bluuebunny/crossref_metadata_2025 huggingface dataset:
What caused the record‐breaking warming in East China Seas during August 2016?
Authors: Tan Hongjian , Cai Rongshuo
Published: September 2018

The East China Seas (ECS) encountered its warmest monthly mean sea surface temperature (SST) in August 2016, based on the high‐resolution satellite SST product (1982–2016). The area‐averaged monthly SST over the ECS (28°–39°N, 120°–130°E) reached up to 28.3 °C, 2 °C above normal that exceeds two times of SD. The isotherms of 28.5 and 30 °C extended to 36° and 32°N, respectively, both reaching their unprecedented northernmost locations. The heat budget analysis indicated that this extreme warming event in the ECS was predominantly attributable to the combined effects of oceanic advection (0.18 °C, ~24%) and net heat flux (0.44 °C, ~58%), with the latter being the dominant contributor. Further, the extreme ECS warming is induced by the strong adiabatic descent motion with increased downward solar radiation due to the anomalous anticyclonic circulation over the north western Pacific, which is closely linked to the negative phase of the Indian Ocean Dipole (IOD) with robust heating over the tropical eastern Indian Ocean and western Pacific. Additionally, the anticyclonic circulation anomalies promoted the intrusion of warm water of the Kuroshio across the ECS shelf, which also contributed to the forming of enhanced ECS warming. It is further found that most of the ECS warming events can be explained by the precursor signals of negative IOD with 1–3 months ahead, which have important implications for prediction.
Biochemical characteristics of a nitroreductase with diverse substrate specificity from Streptomyces mirabilis DUT001
Authors: Yang Jun , Bai Jing , Qu Mingbo , Xie Bo , Yang Qing
Published: September 2018

A nitroreductase‐encoded gene from an efficient nitro‐reducing bacterium Streptomyces mirabilis DUT001, named snr, was cloned and heterogeneously expressed in Escherichia coli. The purified Streptomyces nitroreductase SNR was a homodimer with an apparent subunit molecular weight of 24 kDa and preferred NADH to NADPH as a cofactor. By enzyme incubation and isothermal calorimetry experiments, flavin mononucleotide (FMN) was found to be the preferred flavin cofactor; the binding process was exothermic and primarily enthalpy driven. The enzyme can reduce multiple nitro compounds and flavins, including antibacterial drug nitrofurazone, priority pollutants 2,4‐dinitrotoluene and 2,4,6‐trinitrotoluene, as well as key chemical intermediates 3‐nitrophthalimide, 4‐nitrophthalimide, and 4‐nitro‐1,8‐naphthalic anhydride. Among the substrates tested, the highest activity of kcat(app)/Km(app) (0.234 μM−1 Sec−1) was observed for the reduction of FMN. Multiple sequence alignment revealed that the high FMN reduction activity of SNR may be due to the absence of a helix, constituting the entrance to the substrate pocket in other nitroreductases.
In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn0.9Fe0.1O Anode for Lithium‐Ion Batteries
Authors: Cabo‐Fernandez Laura , Bresser Dominic , Braga Filipe , Passerini Stefano , Hardwick Laurence J.
Published: September 2018

Carbon‐coated Zn0.9Fe0.1O is a promising anode material for lithium‐ion batteries with good cycling performance and a theoretical specific capacity of 966 mAh g−1, as a result of the combined conversion‐alloying reaction during lithiation. The solid electrolyte interphase (SEI) formed on this electrode was investigated by in‐situ Raman spectroscopy and in‐situ shell‐isolated nanoparticles for enhanced Raman spectroscopy (SHINERS) during the first discharge/charge cycle. The spectra collected via in‐situ Raman spectroscopy showed that the carbon coating is also (de)lithiated and it remains mechanically intact after the first complete cycle. There was no evidence of peaks related to the SEI due to the absence of surface enhancement of the Raman effect in this material, as was previously observed for carbon‐coated ZnFe2O4. However, bands assigned to polyethylene oxide species (PEO) and different lithium alkyl carbonate compounds (i. e., ROCO2Li, ROLi and RCOOLi) from the SEI were observed via SHINERS. The enhancement of the Raman effect by Au−SiO2 core‐shell nanoparticles allows the detection of surface films at potentials at which the SEI is formed and their chemical composition, which is not possible otherwise due to the intrinsically weak scattering process. Therefore, these results show that the SHINERS technique is a powerful method to investigate the structural evolution of the electrode material with potential and interfacial reactions on lithium‐ion batteries.
Drug‐delivering nerve conduit improves regeneration in a critical‐sized gap
Authors: Labroo Pratima , Hilgart David , Davis Brett , Lambert Christopher , Sant Himanshu , Gale Bruce , Shea Jill E. , Agarwal Jayant
Published: September 2018

Autologous nerve grafts are the current “gold standard” for repairing large nerve gaps. However, they cause morbidity at the donor nerve site and only a limited amount of nerve can be harvested. Nerve conduits are a promising alternative to autografts and can act as guidance cues for the regenerating axons, without the need to harvest donor nerve. Separately, it has been shown that localized delivery of GDNF can enhance axon growth and motor recovery. FK506, an FDA approved small molecule, has also been shown to enhance peripheral nerve regeneration. This paper describes the design of a novel hole‐based drug delivery apparatus integrated with a polytetrafluoroethylene (PTFE) nerve conduit for controlled local delivery of a protein such as GDNF or a small molecule such as FK506. The PTFE devices were tested in a diffusion chamber, and the bioactivity of the released media was evaluated by measuring neurite growth of dorsal root ganglions (DRGs) exposed to the released drugs. The drug delivering nerve guide was able to release bioactive concentrations of FK506 or GDNF. Following these tests, optimized drug releasing nerve conduits were implanted across 10 mm sciatic nerve gaps in a BL6 yellow fluorescent protein (YFP) mouse model, where they demonstrated significant improvement in muscle mass, compound muscle action potential, and axon myelination in vivo as compared with nerve conduits without the drug. The drug delivery nerve guide could release drug for extended periods of time and enhance axon growth in vitro and in vivo.
Combinatorial lentiviral gene delivery of pro‐oligodendrogenic factors for improving myelination of regenerating axons after spinal cord injury
Authors: Smith Dominique R. , Margul Daniel J. , Dumont Courtney M. , Carlson Mitchell A. , Munsell Mary K. , Johnson Mitchell , Cummings Brian J. , Anderson Aileen J. , Shea Lonnie D.
Published: September 2018

Spinal cord injury (SCI) results in paralysis below the injury and strategies are being developed that support axonal regrowth, yet recovery lags, in part, because many axons are not remyelinated. Herein, we investigated strategies to increase myelination of regenerating axons by overexpression of platelet‐derived growth factor (PDGF)‐AA and noggin either alone or in combination in a mouse SCI model. Noggin and PDGF‐AA have been identified as factors that enhance recruitment and differentiation of endogenous progenitors to promote myelination. Lentivirus encoding for these factors was delivered from a multichannel bridge, which we have previously shown creates a permissive environment and supports robust axonal growth through channels. The combination of noggin+PDGF enhanced total myelination of regenerating axons relative to either factor alone, and importantly, enhanced functional recovery relative to the control condition. The increase in myelination was consistent with an increase in oligodendrocyte‐derived myelin, which was also associated with a greater density of cells of an oligodendroglial lineage relative to each factor individually and control conditions. These results suggest enhanced myelination of regenerating axons by noggin+PDGF that act on oligodendrocyte‐lineage cells post‐SCI, which ultimately led to improved functional outcomes.
High‐throughput identification of factors promoting neuronal differentiation of human neural progenitor cells in microscale 3D cell culture
Authors: Nierode Gregory J. , Gopal Sneha , Kwon Paul , Clark Douglas S. , Schaffer David V. , Dordick Jonathan S.
Published: September 2018

Identification of conditions for guided and specific differentiation of human stem cell and progenitor cells is important for continued development and engineering of in vitro cell culture systems for use in regenerative medicine, drug discovery, and human toxicology. Three‐dimensional (3D) and organotypic cell culture models have been used increasingly for in vitro cell culture because they may better model endogenous tissue environments. However, detailed studies of stem cell differentiation within 3D cultures remain limited, particularly with respect to high‐throughput screening. Herein, we demonstrate the use of a microarray chip‐based platform to screen, in high‐throughput, individual and paired effects of 12 soluble factors on the neuronal differentiation of a human neural progenitor cell line (ReNcell VM) encapsulated in microscale 3D Matrigel cultures. Dose–response analysis of selected combinations from the initial combinatorial screen revealed that the combined treatment of all‐trans retinoic acid (RA) with the glycogen synthase kinase 3 inhibitor CHIR‐99021 (CHIR) enhances neurogenesis while simultaneously decreases astrocyte differentiation, whereas the combined treatment of brain‐derived neurotrophic factor and the small azide neuropathiazol enhances the differentiation into neurons and astrocytes. Subtype specification analysis of RA‐ and CHIR‐differentiated cultures revealed that enhanced neurogenesis was not biased toward a specific neuronal subtype. Together, these results demonstrate a high‐throughput screening platform for rapid evaluation of differentiation conditions in a 3D environment, which will aid the development and application of 3D stem cell culture models.
Spatial and temporal variations of childhood cancers: Literature review and contribution of the French national registry
Authors: Goujon Stéphanie , Kyrimi Evangelia , Faure Laure , Guissou Sandra , Hémon Denis , Lacour Brigitte , Clavel Jacqueline
Published: September 2018

Background

Significant increases in childhood cancer incidence since the 1970s have been consistently reported worldwide, but the persistence of the increase on recent periods is discussed. No conclusion can be drawn concerning the spatial variations of childhood cancer, either. This study is an in‐depth investigation of the spatial and temporal variations of childhood cancer in France. An extensive review of all the studies published since 2000 on those issues is provided.

Methods

The study included 25 877 cases of childhood cancer registered nationwide over 2000‐2014. The spatial heterogeneity (overdispersion, autocorrelation, overall heterogeneity) was tested, on two geographic scales, and two spatial scan methods were used to detect clusters of cases. The annual average percent change (AAPC) in incidence rate was estimated with Poisson regression models, and joinpoint analyses were considered.

Results

Glioma and non‐Hodgkin lymphoma cases exhibited some spatial heterogeneity and two large clusters were detected. Overall, the incidence rate of childhood cancer was stable over 2000‐2014 (AAPC = −0.1% [−0.3%; 0.2%]). A log‐linear positive trend was significantly evidenced for gliomas other than pilocytic astrocytomas (AAPC = 1.8% [0.9%; 2.7%]), with some suggestion of a leveling‐off at the end of the period, while Burkitt lymphoma and germ cell tumor incidence rates decreased (AAPC = −2.2% [−3.8%; −0.5%] and AAPC = −1.9% [−3.4%; −0.3%], respectively). No spatial heterogeneity or significant time variation was evidenced for other cancers.

Conclusion

Several types of childhood cancer displayed some spatial heterogeneity and two large clusters were detected, the origins of which are to be investigated and might include differences in case ascertainment. Overall, the results do not support a sustained increase in incidence rates of childhood cancer in recent years.
Functional Imaging with Nucleic‐Acid‐Based Sensors: Technology, Application and Future Healthcare Prospects
Authors: Wiraja Christian , Yeo David C. , Lio Daniel Chin Shiuan , Zheng Mengjia , Xu Chenjie
Published: September 2018

Timely monitoring and assessment of human health plays a crucial role in maintaining the wellbeing of our advancing society. In addition to medical tools and devices, suitable probe agents are crucial to assist such monitoring, either in passive or active ways (i.e., sensors) through inducible signals. In this review we highlight recent developments in activatable optical sensors based on nucleic acids. Sensing mechanisms and bio‐applications of these nucleic acid sensors in ex vivo assays, intracellular or in vivo settings are described. In addition, we discuss the limitations of these sensors and how nanotechnology can complement/enhance sensor properties to promote translation into clinical applications.
Adventures across the second dimension: Predicting left ventricular outflow tract obstruction following transcatheter mitral valve replacement
Authors: Khan Jaffar M. , Lederman Robert J.
Published: September 2018

Key Points

TMVR can cause fatal LVOT obstruction, especially in the setting of valve‐in‐mitral annular calcification.

A predicted neoLVOT of <190 mm2, measured using computer aided design models of 3‐D datasets with a virtual valve implant, portends a high risk of LVOT obstruction following TMVR.

NeoLVOT predictions may be based on different valve implantation depths, and do not account for body mass, complex neoLVOT time‐varying three‐dimensional geometry, flow, or anterior mitral leaflet dynamics.
The less complex the case is, the more complex is it to choose? The case of lower risk patients with aortic valve stenosis
Authors: Lemos Pedro A. , Makdisse Marcia
Published: September 2018

Key Points

Clinical evidences that prove the value of transcatheter aortic valve replacement (TAVR) for high‐risk patients cannot be directly extrapolated to good candidates for surgery.

Studies specifically designed to evaluate TAVR in low‐to‐intermediate‐risk patients should go beyond traditional clinical outcomes to also include, amongst others, endpoints related to patient‐reported outcome measures (PROMs), such as quality of life and functional status, and a cost analysis over the full cycle of care aiming at demonstrating value on outcomes that matter most to patients.

In this issue of CCI, Garcia and coworkers report on the outcomes of intermediate‐risk patients treated with either TAVR or surgical aortic valve replacement, showing that TAVR was associated with an improvement in clinical outcomes compared to surgery, with lower 30‐day mortality and stroke rates, shorter hospital lengths and higher proportions of patients being discharged home.
Surgical aortic valve replacement and transcatheter aortic valve implantation for severe aortic stenosis: Equipoise remains a tenable assumption
Authors: Chatterjee Arka , Hillegass William B.
Published: September 2018

Key Points

Observational comparisons suggest superior long‐term survival with surgical aortic valve replacement (SAVR) then transcatheter aortic valve implantation (TAVI) for severe aortic stenosis patients.

While subject to residual bias, these observational studies still support at least cautionary equipoise between TAVI and SAVR. Five‐year results from randomized trials will ultimately provide clearer guidance for most patient subsets.

Detailed individual long‐term outcome prediction models will help guide patient and heart team TAVI, SAVR, versus no procedure shared decision‐making.
Subclinical brain lesions after left atrial appendage occlusion: Does silence mean reassurance?
Authors: Ahmad Tariq Ali , Gilchrist IanC.
Published: September 2018

Key Points

Silent acute brain lesions as diagnosed by magnetic resonance imaging (MRI) are common immediately after left atrial closure procedures.

Late, 3‐month MRI imaging often shows resolution of the acute brain lesions with no detectable change in brain function by standard neuro‐cognitive testing and no further formation of new brain lesions in patients treated with only anti‐platelet therapy.

Silent brain lesions appearing after left atrial closure appear associated with the acute procedural technique and not later during endothelialization of the device.
TAVR for low‐risk patients: The final Frontier
Authors: Cilingiroglu Mehmet , Marmagkiolis Konstantinos
Published: September 2018

Key Points

TAVR in low‐risk patients is associated with a similar short‐term but an increased intermediate‐term mortality compared to SAVR.

Off label TAVR use, the imperfect risk assessment by mean STS and logistic EuroSCORE, unrecognized PVL, and older TAVR platforms may explain some of results.

Until further evidence from the PARTNER‐3, NOTION‐2, and the Medtronic Evolut Low Risk Trials, SAVR remains the gold standard for low‐risk patients with symptomatic severe aortic stenosis

© 2017 Wiley Periodicals, Inc.
Submassive pulmonary embolus: The challenge of thrombolytic decision‐making in a heterogenous cohort
Authors: Rothschild Daniel P. , Goldstein James A.
Published: September 2018

Key Points

Submassive PE constitutes a heterogenous hemodynamic spectrum

Escalation‐of‐care to thrombolytic therapy may benefit some patients suffering submassive PE

Comprehensive clinical‐hemodynamic analysis to sub‐stratify submassive PE is essential for thrombolytic decision‐making
Transcoronary pacing threshold predicts myocardial scar: Novel first‐step towards intraprocedural myocardial functional assessment
Authors: Nakamura Kenta , Dean Larry S.
Published: September 2018

Key Points

Transcoronary pacing (TCP) is a novel modality to assess the subtended myocardium during percutaneous coronary intervention (PCI).

In a proof‐of‐concept trial of six patients, TCP threshold discriminated scar from normal myocardium in the left anterior descending coronary distribution.

Further investigation is needed to determine whether TCP can assess myocardial viability to inform intraprocedural decision making.
Same day discharge for peripheral arterial interventions: Who are we trying to satisfy?
Authors: Rassa Allen C. , Cigarroa Joaquin E.
Published: September 2018

Key Points

Same‐day discharge (SDD) following elective outpatient peripheral arterial interventions is safe and feasible.

Patients seem to have a poor understanding of the expected benefit of peripheral percutaneous interventions.

Patients randomized to SDD had lower pain control, perceived level of safety, and confidence scores after the procedure relative to the overnight stay group.
BVS restenosis: “Reappearance of the disappeared stent”
Authors: Seth Ashok , Kumar Dhananjay
Published: September 2018

Key Points

This article describes for the first time the pattern of restenosis within Bioresorbable Vascular Scaffold and its predictors.

The focal in -BVS restenosis can usually be treated with repeat percutaneous coronary intervention.

Longer term follow up beyond one year in a larger cohort is needed to define the impact of restenosis pattern on clinical outcomes.
The Quandary of Volume! How Much Is Enough?
Authors: Brown Christopher L. , Henry Timothy D.
Published: September 2018

Key Points

While the percentage of low‐volume PCI operators (<50/yr) in Taiwan has remained approximately 60% and the percentage of low‐volume centers (<200/yr) has declined from 57% to 33% between 2001 and 2013, the actual number of low‐volume operators and low‐volume centers has increased

Recent data from NCDR confirms a modest but consistent inverse relationship between PCI operator volume and adjusted in‐hospital mortality, which is magnified by being a low‐volume center

Criteria beyond volume such as procedural complexity, operator experience, and appropriate case selection are important factors in providing exceptional patient care
Enhanced Photocatalytic Activity and Selectivity for CO2 Reduction over a TiO2 Nanofibre Mat Using Ag and MgO as Bi‐Cocatalyst
Authors: Xu Feiyan , Meng Kai , Cheng Bei , Yu Jiaguo , Ho Wingkei
Published: September 2018

The design and preparation of novel photocatalysts to enhance photocatalytic activity and selectivity for CO2 reduction is highly important both theoretically and practically. Herein, we develop an electrospinning and wet‐impregnation method to obtain an Ag and MgO co‐modified TiO2 nanofibrous mat. Ag nanoparticles (NPs) as electron traps can effectively separate electron−hole pairs and reduce their recombination in TiO2 nanofibres due to the formation of Schottky barriers. Accumulation of photogenerated electrons in the Ag NPs can enhance the formation of CH4. The obtained Ag−MgO−TiO2 composite mat exhibits extended visible light absorption owing to the surface plasmon resonance effect of the Ag NPs. Deposition of MgO NPs, as basic sites, could facilitate the adsorption of CO2 molecules. The synergetic effects of Ag and MgO as a bi‐cocatalyst contribute to enhanced photocatalytic activity and CH4‐selectivity for CO2 reduction. Isotope (13C) tracer experiments confirm that the products are produced from photocatalytic reduction of the CO2 source instead of organic contaminants. This report highlights the importance of the synergistic effect of Ag and MgO NPs on enhancing the photocatalytic activity and selectivity of TiO2‐based materials.
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

The 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

Owing 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

Three 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

Corrole 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

Hydrated 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

Thermal 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

The 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

Dynamic 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

The 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

Long‐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

Invited 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

The 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

Background

Adolescents 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.

Methods

In 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.

Results

Ninety‐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).

Conclusions

PRISM 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

Inorganic‐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

In 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

To 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

Regarding 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.
Twelve‐Armed Hexaphenylbenzene‐Based Giant Supramolecular Framework for Entrapping Guest Molecules
Authors: Madhu Suresh , Gonnade Rajesh G. , Das Tamal , Vanka Kumar , Sanjayan Gangadhar J.
Published: September 2018

Host‐guest chemistry is a functional model in supramolecular chemistry for understanding specific process occurring in biological systems. Herein, we describe a rationally designed giant multiarmed hexaphenylbenzene (HPB)‐based supramolecular frameworks which encapsulate a variety of guest molecules in the voids of their crystal lattice through the cooperative interplay of multivalency, noncovalent forces and backbone rigidity. In this connection, pseudo‐axially substituted twelve‐armed hexaphenylbenzene was synthesized and its molecular entrapping nature was studied by varying number of H‐bond donor‐acceptor sites in the arms. The per‐methyl esterified HPB acted as a cavitand to include nonpolar and polar aprotic guests in its crystal structure via C−H⋅⋅⋅π, C−H⋅⋅⋅O and C−H⋅⋅⋅N interactions. The corresponding amidated HPB showed unprecedented inclusion of ammonia and segregation of the guest molecules according to their polarity in the lattice. Furthermore, this molecular entrapping system has been used to obtain the crystal structure of a hitherto unproven 2‐azaallenium intermediate, which had been proposed to be involved in aminomethylation of activated arenes.
Social recommendation between urban vehicular social communities
Authors: Liu Lianggui , Wang Lingmin , Sun Hui , Jia Huiling
Published: September 2018

In recent years, social recommendation between communities plays a more and more significant role in urban vehicular social networks. It has become a hot research topic due to its advantage in enhancing the efficiency of information sharing and transmission in urban vehicular social networks. This paper focuses on social recommendation between communities where achieving the optimal configuration of social recommendation is NP‐hard. We proposed an algorithm for the near optimal configuration of social recommendation between urban vehicular social communities (ANOCSR) to make this NP‐hard problem polynomially solvable based on a modified Steiner minimal tree method. Moreover, with the help of the ANOCSR, we propose another algorithm to achieve the optimal configuration of social recommendation between urban vehicular social communities subject to a global external trust value constraint (AOCSRC). We demonstrate that our algorithms are more efficient and effective than existing algorithms through extensive experiments and detailed theoretical analyses.