bluuebunny/crossref_metadata_2025 huggingface dataset:
Biegebemessungsmodell mit einer geschlossenen und iterativen Lösung für Textilbetonbauteile
Authors: Rempel Sergej , Ricker Marcus , Hegger Josef
Published: January 2020

Zur Realisierung der bisherigen Bauprojekte mit textiler Bewehrung wurden Zustimmungen im Einzelfall (ZiE) und allgemeine bauaufsichtliche Zulassungen (abZ) benötigt, wofür kosten‐ sowie zeitintensive Tragfähigkeits‐ und Gebrauchstauglichkeitsuntersuchungen durchgeführt werden mussten. Dabei waren insbesondere umfangreiche Untersuchungen zum Nachweis der Biegetragfähigkeit notwendig. Damit in Zukunft die Anzahl der Versuche deutlich reduziert werden kann, ist ein praxistaugliches Biegebemessungsmodell erforderlich. In diesem Beitrag wird ein allgemeingültiges Ingenieurmodell für eine Biegebeanspruchung mit und ohne Normalkrafteinfluss vorgestellt. Hierfür werden für den Beton die bekannten Materialgesetze nach Norm verwendet. Für die textile Bewehrung wird aufbauend auf den bisherigen Untersuchungen ein Vorschlag für den Spannungs‐Dehnungsverlauf gemacht. Das Modell wird durch umfangreiche experimentelle Untersuchungen verifiziert, bei denen die für die Biegebemessung maßgebenden Parameter variiert werden. Abschließend wird aufbauend auf dem Ingenieurmodell ein Bemessungsmodell vorgeschlagen, bei dem zusätzlich Sicherheitsbeiwerte berücksichtigt werden.
Ribosomal RNA Methyltransferase RsmC Moonlights as an RNA Chaperone
Authors: GC Keshav , Gyawali Prabesh , Balci Hamza , Abeysirigunawardena Sanjaya
Published: January 2020

Ribosomes are ribonucleoprotein particles that are essential for protein biosynthesis in all forms of life. During ribosome biogenesis, transcription, folding, modification, and processing of rRNA are coupled to the assembly of proteins. Various assembly factors are required to synchronize all different processes that occur during ribosome biogenesis. Herein, the RNA chaperone and RNA strand annealing activity of rRNA modification enzyme ribosome small subunit methyltransferase C (RsmC), which modifies guanine to 2‐methylguanosine (m2G) at position 1207 of 16S rRNA (Escherichia coli nucleotide numbering) located at helix 34 (h34), are reported. A 25‐fold increase in the h34 RNA strand annealing rates is observed in the presence of RsmC. Single‐molecule FRET experiments confirmed the ability of protein RsmC to denature a non‐native structure formed by one of the two h34 strands and to form a native‐like duplex. This observed RNA chaperone activity of protein RsmC might play a vital role in the rapid generation of functional ribosomes.
Physicochemical and cooking quality characteristics of South American rice cultivars parboiled at different steaming pressures
Authors: Villanova Franciene Almeida , El Halal Shanise Lisie Mello , Vanier Nathan Levien , Polidoro Edimara , Wang Ya‐Jane , de Oliveira Maurício
Published: January 2020

Background and objectives

Six different long‐slender rice genotypes were studied, being three pure lines (Puita Inta CL, Guri CL, and Irga 424 RI) and three hybrid lines (Titan CL, Lexus CL, and Inov CL). Samples were submitted to parboiling process under different steaming pressures (0.25, 0.50, and 0.75 kgf/cm2).

Findings

Results were dependent on genotype instead of line cluster. Intermediate steaming pressures may be useful for five cultivars; Titan CL was the only exception. Titan CL exhibited the lowest amylose content and the highest amylopectin average chain length, gelatinization temperature, and relative crystallinity. At the intermediate parboiling level of 0.50 kgf/cm2, Titan CL exhibited 8.32% of broken grains while the others exhibited values between 2.10% and 4.72%.

Conclusions

Titan CL had a more stable crystalline structure that hindered water intake into starch granules. For this reason, Titan CL may be parboiled at severe steaming pressure of 0.75 kgf/cm2 in order to achieve the same extent of gelatinization and physicochemical and cooking quality than the other studied cultivars.

Significance and novelty

The main rice cultivars grown in South America were studied. Results may help rice industries that work with long‐slender high‐to‐intermediate‐amylose rice to select proper parboiling parameters for each cultivar.
Heterostructured manganese catalysts for the selective oxidation of 5‐hydroxymethylfurfural to 2,5‐diformylfuran
Authors: Pal Priyanka , Saravanamurugan Shunmugavel
Published: January 2020

A series of manganese oxide catalysts were synthesised in the presence of various precipitants using hydrothermal approach. The manganese oxide synthesised (MnOx−A−U) using manganese acetate tetrahydrate and urea as precursor and precipitant, respectively, was found to be composed of heterostructures of manganese, that is, MnCO3, ϵ‐MnO2 and Mn2O3, and their presence were confirmed by XRD, FTIR and XPS analyses. The catalytic activity of MnOx−A−U towards selective oxidation of HMF to DFF in ethanol afforded 92.0 % conversion along with 88.0 % DFF yield at 120 °C, 30 bar O2, after 4 h of reaction time. Performing HMF oxidation under N2 atmosphere with MnOx−A−U yielded only 15.0 % DFF, revealing that lattice oxygen played a crucial role in the oxidation process, which was confirmed by subjecting the spent catalyst to XPS analysis. Based on the results obtained from XPS analysis, it was speculated that ϵ‐MnO2 and MnCO3 could be the active species which could selectively catalyse the reaction. The MnOx−A−U catalyst was able to recycle for at least three runs with a small loss of activity due to ϵ‐MnO2 content decreased.
Nickel Foam‐Supported Amorphous FeCo(Mn)−O Nanoclusters with Abundant Oxygen Vacancies through Selective Dealloying for Efficient Electrocatalytic Oxygen Evolution
Authors: Wu Shuai‐Na , Qi Yu‐Feng , Wang Qian , Wang Xiu‐Guang , Zhao Xiao‐Jun , Yang En‐Cui
Published: January 2020

Developing earth‐abundant, cost‐effective and high‐performance electrocatalyst towards the oxygen evolution reaction (OER) is a great challenge for large‐scale hydrogen production from electrochemical water splitting. Nickel‐foam‐supported amorphous hierarchical nanoclusters of metal/metal (hydr)oxides with abundant oxygen defects (FeCo(Mn)−O/NF) were prepared from an FeCoMn/NF precursor through chemical dealloying. The FeCo(Mn)−O/NF electrode exhibits enhanced OER activity in alkaline electrolyte with an overpotential of only 235 mV to drive a current density of 10 mA cm−2, a small Tafel slope of 44.5 mV dec−1 and excellent durability over 100 h. The superior OER performance is attributed to the synergistic effect of abundant oxygen vacancies, hierarchical morphology and amorphous structure, which essentially modulate the electronic structures and create more active sites. These interesting findings highlight the significance of dealloying strategy on the structural defects and improved catalytic performance of the electrocatalysts.
Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer
Authors: Wolfe Kody D. , Dervishogullari Dilek , Stachurski Christopher D. , Passantino Joshua M. , Kane Jennings G. , Cliffel David E.
Published: January 2020

Invited for this month's cover picture is the group of Dr. David E. Cliffel from Vanderbilt University (USA). The Cover Picture shows a Photosystem I (PSI) protein complex converting sunlight into chemical energy through an electron transfer reaction with dichlorophenolindophenol (DCPIP). The PSI is entrapped within a macroporous indium tin oxide (ITO) electrode which leverages its high surface area to produce electrical energy from reacted DCPIP. Read the full text of the Article at 10.1002/celc.201901628
Robustness control in bilinear modeling based on maximum correntropy
Authors: Fonseca Diaz Valeria , De Ketelaere Bart , Aernouts Ben , Saeys Wouter
Published: January 2020

We present the development of a bilinear regression model for multivariate calibration on the basis of maximum correntropy criteria (MCC) whose robustness can be easily controlled. MCC regression methods can be more effective when the assumption of normality does not hold or when data are contaminated with outliers. These methods are competitive when the degree of robustness against outliers should be controlled. By controlling the robustness, information from candidate outliers can be partially retained rather than completely included or discarded during calibration. Within the context of bilinear regression models, an MCC approach using statistically inspired modification of the partial least squares (SIMPLS) is proposed, which is named maximum correntropy‐weighted partial least squares (MCW‐PLS). Thanks to the controllable robustness of MCC models, observations are upweighted or downweighted during the calibration process, rendering robust models with soft discrimination of samples. Such a weighting represents an important advantage, especially for cases when samples are not drawn from a normal distribution. Applications to three real case studies are presented. These applications uncovered three main features of MCW‐PLS: robustness control between SIMPLS and robust SIMPLS (RSIMPLS), improvements in prediction performance of bilinear calibration models, and the possibility to detect the most informative samples in a calibration set.
Discrete Supertetrahedral T5 Selenide Clusters and Their Se/S Solid Solutions: Ionic‐Liquid‐Assisted Precursor Route Syntheses and Photocatalytic Properties
Authors: Wang Yanqi , Zhu Zhipeng , Sun Zhaofeng , Hu Qianqian , Li Jianrong , Jiang Jiang , Huang Xiaoying
Published: January 2020

Although supertetrahedral Tn sulfide clusters (n=2–6) have been extensively explored, the synthesis of Tn selenide clusters with n>4 has not been achieved thus far. Reported here are ionic‐liquid (IL)‐assisted precursor route syntheses, characterizations, and the photocatalytic properties of six new M‐In‐Q (M=Cu or Cd; Q=Se or Se/S) chalcogenide compounds, namely [Bmmim]12Cu5In30Q52Cl3(Im) (Q=Se (T5‐1), Se48.5S3.5 (T5‐2); Bmmim=1‐butyl‐2,3‐dimethylimidazolium, Im=imidazole), [Bmmim]11Cd6In28Q52Cl3(MIm) (Q=Se (T5‐3), Se28.5S23.5 (T5‐4), Se16S36 (T5‐5); MIm=1‐methylimidazole), and [Bmmim]9Cd6In28Se8S44Cl(MIm)3 (T5‐6). The cluster compounds T5‐1 and T5‐3 represent the largest molecular supertetrahedral Tn selenide clusters to date. Under visible‐light illumination, the Cu‐In‐Q compounds showed photocatalytic activity towards the decomposition of crystal violet, whereas the Cd‐In‐Q compounds exhibited good photocatalytic H2 evolution activity. Interestingly, the experimental results show that the photocatalytic performances of the selenide/sulfide solid solutions were significantly better than those of their selenide analogues, for example, the degradation time of the organic dye with T5‐2 was much shorter than that with T5‐1, whereas the photocatalytic H2 evolution efficiencies with T5‐3–T5‐6 improved significantly with increasing sulfur content. This work highlights the significance of IL‐assisted precursor route synthesis and the tuning of photocatalytic properties through the formation of solid solutions.
Evidence for Genuine Bimetallic Frustrated Lewis Pair Activation of Dihydrogen with Gold(I)/Platinum(0) Systems
Authors: Hidalgo Nereida , Moreno Juan José , Pérez‐Jiménez Marina , Maya Celia , López‐Serrano Joaquín , Campos Jesús
Published: January 2020

A joint experimental/computational effort to elucidate the mechanism of dihydrogen activation by a gold(I)/platinum(0) metal‐only frustrated Lewis pair (FLP) is described herein. The drastic effects on H2 activation derived from subtle ligand modifications have also been investigated. The importance of the balance between bimetallic adduct formation and complete frustration has been interrogated, providing for the first time evidence for genuine metal‐only FLP reactivity in solution. The origin of a strong inverse kinetic isotopic effect has also been clarified, offering further support for the proposed bimetallic FLP‐type cleavage of dihydrogen.
Current multidisciplinary management of brain metastases
Authors: Moravan Michael J. , Fecci Peter E. , Anders Carey K. , Clarke Jeffrey M. , Salama April K. S. , Adamson Justus D. , Floyd Scott R. , Torok Jordan A. , Salama Joseph K. , Sampson John H. , Sperduto Paul W. , Kirkpatrick John P.
Published: January 2020

Brain metastasis (BM), the most common adult brain tumor, develops in 20% to 40% of patients with late‐stage cancer and traditionally are associated with a poor prognosis. The management of patients with BM has become increasingly complex because of new and emerging systemic therapies and advancements in radiation oncology and neurosurgery. Current therapies include stereotactic radiosurgery, whole‐brain radiation therapy, surgical resection, laser‐interstitial thermal therapy, systemic cytotoxic chemotherapy, targeted agents, and immune‐checkpoint inhibitors. Determining the optimal treatment for a specific patient has become increasingly individualized, emphasizing the need for multidisciplinary discussions of patients with BM. Recognizing and addressing the sequelae of BMs and their treatment while maintaining quality of life and neurocognition is especially important because survival for patients with BMs has improved. The authors present current and emerging treatment options for patients with BM and suggest approaches for managing sequelae and disease recurrence.
Pilot Study to Predict Pharmacokinetics of a Therapeutic Gemcitabine Dose From a Microdose
Authors: Van Nuland M. , Rosing H. , Thijssen B. , Burgers J.A. , Huitema A.D.R. , Marchetti S. , Schellens J.H.M. , Beijnen J.H.
Published: January 2020

Microdose studies are exploratory trials to determine early drug pharmacokinetics in humans. In this trial we examined whether the pharmacokinetics of gemcitabine at a therapeutic dose could be predicted from the pharmacokinetics of a microdose. In this prospective, open‐label microdosing study, a gemcitabine microdose (100 µg) was given intravenously to participants on day 1, followed by a therapeutic dose (1250 mg/m2) on day 2. Gemcitabine and its metabolite 2’,2’‐difluorodeoxyuracil (dFdU) were quantified in plasma and intracellularly by using liquid chromatography‐mass spectrometry). Noncompartmental pharmacokinetic analysis was performed. Ten patients participated in this study. The mean area under the plasma concentration‐time curve (AUC0‐8) of gemcitabine after microdosing was 0.00074 h·mg/L and after therapeutic dosing was 16 h·mg/L. The mean AUC0‐8 of dFdU following the microdose and therapeutic dose were 0.022 h·mg/L and 169 h·mg/L, respectively. Exposure to gemcitabine after the therapeutic dose was within 2‐fold of the exposure following a microdose, when linearly extrapolated to 1250 mg/m2. However, the shape of the concentration‐time curve was different, as reflected by poor scalability in volume of distribution (939 L versus 222 L). Furthermore, intracellularly phosphorylated gemcitabine and phosphorylated dFdU levels could not be predicted from the microdose. The AUC0‐8 of gemcitabine at therapeutic dose was accurately predicted by the pharmacokinetics of a microdose, when linearly extrapolated to 1250 mg/m2. Volume of distribution, elimination rate constant, and intracellular pharmacokinetics of the therapeutic dose could not be predicted from the microdose, which demonstrates limitations of the microdose approach in this case.
Choline Chloride as a Nano‐Crowder Protects HP‐36 from Urea‐Induced Denaturation: Insights from Solvent Dynamics and Protein‐Solvent Interactions
Authors: Maity Atanu , Sarkar Soham , Theeyancheri Ligesh , Chakrabarti Rajarshi
Published: January 2020

Urea at sufficiently high concentration unfolds the secondary structure of proteins leading to denaturation. In contrast, choline chloride (ChCl) and urea, in 1 : 2 molar ratio, form a deep eutectic mixture, a liquid at room temperature, protecting proteins from denaturation. In order to get a microscopic picture of this phenomenon, we perform extensive all‐atom molecular dynamics simulations on a model protein, HP‐36. Based on our calculation of Kirkwood‐Buff integrals, we analyze the relative accumulation of urea and ChCl around the protein. Additional insights are drawn from the translational and rotational dynamics of solvent molecules and hydrogen bond auto‐correlation functions. In the presence of urea, water shows slow subdiffusive dynamics around the protein owing to a strong interaction of water with the backbone atoms. Urea also shows subdiffusive motion. The addition of ChCl further slows down the dynamics of urea, restricting its accumulation around the protein backbone. Adding to this, choline cations in the first solvation shell of the protein show the strongest subdiffusive behavior. In other words, ChCl acts as a nano‐crowder by excluding urea from the protein backbone and thereby slowing down the dynamics of water around the protein. This prevents the protein from denaturation and makes it structurally rigid, which is supported by the smaller radius of gyration and root mean square deviation values of HP‐36.
The genetic architecture of biomechanical traits in sorghum
Authors: Gomez Francisco E. , Mullet John E. , Muliana Anastasia H. , Niklas Karl J. , Rooney William L.
Published: January 2020

Sorghum bicolor (L.) Moench is the fifth most commonly grown cereal crop worldwide with unrivaled drought tolerance compared with other cereal crops. Drought and heat tolerance and high biomass yield potential make sorghum a promising bioenergy crop. However, stem lodging is a significant problem that results in substantial yield losses. Stem biomechanical traits influence the mechanical stability of crops and breeding for desirable biomechanical traits may result in improved lodging resistance. In this study, we report the identification of quantitative trait loci (QTL) for stem mechanical and morphological traits in three recombinant inbred line (RIL; populations from Tx623/Rio, Tx623/Della, and Tx631/Della) crosses between elite grain and sweet sorghum parents. The genetic architecture of stem biomechanical traits in the three RIL populations is multigenic and pleiotropic. Eight QTL affecting mechanical and morphological traits were detected; two main effects of these QTL were consistently found in all populations and colocated with previously identified dwarfing genes Dw1 and Dw3. These results indicate that dwarfing genes affect the mechanical properties of sorghum stems and their lodging resistance, while also having demonstrable effects on stem morphology. The identification of these QTL provides new opportunities for improving stem lodging resistance via genomics‐assisted breeding.
An Efficient and Practical System for the Synthesis of N,N‐Dimethylformamide by CO2 Hydrogenation using a Heterogeneous Ru Catalyst: From Batch to Continuous Flow
Authors: Gunasekar Gunniya Hariyanandam , Padmanaban Sudakar , Park Kwangho , Jung Kwang‐Deog , Yoon Sungho
Published: January 2020

In the context of CO2 utilization, a number of CO2 conversion methods have been identified in laboratory‐scale research; however, only a very few transformations have been successfully scaled up and implemented industrially. The main bottleneck in realizing industrial application of these CO2 conversions is the lack of industrially viable catalytic systems and the need for practically implementable process developments. In this study, a simple, highly efficient and recyclable ruthenium‐grafted bisphosphine‐based porous organic polymer (Ru@PP‐POP) catalyst has been developed for the hydrogenation of CO2 to N,N‐dimethylformamide, which affords a highest ever turnover number of 160 000 and an initial turnover frequency of 29 000 h−1 in a batch process. The catalyst is successfully applied in a trickle‐bed reactor and utilized in an industrially feasible continuous‐flow process with an excellent durability and productivity of 915 mmol h−1 gRu−1.
An improved foraging heuristic considering reduced fog latency
Authors: Wang Qing , Luo Hai‐Wei , Xiong Jian
Published: January 2020

Most often, in centralized distributed computing, users are getting impatient by experiencing the delays in loading the content of the web applications over the internet; it is usually caused by the poor latency management and is becoming a catastrophic situation in availing the services and applications of the centralized‐cloud computing; cloud being a distributed platform, its customers are facing the latencies issues at the various tiers of the cloud. Workloads distributions are occurring concurrently on various virtual cloud platforms. Latency‐oriented applications and services usually in cloud platform are running over various virtual machines and possess the high complexities while interacting and face the difficulties in the consolidations of the various applications containing heterogenetic workloads. In this paper, we study the fog computing and consider that it will be a feasible platform to get rid of the cloud high‐latency issues and to reduce the delay time and workflow across the network. The main purpose is to enhance the latency across the various nodes in a network. The factors like interference, availability, and interaction among various participating nodes with nearer VMware are of importance for reducing the latencies. Reduced latencies will enhance the quality of service parameters, resources, and services availability. Latency can be an important factor for the resource optimization issues in cloud computing. The comparisons with existing technologies greatly show that latency in fog is quite efficient than in the cloud paradigm.
Weighting and aggregating expert ecological judgments
Authors: Hemming Victoria , Hanea Anca M. , Walshe Terry , Burgman Mark A.
Published: January 2020

Performance weighted aggregation of expert judgments, using calibration questions, has been advocated to improve pooled quantitative judgments for ecological questions. However, there is little discussion or practical advice in the ecological literature regarding the application, advantages or challenges of performance weighting. In this paper we (1) illustrate how theIDEAprotocol with four‐step question format can be extended to include performance weighted aggregation from the Classical Model, and (2) explore the extent to which this extension improves pooled judgments for a range of performance measures. Our case study demonstrates that performance weights can improve judgments derived from theIDEAprotocol with four‐step question format. However, there is noa‐prioriguarantee of improvement. We conclude that the merits of the method lie in demonstrating that the final aggregation of judgments provides the best representation of uncertainty (i.e., validation), whether that be via equally weighted or performance weighted aggregation. Whether the time and effort entailed in performance weights can be justified is a matter for decision‐makers. Our case study outlines the rationale, challenges, and benefits of performance weighted aggregations. It will help to inform decisions about the deployment of performance weighting and avoid common pitfalls in its application.
Forest management influences the effects of streamside wet areas on stream ecosystems
Authors: Erdozain Maitane , Emilson Caroline E. , Kreutzweiser David P. , Kidd Karen A. , Mykytczuk Nadia , Sibley Paul K.
Published: January 2020

Riparian zones contain areas of strong hydrological connectivity between land and stream, referred to as variable source areas (VSAs), and are considered biogeochemical control points. However, little is known about whether VSAs influence stream communities and whether this connectivity is affected by forest management. To address this, we used multiple biotic and abiotic indicators to (1) examine the influence of VSAs on riparian vegetation and stream ecosystems by comparing VSA and non‐VSA reaches and (2) explore how forest management may affect the influence of VSAs on stream ecosystems. We detected some significant differences between VSA and non‐VSA reaches in the riparian vegetation (greater understory and lower tree density) and stream ecosystem indicators (greater dissolved organic matter aromaticity, microbial biomass, peroxidase activity and collector‐gatherer density, and lower dissolved organic carbon concentrations, algal biomass, and predatory macroinvertebrate density), which suggests that VSAs may create a more heterotrophic ecosystem locally. However, we show some evidence that forest management activities (specifically, road density) can alter the influence of VSAs and eliminate the differences observed at lower forest management intensities, and that the most hydrologically connected areas seem more sensitive to disturbance. Therefore, we suggest that the heterogeneity in hydrological connectivity along riparian zones should be considered when planning forest harvesting operations and road building (e.g., wider riparian buffers around VSAs).
Synthesis of a Novel Rocksalt‐Type Ternary Nitride Semiconductor MgSnN2 Using the Metathesis Reaction Under High Pressure
Authors: Kawamura Fumio , Imura Masataka , Murata Hidenobu , Yamada Naoomi , Taniguchi Takashi
Published: January 2020

Invited for the cover of this issue is the group of Fumio Kawamura from the National Institute for Materials Science, Tsukuba, Ibaraki, Japan. The cover image shows a crystal of the ternary nitride semiconductor MgSnN2 synthesized in this work, the SEM image of its powder, and a representative high‐pressure apparatus used in the laboratory.
Emblicanin Rich Emblica officinalis Encapsulated Double Emulsion and its Antioxidant Stability during Storage
Authors: Chaudhary Neha , Sabikhi Latha , Hussain Shaik Abdul , Kumar Rajender , Choudhary Urmila
Published: January 2020

Emblicanin rich water‐soluble extract of Emblica officinalis (EEO) is encapsulated in the inner phase of double emulsion (DE) by using emulsifiers in different phases at different concentrations. The effects of other variables like homogenization speed, salt and herbal concentration are also investigated on various phases of DE to obtain a stable matrix. Finally, optimized EEO encapsulated DE has 2% w/w NaCl and 50% w/w EEO in inner (W1) phase, 4% w/w polyglycerol polyricinoleate (PGPR) in middle oil‐phase and 2% w/w low‐methoxy‐pectin and reverse osmosis water in outer (W2) phase. Ultra‐Turrax high shear homogenizer is employed to prepare primary emulsion (W1/O) at 20 000 rpm and DE (W1/O in W2) at 12 000 rpm. The EEO encapsulated DE has been characterized for encapsulation efficiency (>90%), viscosity (0.715 ± 0.18 Pa s), sedimentation stability, zeta potential (−32.17 ±1.17 mV), and particle size. Light and confocal laser microscopy are used for elaborating the microscopic structure of EEO encapsulated DEs. DE has shown storage stability up to 42 days and protect antioxidant activities as compared to control (herbal extract was not encapsulated in the inner phase). The present study demonstrates that the optimized DE matrix can be used to protect the bioactive properties of EEO for its use in functional food formulation.
Ultrasound‐Promoted Radical Synthesis of 5‐Methylselanyl‐4,5‐dihydroisoxazoles
Authors: Araujo Daniela R. , Lima Yanka R. , Barcellos Angelita M. , Silva Márcio S. , Jacob Raquel G. , Lenardão Eder J. , Bagnoli Luana , Santi Claudio , Perin Gelson
Published: January 2020

The ultrasound‐promoted synthesis of 5‐methylselanyl‐4,5‐dihydroisoxazoles through the radical cyclization of unsaturated oximes with diaryl diselenides using Oxone® as an oxidant and ethanol as the solvent is described. The key step of the reaction is the ultrasound‐initiated homolytic cleavage of KHSO5, leading to the formation of sulfate and hydroxyl radicals. The reactions proceed efficiently using several oximes and diselenides containing both electron‐withdrawing and electron‐donating groups in the aromatic ring. The positive effect of the sonication resulted in high selectivity, short reaction times (15 to 40 min) and moderate to excellent yields of the expected products (60–93 %).
Biosynthetic Routes to Natural Isocyanides
Authors: Zhang Xinming , Evanno Laurent , Poupon Erwan
Published: January 2020

As intriguing as it may appear, natural products bearing an isocyanide function are well known in different kingdoms of living organisms. An important question in terms of biochemistry is, of course, the origin of such a functional group and the mechanisms that have evolved in biosynthetic pathways to afford the formation of isocyanides. The latest studies dedicated to such endeavours are analysed therein in view of the producing organism metabolisms (e.g. micro‐organisms, marine invertebrates). The in‐situ reactivity of natural isocyanides is also discussed as well as their biological activities.
Preparation of a Key Tetraene Precursor for the Synthesis of Long Acenes
Authors: Levet Gaspard , Hung Nguyen Khanh , Šámal Michal , Rybáček Jiří , Cisařová Ivana , Jancarik Andrej , Gourdon André
Published: January 2020

The tetraene 7,7‐dimethoxy‐2,3,5,6‐tetramethylenebicyclo[2.2.1]heptane is a key compound for the preparation of a large variety of acenes protected by a carbonyl bridge. We report herein a medium scale preparation in seven steps of this valuable starting material. Diels–Alder addition between 6,6‐dimethtyl fulvene and maleic anhydride, followed by carboxylation, ozonolysis of the double bond, reduction of the four ester groups, then chlorination of the alcohol groups and dehydrochlorination give the target compound in 17 % overall yield.
Permselectivity of Gramicidin A Channels Based on Single‐channel Recordings
Authors: Yamaguchi Takuya , Kitazumi Yuki , Kano Kenji , Shirai Osamu
Published: January 2020

The expression mechanism of permselectivity through a gramicidin A (gA) channel between two aqueous phases (W1 and W2) was investigated. When the concentration of CsCl or CsBr in W1 was equivalent to that in W2, the single‐channel current was proportional to the absolute value of the applied membrane potential. Although the single‐channel current linearly increased with increasing electrolyte concentration in W1 and W2 until about 0.1 M (mol dm−3), it began to level off around 0.1 M, indicating that ion permeation across the channel pore is the rate‐determining step and that the saturation of the transporting ion within the channel pore provokes the leveling off. In the case of asymmetric composition of the electrolyte in W1 and W2, the monovalent cation and the counter anion were transported in the opposite direction through the gA channel pore or the bilayer lipid membrane around the gA channel. Finally, the experimental data was fitted using the Goldman‐Hodgkin‐Katz equation based on the relationship between the membrane potential and the single‐channel current to define the ratio of the diffusion coefficients of Cs+, Cl−, and Br− as 5.7 : 1.0 : 0.26.
The role of salinity in fluvio‐deltaic morphodynamics: A long‐term modelling study
Authors: Zhou Zeng , Chen Luying , Tao Jianfeng , Gong Zheng , Guo Leicheng , van der Wegen Mick , Townend Ian , Zhang Changkuan
Published: January 2020

Salinity difference between terrestrial river discharge and oceanic tidal water plays a role in modifying the local flow field and, as a consequence, estuarine morphodynamics. Although widely recognized, recent numerical studies exploring the long‐term morphological evolution of river‐influenced estuaries with two‐dimensional, depth‐averaged models have mostly neglected salinity. Using a three‐dimensional morphodynamic model, we aim to gain more insight into the effect of salinity on the morphodynamics of fluvio‐deltaic systems. Model results indicate that the resultant estuarine morphology established after 600 years differs remarkably when a salinity gradient is included. A fan‐shaped river‐mouth delta exhibits less seaward expansion and is cut through by narrower channels when salinity is included. The inclusion of salinity tends to generate estuarine circulation, which favours landward sediment transport and hence limits the growth of the delta while enhancing the development of intertidal areas. The formation of deltaic channel–shoal patterns resulting from morphodynamic evolution tends to strengthen salinity stratification, which is characterized by an increased gradient Richardson number. The direction of the depth‐averaged residual sediment transport over a tide may be opposite to the direction of residual velocity, indicating the significant influence of baroclinic effects on the net sediment transport direction (and hence morphological change). The effect of salinity on morphological evolution becomes less profound when the strength of tidal or fluvial forcing is dominant over the other. The effects of sediment type and flocculation, which are particularly important when salinity gradients are present, are also discussed. Overall, this study highlights that neglecting salinity to simulate long‐term estuarine morphodynamics requires more careful justification, particularly when the environment is characterized by fine sediment types (favouring suspended transport), and relatively large river discharge and estuarine depth (favouring baroclinic effects). © 2020 John Wiley & Sons, Ltd.
Exploring an ‘ideal hill': how lithology and transport mechanisms affect the possibility of a steady state during weathering and erosion
Authors: Lebedeva Marina I. , Brantley Susan L.
Published: January 2020

We present a model of chemical reaction within hills to explore how evolving porosity (and by inference, permeability) affects flow pathways and weathering. The model consists of hydrologic and reactive‐transport equations that describe alteration of ferrous minerals and feldspar. These reactions were chosen because previous work emphasized that oxygen‐ and acid‐driven weathering affects porosity differently in felsic and mafic rocks. A parameter controlling the order of the fronts is presented. In the absence of erosion, the two reaction fronts move at different velocities and the relative depths depend on geochemical conditions and starting composition. In turn, the fronts and associated changes in porosity drastically affect both the vertical and lateral velocities of water flow. For these cases, estimates of weathering advance rates based on simple models that posit unidirectional constant‐velocity advection do not apply.

In the model hills, weathering advance rates diminish with time as the Darcy velocities decrease with depth. The system can thus attain a dynamical steady state at any erosion rate where the regolith thickness is constant in time and velocities of both fronts become equal to one another and to the erosion rate. The slower the advection velocities in a system, the faster it attains a steady state. For example, a massive rock with relatively fast‐dissolving minerals such as diabase – where solute transport across the reaction front mainly occurs by diffusion – can reach a steady state more quickly than granitoid rocks in which advection contributes to solute transport. The attainment of a steady state is controlled by coupling between weathering and hydrologic processes that force water to flow horizontally above reaction fronts where permeability changes rapidly with depth and acts as a partial barrier to fluid flow. Published 2020. This article is a U.S. Government work and is in the public domain in the USA.
New fjords, new coasts, new landscapes: The geomorphology of paraglacial coasts formed after recent glacier retreat in Brepollen (Hornsund, southern Svalbard)
Authors: Strzelecki Mateusz C. , Szczuciński Witold , Dominiczak Aleksander , Zagórski Piotr , Dudek Justyna , Knight Jasper
Published: January 2020

Changes in the properties and dynamics of tidewater glacier systems are key indicators of the state of Arctic climate and environment. Calving of tidewater glacier fronts is currently the dominant form of ice mass loss and a major contributor to global sea‐level rise. An important yet under‐studied aspect of this process is transformation of Arctic landscapes, where new lands and coastal systems are revealed due to the recession of marine‐terminating ice masses. The evolution of those freshly exposed paraglacial coastal environments is controlled by nearshore marine, coastal and terrestrial geomorphic processes, which rework glacial‐derived sediments to create new coastal paraglacial landforms and landscapes. Here, we present the first study of the paraglacial coasts of Brepollen, one of the youngest bays of Svalbard revealed by ice retreat. We describe and classify coastal systems and the variety of landforms (deltas, cliffs, tidal flats, beaches) developed along the shores of Brepollen during the last 100 years. We further discuss the main modes of sediment supply to the coast in different parts of the new bay, highlighting the fast rate of coastal transformation as a paraglacial response to rapid deglaciation in the Arctic. This study provides an exemplar of likely coastal responses to be anticipated in similar tidewater settings under future climate change. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd
Qualitative analysis of thermal explosion of sodium droplet with variable thermophysical properties and thermal radiations
Authors: Adegbie K. S. , Obideyi B. D. , Animasaun I. L.
Published: January 2020

There are many coolants frequently used in the industry for controlling not only heat transfer, but also temperature distribution in a confined domain. However, little is known on the thermal properties of sodium droplets. The qualitative analysis of differential equations that model the thermal explosion, nonlinear dynamic of sodium droplet with variable thermophysical properties when thermal radiations are considered as suggested by Cogley et al, Sohrab et al, and P‐1 approximation Sazhin et al is deliberated upon in this study. The governing equations, first‐order nonlinear ordinary differential equations, are nondimensionalized using the appropriate similarity variables. The existence and uniqueness of the solutions, concavity, and convexity of the temperature distribution, and positivity nature of the solutions of the dimensionless governing equations are established. It is concluded that there exists a solution for a certain range of the admissible parameters and when the reduced activation energy is negative and temperature distribution fits concavity. More so, the major criteria to obtain a positive solution are outlined in this study.
Comparative performance evaluation of different HPV tests and triaging strategies using self‐samples and feasibility assessment of thermal ablation in ‘colposcopy and treat’ approach: A population‐based study in rural China
Authors: Zhao Xue‐Lian , Xu Xiao‐Qian , Duan Xian‐Zhi , Rezhake Remila , Hu Shang‐Ying , Wang Yan , Xia Chang‐Fa , Zhang Xun , Qiao You‐Lin , Sankaranarayanan Rengaswamy , Zhao Fang‐Hui , Basu Partha
Published: January 2020

Human papillomavirus (HPV) test, self‐sampling and thermal ablation for cervical intraepithelial neoplasia (CIN) have been developed separately to increase screening coverage and treatment compliance of cervical cancer screening programmes. A large‐scale study in rural China screened 9,526 women with their combinations to explore the optimal cervical cancer‐screening cascade in the real‐world. Participants received careHPV and polymerase chain reaction (PCR) HPV tests on self‐collected samples. Women positive on either HPV test underwent colposcopy, biopsy and thermal ablation in a single visit. Samples positive on either HPV test were retested for genotyping. Absolute and relative performance of HPV tests, triage strategies, ‘colposcopy and thermal ablation’ approach were statistically evaluated. PCR HPV test detected 33.3% more CIN grade two or worse (CIN2+) at a cost of 28.1% more colposcopies compared to careHPV. Sensitivities of PCR HPV and careHPV tests to detect CIN2+ were 96.7 and 72.5%. Specificities for the same disease outcome were 82.1 and 86.0%. Triaging HPV‐positive women with HPV16/18 genotyping considerably improved the positive predictive value for CIN2+ (4.8–5.0 to 18.2–19.2%). Ninety‐six women positive on HPV and having abnormal colposcopy were eligible for thermal ablation and all accepted same‐day treatment, contributing to 64.6% being treated appropriately (CIN1+ on histopathology), which reached up to 84.8% among women positive on HPV 16/18 triage. No serious side‐effects/complications were reported. The combination of PCR HPV test followed by HPV 16/18 triaging on self‐collected samples and colposcopy of triage positive women followed by immediate thermal ablation might be the appropriate screening cascade for rural China.
Integrated clinicomolecular characterization identifies RAS activation and CDKN2A deletion as independent adverse prognostic factors in cancer of unknown primary
Authors: Bochtler Tilmann , Reiling Anna , Endris Volker , Hielscher Thomas , Volckmar Anna‐Lena , Neumann Olaf , Kirchner Martina , Budczies Jan , Heukamp Lukas C. , Leichsenring Jonas , Allgäuer Michael , Kazdal Daniel , Löffler Harald , Weichert Wilko , Schirmacher Peter , Stenzinger Albrecht , Krämer Alwin
Published: January 2020

Cancer of unknown primary (CUP) denotes a malignancy with histologically confirmed metastatic spread while the primary tumor remains elusive. Here, we address prognostic and therapeutic implications of mutations and copy number variations (CNVs) detected in tumor tissue in the context of a comprehensive clinical risk assessment. Targeted panel sequencing was performed in 252 CUP patients. 71.8% of patients had unfavorable CUP according to ESMO guidelines. 74.7% were adeno‐ and 13.7% squamous cell carcinomas. DNA was extracted from microdissected formalin‐fixed, paraffin‐embedded tissues. For library preparation, mostly multiplex PCR‐based Ion Torrent AmpliSeq™ technology with Oncomine comprehensive assays was used. Most frequent genetic alterations were mutations/deletions of TP53 (49.6%), CDKN2A (19.0%) and NOTCH1 (14.1%) as well as oncogenic activation of KRAS (23.4%), FGFR4 (14.9%) and PIK3CA (10.7%). KRAS activation was predominantly found in adenocarcinomas (p = 0.01), PIK3CA activation in squamous cell carcinomas (p = 0.03). Male sex, high ECOG score, unfavorable CUP, higher number of involved organs and RAS activation predicted decreased event‐free and overall survival in multivariate analysis. Deletions of CDKN2A were prognostically adverse regarding overall survival. TP53 mutations did not significantly influence prognosis in the overall cohort, but worsened prognosis in otherwise favorable CUP subtypes. Although not standard in CUP, for 17/198 (8.6%) patients molecularly targeted treatment was recommended and 10 patients (5.1%) were treated accordingly. In conclusion, besides the identification of drug targets, panel sequencing in CUP is prognostically relevant, with RAS activation and CDKN2A deletion emerging as novel independent risk factors in a comprehensive assessment with clinicopathological data.
IMPACTS OF IRRIGATION WATER USER ALLOCATIONS ON WATER QUALITY AND CROP PRODUCTIVITY: THE LCC IRRIGATION SYSTEM IN PAKISTAN
Authors: Culas Richard J. , Baig Irfan A.
Published: January 2020

Irrigated agricultural sectors in many countries are facing the challenge of low crop yields and this trend is made worse by inequality of water allocation among water users. This paper analyses prospects for equitable allocation of canal and groundwater to improve livelihoods of farmers by increasing crop production and reducing the negative effect of groundwater salinity on crop yield. Using data from farm surveys conducted in the 2010 and 2012 cropping seasons in the Lower Chenab Canal (LCC) irrigation system in Pakistan, this study uses econometric models to analyse crop productivity under different water‐use scenarios. The results show that the distributary at the head location of the system can extract more of the groundwater while the one at the tail end of the system should utilize more of the canal (surface) water. Further, an input‐oriented data envelope analysis (DEA) was conducted to measure the efficiency of resources use related to the crops produced in the study area. The DEA estimates show that farmers at the tail end of the system are more efficient in relation to resource use. A redistribution of the water use (optimal scenario) can therefore improve groundwater quality, water productivity and crop productivity in the system. © 2020 John Wiley & Sons, Ltd.
Repurposing biodegradable tissue engineering scaffolds for localized chemotherapeutic delivery
Authors: Cyphert Erika L. , Bil Monika , von Recum Horst A. , Święszkowski Wojciech
Published: January 2020

While highly porous biodegradable sponges have typically been used as tissue engineering scaffolds, they could be applicable in settings requiring drug delivery. Since most drug delivery devices are intentionally solid, nonporous polymers, a detailed structure–function relationship of delivery from a porous degradable sponges would allow researchers to develop such devices for either delivery alone, or in conjunction with tissue engineering. Two fabrication techniques (salt‐leaching and solvent‐quenching) were used to prepare several different variations of poly(DL‐lactide‐glycolide) and poly(caprolactone)‐co‐poly(lactide) porous sponges. Upon fabrication, an in‐depth structure–function analysis was carried out where the functions of loading capacity and release profile of cisplatin, as a model drug, were evaluated in terms of the swelling, porosity, and degradation properties of the sponges. Swelling, pore volume fraction, and the number of pores per volume were all found to be positively correlated with both the loading capacity and amount of cisplatin released after 2 hr. Knowledge of these relationships can be used to assist in the design of other porous delivery systems.
Use of chitosan as pharmaceutical excipient in ocular drug delivery systems: Sterilization and pharmacokinetics
Authors: Franca Juçara R. , Fuscaldi Leonardo L. , Ribeiro Tatiana G. , Foureaux Giselle , Cesar Aina L. A. , Castilho Rachel O. , Cronemberger Sebastião , Ferreira Anderson J. , Fernandes Simone O. A. , Cardoso Valbert N. , Faraco André A. G.
Published: January 2020

The use of chitosan as a pharmaceutical excipient in the ocular field is already established. Nevertheless, some aspects related to its ocular administration, such as sterilization and excipient's pharmacokinetics, remain unclear. So, in this study, we evaluated those two relevant aspects, related to chitosan administration in eye. We used chitosan‐based ocular inserts (CI) as formulation model. CI were produced by solvent/casting method and sterilized by saturated steam. Sterilization was confirmed by direct inoculation of inserts in suitable microbiological growth media. Physicochemical characterization of inserts before and after sterilization was performed. Results suggested that, although steam sterilization changed the arrangement of the matrix, the heat and the humidity did not modify the structure of the main polymeric chain. Pharmacokinetics of CI radiolabeled with technetium‐99m (99mTc) was assessed by scintigraphic images and ex vivo biodistribution study, after ocular administration in male Wistar rats. Scintigraphic and images analysis and ex vivo biodistribution study showed that the insert remained mainly in the eye until 6 hr after administration and its degradation products began to migrate to the abdominal cavity after 18 hr. Together, these data represent an important step forward the manufacturing and the clinical application of CI in the ophthalmic field.