bluuebunny/crossref_metadata_2025 huggingface dataset:
Occurrence of Hardened Matters in the Andosolic Cover from the Western Highlands of Cameroon: Case Study of Those Risen on Trachyte in the Southern Side of the Bambouto Mountains
Authors: Tuebue J. C. Fopoussi , Basga S. D. , Tematio P. , Nguetnkam J. P.
Published: November 2019

The aim of the present study is to acquire knowledge about the hardened materials present in the andosolic cover from the Bambouto Mounts. For that purpuse, petrographic, mineralogical, and geochemical characteristics of the hardened materials, isalteritic blocks, and the parent rock were investigated in order to put into relief the different facies found, the genetic relationship between those geological matters, and the mechanism governing the formation and the evolution of the hardened materials found in the Andosols from the Bambouto mounts. These matters have low thickness, are highly hardened, with different aspects and locations. They are present within the soils, at the point of emergence of streams, on the flatty areas on top of hills and at the foot of interfluves. Microscopically, their plasmas are respectively isotic and cristic. Gibbsite, goethite, and halloysite are respectively their main minerals. Geochemically, both facies are highly aluminous. During the weathering, Sanidine changes sequentially into Allophane, Halloysite, and Gibbsite; Pyroxen and Ilmenite for their own contribute to the formation of Goethite. There is a direct genetic relationship between the hardened materials, the isalteritic blocks, and the parent rock. The uphill position is the eluvial part and the downhill position the illuvial part; this generates the evolution of the hardened materials from their translucent initial status towards their reddening and tanning final status. The characteristics of the hardened materials make them bauxitic hardened materials, organized into two different facies: A lithorelictuel and a vitreous facies. The presence of those hardened materials in the Andosols from the Western Highlands of Cameroon is harmful for farming. The present study is then a high contribution to the management of the mine ore deposit within the Western Highlands of Cameroon.
An Approximate Solution for a Nonlinear Duffing – Harmonic Oscillator
Authors: Hieu – Dang Van
Published: November 2019

The equivalent linearization method introduced by Caughey is a powerful tool for analyzing random oscillations. The method is also easy to apply for deterministic oscillations. However, with strong nonlinear systems, the error of this method is usually quite large and even not acceptable. In conjunction with a weighted averaging, the equivalent linearization method has shown more accuracy than the classical one in which the conventional averaging value is used. Combining advantages of the classical equivalent linearization method and accuracy of the weighted averaging, the proposed method has shown that it is a useful tool for analyzing nonlinear oscillations including strong nonlinear systems. In this paper, the proposed method is applied to analyze a nonlinear Duffing – harmonic oscillator. The present results are compared with the results obtained by using other analytical methods, exact results and numerical results.
INDEPENDÊNCIA, PODER JUDICIÁRIO E MINISTÉRIO PÚBLICO
Authors: Kerche Fábio
Published: November 2019

Os estudos acadêmicos sobre a questão da independência do Poder Judiciário e dos juízes, tanto do ponto de vista normativo quanto descritivo, são razoavelmente desenvolvidos. A produção é significativa e discute os dilemas e as dificuldades da existência de um Poder de Estado com altas doses de autonomia em regimes democráticos. Do ponto de vista da democracia, a questão é como atores pouco accountable convivem em um sistema baseado fundamentalmente no voto dos cidadãos. Em relação a esse debate, menor atenção é dada ao Ministério Público e aos promotores. Este ensaio bibliográfico analisa, sintetiza e reinterpreta parte da produção acadêmica sobre independência e suas tensões na democracia em relação ao Poder Judiciário e apresenta uma proposta de como estudar o mesmo tema em relação ao Ministério Público.

INDEPENDENCE, JUDICIARY AND PUBLIC PROSECUTOR’S OFFICE

Academic studies on the issue of the Judiciary and judges’ independence, both normatively and descriptively, are reasonably developed. The current academic production is significant and discusses both the dilemmas and difficulties of there being a branch of the government with high doses of autonomy in democratic regimes. From the democratic point of view, the issue is how barely-accountable actors coexist in a system based fundamentally on citizens’ vote. In relation to this debate, less attention is given to the Public Prosecutor’s Office and the prosecutors. This bibliographic essay analyzes, synthesizes and reinterprets part of the academic production on independence and its tensions in democracy in relation to the Judiciary and also presents a proposal of how to study the same subject in the Public Prosecutor’s Office.

Key words: Judiciary; Public Prosecutor’s Office; Independency; Democracy

INDÉPENDANCE, POUVOIR JUDICIAIRE ET MINISTÈRE PUBLIC

Les études académiques sur la question de l’indépendance du Judiciaire et des juges, tant sur le plan normatif que sur le plan descriptif, sont raisonnablement développés. La production est significative et discute les dilemmes et les difficultés de l’existence d’un pouvoir d’Etat avec de fortes doses d’autonomie dans les régimes démocratiques. Du point de vue de la démocratie, la question est de savoir comment des acteurs si peu responsables coexistent dans un système basé fondamentalement sur le vote des citoyens. Moins d´attention est accordée au Ministère Public et aux procureurs en ce qui concerne ce débat. Cet essai bibliographique analyse, synthétise et réinterprète une partie de la production académique sur l’indépendance et ses tensions dans la démocratie par rapport à la magistrature et présente une proposition sur la façon d’étudier le même sujet par rapport au Ministère Public.

Key words: Judiciaire; Ministère Public; Indépendance; Démocratie
O RECONHECIMENTO JURÍDICO DAS VIOLÊNCIAS PSICOLÓGICAS NAS RELAÇÕES DE TRABALHO NO BRASIL
Authors: Magno e Silva Barbosa Attila , Bender Mateus
Published: November 2019

No Brasil, as violências psicológicas no trabalho são atualmente caracterizadas como afrontas aos direitos fundamentais do trabalho, ao princípio da dignidade da pessoa humana e ao valor social do trabalho. Embora não haja uma legislação específica sobre violências psicológicas no ambiente de trabalho, o judiciário tem apresentado um recente e crescente reconhecimento jurídico do tema, norteando-se, principalmente, por princípios constitucionais e de proteção à saúde do trabalhador. O objetivo deste artigo é demonstrar como tem ocorrido o reconhecimento jurídico da proteção à saúde psicológica no ambiente de trabalho. Para tal, utilizamos o procedimento monográfico e nos baseamos na realização de pesquisa bibliográfica e jurisprudencial.

 

THE LEGAL RECOGNITION OF PSYCHOLOGICAL VIOLENCES IN LABOR RELATIONS IN BRAZIL

Psychologically violence at work, in Brazil, has only recently been recognized as a transgression to the fundamental rights of work, to the principle of the dignity of the human person and to the social value of work. Although there is no specific legislation on psychological violence at the workplace, the judiciary has presented a recent and growing juridical recognition to the subject, being guided mainly by constitutional principles as well as by principles related to the protection of the health of the worker. The aim of this article is to discuss how has been occurred the legal recognition of the protection of the psychological health at the work environment. In order to reach the aim of this article, we analyse a specific monographic procedure as well as bibliographical and jurisprudential research.

Key words: Psychologically violence at work; Moral harassment; Legal recognition

 

LA RECONNAISSANCE JURIDIQUE DES VIOLEN-CES PSYCHOLOGIQUES DANS LES RAPPORTS DE TRAVAIL AU BRÉSIL

Au Brésil, les violences psychologiques au travail sont actuellement caractérisés comme un affront aux droits fondamentaux du travail, au principe de la dignité humaine et à la valeur sociale du travail. Bien qu’il n’existe pas de législation spécifique sur les violences psychologiques dans l’environnement de travail, le pouvoir judiciaire a présenté une reconnaissance juridique récente et croissante du thème, principalement guidée par des principes constitutionnels et de protection de la santé des travailleurs. Le but de cet article est démontrer le processus de reconnaissance juridique de la protection de la santé psychologique dans l’environnement de travail. Pour cela, nous avons utilisé la procédure monographique et recherches bibliographiques et jurisprudentielles.

Key words: Violence psychologique au travail; Harcèlement moral; Reconnaissance juridique
Ultrafine‐Grained Titanium‐Based Alloys: Structure and Service Properties for Engineering Applications
Authors: Semenova Irina P. , Polyakova Veronika V. , Dyakonov Grigory S. , Polyakov Alexander V.
Published: November 2019

Herein, an overview of the recent research on the relationship between the ultrafine‐grained (UFG) structure of titanium and its alloys and the physical and mechanical properties of the materials, as well as the formation of advanced functional and service properties, including fatigue strength, creep behavior, and impact and fracture toughness is presented. It is shown that due to the record properties achieved in UFG titanium and its alloys, these materials have an innovative potential for successful application in medicine and engineering industries. Some of these works are carried out in cooperation with the team of Prof. Terence G. Langdon. Professor Langdon made a significant contribution to the development of modern materials science in the field of nanostructured metallic materials.
Botanical‐Inspired 4D Printing of Hydrogel at the Microscale
Authors: Hu Yanlei , Wang Zhongyu , Jin Dongdong , Zhang Chenchu , Sun Rui , Li Ziqin , Hu Kai , Ni Jincheng , Cai Ze , Pan Deng , Wang Xuewen , Zhu Wulin , Li Jiawen , Wu Dong , Zhang Li , Chu Jiaru
Published: November 2019

Botanical systems have evolved the intriguing ability to respond to diverse stimuli due to long‐term survival competition. Mimicking these dynamic behaviors has greatly advanced the developments in wide fields ranging from soft robotics, precision sensors to drug delivery and biomedical devices. However, realization of stimuli‐responsive components at the microscale with high response speed still remains a significant challenge. Herein, the miniature biomimetic 4D printing of pH‐responsive hydrogel is reported in spatiotemporal domain by femtosecond laser direct writing. The dimension of the printed architectures is at the microscale (<102 µm) and the response speed is reduced down to subsecond level (<500 ms). Shape transformation with multiple degrees of freedom is accomplished by taking advantage of pH‐triggered expansion, contraction, and torsion. Biomimetic complex shape‐morphing is enabled by adopting flexible scanning strategies. In addition, application of this 4D‐printed micro‐architecture in selective micro‐object trapping and releasing is demonstrated, showcasing its possibilities in micromanipulation, single‐cell analysis, and drug delivery.
Density Modulation of Embedded Nanoparticles via Spatial, Temporal, and Chemical Control Elements
Authors: Tan Edward K. W. , Shrestha Pawan K. , Pansare Amol V. , Chakrabarti Subhananda , Li Shunpu , Chu Daping , Lowe Christopher R. , Nagarkar Amit A.
Published: November 2019

Nanoparticle polymer composites have enabled material multifunctionalities that are difficult to obtain otherwise. A simple modification to a commercially available resin system enables a universal methodology to embed nanoparticles in resins via spatial, temporal, thermal, concentration, and chemical control parameters. Changes in nanoparticle density distribution are exploited to demonstrate dynamic optical and electronic properties that can be processed on‐demand, without the need for expensive equipment or cleanroom facilities. This strategy provides access to the control of optical (cooperative plasmonic effects), electronic (insulator to a conductor), and chemical parameters (multimetal patterning). Using the same composite resin system, the followings are fabricated: i) diffraction gratings with tuneable diffraction efficiencies (10–78% diffraction efficiencies), ii) organic electrochemical transistors with a low drive voltage, and iii) embedded electrodes in confined spaces for potential diagnostic applications.
Ligand‐Controlled C−O Bond Coupling of Carboxylic Acids and Aryl Iodides: Experimental and Computational Insights
Authors: Li Li , Song Feifei , Zhong Xiumei , Wu Yun‐Dong , Zhang Xinhao , Chen Jiean , Huang Yong
Published: November 2019

Palladium‐catalyzed cross‐coupling reactions between carboxylic acids and aryl halides have several possible competitive pathways. Decarboxylative C−C bond coupling and C−H arylation are well established in the literature. However, direct C−O bond coupling between carboxylic acids and aryl halides has received little success. In this report, we describe a protocol for exclusive C−O bond formation, enabled by a bidentate N,N‐ligand such as 1,10‐phenanthroline. The reaction is general for a broad range of carboxylic acids and iodoarenes. Experimental evidence and computational results suggest a high energy barrier for the alternative pathway of decarboxylative carbon‐carbon bond coupling.

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Advances in Chemocatalytic Asymmetric Baeyer–Villiger Oxidations
Authors: Liu Chao , Wen Kai‐Ge , Zeng Xing‐Ping , Peng Yi‐Yuan
Published: November 2019

Baeyer–Villiger oxidations, first reported by Adolf von Baeyer and Victor Villiger 120 years ago, are highly efficient methodologies for the syntheses of esters or lactones from ketones. The asymmetric Baeyer–Villiger oxidations using racemic, prochiral and meso‐cyclic ketones allow a rapid access to chiral lactones, which are valuable intermediates for the subsequent synthesis of bioactive compounds and natural products. The current review provides a summary on the advances in chemocatalytic enantioselective B‐V oxidations. The latest achievements in this field and their applications are presented.

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Halogen Engineering for Operationally Stable Perovskite Solar Cells via Sequential Deposition
Authors: Li Qi , Zhao Yao , Zhou Wenke , Han Zhengyuan , Fu Rui , Lin Fang , Yu Dapeng , Zhao Qing
Published: November 2019

The performance of perovskite solar cells (PSCs) relies on the synthesis method and chemical composition of the perovskite materials. So far, PSCs that have adopted two‐step sequential deposited perovskite with the state‐of‐art composition (FAPbI3)1−x(MAPbBr3)x (x < 0.05) have achieved record power conversion efficiency (PCE), while their one‐step antisolvent dripping counterparts with typical composition Cs0.05FA0.81MA0.14Pb(I0.85Br0.15)3 with more bromine have exhibited much better long‐term operational stability. Thus, halogen engineering that aims to elevate bromine content in sequential deposited perovskite film would push operational stability of PSCs toward that of antisolvent dripping deposited perovskite materials. Here, a Br‐rich seeding growth method is devised and perovskite seed solution with high bromine content is introduced into a PbI2 precursor, leading to bromine incorporation in the resulting perovskite film. Photovoltaic devices fabricated by Br‐rich seeding growth method exhibit a PCE of 21.5%, similar to 21.6% for PSCs having lower bromine content. Whereas, the operational stability of PSCs with higher bromine content is significantly enhanced, with over 80% of initial PCE retained after 500 h tracking at maximum power point under 1‐sun illumination. This work highlights the vital importance of halogen composition for the operational stability of PSCs, and introduces an effective way to incorporate bromine into mixed‐cation‐halide perovskite film via sequential deposition method.
Nonthermal plasma (NTP) activated metal–organic frameworks (MOFs) catalyst for catalytic CO2 hydrogenation
Authors: Chen Huanhao , Mu Yibing , Shao Yan , Chansai Sarayute , Xiang Huan , Jiao Yilai , Hardacre Christopher , Fan Xiaolei
Published: November 2019

A systematic study of Ni supported on metal–organic frameworks (MOFs) catalyst (i.e., 15Ni/UiO‐66) for catalytic CO2 hydrogenation under nonthermal plasma (NTP) conditions was presented. The catalyst outperformed other catalysts based on conventional supports such as ZrO2, representing highest CO2 conversion and CH4 selectivity at about 85 and 99%, respectively. We found that the turnover frequency of the NTP catalysis system (1.8 ± 0.02 s−1) has a nearly two‐fold improvement compared with the thermal catalysis (1.0 ± 0.06 s−1). After 20 hr test, XPS and HRTEM characterizations confirmed the stability of the 15Ni/UiO‐66 catalyst in the NTP‐activated catalysis. The activation barrier for the NTP‐activated catalysis was calculated as ~32 kJ mol−1, being lower than the activation energy of the thermal catalysis (~70 kJ mol−1). In situ DRIFTS characterization confirmed the formation of multiple carbonates and formates on catalyst surface activated by NTP, surpassing the control catalysts (e.g., 15Ni/α‐Al2O3 and 15Ni/ZrO2).
An overview of the Department of Energy's CarbonSAFE Initiative: Moving CCUS toward commercialization
Authors: Sullivan Mary , Rodosta Traci , Mahajan Kanwal , Damiani Darin
Published: November 2019

The U.S. Department of Energy (DOE) Office of Fossil Energy (FE) National Energy Technology Laboratory (NETL) Carbon Storage Program helps develop technologies that safely and permanently store carbon dioxide (CO2) without adversely impacting natural resources or hindering economic growth. Since 1997, the program has significantly advanced carbon capture, utilization, and storage (CCUS) science and technology, with more than 10.5 million metric tons (MMT) of CO2 safely stored. However, key gaps in experience and knowledge remain (e.g., the technology, expertise, and processes needed to safely characterize and monitor 50+ MMT‐scale geologic CO2 storage sites). DOE's Carbon Storage Assurance Facility Enterprise (CarbonSAFE) Initiative (launched in FY16) is beginning to address this gap. The CarbonSAFE Initiative currently consists of 13 projects in Phase I: Integrated Carbon Capture and Storage (CCS) Pre‐Feasibility and six projects in Phase II: Storage Complex Feasibility. This article includes the latest updates from the CarbonSAFE Initiative.
Total disability days in interprovincial and home‐province workers injured in Alberta, Canada: A mixed‐methods study with matched‐pair analysis of compensation data and participant interviews
Authors: Cherry Nicola , Galarneau Jean‐Michel , Haynes Whitney
Published: November 2019

Introduction

Workers moving between states or provinces to find employment are reported to take longer to return to work after the injury.

Methods

The Alberta Workers Compensation Board (WCB) identified all workers from four Canadian Atlantic provinces who sustained a work injury in Alberta resulting in greater than 5 total temporary disability days (TTDDays) from January 2015 to June 2017. Each was matched on sex, age, and injury date with an Alberta claimant also with greater than 5 TTDDays. WCB information extracted included employment, injury, cost and place of treatment, and modified work. Cox regression identified factors associated with TTDDays. Semi‐structured interviews were also undertaken.

Results

Two‐hundred forty pairs were identified and 60 interviews completed. Those from the Atlantic provinces had more TTDDays (median 63 days) than Alberta (median 22 days) with an unadjusted hazard ratio (HR) 0.50 (95% confidence interval [CI], 0.42‐0.61). When adjusted for all factors, the HR moved closer to unity (HR = 0.62; 95% CI, 0.50‐0.76). Total health care costs were the strongest predictor, with modified work, injury type, and claim status also explanatory factors. Among the Atlantic workers, leaving Alberta for treatment was strongly related to a lower likelihood of ending wage replacement (HR = 0.45; 95% CI, 0.32‐0.62). Participants in the interview study emphasized the importance of returning to the family after injury and the financial difficulties of maintaining a second home with reduced income after the injury.

Conclusion

The higher costs of wage replacement associated with extended time off work may be inherent to the practice of employing out‐of‐province workers for jobs for which there is a shortage of local labor.
Interleukin 1α and 1β gene variations are associated with tuberculosis in silica exposed subjects
Authors: Salum Kaio Cezar Rodrigues , de Castro Marcos Cesar Santos , Moreira Valéria Barbosa , Nani Angela Santos Ferreira , Kohlrausch Fabiana Barzotto
Published: November 2019

Introduction

Silicosis is a fibrotic lung disease resulting from the inhalation of crystalline silica and can be classified as simple or complicated according to the International Labour Organization criteria. Furthermore, individuals exposed to crystalline silica also have a higher risk for the development of tuberculosis (Tb). The contribution of inflammatory cytokines to the risk of silicosis and Tb in different populations has previously been reported. Since genetic background might be related to susceptibility to silicosis and Tb, the study of polymorphisms within IL‐1α, IL‐1β, and tumor necrosis factor protein‐coding genes may contribute to elucidating the genetic basis of these diseases.

Methods

Single nucleotide polymorphisms (SNPs) were genotyped by polymerase chain reaction using restriction fragment length polymorphism or by Taqman methodology, in a sample of 102 silica‐exposed patients from Brazil.

Results

No significant associations were observed between the SNPs studied and the severity of silicosis. However, significant associations were found between Tb and the C allele (odds ratio [OR] = 1.93, 95% confidence interval [CI], 1.01‐3.73) and the CC genotype (OR = 2.34, 95% CI, 1.04‐5.31) of IL1A −899C>T. The IL1B +3954C>T polymorphism also showed an association with Tb (T allele dominant model OR = 2.38, 95% CI, 1.04‐5.41).

Conclusion

These preliminary results demonstrate that the IL1A and IL1B gene variations may contribute to some extent to susceptibility to Tb, but not silicosis. However, additional studies are still needed to confirm these results.
A dyadic genotype–phenotype approach to diagnostic criteria for Proteus syndrome
Authors: Sapp Julie C. , Buser Anna , Burton‐Akright Jasmine , Keppler‐Noreuil Kim M. , Biesecker Leslie G.
Published: November 2019

Phenotype‐based diagnostic criteria were developed for Proteus syndrome in 1999 and updated in 2006. Subsequently, the causative mosaic gene alteration was discovered, the c.49G>A p.E17K variant in AKT1. As well, a number of overlapping overgrowth disorders attributable to mosaic PIK3CA variants have now been characterized, leading to the designation of PIK3CA‐related overgrowth spectrum (PROS). Finally, ongoing work to better characterize Proteus syndrome has led to identification of additional features of that disorder that could be useful in diagnostic criteria. We have taken the opportunity of these discoveries to re‐evaluate the Proteus syndrome diagnostic criteria. Here we propose a new set of diagnostic criteria that establishes a weighted, point‐based system for the phenotypic attributes and then integrates that with the potential molecular test results to result in one of two designations: AKT1‐related Proteus syndrome or AKT1‐related overgrowth spectrum. A patient whose only manifestation is an AKT1 c.49G>A‐positive tumor would receive neither of these designations. Here we review the rational basis of diagnostic criteria and argue that a unitary diagnostic entity is a distinct gene‐phenotype dyad and that this should be the model for all mendelian disorders. The gene‐alone or phenotype‐alone approach is inadequate to rigorously delineate a unitary diagnostic entity.
Promoter Activation in Δhfq Mutants as an Efficient Tool for Specialized Metabolite Production Enabling Direct Bioactivity Testing
Authors: Bode Edna , Heinrich Antje K. , Hirschmann Merle , Abebew Desalegne , Shi Yan‐Ni , Vo Tien Duy , Wesche Frank , Shi Yi‐Ming , Grün Peter , Simonyi Svenja , Keller Nadine , Engel Yvonne , Wenski Sebastian , Bennet Reuel , Beyer Sophie , Bischoff Iris , Buaya Anthony , Brandt Sophie , Cakmak Ibrahim , Çimen Harun , Eckstein Simone , Frank Denia , Fürst Robert , Gand Martin , Geisslinger Gerd , Hazir Selcuk , Henke Marina , Heermann Ralf , Lecaudey Virginie , Schäfer Wilhelm , Schiffmann Susanne , Schüffler Anja , Schwenk Rebecca , Skaljac Marisa , Thines Eckhard , Thines Marco , Ulshöfer Thomas , Vilcinskas Andreas , Wichelhaus Thomas A. , Bode Helge B.
Published: November 2019

Natural products (NPs) from microorganisms have been important sources for discovering new therapeutic and chemical entities. While their corresponding biosynthetic gene clusters (BGCs) can be easily identified by gene‐sequence‐similarity‐based bioinformatics strategies, the actual access to these NPs for structure elucidation and bioactivity testing remains difficult. Deletion of the gene encoding the RNA chaperone, Hfq, results in strains losing the production of most NPs. By exchanging the native promoter of a desired BGC against an inducible promoter in Δhfq mutants, almost exclusive production of the corresponding NP from the targeted BGC in Photorhabdus, Xenorhabdus and Pseudomonas was observed including the production of several new NPs derived from previously uncharacterized non‐ribosomal peptide synthetases (NRPS). This easyPACId approach (easy Promoter Activated Compound Identification) facilitates NP identification due to low interference from other NPs. Moreover, it allows direct bioactivity testing of supernatants containing secreted NPs, without laborious purification.
Intermolekulare stereospezifische Substitution von underivatisierten enantiomerenangereicherten sekundären Alkoholen durch Organokatalyse
Authors: Akkarasamiyo Sunisa , Samec Joseph S. M.
Published: November 2019

Die stereospezifische Substitution von nicht‐derivatisierten und nicht‐allylischen enantiomerenangereicherten Alkoholen, bei der lediglich Wasser als Beiprodukt anfällt, würde die Verwendung von leicht verfügbaren Alkoholen als Substrat für nachhaltige Transformationen ermöglichen. Die schlechte Abgangsgruppenfähigkeit der OH‐Gruppe hat jedoch die Entwicklung eines solchen Prozesses bislang behindert. Denton und Mitarbeiter beschrieben nun kürzlich die Verwendung von (2‐Hydroxybenzyl)diphenylphosphinoxid als Katalysator einer redoxneutralen und abfallfreien Mitsunobu‐Reaktion. Dieser innovative Prozess stellt die erste intermolekulare stereospezifische Substitution von nicht‐allylischen Alkoholen dar und könnte industrielle Anwendung finden.
Asymmetric Wacker‐Type Oxyallenylation and Azaallenylation of Cyclic Alkenes
Authors: Teng Shenghan , Jiao Zhiwei , Chi Yonggui Robin , Zhou Jianrong Steve
Published: November 2019

Palladium‐catalyzed three‐component carboetherification of cyclic alkenes proceeded to give trans adducts exclusively with excellent enantioselectivity through a Wacker‐type pathway. The reaction is also applicable to other oxygen nucleophiles, such as water, phenols, and carboxylic acids, as well as some electron‐poor aryl amines.
Sequence‐Dependent Stereodivergent Allylic Alkylation/Fluorination of Acyclic Ketones
Authors: Liu Xi‐Jia , Jin Shicheng , Zhang Wen‐Yun , Liu Qiang‐Qiang , Zheng Chao , You Shu‐Li
Published: November 2019

The stereodivergent iridium‐catalyzed allylic alkylation and fluorination of acyclic ketones is described. α‐Pyridyl‐α‐fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities. Distinct from known stereodivergent synthesis, for which two different chiral catalysts are required in general, herein we report a sequence‐dependent stereodivergent synthesis. With only a single chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.
Oxodealkenylative Cleavage of Alkene C(sp3)−C(sp2) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials
Authors: Smaligo Andrew J. , Wu Jason , Burton Nikolas R. , Hacker Allison S. , Shaikh Aslam C. , Quintana Jason C. , Wang Ruoxi , Xie Changmin , Kwon Ohyun
Published: November 2019

Reported herein is a one‐pot protocol for the oxodealkenylative introduction of carbonyl functionalities into terpenes and terpene‐derived compounds. This transformation proceeds by Criegee ozonolysis of an alkene, reductive cleavage of the resulting α‐alkoxy hydroperoxide, trapping of the generated alkyl radical with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO), and subsequent oxidative fragmentation with MMPP. Using readily available starting materials from chiral pool, a variety of carbonyl‐containing products have been accessed rapidly in good yields.
Efficient removal of Congo red from pH‐unregulated aqueous solutions by lignosulfonate‐based polycatecholamine
Authors: Gao Song , Wei Gang , Liu Qiang , Liu Qinze , Gao Tingting , Yao Jinshui
Published: November 2019

Lignosulfonate‐based polycatecholamine (PCEA‐LS) was synthesized by a two‐stage approach involving Mannich and catechol–amine reactions, and it was directly used to adsorb Congo red (CR) from the pH‐unadjusted aqueous solution. PCEA‐LS was characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT‐IR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). Various factors affecting on removal of CR by PCEA‐LS were investigated in depth, including contact time, adsorbent dosage, and initial concentration of CR and adsorption temperature. The adsorption kinetics, isotherm, and thermodynamics of PCEA‐LS for CR were explored in detail, and then its adsorption mechanism was systematically elucidated. Results indicated that the removal process of CR followed the pseudo‐second‐order kinetic model, and the isotherm data fitted the Langmuir model well. The maximum adsorption capacity reached 972.6 mg g−1 at 30°C in the pH‐unadjusted (pH = 6.25) solution possibly due to the hydrogen bond, π–π stacking, and electrostatic interaction between PCEA‐LS and CR. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48640.
Synthesis of a “Butterfly Cage” Based on a Double‐Decker Silsesquioxane
Authors: Kunthom Rungthip , Adachi Takuto , Liu Yujia , Takeda Nobuhiro , Unno Masafumi , Tanaka Ryoji
Published: November 2019

Novel polyhedral structures were prepared with a butterfly‐shape composed of oligosiloxane wings and a double‐decker silsesquioxane (DDSQ) body. The compounds were synthesized in two steps from commercially available alkoxysilanes, and their structures were confirmed using spectroscopic methods and X‐ray crystallography. Not like other phenyl‐substituted cage silsesquioxanes, these butterfly cages show very good solubility in common organic solvents. The crystal structures clearly showed their unique features: a larger space with longer siloxane chains and a very flexible framework. Moreover, these compounds are thermally stable with a Td5 (5 % weight loss temperature) over 320 °C.
Multi‐Cation Coordination in Porphyrinoids
Authors: Stawski Wojciech , Kijewska Monika , Pawlicki Miłosz
Published: November 2019

Porphyrinoid macrocycles are unbreakably linked with the coordination of central cations that drastically influence the observed behavior. A specific place has been recorded for structures where more than one cation is entrapped in a single macrocycle. It has been a characteristic feature of expanded porphyrinoids where the increased coordination space allows a multiple coordination. Because of specific steric confinements, an incorporation of more than one cation within regular or contracted porphyrinoids is more demanding but it can be realized on several ways significantly modifying the observed behavior. We will discuss synthetic strategies leading to structures with increased number of cations and the influence on the observed behavior of such modification.
Synthesis of Tofisopam by Way of Photoinduced CO2 Fixation
Authors: Masuda Yusuke , Makita Katsuhiko , Ishida Naoki , Murakami Masahiro
Published: November 2019

Herein reported is a unique synthetic route of Tofisopam, an anxiolytic drug containing a 2,3‐benzodiazepine core structure. 3,4‐Dimethoxypropylbenzene and 3,4‐dimethoxybenzoic acid, which are both of plant origin, and CO2 constitute its carbon skeleton. These three renewable substances are united by two C−C bond forming reactions, i.e., a Friedel–Crafts acylation reaction and a photoinduced carboxylation reaction to construct the major carbon framework. Finally, a methyl group is introduced by a Kumada‐type cross‐coupling reaction to furnish Tofisopam. Various analogs of Tofisopam are readily synthesized by introducing other substituents than a methyl group at the last C−C bond forming step.
A utility approach to individualized optimal dose selection using biomarkers
Authors: Li Pin , Taylor Jeremy M.G. , Kong Spring , Jolly Shruti , Schipper Matthew J.
Published: November 2019

In many settings, including oncology, increasing the dose of treatment results in both increased efficacy and toxicity. With the increasing availability of validated biomarkers and prediction models, there is the potential for individualized dosing based on patient specific factors. We consider the setting where there is an existing dataset of patients treated with heterogenous doses and including binary efficacy and toxicity outcomes and patient factors such as clinical features and biomarkers. The goal is to analyze the data to estimate an optimal dose for each (future) patient based on their clinical features and biomarkers. We propose an optimal individualized dose finding rule by maximizing utility functions for individual patients while limiting the rate of toxicity. The utility is defined as a weighted combination of efficacy and toxicity probabilities. This approach maximizes overall efficacy at a prespecified constraint on overall toxicity. We model the binary efficacy and toxicity outcomes using logistic regression with dose, biomarkers and dose–biomarker interactions. To incorporate the large number of potential parameters, we use the LASSO method. We additionally constrain the dose effect to be non‐negative for both efficacy and toxicity for all patients. Simulation studies show that the utility approach combined with any of the modeling methods can improve efficacy without increasing toxicity relative to fixed dosing. The proposed methods are illustrated using a dataset of patients with lung cancer treated with radiation therapy.
Enhancing Energy Storage Devices with Biomacromolecules in Hybrid Electrodes
Authors: Ajjan Fatima Nadia , Mecerreyes David , Inganäs Olle
Published: November 2019

The development of energy storage devices with higher energy and power outputs, and long cycling stability is urgently required in the pursuit of the expanding challenges of electrical energy storage. The utilization of biologically renewable redox compounds holds a great potential in designing sustainable energy storage systems and contributes in reducing the dependence on fossil fuels for energy materials. Quinones are the principal redox centers in natural organic materials and play a key role as charge storage electrode materials because of their abundance, multiple forms and integration into the materials flow through the biosphere. Electrical energy storage devices and systems can be significantly improved by the combination of scalable quinone‐based biomaterials with good electronic conductors. This review uses recent examples to show how biopolymers are providing new directions in the development of renewable biohybrid electrodes for energy storage devices.
Rice lectin receptor‐like kinase provides salinity tolerance by ion homeostasis
Authors: Passricha Nishat , Saifi Shabnam K. , Kharb Pushpa , Tuteja Narendra
Published: November 2019

Sensing stress and activating the downstream signaling pathways is the imperative step for stress response. Lectin receptor‐like kinase (LecRLK) is an important family that plays a key role in sensing stress conditions through lectin receptor and activates downstream signaling by kinase domain. We identified the role of OsLecRLK gene for salinity stress tolerance and hypothesized its role in Na+ extrusion from cell. OsLecRLK overexpression and downregulation (through artificial miRNA) transgenic lines were developed and its comparison with wild‐type (WT) plants were performed overexpression transgenic lines showed better performance, whereas downregulation showed poor performance than WT. Lower accumulation of reactive oxygen species (ROS), malondialdehyde and toxic ion, and a higher level of proline, RWC, ROS scavengers in overexpression lines lead us to the above conclusion. Based on the relative expression of stress‐responsive genes, ionic content and interactome protein, working model highlights the role of OsLecRLK in the extrusion of Na+ ion from the cell. This extrusion is facilitated by a higher expression of salt overly sensitive 1 (Na+/K+ channel) in overexpression transgenic line. Altered expression of stress‐responsive genes and changed biochemical and physiological properties of cell suggests an extensive reprogramming of the stress‐responsive metabolic pathways by OsLecRLK under stress condition, which could be responsible for the salt tolerance capability.
Trainee performance in radical gastrectomy and its effect on outcomes
Authors: Navidi M. , Madhavan A. , Griffin S. M. , Prasad P. , Immanuel A. , Hayes N. , Phillips A. W.
Published: November 2019

Background

This study aimed to determine whether trainee involvement in D2 gastrectomies was associated with adverse outcomes.

Methods

Data from a prospectively created database of consecutive patients undergoing open D2 total (TG) or subtotal (STG) gastrectomy with curative intent between January 2009 and January 2014 were reviewed. Short- and long-term clinical outcomes were compared in patients operated on by consultants and those treated by trainees under consultant supervision.

Results

A total of 272 D2 open gastrectomies were performed, 123 (45·2 per cent) by trainees. There was no significant difference between consultants and trainees in median duration of surgery (TG: 240 (range 102–505) versus 240 (170–375) min respectively, P = 0·452; STG: 225 (150–580) versus 212 (125–380) min, P = 0·192), number of resected nodes (TG: 30 (13–101) versus 30 (11–102), P = 0·681; STG: 26 (5–103) versus 25 (1–63), P = 0·171), length of hospital stay (TG: 15 (7–78) versus 15 (8–65) days, P = 0·981; STG: 10 (6–197) versus 14 (7–85) days, P = 0·242), overall morbidity (TG: 44 versus 49 per cent, P = 0·314; STG: 34 versus 25 per cent, P = 0·113) or mortality (TG: 4 versus 2 per cent; P = 0·293). No difference in predicted 5-year overall survival was noted between the two cohorts (TG: 68 per cent for consultants versus 77 per cent for trainees, P = 0·254; STG: 70 versus 75 per cent respectively, P = 0·512). The trainee cohort had lower median blood loss for both TG (360 (range 90–1200) ml versus 600 (70–2350) ml for consultants; P = 0·042) and STG (235 (50–1000) versus 360 (50–3000) ml respectively; P = 0·053).

Conclusion

Clinical outcomes were not compromised by supervised trainee involvement in D2 open gastrectomy.
Bio‐analytical methods for investigating the effect of age, body mass index and gender on the PK/PD ratio of antibiotics
Authors: ElKady Ehab F. , Abo‐Elwafa Ahmed A. , Farouk Faten
Published: November 2019

The effectiveness of antibiotics (ABs) is governed by achieving the adequate pharmacokinetic (PK)/pharmacodynamics (PD) ratio. In this study, fast LC–MS/MS methods were developed and validated for the bioanalysis of cefaclor (CFC), ciprofloxacin (CFC), roxithomycin (RXM) and clindamycin (CLD). Chromatographic separation was performed on a C18 Zorbax‐Eclipse Plus (3.5 μm, 100 × 4.6 mm) using isocratic elution. Detection was performed by positive electrospray ionization. The methods were applied for the assessment of PK parameters in volunteers (n = 101, 64 male and 37 female) and the effects of age, body mass index (BMI) and gender were investigated. Good linearity (r2 ≥ 0.99), accuracy (>86%), precision (CV% ≤ 11) and extraction recovery (>83%) were observed for CFC, CFX, RXM and CLD. Application to PK studies revealed that age and BMI affected the Thalf and the AUC of RXM and CLD (p < 0.023). Gender difference affected the critical PK parameters of the four ABs (Thalf (U = 18; P = 0.036) of CFC, the Cmax of CFX (U = 30; P = 0.017), the Thalf (U = 23; P = 0.009) and AUC (U = 26; P = 0.008) of RXM and CLD), respectively. These results highlight the significance of age and BMI variations for RXM and CLD dosing. Furthermore, it indicates that the gender difference may be considered when adjusting the AB dose.
Spectrum–effect relationship of antioxidant and anti‐inflammatory activities of Laportea bulbifera based on multivariate statistical analysis
Authors: Chen Yinrui , Zou Shuhan , Xu Wenfen , Sun Qingwen , Yun Li
Published: November 2019

Laportea bulbifera, named Hong He Ma in Chinese, is a Chinese herbal medicine commonly used by the Miao nationality of China. In this study, 43 batches of L. bulbifera were collected from different origins in China. Ethanol, ethyl acetate and petroleum ether were used to prepare different extracts of the plant. UHPLC technique was used to establish the fingerprints, whereas DPPH assay and RAW264.7 inflammatory cell models were used to evaluate the antioxidant and anti‐inflammatory activities, respectively. Moreover, the spectrum–effect relationship between relative peak area of common peaks and efficacy value was set up by multivariate statistical analysis. Furthermore, 10 batches were selected randomly for validation of those models. The results showed that ethyl acetate and petroleum ether extracts possess excellent antioxidant and anti‐inflammatory activities, respectively. Peaks A6 and A7 demonstrated the greatest antioxidant activity, while peak A17 showed the strongest anti‐inflammatory activity. After a verified experiment, the result was obtained and illustrated that the spectrum–effect relationship which we established could reliably infer antioxidant and anti‐inflammatory compounds of the Chinese herbal medicine.
Comorbidity in trichotillomania (hair‐pulling disorder): A cluster analytical approach
Authors: Lochner Christine , Keuthen Nancy J. , Curley Erin E. , Tung Esther S. , Redden Sarah A. , Ricketts Emily J. , Bauer Christopher C. , Woods Douglas W. , Grant Jon E. , Stein Dan J.
Published: November 2019

Background

A promising approach to reducing the phenotypic heterogeneity of psychiatric disorders involves the identification of homogeneous subtypes. Careful study of comorbidity in obsessive‐compulsive disorder (OCD) contributed to the identification of the DSM‐5 subtype of OCD with tics. Here we investigated one of the largest available cohorts of clinically diagnosed trichotillomania (TTM) to determine whether subtyping TTM based on comorbidity would help delineate clinically meaningful subgroups.

Methods

As part of an ongoing international collaboration, lifetime comorbidity data were collated from 304 adults with pathological hair‐pulling who fulfilled criteria for DSM‐IV‐TR or DSM‐5 TTM. Cluster analysis (Ward's method) based on comorbidities was undertaken.

Results

Three clusters were identified, namely Cluster 1: cases without any comorbidities (n = 63, 20.7%) labeled “simple TTM,” Cluster 2: cases with comorbid major depressive disorder only (N = 49, 16.12%) labeled “depressive TTM,” and Cluster 3: cases presenting with combinations of the investigated comorbidities (N = 192, 63.16%) labeled “complex TTM.” The clusters differed in terms of hair‐pulling severity (F = 3.75, p = .02; Kruskal–Wallis [KW] p < .01) and depression symptom severity (F = 5.07, p = <.01; KW p < .01), with cases with any comorbidity presenting with increased severity. Analysis of the temporal nature of these conditions in a subset suggested that TTM onset generally preceded major depressive disorder in (subsets of) Clusters 2 and 3.

Conclusions

The findings here are useful in emphasizing that while many TTM patients present without comorbidity, depression is present in a substantial proportion of cases. In clinical practice, it is crucial to assess comorbidity, given the links demonstrated here between comorbidity and symptom severity. Additional research is needed to replicate these findings and to determine whether cluster membership based on comorbidity predicts response to treatment.
White matter hypointensities and hyperintensities have equivalent correlations with age and CSF β‐amyloid in the nondemented elderly
Authors: Wei Ke , Tran Thao , Chu Karen , Borzage Matthew T. , Braskie Meredith N. , Harrington Michael G. , King Kevin S.
Published: November 2019

Introduction

T1‐ and T2‐weighted sequences from MRI often provide useful complementary information about tissue properties. Leukoaraiosis results in signal abnormalities on T1‐weighted images, which are automatically quantified by FreeSurfer, but this marker is poorly characterized and is rarely used. We evaluated associations between white matter hyperintensity (WM‐hyper) volume from FLAIR and white matter hypointensity (WM‐hypo) volume from T1‐weighted images and compared their associations with age and cerebrospinal fluid (CSF) β‐amyloid and tau.

Methods

A total of 56 nondemented participants (68–94 years) were recruited and gave informed consent. All participants went through MR imaging on a GE 1.5T scanner and of these 47 underwent lumbar puncture for CSF analysis. WM‐hypo was calculated using FreeSurfer analysis of T1 FSPGR 3D, and WM‐hyper was calculated with the Lesion Segmentation Toolbox in the SPM software package using T2‐FLAIR.

Results

WM‐hyper and WM‐hypo were strongly correlated (r = .81; parameter estimate (p.e.): 1.53 ± 0.15; p < .0001). Age was significantly associated with both WM‐hyper (r = .31, p.e. 0.078 ± 0.030, p = .013) and WM‐hypo (r = .42, p.e. 0.055 ± 0.015, p < .001). CSF β‐amyloid levels were predicted by WM‐hyper (r = .33, p.e. −0.11 ± 0.044, p = .013) and WM‐hypo (r = .42, p.e. −0.24 ± 0.073, p = .002). CSF tau levels were not correlated with either WM‐hyper (p = .9) or WM‐hypo (p = .99).

Conclusions

Strong correlations between WM‐hyper and WM‐hypo, and similar associations with age, abnormal β‐amyloid, and tau suggest a general equivalence between these two imaging markers. Our work supports the equivalence of white matter hypointensity volumes derived from FreeSurfer for evaluating leukoaraiosis. This may have particular utility when T2‐FLAIR is low in quality or absent, enabling analysis of older imaging data sets.