bluuebunny/crossref_metadata_2025 huggingface dataset:
SPME‐GC/MS Analysis of Volatile Compounds Contained in the Insect Larvae of Tenebrio molitor and Leptinotarsa decemlineata before and after Using Insecticides
Authors: Wojciechowska Marta , Gołębiowski Marek
Published: February 2020

The larvae of two harmful insect species Tenebrio molitor and Leptinotarsa decemlineata were analyzed. The insects were sprayed with insecticides containing the active substances cyfluthrin and deltamethrin (T. molitor), and thiamethoxam and acetamiprid (L. decemlineata). The sprayed insect larvae were left for 24, 48 and 72 h. Samples were then prepared using SPME fiber to identify the volatile compounds contained in the larvae. The determinations were made by gas chromatography coupled with mass spectrometry (GC/MS). Chemical compounds were found in the analyzed samples: alkanes, aldehydes, ketones, esters, terpenes, fatty acids. In the samples prepared from T. molitor larvae, more than 20 % of aldehydes and 8–41 % of alkanes were determined. In the samples from L. decemlineata, fatty acids were 8–65 % depending on the length of time after applying the insecticide.
Ruthenium‐Catalyzed Double C(sp2)−H Functionalizations of Fumaramides with Alkynes for the Divergent Synthesis of Pyridones and Naphthyridinediones
Authors: Han Zhi‐Jian , Zhang Ze‐Xuan , Li Wei‐Ping , Du Zhi‐Hong , Tao Bao‐Xiu , Da Chao‐Shan , Jiao Zuo‐Yi , Chen Hao , Li Yumin
Published: February 2020

Transition‐metal‐catalyzed C−H functionalization of aromatic secondary amides with alkynes mainly undergo C−H/N−H annulation but rarely undergo ortho‐alkenylation. It is particularly challenging to selectively realize both oxidative annulation and ortho‐alkenylation of aromatic secondary amides with alkynes in the transition‐metal‐catalysis. In this article, we synthesized fully‐substituted 2‐pyridones and 2,6‐naphthyridine‐1,5‐diones via C(sp2)−H functionalization of fumaramides for the first time. Under the Ru‐catalysis, fumaramides and 1,2‐diaryl ethynes first undergo C−H/N−H annulation leading to the intermediate 2‐pyridone with an exocyclic secondary amide, and subsequently undergo the unexpected stereoselective C−H alkenylation to realize fully substituted 2‐pyridones bearing an exocyclic anti alkenyl group. On the addition of K2CO3, however, the transformation of fumaramides with 1,2‐dialkyl ethyne undergoes two conventional C−H/N−H annulations to provide 2,6‐naphthyridine‐1,5‐diones in high yield. The two procedures can be successfully enlarged to gram‐scales without erosion of the yields. In addition, some 2‐pyridones and 2,6‐naphthyridine‐1,5‐diones emitting clear ultraviolent and fluorescent light, indicating the potential utility of this work in organic light‐emitting materials.
Fabrication of Copper‐based Silica‐coated Magnetic Nanocatalyst for Efficient One‐pot Synthesis of Chalcones via A3 Coupling of Aldehydes‐Alkynes‐Amines
Authors: Yadav Priya , Yadav Manavi , Gaur Rashmi , Gupta Radhika , Arora Gunjan , Rana Pooja , Srivastava Anju , Sharma Rakesh K.
Published: February 2020

In the present work, we have synthesized bioactive and pharmacologically important chalcone motifs by employing green and efficient silica‐coated magnetically separable catalyst, Cu@DBM@ASMNPs. The highly proficient nanocatalyst proves its invincibility for the solvent‐free one‐pot synthesis of chalcone moieties by A3 coupling of aldehydes‐alkynes‐amines in good to excellent yields. The fabricated Cu@DBM@ASMNPs was structurally and chemically analyzed by various techniques such as FT‐IR, SEM, TEM, VSM, ICP‐MS, ED‐XRF and XPS. The programmed catalytic protocol has been proceeded via isomerization‐hydrolysis reaction of aldehydes and terminal alkynes. The present strategy offered much greener and efficacious synthesis of chalcones by adding benefits such as solvent‐less synthetic protocol and much shorter reaction time. Other interesting and noteworthy features of this methodology are broad substrate scope, mild reaction conditions, and reusability up to seven runs without significant loss of its catalytic activity which renders it an environmentally friendly and remarkable protocol from industrial point of view.
A High‐Performance Membraneless Microfluidic Microbial Fuel Cell for Stable, Long‐Term Benchtop Operation Under Strong Flow
Authors: Amirdehi Mehran Abbaszadeh , Khodaparastasgarabad Nastaran , Landari Hamza , Zarabadi Mir Pouyan , Miled Amine , Greener Jesse
Published: February 2020

Strong control over experimental conditions in microfluidic channels provides a unique opportunity to study and optimize membraneless microbial fuel cells (MFCs), particularly with respect to the role of flow. However, improved performance and transferability of results to the wider MFC community require improvements to device stability under all applied operational conditions. To address these challenges, we present an easy‐to‐fabricate membraneless MFC that combines i) O2 protection via a gas diffusion barrier, ii) integrated graphite electrodes, and iii) optimized electrode placement to avoid cross‐contamination under all applied flow rates. Attention to all of these design features in the same platform resulted in the operation of a MFC with a pure‐culture anaerobic Geobacter sulfurreducens biofilm for half a year, that is, six times longer than previously reported, without the use of an oxygen scavenger. As a result of higher device stability under high flow rates, power densities were four times higher than reported previously for microfluidic MFCs with the same biofilm.
Compressing a Non‐Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene
Authors: Lousen Bodil , Pedersen Stephan K. , Bols Pernille , Hansen Kasper H. , Pedersen Michelle R. , Hammerich Ole , Bondarchuk Sergey , Minaev Boris , Baryshnikov Glib V. , Ågren Hans , Pittelkow Michael
Published: February 2020

This work describes a synthetic approach where a non‐planar aromatic heterocyclic [7]helicene is compressed to yield a hetero[8]circulene containing an inner antiaromatic cyclooctatetraene (COT) core. This [8]circulene consists of four benzene rings and four heterocyclic rings, and it is the first heterocyclic [8]circulene containing three different heteroatoms. The synthetic pathway proceeds via a the flattened dehydro‐hetero[7]helicene, which is partially a helicene and partially a circulene: it is non‐planar and helically chiral as helicenes, and contains a COT motif like [8]circulenes. The antiaromaticity of the COT core is confirmed by nucleus independent chemical shift (NICS) calculations. The planarization from a helically π‐conjugated [7]helicene to a fully planar heterocyclic [8]circulene significantly alters the spectroscopic properties of the molecules. Post‐functionalization of the [7]helicenes and the [8]circulenes by oxygenation of the thiophene rings to the corresponding thiophene‐sulfones allows an almost complete fluorescence emission coverage of the visible region of the optical spectrum (400–700 nm).
Fundamental Insights into the Covalent Silane Functionalization of NiFe Layered Double Hydroxides
Authors: Carrasco Jose A. , Seijas‐Da Silva Alvaro , Oestreicher Víctor , Romero Jorge , Márkus Bence G. , Simon Ferenc , Vieira Bruno J. C. , Waerenborgh João C. , Abellán Gonzalo , Coronado Eugenio
Published: February 2020

Layered double hydroxides (LDHs) are a class of 2D anionic materials exhibiting wide chemical versatility and promising applications in different fields, ranging from catalysis to energy storage and conversion. However, the covalent chemistry of this kind of 2D materials is still barely explored. Herein, the covalent functionalization with silanes of a magnetic NiFe‐LDH is reported. The synthetic route consists of a topochemical approach followed by anion exchange reaction with surfactant molecules prior to covalent functionalization with the (3‐aminopropyl)triethoxysilane (APTES) molecules. The functionalized NiFe‐APTES was fully characterized by X‐ray diffraction, infrared spectroscopy, electron microscopy, thermogravimetric analysis coupled with mass spectrometry and 29Si solid‐state nuclear magnetic resonance, among others. The effect on the electronic properties of the functionalized LDH was investigated by a magnetic study in combination with Mössbauer spectroscopy. Moreover, the reversibility of the silane‐functionalization at basic pH was demonstrated, and the quality of the resulting LDH was proven by studying the electrochemical performance in the oxygen evolution reaction in basic media. Furthermore, the anion exchange capability for the NiFe‐APTES was tested employing CrVI, resulting in an increase of 200 % of the anion retention. This report allows for a new degree of tunability of LDHs, opening the door to the synthesis of new hybrid architectures and materials.
A Reusable CNT‐Supported Single‐Atom Iron Catalyst for the Highly Efficient Synthesis of C−N Bonds
Authors: Ding Qifeng , Yu Yang , Huang Fei , Zhang Lihui , Zheng Jian‐Guo , Xu Mingjie , Baell Jonathan B. , Huang He
Published: February 2020

C−N bond formation is regarded as a very useful and fundamental reaction for the synthesis of nitrogen‐containing molecules in both organic and pharmaceutical chemistry. Noble‐metal and homogeneous catalysts have frequently been used for C−N bond formation, however, these catalysts have a number of disadvantages, such as high cost, toxicity, and low atom economy. In this work, a low‐toxic and cheap iron complex (iron ethylene‐1,2‐diamine) has been loaded onto carbon nanotubes (CNTs) to prepare a heterogeneous single‐atom catalyst (SAC) named Fe‐Nx/CNTs. We employed this SAC in the synthesis of C−N bonds for the first time. It was found that Fe‐Nx/CNTs is an efficient catalyst for the synthesis of C−N bonds starting from aromatic amines and ketones. Its catalytic performance was excellent, giving yields of up to 96 %, six‐fold higher than the yields obtained with noble‐metal catalysts, such as AuCl3/CNTs and RhCl3/CNTs. The catalyst showed efficacy in the reactions of thirteen aromatic amine substrates, without the need for additives, and seventeen enaminones were obtained. High‐angle annular dark‐field scanning transmission electron microscopy in combination with X‐ray absorption spectroscopy revealed that the iron species were well dispersed in the Fe‐Nx/CNTs catalyst as single atoms and that Fe‐Nx might be the catalytic active species. This Fe‐Nx/CNTs catalyst has potential industrial applications as it could be cycled seven times without any significant loss of activity.
Magnesocenophane‐Catalyzed Amine Borane Dehydrocoupling
Authors: Wirtz Lisa , Haider Wasim , Huch Volker , Zimmer Michael , Schäfer André
Published: February 2020

The Lewis acidities of a series of [n]magnesocenophanes (1 a–d) have been investigated computationally and found to be a function of the tilt of the cyclopentadienyl moieties. Their catalytic abilities in amine borane dehydrogenation/dehydrocoupling reactions have been probed, and C[1]magnesocenophane (1 a) has been shown to effectively catalyze the dehydrogenation/dehydrocoupling of dimethylamine borane (2 a) and diisopropylamine borane (2 b) under ambient conditions. Furthermore, the mechanism of the reaction with 2 a has been investigated experimentally and computationally, and the results imply a ligand‐assisted mechanism involving stepwise proton and hydride transfer, with dimethylaminoborane as the key intermediate.
A Phosphinine‐Derived 1‐Phospha‐7‐Bora‐Norbornadiene: Frustrated Lewis Pair Type Activation of Triple Bonds
Authors: Leitl Julia , Jupp Andrew R. , Habraken Evi R. M. , Streitferdt Verena , Coburger Peter , Scott Daniel J. , Gschwind Ruth M. , Müller Christian , Slootweg J. Chris , Wolf Robert
Published: February 2020

Salt metathesis of 1‐methyl‐2,4,6‐triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1‐phospha‐7‐bora‐norbornadiene derivative 2. The C≡N triple bonds of nitriles insert into the P−B bond of 2 with concomitant C−B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4‐phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus–boron bond in 2, which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P−B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4‐addition.
Risk stratification biomarkers for Staphylococcus aureus bacteraemia
Authors: Cao Yi , Guimaraes Alessander O , Peck Melicent C , Mayba Oleg , Ruffin Felicia , Hong Kyu , Carrasco‐Triguero Montserrat , Fowler Vance G , Maskarinec Stacey A , Rosenberger Carrie M
Published: February 2020

Objectives

To identify risk stratification biomarkers to enrich for the subset of Staphylococcus aureus bacteraemia patients who develop deep‐seated tissue infections with high morbidity and mortality to guide clinical trial enrolment and clinical management.

Methods

We evaluated the prognostic value of eight biomarkers for persistent bacteraemia, mortality and endovascular infection foci in a validation cohort of 160 patients with S. aureus bacteraemia enrolled consecutively over 3 years.

Results

High levels of IL‐17A, IL‐10 or soluble E‐selectin at bacteraemia diagnosis correlated with the duration of positive blood cultures. When thresholds defined in an independent cohort were applied, these biomarkers were robust predictors of persistent bacteraemia or endovascular infection. High serum levels of IL‐17A and IL‐10 often preceded the radiographic diagnosis of infective endocarditis, suggesting potential utility for prioritising diagnostic radiographic imaging. High IL‐8 was prognostic for all‐cause mortality, while IL‐17A and IL‐10 were superior to clinical metrics in discriminating between attributable mortality and non‐attributable mortality. High IL‐17A and IL‐10 identified more patients who developed microbiological failure or mortality than were identified by infective endocarditis diagnosis.

Conclusion

These biomarkers offer potential utility to identify patients at risk of persistent bacteraemia to guide diagnostic imaging and clinical management. Low biomarker levels could be used to rule out the need for more invasive TEE imaging in patients at lower risk of infective endocarditis. These biomarkers could enable clinical trials by enriching for patients with the greatest need for novel therapies.
Trait means predict performance under water limitation better than plasticity for seedlings of Poaceae species on the eastern Tibetan Plateau
Authors: Li Honglin , Li Xilai , Zhou Xiaolong
Published: February 2020

Water availability may be altered by changes in precipitation under global climate change in alpine areas. Trait means and plasticity are important for plants in response to a changing environment. In an examination of alpine plant responses to changed water availability, and for determination of how trait means and plasticity predict the performance (e.g., biomass) of these species, seeds of ten Poaceae species from the eastern Tibetan Plateau were sown and grown in a manipulated environment during a growing season in which rainfall was removed and other climate conditions remained unchanged. Growth and leaf traits of these species were measured. We found significant effects of moderate water stress on the seedling biomass of these species; however, the responses of these species to changed water condition were strongly dependent on species identity. For example, the biomass of some species significantly decreased under moderate drought, whereas that of others were either significantly increased or unaffected. This pattern was also observed for growth and leaf traits. Overall, the alpine Poaceae species showed low plasticity of traits in response to water availability relative to reports from other areas. Notably, the results show that trait means were better correlated with the productivity than with the plasticity of traits; thus, we argue that the trait means were better predictors of performance than plasticity for alpine Poaceae species. Poaceae species in alpine areas are important for forage production and for water catchment health worldwide, and these species may face water shortage because of current and future climate change. Understanding the response of alpine Poaceae species to water availability would facilitate our ability to predict the impacts of climate change on the alpine vegetation.
Equitable transform applied to phenology and temperature in a changing climate: Scaling to maintain individuality
Authors: Elphinstone Cassandra , Henry Greg H. R.
Published: February 2020

We describe an equitable transform that can be used to estimate missing data points, determine systematic patterns in data, observe baseline changes, and detect different amplitudes in replicated sequences. It is applicable to short discrete two‐ or three‐dimensional data sets such as biological life cycles or water content in similar media. The technique is independent of the continuity or ordering of sequences but is distinct from methods such as principal component analysis. It is ideally used to preprocess noisy or incomplete data sets prior to analysis with other well‐established techniques. This transformation maintains systematic differences between individual sequences when the underlying pattern is a separable function in two variables added to another function in one of these variables. The equitable transform partitions the original noisy data into the underlying signal determined from the data and its residuals. Points from one sequence can be transformed to any other sequence without losing any information. Information about one or more sequences can be used to infer others with missing data. A link to a github R package is provided so the transform can easily be run on any two‐dimensional data set. Simulated two‐dimensional data sets are used to demonstrate its utility in recovering missing data and scaling/offsetting in one of the dimensions. We used the transform to determine that winter temperatures at a High Arctic site have warmed by 1.8° ± 0.4°C/decade and summer temperatures by 1.1° ± 0.2°C/decade from 1986 to 2007. Applied to 18 yr of phenology data for the tundra plant Dryas integrifolia at the same site, we determined that the annual cycles of phenology events could be modeled accurately. Phenology, in some circumstances, can be described as offsetting and scaling the rate at which life cycle events occur. We introduce the idea of scaling and shifting the seasonal cycle of a reference plant via the equitable transform in order to approximate the behavior of multiple phenological cycles. Relative phenology rates of Dryas integrifolia were found to have increased over time indicating duration of phenological stages have become shorter in recent years, likely in response to the warming climate.
Neutral Lipophilic Palladium(II) Complexes and their Applications in Electrocatalytic Hydrogen Production and C‐C Coupling Reactions
Authors: Cuzan‐Munteanu Olesea , Sirbu Dumitru , Giorgi Michel , Shova Sergiu , Gibson Elizabeth A. , Réglier Marius , Orio Maylis , Martins Luísa M. D. R. S. , Benniston Andrew C.
Published: February 2020

Three neutral palladium(II) complexes [Pd(Ln)2] (n = 1,2,3) containing benzotriazole‐phenolate ligands HL1 = 2‐(2H‐benzotriazol‐2‐yl)‐6‐dodecyl‐4‐methylphenol; HL2 = 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐di‐tert‐pentylphenol; HL3 = 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐bis(1‐methyl‐1‐phenylethyl)phenol were synthesized and characterized by several spectroscopic methods (1H, 13C NMR, UV‐Visible), ESI mass spectrometry and single‐crystal X‐ray diffraction. The geometry around the palladium(II) centre for each complex is described as distorted square planar. The complexes were tested as potential catalysts for electrochemical proton reduction in DMF using trifluoroacetic acid (TFA). Gas analysis under electrocatalytic conditions at a boron‐doped diamond working electrode confirmed the hydrogen production. After performing similar gas analysis experiments using a working mercury pool electrode, no hydrogen was detected which supports the concept that the active species of the catalytic process are palladium particles formed on the surface of the working electrode. The palladium(II) benzotriazolyl phenolate complexes facilitate the formation of particles for electrocatalytic hydrogen production. Furthermore, the palladium(II) complexes PdL2 and PdL3 were able to catalyse microwave‐assisted Heck and Sonogashira C–C coupling reactions.
Mild Liquid Phase Oxidation of Benzyl Alcohol in the Presence of Microporous Framework Copper Silicates
Authors: Neves Patrícia , Valente Anabela A. , Lin Zhi
Published: February 2020

The microporous framework copper silicates CuSH‐1NaK (1) and SGU‐29 (2) – prepared using hydrothermal conditions – are effective heterogeneous oxidation catalysts for producing benzaldehyde (BzAld) and benzoic acid (BzAcid) from benzyl alcohol (BzOH), under mild reaction conditions (approximately atmospheric pressure, 70 °C). The copper silicate heterogeneous catalysts triggered a radical reaction mechanism leading to the target products; in particular, BzAcid was formed in up to 94 % yield and 100 % selectivity from BzAld. The type of oxidant and solvent influenced the catalytic performances.
In‐Silico Thermodynamic Description of Heusler Compounds Applied to Magnetocalorics by Monte Carlo Simulations Starting from Ab‐Initio
Authors: Amorim Carlos O. , Gonçalves João N. , Amaral Vítor S. , Amaral João S.
Published: February 2020

Heusler compounds are one of the most versatile families of materials, showing a wide range of technological applications. Here we present a pure in‐silico approach to fully study the physical properties of this promising family of materials as potential competitive magnetocalorics. The temperature and field dependence of the magnetization of three ternary Heusler compounds (Co2CrGa, Co2FeGa and Co2MnGa), as well as of two quaternary Heusler types (Co2CrxY1–xGa, Y=Fe and Mn) was simulated using DFT ab‐initio and Random Path Sampling Monte Carlo methods. These approaches also allowed the calculation of their corresponding Curie temperatures and their isothermal magnetic entropy change. This manuscript also illustrates a proof of concept of guiding magnetocaloric research using purely computational resources, through the synergy between ab‐initio and the Random Path Sampling, in line with recent high‐throughput computational materials design approaches.
Relevance of Chemical vs. Electrochemical Oxidation of Tunable Carbene Iridium Complexes for Catalytic Water Oxidation
Authors: Olivares Marta , van der Ham Cornelis J. M. , Mdluli Velabo , Schmidtendorf Markus , Müller‐Bunz Helge , Verhoeven Tiny W. G. M. , Li Mo , Niemantsverdriet J. W. (Hans) , Hetterscheid Dennis G. H. , Bernhard Stefan , Albrecht Martin
Published: February 2020

Based on previous work that identified iridium(III) Cp* complexes containing aC,N‐bidentate chelating triazolylidene‐pyridyl ligand (Cp* = pentamethylcyclopentadienyl, C5Me5–) as efficient molecular water oxidation catalysts, a series of new complexes based on this motif has been designed and synthesized in order to improve catalytic activity. Modifications include specifically the introduction of electron‐donating substituents into the pyridyl unit of the chelating ligand (H,a; 5‐OMe,b; 4‐OMe,c; 4‐tBu,d; 4‐NMe2,e), as well as electronically active substituents on the triazolylidene C4 position (H,8; COOEt,9; OEt,10; OH,11; COOH,12). Chemical oxidation using cerium ammonium nitrate (CAN) indicates a clear structure‐activity relationship with electron‐donating groups enhancing catalytic turnover frequency, especially when the donor substituent is positioned on the triazolylidene ligand fragment (TOFmax= 2500 h–1for complex10with a MeO group on pyr and a OEt‐substituted triazolylidene, compared to 700 h–1for the parent benchmark complex without substituents). Electrochemical water oxidation does not follow the same trend, and reveals that complex8bwithout a substituent on the triazolylidene fragment outperforms complex10by a factor of 5, while in CAN‐mediated chemical water oxidation, complex10is twice more active than8b. This discrepancy in catalytic activity is remarkable and indicates that caution is needed when benchmarking iridium water oxidation catalysts with chemical oxidants, especially when considering that application in a potential device will most likely involve electrocatalytic water oxidation.
Metal‐Free Decarboxylative A3‐Coupling/Pictet–Spengler Cascade Accessing Polycyclic Scaffolds: Propiolic Acids Exceed Alkynes
Authors: Hu Yingxin , Shen Yangpeng , Huang Liliang , Van der Eycken Erik V. , Feng Huangdi
Published: February 2020

Herein, we describe the development of a metal‐free decarboxylative A3‐coupling and Pictet–Spengler cascade process to directly generate functionalized tetrahydroisoquinolines from a 2‐phenylethanamine, formaldehyde, and a propiolic acid. The key feature of this efficient reactivity is the utilization of a propiolic acid as the alkyne source, with TFA as promoter. This transformation was also demonstrated to be amenable to the construction of N‐propargyl thienotetrahydropyridine and benzodiazepine skeletons under mild conditions.
Revisiting the Addition of in‐situ Nucleophiles to Allenic Ketones: An Entry Towards Synthesis of Benzodioxins
Authors: Sahoo Sushree Ranjan , Sarkar Debayan
Published: February 2020

The manuscript delineates a revisit towards regioselective addition of in situ generated negative nucleophiles to allenic ketones in the presence of a base. A wide variety of allenic ketones as well as nucleophiles are viable in this transformation. A direct ring annulation towards the challenging benzodioxin skeleton synthesis has been developed. Environmentally benign protocol and wide substrate scope are the notable features of this methodology.
Palladium‐Catalyzed Direct α‐Arylation of Arylacetonitriles with Aryl Tosylates and Mesylates
Authors: Yuen On Ying , Chen Xiangmeng , Wu Junyu , So Chau Ming
Published: February 2020

The first general palladium‐catalyzed α‐arylation of arylacetonitriles with aryl and heteroaryl sulfonates are reported. Pd(OAc)2 associated with XPhos serves as the effective catalyst to facilitate this reaction. A broad range of electron‐rich, ‐neutral, ‐deficient, and sterically hindered aryl/heteroaryl tosylates and mesylates are coupled with arylacetonitriles bearing different substituents to give the corresponding products in good to excellent yields. Catalyst loading down to 0.1 mol‐% Pd was achieved, and 22 unprecedented compounds were synthesized from 43 demonstrated examples using this method. Its applicability with the modification of biological phenolic compounds was successfully demonstrated. The Pd/XPhos system catalyzed the α‐arylation and followed by alkylation in one‐pot sequential conditions, resulting in the direct synthesis of compounds containing quaternary center‐ and deuterium‐containing compounds in good to excellent yields.
Assessment of Glucose Oxidase Based Enzymatic Fuel Cells Integrated With Newly Developed Chitosan Membranes by Electrochemical Impedance Spectroscopy
Authors: Bahar Tahsin , Yazici M. Suha
Published: February 2020

Considerably stable enzymatic fuel‐cells (single cell and 5‐cells stack) were prepared by using chitosan based membranes along with glucose oxidase attached bioanode. Continuous operation of fuel‐cells were monitored under short circuit conditions reaching half‐life over a week. Detailed analysis for the effects of pH, temperature, buffer types and concentration on different type of in‐house produced chitosan membranes were performed by electrochemical impedance spectroscopy (EIS). EIS was utilized to observe, total electrolyte resistance, charge transfer properties, mass transfer and double layer effects on integrated fuel cells (single cell and 5‐cells stack). Performance of the fuel cells was also analyzed by the polarization experiments. Current density of the fuel cell increased at higher operation temperatures not only due to better enzyme kinetics, but also due to increase in electrolyte (membrane+buffer solution) conductivity. Buffer concentration in the fuel (glucose) solution was found as an important parameter. Under optimum fuel cell operation conditions (i. e. 30–40 °C, pH 5 0.3 M buffer solution), maximum current densities of 3.0–3.2 mA cm−2 were reached. Low‐power devices (i. e. a calculator, step motor) were powered with 5‐cell stack producing 3 mW at 1.3 V.
Profiling of essential oil chemical composition of some Lamiaceae species extracted using conventional and microwave‐assisted hydrodistillation extraction methods via chemometrics tools
Authors: Hassanein Heba D. , El‐Gendy Abd El‐Nasser G. , Saleh Ibrahim A. , Hendawy Saber F. , Elmissiry Moustafa M. , Omer Elsayed A.
Published: February 2020

This study investigated the potential use of microwave energy as an effective technique for the extraction of essential oil (EO) from some plant species belonging to Lamiaceae family growing in Egypt, involving Origanum majorana L., Mentha pipereta L., Mentha longifolia L., Origanum syriacum L., Lavandula angustifolia L., Rosmarinus officinalis L., and Thymus vulgaris L., in comparison with conventional extraction using hydrodistillation (HD) approach, in terms of extraction time, oil yields, and chemical composition. The results showed that the use of microwave in a relevant technique, namely microwave‐assisted hydrodistillation (MAHD) required an extraction of 60 minutes, while HD required 180 minutes. In general, EO yield being extracted by MAHD was higher than those extracted by HD. Gas chromatography in combination with mass spectrometry (GC/MS) analysis indicated noticeable quantitative changes in EOs composition extracted by MAHD and HD extraction methods. Except for O majorana L., GC/MS analysis of extracted oils using MAHD showed higher amounts of oxygenated constituents compared to HD extraction. The results of this study introduced MAHD as rapid, economical and environmental friendly extraction method. A comparative analysis was stated here between the EOs of all plant species under study on chemometric tools such as principal components analysis (PCA) and agglomerative hierarchical clustering (AHC). In general, the PCA results showed that there is significant variation between species in the quality and quantity of EO composition. However, no significant difference is observed based on the extraction method used (HD and MAHD).
The effectiveness of living well multicultural‐lifestyle management program among ethnic populations in Queensland, Australia
Authors: Gallegos Danielle , Do Hong , To Quyen Gia , Vo Brenda , Goris Janny , Alraman Hana
Published: February 2020

Issue

Some migrant groups have higher risks of deaths and chronic diseases due to barriers associated with socioeconomic disadvantage, social isolation, racism, language, poor access to health services and low levels of health literacy. However, few culturally tailored interventions have targeted ethnic groups in Australia. This study evaluated the effectiveness of the Living Well Multicultural‐Lifestyle Management Program (LWM‐LMP) in Queensland, Australia.

Methods

The LWM‐LMP was originally co‐designed with the targeted communities. Participants aged ≥18 years were eligible to participate without a fee. The evaluation was a quasi‐experimental design without a control group, with data collected at baseline, the end of the programme and after‐programme follow‐up at week 14. The programme lasted 8 weeks with one group‐based session of 120 minutes delivered each week in local community venues. Each session also included time to undertake physical activity (PA). Eating and PA behaviours were self‐reported. Weight, height, waist circumference and blood pressure were measured using standard protocols.

Results

Participants were more likely to consume ≥2 servings of fruit/day, five servings of vegetable/day, low‐fat milk, processed meat, fast food, hot chips/fries, salty snacks, sweet snacks, sweet beverages less than once per week and meet the PA recommendation of ≥150 minutes/wk (P < .001) at week 8. Weight, BMI, waist circumference, waist‐to‐height ratio and blood pressure were also improved at week 8. Many of the changes were sustained at week 14.

Conclusions

The LWM‐LMP was effective in improving participants’ lifestyle behaviours and cardiometabolic indicators.

So what

Engaging targeted communities in designing interventions focussed on healthy personal behaviours helps with delivery and implementation. Behavioural interventions should be culturally tailored to increase their effectiveness.
The determination of the optimal strip‐thickness of anti‐scatter grids for a given grid ratio and strip height
Authors: Zhou Abel , Yin Yuming , Tan Qi , L. White Graeme , Davidson Rob
Published: February 2020

In X‐ray imaging, anti‐scatter grids are used to reduce scatter radiation reaching image receptors, hence improving image quality. Optimization of grid performance is essential for improving image diagnostic quality and minimizing radiation doses to patients. This work investigated the performance of a series of grid designs modeled from the design of typically focused grid with grid ratio 8:1 (r8) and strip height 1.7 mm (h1.7) for high‐energy radiographic applications. Monte Carlo simulation was used to evaluate designs (r8h1.7) which had the strip thickness changed from 6 to 150 μm in 2 μm increments and the interspace distance fixed at 214 μm. The transmissions of radiation in grid materials were modeled by using a regression with radial‐basis‐function‐networks (RBFNS). KSNR was then determined from RBFNS models of radiation transmissions. The optimal strip‐thickness was obtained at the maximum signal‐to‐noise ratio (SNR) improvement factor (KSNR). For high‐energy applications at 100 peak‐kilo‐voltage (kVp) and 30 cm PMMA thickness, the optimal lead‐strip‐thickness was found approximately 74 μm resulting in a strip‐frequency approximately 35 per cm (N35). Using the optimal thickness for imaging condition at 100 kVp and 30 cm thickness, the KSNR would increase by approximately 5.3%. This work showed the existence of optimal strip‐thickness for a series of grids with a given grid‐ratio, strip‐height, strip‐, and interspace materials. The findings are useful and provide guidance to improve grid designs for better performance that will essentially lead to better image quality and better radiation protection for patients.
Fracture Healing in Collagen-Related Preclinical Models of Osteogenesis Imperfecta
Authors: Zieba Jennifer , Munivez Elda , Castellon Alexis , Jiang Ming-Ming , Dawson Brian , Ambrose Catherine G , Lee Brendan
Published: February 2020

Osteogenesis imperfecta (OI) is a genetic bone dysplasia characterized by bone deformities and fractures caused by low bone mass and impaired bone quality. OI is a genetically heterogeneous disorder that most commonly arises from dominant mutations in genes encoding type I collagen (COL1A1 and COL1A2). In addition, OI is recessively inherited with the majority of cases resulting from mutations in prolyl-3-hydroxylation complex members, which includes cartilage-associated protein (CRTAP). OI patients are at an increased risk of fracture throughout their lifetimes. However, non-union or delayed healing has been reported in 24% of fractures and 52% of osteotomies. Additionally, refractures typically go unreported, making the frequency of refractures in OI patients unknown. Thus, there is an unmet need to better understand the mechanisms by which OI affects fracture healing. Using an open tibial fracture model, our study demonstrates delayed healing in both Col1a2 G610c/+ and Crtap −/− OI mouse models (dominant and recessive OI, respectively) that is associated with reduced callus size and predicted strength. Callus cartilage distribution and chondrocyte maturation were altered in OI, suggesting accelerated cartilage differentiation. Importantly, we determined that healed fractured tibia in female OI mice are biomechanically weaker when compared with the contralateral unfractured bone, suggesting that abnormal OI fracture healing OI may prime future refracture at the same location. We have previously shown upregulated TGF-β signaling in OI and we confirm this in the context of fracture healing. Interestingly, treatment of Crtap −/− mice with the anti-TGF-β antibody 1D11 resulted in further reduced callus size and predicted strength, highlighting the importance of investigating dose response in treatment strategies. These data provide valuable insight into the effect of the extracellular matrix (ECM) on fracture healing, a poorly understood mechanism, and support the need for prevention of primary fractures to decrease incidence of refracture and deformity in OI patients. © 2020 American Society for Bone and Mineral Research.
Identification of downregulated circRNAs from tissue and plasma of patients with gastric cancer and construction of a circRNA‐miRNA‐mRNA network
Authors: Liu Jingfu , Li Zhen , Teng Wenhao , Ye Xianren
Published: February 2020

The connection between circular RNAs (circRNAs) and gastric cancer has been reported widely in recent years. However, previous studies have focused mainly on circRNAs from gastric cancer tissue. The objectives of the present study were to detect dysregulated circRNAs from both tissue and plasma of patients with gastric cancer and to explore their potential roles in the pathogenesis of gastric cancer. Expression profiles of circRNAs were obtained from the Gene Expression Omnibus (GEO) and analyzed using the GEO2R tool to identify differential expressed circRNAs. The significance threshold was set as |log2 (fold change)| > 2 and adjusted P < .05. The microRNA (miRNA) binding sites of the differentially expressed circRNAs were predicted using the Circular RNA Interactome web tool. TargetScan and the miRNet database were used to predict the miRNA target genes. Gene Ontology and Kyoto Encyclopedia of Genes and Genomes pathway analyses were performed using Database for Annotation Visualization and Integrated Discovery. Hub genes were identified and a network was constructed with Cytoscape. The overall survival rates for the selected miRNAs and messenger RNAs were evaluated by Kaplan‐Meier Plotter. A total of three downregulated circRNAs (hsa_circ_0001190, hsa_circ_0036287, and hsa_circ_0048607) were identified in this study. Six miRNAs and eight hub genes met the significance criteria and were selected for further analysis. A circRNA‐miRNA‐hub gene network was constructed based on three circRNAs, six miRNAs, and eight hub genes. Evaluation of overall survival rates for the hub genes showed that low expression levels of GADD45A, PPP1CB, PJA2, and KLF2 were associated with poor overall survival. This study identified potential novel plasma circRNA biomarkers and provides insights into the underlying mechanisms of gastric cancer pathogenesis.
Putative functional variants of PI3K/AKT/mTOR pathway are associated with knee osteoarthritis susceptibility
Authors: Wang Kejie , Chu Minjie , Wang Feng , Zhao Yiwen , Chen Haifeng , Dai Xiaoyu
Published: February 2020

Background

Osteoarthritis (OA) is a degenerative musculoskeletal disease which causes joint deformity and pain and finally leads to limb dysfunction. Knee osteoarthritis (KOA) has the highest incidence among all kinds of OA. Strong evidence leads to the understanding that P13K/AKT/mTOR signaling is very important in cartilage degeneration.

Methods

This research sought to understand the association between genetic variation of PI3K/AKT/mTOR genes and KOA susceptibility among Chinese population. All the genetic variants of PI3K/AKT/mTOR pathway were graded and selected using RegulomeDB database, and then, an association study including 278 osteoarthritis patients and 289 controls was conducted.

Results

Finally, eight SNPs' genotypes' distributions and susceptibility to KOA were presented. AKT1 rs2498789 was associated with KOA susceptibility in dominate genetic model (AA + GA vs GG) after adjusted for BMI, age, and gender: OR = 1.46, 95% CI: 1.03‐2.05, P = .03. PIK3CA rs7646409 was also associated with KOA susceptibility (TC vs TT) after adjusted for BMI, age, and gender: OR = 0.58, 95% CI: 0.36‐0.93, P = .02. PIK3CA rs7646409 (TC vs TT) with KOA risk was more significant in age < 60 group (P for heterogeneity was .03). Risk score showed significant association with KOA susceptibility after cumulative analysis (OR = 2.45, 95% CI: 1.35‐4.45, P = .003).

Conclusions

This study shows that genetic variation of PI3K/AKT/mTOR is associated with KOA susceptibility in Chinese Han population, indicating that PI3K/AKT/mTOR is very important in KOA pathogenesis.
Ketamine treatment affects hippocampal but not cortical mitochondrial function in prepubertal rats
Authors: Czerniczyniec Analía , Karadayian Analía G. , Bustamante Juanita , Lores‐Arnaiz Silvia
Published: February 2020

Previous reports have shown that ketamine triggered apoptosis in immature developing brain involving mitochondrial‐mediated pathways. However, no data for ketamine effects on hippocampal and cortical mitochondrial function are available in prepubertal rats. Twenty‐one‐day‐old Sprague–Dawley rats received ketamine (40 mg/kg i.p.) for 3 days and were killed 24 hr after the last injection. Hippocampal mitochondria from ketamine‐treated rats showed decreased malate‐glutamate state 4 and 3 respiratory rates and an inhibition in complex I and IV activities. Hippocampal mitochondrial membrane depolarization and mitochondrial permeability transition induction were observed. This was not reflected in an increment of H2O2 production probably due to increased Mn‐SOD and catalase activities, 24 hr after treatment. Interestingly, increased H2O2 production rates and cardiolipin oxidation were found in hippocampal mitochondria shortly after ketamine treatment (45 min). Unlike the hippocampus, ketamine did not affect mitochondrial parameters in the brain cortex, being the area less vulnerable to suffer ketamine‐induced oxidative damage. Results provide evidences that exposure of prepubertal rats to ketamine leads to an induction of mitochondrial ROS generation at early stages of treatment that was normalized by the triggering of antioxidant systems. Although hippocampal mitochondria from prepubertal rats were capable of responding to the oxidative stress, they remain partially dysfunctional.
Molecular docking and biological assessment of substituted phthalazin‐1(2H)‐one derivatives
Authors: Mahmoud Naglaa F. H. , Elsayed Galal A.
Published: February 2020

2, 4‐Disubstituted phthalazin‐1(2H)‐one derivatives were synthesized via nucleophilic attack of N‐2 of phthalazin‐1(2H)‐one derivatives on different alkyl halides. In addition, reactive phthalazinone acetohydrazide derivative was utilized as a scaffold to synthesize different heterocyclic systems. The assigned structures for all the newly synthesized derivatives were confirmed on the basis of elemental analyses and spectral data. Mechanistic illustrations for some of the synthesized compounds were also discussed. The synthesized compounds were evaluated for in vitro antimicrobial and antitumor activity. Most of the tested compounds exhibited significant potency as antimicrobial and antitumor agents. Moreover, MOE 2014.09 software was utilized to carry out computational studies to support the biological activity results.
1,2,4‐Oxadiazole ring–containing pyridylpyrazole‐4‐carboxamides: Synthesis and evaluation as novel insecticides of the anthranilic diamide family
Authors: Khallaf Abdalla , Wang Ping , Liu Hui , Zhuo Shuping , Zhu Hongjun
Published: February 2020

Herein, we describe the preparation of pyridylpyrazole‐4‐carboxamides containing a 1,2,4‐oxadiazole ring as novel anthranilic diamide derivatives and compare their insecticidal activities to that of chlorantraniliprole, a well‐established potent insecticide. Biological activity tests reveal that all compounds had good insecticidal activities, with the most potent species achieving diamondback moth (Plutella xylostella) mortalities of 100% and 57% at concentrations of 400 and 200 μg mL−1, respectively.
TCR-α/β CD4− CD8− double negative T cells arise from CD8+ T cells
Authors: Rodríguez-Rodríguez Noé , Flores-Mendoza Giovanna , Apostolidis Sokratis A , Rosetti Florencia , Tsokos George C , Crispín José C
Published: February 2020

The cellular origin of CD4− CD8− (double negative, DNT) TCR-α/β+ T cells remains unknown. Available evidence indicates that they may derive from CD8+ T cells, but most published data have been obtained using cells that bear an invariant transgenic T cell receptor that recognizes an Ag that is not present in normal mice. Here, we have used complementary fate mapping and adoptive transfer experiments to identify the cellular lineage of origin of DNT cells in wild-type mice with a polyclonal T cell repertoire. We show that TCR-α/β+ DNT cells can be traced back to CD8+ and CD4+CD8+ double positive cells in the thymus. We also demonstrate that polyclonal DNT cells generated in secondary lymphoid organs proliferate upon adoptive transfer and can regain CD8 expression in lymphopenic environment. These results demonstrate the cellular origin of DNT cells and provide a conceptual framework to understand their presence in pathological circumstances.
Wing and tail myology of Tyto furcata (Aves, Tytonidae)
Authors: Lo Coco Gastón E. , Motta Matías J. , Mosto María Clelia , Picasso Mariana B. J.
Published: February 2020

Barn Owls (Tytonidae) are nocturnal raptors with the largest geographical distribution among Strigiformes. Several osteological, morphometrical, and biomechanical studies of this species were performed by previous authors. Nevertheless, the myology of forelimb and tail of the Barn Owls is virtually unknown. This study is the first detailed myological study performed on the wing and tail of the American Barn Owl (Tyto furcata). A total of 11 specimens were dissected and their morphology and muscle masses were described. Although T. furcata has the wing and tail myological pattern present in other species of Strigiformes, some peculiarities were observed including a difference in the attachment of m. pectoralis propatagialis due to the lack of the os prominence, and the presence of an osseous arch in the radius that seems to widen the anchorage area of the mm. pronator profundus, extensor longus alulae, and extensor longus digiti majoris. Furthermore, the m. biceps brachii has an unusual extra belly that flexes the forearm. The interosseous muscles have a small size and lacks ossified tendons. This feature may be indicative of a lower specialization in the elevation and flexion of the digiti majoris. Forelimb and tail muscle mass account for 10.66 and 0.24% of the total body mass, respectively. Forelimb muscle mass value is similar to the nocturnal (Strigiformes) and diurnal (Falconidae and Accipitridae) raptors, while the tail value is lower than in the diurnal raptors (Falconidae and Accipitridae). The myological differences with other birds of prey are here interpreted in association with their “parachuting” hunting style. This work complements our knowledge of the axial musculature of the American Barn owls, and provides important information for future studies related to functional morphology and ecomorphology.