bluuebunny/crossref_metadata_2025 huggingface dataset:
Steuerung des Grenzflächen‐Ladungstransfers und des Fill‐Factors in CuO‐basierten Grätzel‐Tandemzellen
Authors: Langmar Oliver , Fazio Ettore , Schol Peter , de la Torre Gema , Costa Rubén D. , Torres Tomás , Guldi Dirk M.
Published: December 2018

Eine neue Klasse elektronenakzeptierender Zink(II)phthalocyanine (ZnPc) wurde entwickelt und in p‐DSSCs, die auf CuO‐Photokathoden basierten, getestet. Durch die Einstellung eines genauen Gleichgewichts zwischen dem Grenzflächen‐Ladungstransfers und der Grenzflächen‐Rekombination wurden optimierte FFs von 0.43 erreicht. Nachdem es gelang den FF in p‐DSSCs einzustellen, wandten wir uns t‐DSSCs zu, in denen zum ersten Mal CuO‐basierte p‐DSSCs und TiO2‐basierte n‐DSSCs kombiniert wurden. Als Farbstoffe dienten hierbei jeweils ZnPc und N719. Die hergestellten t‐DSSCs zeigten einen Voc von 0.86 V, der die Summe der Vocs der jeweiligen p‐ und n‐DSSCs darstellte, und einen FF von 0.63. Letztlich, ist die Effizienz der t‐DSSCs von 0.69 % nur durch ihre geringen Jscs begrenzt.
Palladium(II)‐Initiated Catellani‐Type Reactions
Authors: Cheng Hong‐Gang , Chen Shuqing , Chen Ruiming , Zhou Qianghui
Published: December 2018

The Catellani reaction is known as a powerful strategy for the expeditious synthesis of highly substituted arenes and benzo‐fused rings, which are usually difficult to access through traditional cross‐coupling strategies. It utilizes the synergistic interplay of palladium and norbornene catalysis to facilitate sequential ortho C−H functionalization and ipso termination of aryl halides in a single operation. In classical Catellani‐type reactions, aryl halides are mainly used as the substrates, and a Pd0 catalyst is required to initiate the reaction. Nevertheless, recent advances showcase that Catellani‐type reactions can also be initiated by a PdII catalyst with different starting materials instead of aryl halides via different reaction mechanisms and under different conditions. This emerging concept of PdII/norbornene cooperative catalysis has significantly advanced Catellani‐type reactions, thus enabling future developments of this field. In this Minireview, PdII‐initiated Catellani‐type reactions and their application in the synthesis of bioactive molecules are summarized.
Activating a Peroxo Ligand for C−O Bond Formation
Authors: del Río M. Pilar , Abril Paula , López José A. , Sodupe Mariona , Lledós Agustí , Ciriano Miguel A. , Tejel Cristina
Published: December 2018

Dioxygen activation for effective C−O bond formation in the coordination sphere of a metal is a long‐standing challenge in chemistry for which the design of catalysts for oxygenations is slowed down by the complicated, and sometimes poorly understood, mechanistic panorama. In this context, olefin–peroxide complexes could be valuable models for the study of such reactions. Herein, we showcase the isolation of rare “Ir(cod)(peroxide)” complexes (cod=1,5‐cyclooctadiene) from reactions with oxygen, and then the activation of the peroxide ligand for O−O bond cleavage and C−O bond formation by transfer of a hydrogen atom through proton transfer/electron transfer reactions to give 2‐iradaoxetane complexes and water. 2,4,6‐Trimethylphenol, 1,4‐hydroquinone, and 1,4‐cyclohexadiene were used as hydrogen atom donors. These reactions can be key steps in the oxy‐functionalization of olefins with oxygen, and they constitute a novel mechanistic pathway for iridium, whose full reaction profile is supported by DFT calculations.
Selective C−H Functionalization of Methane and Ethane by a Molecular SbV Complex
Authors: Koppaka Anjaneyulu , Park Sae Hume , Hashiguchi Brian G. , Gunsalus Niles J. , King Clinton R. , Konnick Michael M. , Ess Daniel H. , Periana Roy A.
Published: December 2018

Owing to the strong nonpolar bonds involved, selective C−H functionalization of methane and ethane to esters remains a challenge for molecular homogeneous chemistry. We report that the computationally predicted main‐group p‐block SbV(TFA)5 complex selectively functionalizes the C−H bonds of methane and ethane to the corresponding mono and/or diol trifluoroacetate esters at 110–180 °C with yields for ethane of up to 60 % with over 90 % selectivity. Experimental and computational studies support a unique mechanism that involves SbV‐mediated C−H activation followed by functionalization of a SbV‐alkyl intermediate.
Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X‐Ray Spectroscopy
Authors: Tesch Marc F. , Bonke Shannon A. , Jones Travis E. , Shaker Maryam N. , Xiao Jie , Skorupska Katarzyna , Mom Rik , Melder Jens , Kurz Philipp , Knop‐Gericke Axel , Schlögl Robert , Hocking Rosalie K. , Simonov Alexandr N.
Published: December 2018

Manganese oxide (MnOx) electrocatalysts are examined herein by in situ soft X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L‐edge XAS data with previous mechanistic studies indicates MnIV is the highest oxidation state involved in the catalytic mechanism. MnOx is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn−O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K‐edge provide complementary evidence for such a transition. This step is crucial for the formation of O2 from water.
A Stable Lithium–Oxygen Battery Electrolyte Based on Fully Methylated Cyclic Ether
Authors: Huang Zhimei , Zeng Haipeng , Xie Meilan , Lin Xing , Huang Zhaoming , Shen Yue , Huang Yunhui
Published: December 2018

Ether‐based electrolytes are commonly used in Li–O2 batteries (LOBs) because of their relatively high stability. But they are still prone to be attacked by superoxides or singlet oxygen via hydrogen abstract reactions, which leads to performance decaying during long‐term operation. Herein we propose a methylated cyclic ether, 2,2,4,4,5,5‐hexamethyl‐1,3‐dioxolane (HMD), as a stable electrolyte solvent for LOBs. Such a compound does not contain any hydrogen atoms on the alpha‐carbon of the ether, and thus avoids hydrogen abstraction reactions. As the result, this solvent exhibits excellent stability with the presence of superoxide or singlet oxygen. In addition the CO2 evolution during charge process is prohibited. The LOB with HMD‐based electrolyte was able to run up to 157 cycles, 4 times more than with 1,3‐dioxolane (DOL) or 1,2‐dimethoxyethane (DME) based electrolytes.
Dual Photoredox/Copper Catalysis for the Remote C(sp3)−H Functionalization of Alcohols and Alkyl Halides by N‐Alkoxypyridinium Salts
Authors: Bao Xu , Wang Qian , Zhu Jieping
Published: December 2018

Under mild dual photoredox/copper catalysis, the reaction of N‐alkoxypyridinium salts with readily available silyl reagents (TMSN3, TMSCN, TMSNCS) afforded δ‐azido, δ‐cyano, and δ‐thiocyanato alcohols in high yields. The reaction went through a domino process involving alkoxy radical generation, 1,5‐hydrogen atom transfer (1,5‐HAT) and copper‐catalyzed functionalization of the resulting C‐centered radical. Conditions for catalytic enantioselective δ‐C(sp3)−H cyanation were also documented.
Modelling and analysis of impact forces acting on elbow in gas–liquid slug flow
Authors: Xiao Fei , Jing Jiaqiang , Han Li , Yang Lu , Wang Shuai
Published: December 2018

The impact forces caused by gas–liquid slug flow can lead to the vibration of process system or fatigue failure of pipe fittings. In this study, a piston‐flow‐model coupling with slug model is developed to calculate the impact forces, which can contribute to the structure design and flow assurance. An experiment installation is installed to study the characteristics of slug flow and validate the reliability of the model. The accuracy of this model is above 90% for the superficial velocity of gas below 2 m/s, whereas the average deviation is 29.2% for the cases of superficial velocity of gas above 2 m/s. The modified model addressing the liquid holdup agrees well with the experimental data, of which the average deviation is 6.25%.
A Novel Grading Strategy for Team‐Based Learning Exercises in a Hands‐on Course in Molecular Biology for Senior Undergraduate Underrepresented Students in Medicine Resulted in Stronger Student Performance
Authors: Carrasco Gonzalo A. , Behling Kathryn C. , Lopez Osvaldo J.
Published: December 2018

We developed a hands‐on course in molecular biology for undergraduate underrepresented in medicine (URM) students. To incentivize student preparation for team‐based learning (TBL) activities, we implemented a novel grading schema that requires a minimum individual readiness assurance test (iRAT) score to share the team group readiness assurance test (gRAT) score. Fifty‐one students participated in this 2‐year study and were divided in teams of five or six students that worked throughout the course on a unique, hands‐on project and also participated in TBL exercises. In the laboratory sessions, students isolated RNA from cultured neuronal cells, synthesized complementary DNA (cDNA), and used gene sequencing to identify a gene relevant in human health and disease. Student participation in TBL was quantified and correlated with performance on individual iRATs and the course final examination. We found that implementation of the novel incentive structure lowered the variance of TBL scores (iRAT and gRAT) and strengthened the correlation between final examination scores and either iRAT scores or percentage participation in TBL. Subgroup analysis showed that with the new grading schema, stronger students benefited more from the gRAT exercises, while more poorly performing students were better helped by individual preparation prior to the iRAT exercise. A combination of two active learning strategies, TBL and hands‐on sessions, may strengthen student acquisition of course content and promote teamwork skills. The new incentive structure seems to reduce the disparity in knowledge amongst our students as demonstrated by the reduced iRAT and gRAT score variances. © 2018 International Union of Biochemistry and Molecular Biology, 47(2): 115–123, 2019.
Survival of the fittest: The impact of eco‐certification and reputation on firm performance
Authors: Fanasch Patrizia
Published: December 2018

Owing to the increased trend for organic products and the concept of sustainable development, firms must invest in valuable and unique resources to achieve long‐term success and gain competitive advantages. Building on insights from the resource‐based view and natural‐resource‐based view of the firm, the study focuses on the contribution of corporate reputation and eco‐certification as intangible influences on corporate performance. Duration analysis is applied on a sample of 1,572 German wineries over the period 1994 to 2017. The results indicate that individual reputation and eco‐certification have a statistically significant and positively impact on corporate performance, whereas there is no clear evidence of this relationship for collective reputation. In addition, especially those firms with high individual reputation benefit most from eco‐certification. These results are robust across different parametric and semiparametric model estimations.
Selective Delivery of Doxorubicin to EGFR+ Cancer Cells by Cetuximab–DNA Conjugates
Authors: Liu Tianqiang , Song Ping , Märcher Anders , Kjems Jørgen , Yang Chuanxu , Gothelf Kurt V.
Published: December 2018

Doxorubicin is a hydrophobic anticancer drug that has poor selectivity, due to the lack of active targeting capability. Here, learning lessons from the success of antibody–drug conjugates, we have designed a new doxorubicin delivery system without conjugating doxorubicin to antibody directly. In this setup, cetuximab, an antibody that targets the epidermal growth factor receptor (EGFR) in cancer cells, was conjugated to a single‐stranded DNA with a carefully designed sequence in a site‐selective manner by using the DNA‐templated protein conjugation (DTPC) method. The DNA duplex in the conjugates serves as a carrier of doxorubicin through noncovalent intercalation, and cetuximab functions as the targeting agent; this could drastically decrease systemic toxicity and potentially avoid under‐ or overdosing. The size of conjugates loaded with doxorubicin was about 8.77 or 16.61 nm when characterized by dynamic light scattering and atomic force microscopy, respectively. In vitro cytotoxicity and selective cancer cell killing was investigated against two EGFR+ cell lines (KB and MDA‐MB‐231) and one EGFR− cell line (NIH‐3T3). Cytotoxicity and flow cytometry data showed that doxorubicin loaded in cetuximab–DNA conjugates was more potent in terms of cell cytotoxicity than free doxorubicin in EGFR‐overexpressed cell lines, thus suggesting that the conjugates were more selectively and easily taken up into cells, followed by rapid release of doxorubicin from the system into the cytoplasm from endosomes.
A comparison of valve‐in‐valve transcatheter aortic valve replacement in failed stentless versus stented surgical bioprosthetic aortic valves
Authors: Choi Charles H. , Cheng Vivian , Malaver Diego , Kon Neal , Kincaid Edward H. , Gandhi Sanjay K. , Applegate Robert J. , Zhao David X. M.
Published: December 2018

Objectives

The objectives of this study were to compare short‐ and intermediate‐term clinical outcomes, procedural complications, TAVR prosthesis hemodynamics, and paravalvular leak (PVL) in stentless and stented groups.

Background

Valve‐in‐valve (ViV) transcatheter aortic valve replacement (TAVR) is an alternative to surgical redo for bioprosthetic valve failure. There have been limited data on ViV in stentless surgical valves.

Methods

We retrospectively analyzed 40 patients who underwent ViV TAVR in prior surgical bioprosthetic valves at Wake Forest Baptist Medical Center from October 2014 to September 2017. Eighty percent (32/40) ViV TAVRs were in stentless, while 20% (8/40) were in stented bioprosthetic valves.

Results

The primary mode of bioprosthetic valve failure for ViV implantation in the stentless group was aortic insufficiency (78%, 25/32), while in the stented group was aortic stenosis (75%, 6/8). The ViV procedure success was 96.9% (31/32) in stentless group and 100% in stented group (8/8). There were no significant differences in all‐cause mortality at 30 days between stentless and stented groups (6.9%, 2/31 versus 0%, 0/8, P = 0.33) and at 1 year (0%, 0/25 versus 0%, 0/5). In the stentless group, 34.4% (11/32) required a second valve compared to the stented group of 0% (0/8). There was a significant difference in the mean aortic gradient at 30‐day follow‐up (12.33 ± 6.33 mmHg and 22.63 ± 8.45 mmHg in stentless and stented groups, P < 0.05) and at 6‐month follow‐up (9.75 ± 5.07 mmHg and 24.00 ± 11.28 mmHg, P < 0.05), respectively.

Conclusions

ViV in the stentless bioprosthetic aortic valve has excellent procedural success and intermediate‐term results. Our study shows promising data that may support the application of TAVR in stentless surgical aortic valve. However, further and larger studies need to further validate our single center's experience.
Synthesis of [7]Helicene Enantiomers and Exploratory Study of Their Conversion into Helically Chiral Iodoarenes and Iodanes
Authors: Antien Kevin , Pouységu Laurent , Deffieux Denis , Massip Stéphane , Peixoto Philippe A. , Quideau Stéphane
Published: December 2018

The facile and convenient preparation of both enantiomers of a [7]helicene scaffold from inexpensive (l)‐(+)‐tartaric acid and 4‐methylstyrene is described. These helical structures were transformed into bis‐iodinated ether derivatives in order to explore their potential as precursors of novel chiral organoiodane reagents or as iodoarene pre‐catalysts. Promising results were obtained in hydroxylative phenol dearomatization/[4+2] cycloaddition cascade and dearomative spirolactonization reactions with encouraging enantiomeric excesses.
Anti‐noise image source identification
Authors: Liu Yuying , Huang Yonggang , Zhang Jiao , Shen Hualei
Published: December 2018

Image source identification plays an important role in image forensics. Traditional image source identification techniques rely on the assumption that the training datasets are well labeled. However, in the real world, this assumption may not be the truth, and some noisy samples may exist in the training datasets. In this paper, firstly, we theoretically investigate the influence of noisy samples to the identification performance. Then, a new image source identification approach, namely, Anti‐noise Image Source Identification (AISI), is proposed to deal with those noisy samples. AISI has three steps, ie, noise level evaluation, noise level based sampling, and multi‐classification. Noise level evaluation aims to assign each sample with a noise level that indicates the probability of being noisy. The basic idea of noise level based sampling is to sample images according to their noise levels. We provide a theoretically justification to demonstrate the effectiveness of AISI. Experiments conducted on a real‐world image collection confirm that the proposed AISI can alleviate the influence of noisy samples and can improve the identification accuracy while noise exists.
Induction of Mild Hyperbilirubinemia: Hype or Real Therapeutic Opportunity?
Authors: Vitek Libor , Bellarosa Cristina , Tiribelli Claudio
Published: December 2018

Observational epidemiological studies showed that mild hyperbilirubinemia has beneficial effects on the prevention of cardiovascular disease, type 2 diabetes mellitus, and metabolic syndrome. In mammals, bilirubin plays a major role as a potent antioxidant. Uridine 5’‐diphospho‐glucuronosyl transferase (UGT)1A1 variants coding for bilirubin UDP‐glucuronosyl transferase resulting in mild hyperbilirubinemia (as in Gilbert syndrome (GS)) may confer a strong genetic advantage. Strategies to boost bioavailability of bilirubin or to mimic GS represent an attractive approach to prevent many oxidative stress and inflammation‐mediated diseases. Even a tiny, micromolar increase in serum bilirubin concentrations substantially decreases the risk of oxidative stress–mediated diseases. There are several possible ways to achieve this, including lifestyle changes, changes in dietary patterns, regular physical activities, or use of chemical drug or of specific plant products either in the form of regular food items or nutraceuticals. Further basic and experimental research is required to fully uncover this promising therapeutic field.
Solar Water Oxidation by a Visible‐Light‐Responsive Tantalum/Nitrogen‐Codoped Rutile Titania Anode for Photoelectrochemical Water Splitting and Carbon Dioxide Fixation
Authors: Nakada Akinobu , Uchiyama Tomoki , Kawakami Nozomi , Sahara Go , Nishioka Shunta , Kamata Ryutaro , Kumagai Hiromu , Ishitani Osamu , Uchimoto Yoshiharu , Maeda Kazuhiko
Published: December 2018

The front cover artwork is provided by the Ishitani and Maeda group at the School of Science at the Tokyo Institute of Technology (Japan). The image shows CO2 reduction and H2 production coupled to water oxidation by a photoelectrochemical system based on a Ta/N codoped rutile TiO2 anode under sunlight. Read the full text of the Article at 10.1002/cptc.201800157.
Energy‐efficient relay deployment in cellular systems using fractional frequency reuse and transmit antenna selection techniques
Authors: Oh Hyun Seob , Jeong Dong Geun , Jeon Wha Sook
Published: December 2018

To cope with the steep surge in mobile traffic, network operators are now expanding their infrastructure for mobile access networks. However, since energy costs and greenhouse gas emissions are a large burden to network operators, they are making great efforts to improve the energy efficiency (EE) of their networks by promising techniques, including relaying and multiple‐input multiple‐output (MIMO). Relaying technique can considerably improve the EE when the interference between base stations (BSs) and relay stations (RSs) is effectively coordinated by an elaborate relay deployment using the fractional frequency reuse (FFR) technique. Also, MIMO techniques improve the radio channel quality through diversity gains, so the system capacity and the EE can be improved. Therefore, a combination of relaying/MIMO techniques can be considered to achieve the higher performance, particularly, if the system complexity and costs of using such techniques are low. Since the transmit antenna selection (TAS), one of MIMO techniques, can provide a sufficient transmit diversity gain and satisfy the requirements for low complexity and cost (thus, practical), the TAS is recommended for use with the relaying technique. In this paper, for an energy‐efficient relay deployment using FFR and TAS techniques, we derive the EE and the resource partitioning according to RS positions and the number of BS antennas by a mathematical analysis. Then, the optimal RS positions according to the number of antennas can be determined by an optimization approach. The numerical and simulation results indicate that the proposed analysis method can efficiently analyze the EE and locate the RSs.
Compounding effects of climate change reduce population viability of a montane amphibian
Authors: Kissel Amanda M. , Palen Wendy J. , Ryan Maureen E. , Adams Michael J.
Published: December 2018

Anthropogenic climate change presents challenges and opportunities to the growth, reproduction, and survival of individuals throughout their life cycles. Demographic compensation among life‐history stages has the potential to buffer populations from decline, but alternatively, compounding negative effects can lead to accelerated population decline and extinction. In montane ecosystems of the U.S. Pacific Northwest, increasing temperatures are resulting in a transition from snow‐dominated to rain‐dominated precipitation events, reducing snowpack. For ectotherms such as amphibians, warmer winters can reduce the frequency of critical minimum temperatures and increase the length of summer growing seasons, benefiting post‐metamorphic stages, but may also increase metabolic costs during winter months, which could decrease survival. Lower snowpack levels also result in wetlands that dry sooner or more frequently in the summer, increasing larval desiccation risk. To evaluate how these challenges and opportunities compound within a species’ life history, we collected demographic data on Cascades frog (Rana cascadae) in Olympic National Park in Washington state to parameterize stage‐based stochastic matrix population models under current and future (A1B, 2040s, and 2080s) environmental conditions. We estimated the proportion of reproductive effort lost each year due to drying using watershed‐specific hydrologic models, and coupled this with an analysis that relates 15 yr of R. cascadae abundance data with a suite of climate variables. We estimated the current population growth (λs) to be 0.97 (95% CI 0.84–1.13), but predict that λs will decline under continued climate warming, resulting in a 62% chance of extinction by the 2080s because of compounding negative effects on early and late life history stages. By the 2080s, our models predict that larval mortality will increase by 17% as a result of increased pond drying, and adult survival will decrease by 7% as winter length and summer precipitation continue to decrease. We find that reduced larval survival drives initial declines in the 2040s, but further declines in the 2080s are compounded by decreases in adult survival. Our results demonstrate the need to understand the potential for compounding or compensatory effects within different life history stages to exacerbate or buffer the effects of climate change on population growth rates through time.
Revisiting Scientific Issues for Industrial Applications of Lithium–Sulfur Batteries
Authors: Liu Bo , Fang Ruyi , Xie Dong , Zhang Wenkui , Huang Hui , Xia Yang , Wang Xiuli , Xia Xinhui , Tu Jiangping
Published: December 2018

Inspired by high theoretical energy density (~2600 W h kg−1) and cost‐effectiveness of sulfur cathode, lithium–sulfur batteries are receiving great attention and considered as one of the most promising next‐generation high‐energy‐density batteries. However, over the past decades, the energy density and reliable safety levels as well as the commercial progress of lithium–sulfur batteries are still far from satisfactory due to the disconnection and huge gap between fundamental research and practical application. Therefore, it is highly necessary to revisit the scientific issues for the industrial applications of lithium–sulfur batteries. In this review, we focus on discussing the impact of design parameters (such as compaction density, sulfur loading, and electrolyte/sulfur ratio) on the electrochemical performance of lithium–sulfur batteries and corresponding inherent relationship and rules between them. We also propose the practical design rules of advanced sulfur electrodes. Moreover, safety hazard in respect of electrolyte, separator, and lithium metal anode is also illustrated in detail. With the target of paving the way for practical application of lithium–sulfur batteries, feasible solutions and strategies are brought up to address the aforementioned problems. Finally, we will discuss the current challenges and future research chance of lithium–sulfur batteries.
Ruddlesden–Popper Perovskite for Stable Solar Cells
Authors: Liang Chao , Zhao Dandan , Li Yan , Li Xiaojun , Peng Shaomin , Shao Guosheng , Xing Guichuan
Published: December 2018

Three‐dimensional metal‐halide perovskites have emerged as promising light harvesting materials for converting sunlight to electricity in the last few years. High power conversion efficiency of 23.3% has been demonstrated. However, the main challenge that currently limits the application of the perovskite solar cells is the long‐term stability, which has ambient, thermal, and photo stability weaknesses. Recently, the quasi two‐dimensional Ruddlesden–Popper perovskites have showed great potential to enhance the stability and achieved an acceptable power conversion efficiency (>13%) compared to the traditional three‐dimensional perovskites. The long organic cations in low‐dimensional perovskites are more hydrophobic than the typically used short methylammonium cation in three‐dimensional perovskites. Here, we summarize recent developments of the Ruddlesden–Popper perovskite solar cells, including Lead‐based quasi two‐dimensional and Lead‐free quasi two‐dimensional perovskite structure. The light harvesting performance and charge‐carrier dynamics in these perovskite solar cells are reviewed. In addition, critical challenges that limit the performance of Ruddlesden–Popper perovskite solar cells are discussed. Perspectives and future directions are proposed.
Synthesis of a Trivalent P‐Chloro‐Dithienophosphole and Its Reactivity with Organometallic Reagents
Authors: Gaffen Joshua R. , Wang Zisu , Baumgartner Thomas
Published: December 2018

P‐chloro‐dithieno[3,2‐b:2′,3′‐d]phosphole was synthesized and isolated from the reaction of an aminophosphole and HCl. Developed to act as a common starting material for P‐functionalized phospholes, the compound exhibits a surprising reactivity by generating dimeric biphospholes. Despite this apparent sensitivity, when reacting with organolithium and Grignard reagents, a series of differently P‐functionalized dithieno[3,2‐b:2′,3′‐d]phospholes was accessible. Unexpectedly, organolithium reagents showed reduced reactivity with the chlorophosphole, limiting yields of the desired products due to the competing dimerization. Nonetheless, P‐functionalized phospholes were isolated from reactions of the title compound with both Grignard and organolithium reagents in yields equivalent to, or higher, than by previous methods. A bithiophene‐bridged bisphosphole system was also successfully synthesized without the necessity of generating a bis(dichlorophosphino) reagent. Finally, the isolated P‐functionalized phospholes were analyzed for their photophysical properties. In general, these compounds are strong absorbers in the UV/Vis range of the optical spectrum. The phospholes' emissions were consistent with several previously reported, however, with low quantum yields.
Biomass‐Derived Poly(Furfuryl Alcohol)–Protected Aluminum Anode for Lithium‐Ion Batteries
Authors: Ling Han Yeu , Su Zhong , Chen Hao , Hencz Luke , Zhang Miao , Tang Yongbing , Zhang Shanqing
Published: December 2018

Aluminum is one of the promising alternative anode materials due to its high specific capacity. However, some critical problems seriously limit its practical applications, such as the low coulombic efficiency and poor cycle performance resulting from the huge volume change during cycling. Herein, a novel poly(furfuryl alcohol)/carbon black binder composite is coated on the surface of aluminum foil as a robust and conductive protective layer to maintain the integrity of the hybrid aluminum anode. The results show that 150 cycles under the preset cutoff capacity loading of 400 mA h g−1 are obtained and exhibit obvious advantages over a bare aluminum anode, which will crack after just 25 cycles. For full‐cell testing paired with a LiFePO4 cathode, the cell using the hybrid aluminum anode has a better capacity retention against the unprotected aluminum anode.
Verbal fluency in a national sample: Telephone administration methods
Authors: Marceaux Janice C. , Prosje Michelle A. , McClure Leslie A. , Kana Bhumika , Crowe Michael , Kissela Brett , Manly Jennifer , Howard George , Tam Joyce W. , Unverzagt Frederick W. , Wadley Virginia G.
Published: December 2018

Objectives

Describe novel methods for ascertaining verbal fluency in a large national sample of adults, examine demographic factors influencing performance, and compare scores to studies using in‐person assessment.

Methods/design

Participants were from the Reasons for Geographic and Racial Differences in Stroke (REGARDS) study, a national, population‐based, longitudinal study of stroke in adults aged 45 years and older. Letter and semantic fluency were gathered, using Letter “F” and Animal Naming, via a telephone‐based assessment with computer‐assisted scoring of digital recordings.

Results

Initial letter and semantic fluency scores were obtained on 18 505 and 18 072 participants, respectively. For both fluency tests, scores were normally distributed. Younger age and more years of education were associated with better performances (p < 0.0001). The mean and standard deviation for matched subgroups, based on age, gender, and education, were quite comparable with scores reported out of samples using an in‐person administration format. Telephone‐based assessment also allowed for a level of quality control not available via in‐person measurement.

Conclusions

Telephone‐based assessment of verbal fluency and computer‐assisted scoring programs designed for this study facilitated large‐scale data acquisition, storage, and scoring of protocols. The resulting scores have similar characteristics to those obtained by traditional methods. These findings extend validation of cognitive assessment methods, using survey research staff and computer‐assisted technology for test administration.
Streamwater ages in nested, seasonally cold Canadian watersheds
Authors: Bansah Samuel , Ali Genevieve
Published: December 2018

The mean transit time (MTT) is an important descriptor of water storage and release dynamics in watersheds. Although MTT studies are numerous for many regions around the world, they are rare for prairie watersheds where seasonally cold or dry conditions require adequate methodological choices towards MTT estimation, especially regarding the handling of sparse data records and tracer selection. To examine the impact of such choices, we used timeseries of δ18O and δ2H from two contrasted years (2014 and 2015) and relied on two metrics and two modelling methods to infer MTTs in prairie watersheds. Our focus was on nested outlets with different drainage areas, geologies, and known run‐off generation mechanisms. The damping ratio and young water fraction (i.e., the fraction of streamflow with transit times lesser than 3 months) metrics, as well as the sine‐wave modelling and time‐based convolution modelling methods, were applied to year‐specific data. Results show that young water fractions and modelled MTT values were, respectively, larger and smaller in 2014, which was a wet year, compared with that in 2015. In 2014, most outlets had young water fractions larger than 0.5 and MTT values lesser than 6 months. The damping ratio, young water fraction, and sine‐wave modelling methods led to convergent conclusions about watershed water storage and release dynamics for some of the monitored sites. Contrasting results were, however, obtained when the same method was applied using δ2H instead of δ18O, due to differing evaporation fractionation, or when the time‐based convolution modelling method was used. Some methods also failed to provide any robust results during the dry year (i.e., 2015), highlighting the difficulty in inferring MTTs when data are sparse due to intermittent streamflow. This study therefore allowed the formulation of empirical recommendations for MTT estimation in prairie environments as a function of data availability and antecedent wetness conditions.
Inhibition of NLRP3 inflammasome attenuates spinal cord injury‐induced lung injury in mice
Authors: Jiang Wu , Li Maoqiang , He Fan , Zhu Liulong
Published: December 2018

Spinal cord injury (SCI) is one kind of severe traumatic injury, resulting in systemic inflammatory response syndrome and secondary lung injury, which is an important pathological basis of respiratory complications. The nucleotide‐binding domain‐like receptor protein 3 (NLRP3) inflammasome is an important cytosolic protein complex in many inflammatory diseases. Hence, it is inescapable to explore the effect of inhibition of NLRP3 inflammasome by inhibitors in a mouse SCI model, which was conducted by using the method of 30‐G closing force aneurysm clipping at T6–T7 spinal segment for 1 min, followed by assessment of edema, histology, alveolar type II cell apoptosis, mitochondrial dysfunction, and neutrophil infiltration. In brief, our results showed that, NLRP3 inflammasome inhibitor BAY 11‐7082 or A438079 inhibited activation of NLRP3 inflammasome, alleviated mitochondrial dysfunction, the number of macrophage and neutrophil, thereby attenuating alveolar type II cell apoptosis, lung edema, and histological injury. Taken together, our data reveal that NLRP3 inflammasome inhibitor BAY 11‐7082 or A438079 attenuates the inflammatory response, reverses mitochondrial dysfunction, and subsequently alleviates secondary lung injury following SCI.
Sirtuin 3 suppresses the formation of renal calcium oxalate crystals through promoting M2 polarization of macrophages
Authors: Xi Junhua , Chen Yang , Jing Junfeng , Zhang Yanbin , Liang Chaozhao , Hao Zongyao , Zhang Li
Published: December 2018

This study aims to verify whether the inhibitory effect of Sirtuin 3 (SIRT3) on the formation of renal calcium oxalate crystals was mediated through promoting macrophages (Mϕs) polarization. Identification and quantification of M1 and M2 monocytes were performed using fluorescence‐activated cell sorting analysis. SIRT3 protein level and forkhead box O1 (FOXO1) acetylation level were measured using western blot analysis. Cell apoptosis of HK‐2 was detected by flow cytometry. Mouse kidney tissues were subjected to Von Kossa staining, terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) staining, and immunohistochemical staining for detection of kidney crystals deposition, apoptosis, and expression of crystal‐related molecules, respectively. The results showed that human peripheral blood monocytes from patients with kidney stone (KS) exhibited decreased M2 monocytes percentage and SIRT3 expression, whereas increased FOXO1 acetylation compared with the normal controls. In vitro assay revealed that SIRT3 overexpression in bone marrow‐derived M0/M1/M2 Mϕs induced M2 polarization and decreased FOXO1 acetylation. Furthermore, FOXO1 knockdown reversed SIRT3‐mediated induction of M2 polarization and inhibition of HK‐2 (human proximal tubular cell line) apoptosis. Further in vivo experiments demonstrated that SIRT3‐overexpressing Mϕs transfusion not only induced M2 polarization, but also alleviated inflammation, apoptosis, and crystals deposition in glyoxylate‐induced KS mice. In conclusion, SIRT3 suppresses formation of renal calcium oxalate crystals through promoting M2 polarization via deacetylating FOXO1.
Priorities for Nutrition Research in Pediatric Critical Care
Authors: Tume Lyvonne N. , Valla Frédéric V. , Floh Alejandro A. , Goday Praveen , Jotterand Chaparro Corinne , Larsen Bodil , Lee Jan Hau , Moreno Yara M. F. , Pathan Nazima , Verbruggen Sascha , Mehta Nilesh M.
Published: December 2018

Background

Widespread variation exists in pediatric critical care nutrition practices, largely because of the scarcity of evidence to guide best practice recommendations.

Objective

The objective of this paper was to develop a list of topics to be prioritized for nutrition research in pediatric critical care in the next 10 years.

Methods

A modified 3‐round Delphi process was undertaken by a newly established multidisciplinary group comprising 11 international researchers in the field of pediatric critical care nutrition. Items were ranked on a 5‐point Likert scale.

Results

Forty‐five research topics (with a mean priority score >3(0‐5) were identified within the following 10 domains: the pathophysiology and impact of malnutrition in critical illness; nutrition assessment: nutrition risk assessment and biomarkers; accurate assessment of energy requirements in all phases of critical illness; the role of protein intake; the role of pharmaco‐nutrition; effective and safe delivery of enteral nutrition; enteral feeding intolerance: assessment and management; the role of parenteral nutrition; the impact of nutrition status and nutrition therapies on long‐term patient outcomes; and nutrition therapies for specific populations. Ten top research topics (that received a mean score >4(0‐5) were identified as the highest priority for research.

Conclusions

This paper has identified important consensus‐derived priorities for clinical research in pediatric critical care nutrition. Future studies should determine topics that are a priority for patients and parents. Research funding should target these priority areas and promote an international collaborative approach to research in this field, with a focus on improving relevant patient outcomes.
Factors affecting implantation failure in roe deer
Authors: Chirichella Roberta , Pokorny Boštjan , Bottero Elisa , Flajšman Katarina , Mattioli Luca , Apollonio Marco
Published: December 2018

Reproductive performance is one of the most important life‐history traits that should be routinely studied and considered in adaptive wildlife management. In the case of roe deer (Capreolus capreolus), a species with delayed implantation, which complicates studies on fetuses, corpora lutea (CL) counting is the only alternative for routine monitoring. However, because of a possible implantation failure, the reliability of this method is questionable, and factors influencing implantation success have been poorly understood so far. We analyzed 2,594 intact uteri of roe deer hunted from 2006–2015 in an Apennine population, central Italy, during winter (mid‐Jan to mid‐Mar). By comparing the number of CL and fetuses in the same individuals (i.e., success in blastocyst implantation), we revealed a mean implantation failure of 8.6% in a pooled sample set (regardless of the age and origin of animals), with a high inter‐annual variability (range = 3.6–19.8%). Contrary to adults ( ± SE = 11.1 ± 1.9%), the implantation failure in yearlings was low (4.4 ± 1.9%). Implantation success was affected by individual maternal characteristics (positive effect of body mass and negative effect of age), climatic condition in summer (positive effect of July temperature up to 23.4°C, and negative effect above this threshold), winter harshness (negative effect of snow cover duration), and altitude (negative relation with the elevation). Reproductive performance of adult female roe deer cannot be adequately measured by CL counts because of high inter‐annual variability in implantation failure and important effects of female attributes and environmental factors. However, for yearlings, which also express the highest variability in the ovulation rates, CL counts provide important information on their reproductive outcome because they have low implantation failure. © 2018 The Wildlife Society.
The glottis is not round: Teardrop‐shaped glottic dilation for early posterior glottic stenosis
Authors: Rosen Clark A. , Wang Hailun , Cates Daniel J. , Smith Libby J.
Published: December 2018

Objectives

Posterior glottic stenosis (PGS) results in severe derangement of laryngeal configuration and function with significant morbidity as a sequalae. Presently, there is no treatment for patients with “early” PGS. Dilation is often used for stenotic disease, but present dilation methods are limited to a round shape and the glottis is a sector (teardrop‐shaped). Round dilation of the larynx results in compression of the membranous vocal folds (with potential for injury) and minimal expansion of the posterior larynx. We present a novel laryngeal dilation method that matches the unique anatomic shape of the glottis: teardrop‐shaped glottis dilation (TSGD).

Methods

We present a clinical series of early PGS patients treated with a TSGD. Five patients with dyspnea and significantly reduced vocal fold mobility due to early PGS were treated with TSGD, which involves placement of a triangular static stent in the anterior glottis, with simultaneous use of a round balloon dilator in the posterior glottis.

Results

All patients reported improved ease of breathing and decrease in Dyspnea Index score and were decannualated following treatment. Video perceptual analysis of pre‐/postlaryngoscopy examinations was performed with five blinded reviewers, and all patients were scored to have improved posterior glottic airway space following treatment with a mean improvement of 2.4 on a 11‐point scale.

Conclusion

These clinical results demonstrate that there is enormous potential for the identification and treatment of patients with early PGS and use of a laryngeal dilation technique that matches the anatomic configuration of the glottis.

Level of Evidence

4

Laryngoscope, 129:1428–1432, 2019
The medial sural artery perforator flap: A better option in complex head and neck reconstruction?
Authors: Taufique Zahrah M. , Daar David A. , Cohen Leslie E. , Thanik Vishal D. , Levine Jamie P. , Jacobson Adam S.
Published: December 2018

Objectives

The medial sural artery perforator (MSAP) free flap is an uncommonly utilized soft tissue flap in head and neck reconstruction. It is a thin, pliable, fasciocutaneous flap that provides significant pedicle length. The donor site can be closed primarily, and its location is more aesthetically pleasing to patients. We aim to describe the MSAP flap and compare it to other commonly used free flaps in the head and neck.

Study Design

Retrospective case series.

Methods

A retrospective review of all MSAP cases performed at New York University Langone Health was performed from July 2016 to November 2017. We examined the patients’ age, diagnosis, history of prior radiation therapy, and comorbidities, as well as flap‐specific information and recipient site.

Results

Twenty‐one patients underwent a variety of different head and neck procedures with coverage using an MSAP flap. Recipient sites included tongue, cheek, soft and hard palate, cervical esophagus, and pharynx. Pedicle length ranged from 8 cm to 12 cm. The smallest surface area harvested was 24 cm2 (6 cm × 4 cm), and the largest was 120 cm2 (15 cm × 8 cm). The flaps ranged from 5 to 12 mm in thickness. Venous coupler size ranged from 2.0 to 3.5 mm. Primary closure of the donor site was achieved in 18 of 21 flaps. Twenty of 21 flaps were transferred successfully.

Conclusion

The MSAP flap is a highly versatile and reliable option for a thin, pliable soft tissue flap with a donor site that may be preferable over the radial forearm free flap and anterolateral thigh flap in complex head and neck reconstruction.

Level of Evidence

4

Laryngoscope, 129:1330–1336, 2019
Safety of outpatient unilateral medialization laryngoplasty across two academic institutions
Authors: Chau Steven M. , Kim Christine M. , Vahabzadeh‐Hagh Andrew , Verma Sunil P. , Chhetri Dinesh K.
Published: December 2018

Objectives/Hypothesis

Unilateral ML is a commonly performed surgery for dysphonia secondary to glottic insufficiency. The safety of this procedure performed in the outpatient setting has not been extensively examined. The purpose of the study was to assess the safety of outpatient unilateral ML in adults and determine the incidence and timing of postoperative complications across two tertiary‐care academic medical centers.

Study Design

Retrospective chart review,

Methods

A review of patients undergoing unilateral ML at two tertiary‐care academic centers from 2011 to 2017 was performed. Patients undergoing bilateral medialization laryngoplasty, revision surgery, or those undergoing additional laryngeal framework procedures including arytenoid adduction were excluded. Patient demographics, operative details, and perioperative and postoperative complications were recorded. Comparisons were made between those individuals who underwent inpatient versus outpatient ML.

Results

One hundred three total procedures met inclusion criteria. Fifty‐seven were performed as outpatient procedures, and 46 individuals were observed for at least 23 hours following surgery. Silastic or Gore‐Tex implants were used in all but two surgeries. There were no postoperative complications in either setting, including hematoma, dyspnea, wound infections or seromas.

Conclusions

The incidence of adverse events during and immediately following unilateral ML is very low. Patients can be discharged safely the day of surgery without geographic restrictions.

Level of Evidence

4

Laryngoscope, 129:1647–1649, 2019
Longterm Impact of Living Liver Donation: A Self‐Report of the Donation Experience
Authors: LaPointe Rudow Dianne , DeLair Samantha , Feeley Thomas , Florman Sander , Guarrera James , Kinkhabwala Milan , Orloff Mark , Teperman Lewis , Morgan Glyn
Published: December 2018

Outcomes for adult‐to‐adult living liver donors (LDs) are largely based on short‐term data drawn from single‐center studies. The aim of this study was to determine how living liver donation (LLD) impacts self‐reported quality‐of‐life (QOL) up to 6 years after donation in a sample of residents from New York State. New York transplant programs are state‐mandated to track LDs as part of a quality assurance and patient safety effort. Donor‐reported QOL within 1 year of donation and longitudinal data over a 10‐year period were analyzed. Self‐reported surveys include the following domains: employment, finances, health/life insurance, activities of daily living, physical/emotional health, donor experience, relationships, and LD opinions. There were 220 LDs in New York (2004‐2013) who completed a survey over the 10‐year period with many donors completing surveys at several points in time. Overall, longterm LDs remain as comfortable about LLD as they were during the first year after donation (95%). The majority of LDs reported feeling as well as before LLD (72%). At 1 year after donation, 60% of subjects self‐reported medical problems, and 30% reported emotional issues. However, the majority reported that they would willingly donate again. In conclusion, LDs remain satisfied with their decision to donate over time. A minority of LDs report longterm medical and emotional issues. The conclusions provide information for educational interventions to improve informed choice to those considering donation.