pediatric Quality of Life modules], psychological distress [Kessler‐6], and anxiety/depression [Hospital Anxiety and Depression]) at 6 months.ResultsNinety‐two AYAs were enrolled, were randomized, and completed baseline surveys (48 in the PRISM group and 44 in the UC group); 73% were 12 to 17 years old, and 62% had leukemia or lymphoma. Attrition was primarily due to medical complications and/or death; 36 PRISM participants and 38 UC participants completed 6‐month surveys. PRISM was associated with improved resilience (+3.0 points; 95% confidence interval [CI], 0.5‐5.4; P = .02) and cancer‐specific quality of life (+9.6; 95% CI, 2.6‐16.7; P = .01) and reduced psychological distress (–2.1; 95% CI, –4.1 to –0.2; P = .03) but not generic quality of life (+7.2; 95% CI, –0.8 to 15.2; P = .08). Although anxiety was similar between the groups, 2 PRISM participants (6%) and 8 UC participants (21%) met the criteria for depression at 6 months (odds ratio, 0.09; 95% CI, 0.01‐1.09; P = .06).ConclusionsPRISM was associated with improved psychosocial outcomes in comparison with UC, suggesting that brief, skills‐based interventions for AYAs may provide a benefit.
Fluorescent Inorganic‐Organic Hybrid Nanoparticles
Authors: Neumeier B. Lilli , Khorenko Mikhail , Alves Frauke , Goldmann Oliver , Napp Joanna , Schepers Ute , Reichardt Holger M. , Feldmann Claus 
Published: September 2018

AbstractInorganic‐organic hybrid nanoparticles (IOH‐NPs) with a general composition [ZrO]2+[RDyeOPO3]2−, [Ln]3+n/3[RDye(SO3)n]n−, [Ln(OH)]2+n/2[RDye(SO3)n]n−, or [LnO]+n[RDye(SO3)n]n−(Ln: lanthanide) are a novel class of nanomaterials for fluorescence detection and optical imaging. IOH‐NPs are characterized by an extremely high load of the fluorescent dye (70–85 wt‐%), high photochemical stability, straightforward aqueous synthesis, low material complexity, intense emission and high cell uptake at low toxicity. Besides full‐color emission, IOH‐NPs are suitable for multimodal imaging, singlet‐oxygen generation as well as drug delivery and drug release. This focus review presents the material concept of the IOH‐NPs as well as their synthesis and characterization. Their characteristic features are illustrated by selectedin vitroandin vivostudies to initiate application in biology and medicine.
TopoLens: Building a CyberGIS community data service for enhancing the usability of high‐resolution national topographic datasets
Authors: Hu Hao , Yin Dandong , Liu Yan Y. , Terstriep Jeff , Hong Xingchen , Wendel Jeff , Wang Shaowen 
Published: September 2018

SummaryIn recent years, geospatial data have exploded to massive volume and diversity and subsequently cause serious usability issues for researchers in various scientific areas. This paper describes a cyberGIS community data service framework to facilitate geospatial big data access, processing, and sharing based on a hybrid supercomputer architecture. Specifically, the framework aims to enhance the usability of national elevation dataset released by the U.S. Geological Survey in the contiguous United States at the resolution of
arc‐second. A community data service, namely TopoLens, is created to demonstrate the workflow integration of national elevation dataset and the associated computation and analysis. Two user‐friendly environments, including a publicly available web application and a private workspace based on the Jupyter notebook, are provided for users to access both precomputed and on‐demand computed high‐resolution elevation data. The system architecture of TopoLens is implemented by exploiting the ROGER supercomputer, the first cyberGIS supercomputer dedicated to geospatial problem‐solving. The usability of TopoLens has been acknowledged in the topographic user community evaluation.
Video denoising for security and privacy in fog computing
Authors: Zhang Hong , Yang Yifan , Yuan Ding , Sun Daniel , Zhang Jun , Li Guoqiang , Sun Mingui 
Published: September 2018

SummaryTo reduce heavy noise from degraded video in low or predictable latency and preserve privacy, a powerful and efficient video denoising algorithm is proposed based on fog computing for Visual Internet of Things. The conventional method is to remove noise in the cloud; however, this may overload computation and communication and raise security and privacy issues. The proposed denoising algorithm is distributed to heterogeneous devices at network edges to preserve privacy and avoid security risks as noise can be reduced in the fog rather than the cloud. To address the problems of latency, communication rate, and extremely heavy noise, structure registration, inter‐frame and inner‐frame filters, and distribution compensation are applied in the proposed algorithm. A scheme for encrypting the denoised data at network edges is provided so that security and privacy issues may be avoided during transmission and storage. Compared with other denoising approaches under extremely heavy noise conditions, the experimental results demonstrate that the proposed approach achieves superior denoising performance in terms of peak signal‐noise ratio and visual quality at low computational cost, high bandwidth efficiency, and low‐latency response in a fog computing manner.
Targeting malware discrimination based on reversed association task
Authors: Han Lansheng , Zhou Man , Han Shuxia , Jia Wenjing , Sun Changhua , Fu Cai 
Published: September 2018

SummaryRegarding the current situation that the recognition rate of malware is decreasing, the article points out that the reason for this dilemma is that more and more targeting malware have emerged, which share little or no common feature with traditional malware. The premise of malware recognition judging whether a software is malicious or benign is actually a decision problem. We propose that malware discrimination should resort to the corresponding task or purpose. We first present a formal definition of a task and then provide further classifications of malicious tasks. Based on the decidable theory, we prove that task performed by any software is recursive and determinable. By establishing a mapping from software to task, we prove that software is many‐to‐one reducible to corresponding tasks. Thus, we demonstrate that software, including malware, is also recursive and can be determined by the corresponding tasks. Finally, we present the discrimination process of our method. Nine real malwares are presented, which were firstly discriminated by our method but at that time could not be identified by Kaspersky, McAfee, Symantec Norton, or Kingsoft Antivirus.