bluuebunny/crossref_metadata_2025 huggingface dataset:
Comportamento intraempreendedor e abordagens de inovação no setor público: um estudo a partir de laboratórios de inovação em governos na América do Sul
Authors:   , Silva Junior Alessandro Carlos da
Published: August 2022

Este estudo tem o objetivo de analisar se os laboratórios de inovação em governo têm promovido o comportamento intraempreendedor de servidores públicos e se contribuem para superar as barreiras deste comportamento. Para tal, utilizou-se de uma abordagem qualitativa e quantitativa, de natureza descritiva e exploratória, por meio de um estudo de casos múltiplos exploratório e holístico. Os dados foram coletados a partir de fontes documentais e bibliográficas, entrevistas exploratórias e a aplicação de dois questionários estruturados. Foram identificados 24 laboratórios em governos atuantes no contexto sul-americano, sendo que a pesquisa contemplou 19 deles, com um total de 40 questionários respondidos. Para análise dos dados, utilizou-se a Análise de Conteúdo e a proposição do Indicador de Comportamento Intraempreendedor no Setor Público (ICISP). Como resultados, identificou-se que a maior parte dos laboratórios de inovação em governo na América do Sul, possuem uma orientação organizacional, voltados a gerar transformações na mentalidade dos servidores públicos, nos processos, serviços e políticas públicas. Destaca-se também, que os laboratórios em governo têm estimulado o comportamento intraempreendedor no setor público, sendo que as dimensões mais representativas foram Proatividade e Liderança. Além disso, observa-se também contribuições importantes nas barreiras ao comportamento intraempreendedor, minimizando aspectos de burocratização de processos, baixa flexibilidade, resistência a mudança, falhas de comunicação e a arrogância. Enquanto contribuições, destaca-se que o dinamismo e as metodologias ágeis utilizadas pelos laboratórios de inovação em governo são fatores motivadores para a sua criação, oferecendo respostas rápidos aos problemas, como os ocasionados pela pandemia COVID-19. Destaca-se também, que esses espaços têm contribuído para a aprendizagem empreendedora nos servidores, capacitando-os a modificar a forma de enxergar os problemas públicos e lidar com as atividades, incentivando, também, a escuta ativa das demandas cidadãs. Palavras-chave: Gestão pública. Empreendedorismo público. Inovação.
بدھ مت کے اخلاقیات میں اخلاقی جہات ِ ثمانیہ ( آریہ ستیہ) اور اسلامی متقابل اخلاقی تعلیمات : ایک تحقیقی جائزہ
Authors: Sadat Mian Mujahid Shah , Zakir Zakir ullah , Irfan Irfan ullah
Published: August 2022

This article provides a comparative overview of the specific moral aspects of the two religions "Islam and Buddhism". In which, an attempt has been made to prove this, Why wars and conflict are connected to religions? Why peaceful and ethical teaching of religions are hidden from lay community? For this, I adopted comparative study and critical temperament has been used to a lesser extent in order to gain access to the distinct moral teachings from the literature of other atheists and to pave the way for the followers of different religions to expand. Where other problems and difficulties surround religions, the issues that stand in the way of religions, they present to you how religion leads to decline, the following issues:
Science, Atheism, Social Interaction, Philosophy of Religions, Feminism Movements, Sectarianism/Inter sects, Secularism, Inter Marriages. These are some of the things that hinder the progress of religion. Therefore, the religious people are requested, not to ignore the above mentioned issues but to look at them and teach religious teachings and at the same time take care of them as there is a lack of ethics and work in all areas, adhering to moral teachings.
وقف کے بعض عصری مسائل سے استحسان کی تطبیقات کا تحقیقی جائزہ
Authors: Atiq Ur Rahman Dr. Muhammad , Rao Dr. Muhammad Atif Aslam
Published: August 2022

Istihsan distinguishes issues from their perspective based on a specific argument. An argument that demands a shift from one order to another requires justice. With this concept, Istihsan is not a matter of dispute. However, in the case of a disagreement among scholars, the mujtahid has to apply Istihsan to something known and reasonable based on his intellect following its basic rules such as the compliment should be for Shariah and should not oppose it and the person making the compliment should be well familiar with Shariah.
The primary issue is to sort out that it is permissible to research the applications of Istihsan from some contemporary issues of Istihsan. This article is aimed to present a study of some of the current issues of Istihsan in which the argument of praise is effective and hold a difference among the leading and the last scholars. Along with the introduction, conditions, and types of Istihsan, the article discusses the influence of two forms of Istihsan in contemporary issues.
The first is the Istihsan of secret conjecture instead of assumption, and the second is the Istihsan for any expediency. Istihsan is similar to a sale in which it is not permissible to set a time. However, the secret implication is that the endowment's purpose is to benefit those suspended.
The research made proves the significance and the broader exposure of Islamic laws. Moreover, it invites the learners to indulge in this aspect of Sharia laws and brings out a beneficial study for the Muslim Ummah.
خواجا محمد عارف کی حمد یہ اورنعتیہ شاعری میں قرآنی تعلیمات کے اشارے:ایک مطالعہ
Authors: Mir Dr. Mir Yousaf , Islam Sana ul , Khwaja Dr. Ambreen
Published: August 2022

The current research paper sheds the light on the very significant topic. The researcher has diligently studied the relevant material from various sources. There is clear indication of that adventure depicted in this research paper. Praise and Naat belong to a pure and sacred genre whose tradition is present in the major languages ​​of the world. The purpose of the present study is to highlight the genre of Naat in this particular area. There are different opinions but there is uniformity everywhere in terms of subject matter. It is difficult to say in the language of poetry because poetry contains exaggeration, imagination, emphasis and other poetic devices. Khawaja Muhammad Arif is an important name in Urdu Hymd and Naat recitation nowadays in Azad Jammu and kashir. He has recited very beautifully. There is no limit to the virtues of the Holy Prophet (PBUH). The researcher has collected the data through qualitative method. This collection of praise and Naat is growing with the passage of time. Khawaja Muhammad Arif has also contributed his share in this collection and has recited very admirable poems. Numerous references are present in his Hamdiya and Naatiya poetry. This research paper can explicitly be concluded that Hymnd and Naat have wonderful didactic effects on human being. It can be termed a very valuable asset for upcoming researchers.
Metabolomic Profiling of Different Maca Color Types Using Nuclear Magnetic Resonance Spectroscopy and Multivariate Data Analysis
Authors: Jingwei Lv Jingwei Lv , Chunnan Li Chunnan Li , Nanxi Zhang Nanxi Zhang , Kaiyue Z Kaiyue Z , Xiaochen Gao Xiaochen Gao , Na Li Na Li , Lingwen M Lingwen M , Yinping Y Yinping Y , Hui Zhang and Jiaming Sun Hui Zhang and Jiaming Sun
Published: August 2022

This study aimed to explore significant differences in chemical composition among maca (Lepidium meyenii Walp.) types with different colors in Yunnan province, China. 1H-NMR spectroscopy, in combination with principal component analysis and partial least squares discriminant analysis, was used to investigate the compounds responsible for compositional differences. Different maca color types in Yunnan were clearly distinguished by 11 differential metabolites. Furthermore, network pharmacology results showed that 30 active components were related to Alzheimer’s disease. Nine intersecting compounds among the 11 differential metabolites and 30 active components, namely, lysine, isoleucine, phenylalanine, β-hydroxybutyrate, tryptophan, pyroglutamate, proline, glutamine, and fructose, were used as bioactive markers to identify different maca color types. The results showed the bioactive markers among different maca color types holistically, providing a scientific basis for assessing the quality of commercial products derived from different maca color types.
Electrochemical and Computational Study of Copper Histidine Complex via Cyclic Voltammetry
Authors: Atya Hassan Atya Hassan , Sana Gul Sana Gul , Taswar Ali Chandio and Muhammad Ali Minhas Taswar Ali Chandio and Muhammad Ali Minhas
Published: August 2022

L-Histidine regulates body function and involve in the synthesis of hemoglobin, repairing of tissues and strengthens of immune system. In this study, Cyclic Voltammetry (CV) is used with 0.1 M Potassium Chloride as a supporting electrolyte to determine the accurate metal ligand ratio between Cu+2 and L-Histidine. In CV potential window is set between +0.6 to -0.4V to record theVoltammogram. Voltammograms were recorded by varying scan rate from 50mV/s to 300mV/s. Cyclic Voltammetry is used to analyzed the interfacial performance of the complex and repeated CyclicVoltammograms (07 cycles) were recorded at Glassy Carbon Electrode (GCE), that shows no change in peak current intensity of both anodic and cathodic peak. Further, neither pre nor any post peak was observed. These interpretation express that reactant and product are not involve in the adsorption-desorption process at the surface of Glassy Carbon Electrode (GCE). These remarks suggest that it is diffusion controlled process in the above mentioned system. The interaction of Cu+2 and L-Histidine were not reported before through Cyclic Voltammetry. Furthermore, in this study structure of Cu+2 vs. L-Histidine complex is investigated from a theoretical perspective. Optimization of Cu+2 vs. L-Histidine complex was carried out by DFT method and result verifies that stable structure of Cu+2 vs. L-Histidine complex exist as square planar structure in 1:2 ratio respectively. The computed structure has correlation with experimental results and Voltammogram of 1:2 ratio complex of Cu+2 vs. L-Histidine suggested that it exist in Square planar geometry.
Using Google classroom platform in learning comprehension materials among second stage students of the English language department
Authors: Abdullah Ethar Riyadh , Sallal Ibtihal Ahmed , Adeep Ahmed  Riyadh
Published: August 2022

The study attempts to investigate the issue of using Google classroom platform in learning comprehension materials among students in the second stage of the English language department. The study aims to determine the impact of using Google classroom on learning comprehension materials. The study sample consists of (60) students in the second grade in the department of English at the college of Basic Education at the University of Diyala. The sample is divided into two groups, the control group consists of 30 students, and the experimental group consists of 30 students. The study findings reveal that the use of Google classroom promoted the mastery of comprehension materials among students. The findings also stress the necessity of face-to-face instruction.
CURANDEIROS, FANÁTICOS E POSSUÍDOS: GESTÃO DO IMAGINÁRIO E BIOPOLÍTICA DOS INGOVERNÁVEIS (SANTA CATARINA, PRIMEIRA REPÚBLICA, 1898-1905).
Authors: Vaz Rafael Araldi
Published: August 2022

No espaço de tempo que coincide com a construção da Primeira República no Brasil, padres franciscanos de origem alemã protagonizaram ações missionárias no planalto catarinense, inseridas no bojo da reforma católica que entrava em curso no país com o fim do Segundo Reinado.
a östpolitik vaticana: diálogos entre igreja e comunismo soviético no papado de João XXIII
Authors: Guedes Edson Claiton , Nunes Marcus Vinicius de Souza
Published: August 2022

O período de Angelo Giuseppe Roncalli como Papa João XXIII (1958-1963) no trono da Santa Sé foi breve, mas repleto de iniciativas que marcaram sua gestão como uma das mais intensas e modernizantes dos últimos séculos. Eleito como um “papa de transição” devido à falta de consenso entre os cardeais no Conclave de outubro de 1958, Roncalli passou à história como o aquele que convocou o Concílio Vaticano II (1962-1965), caracterizado como o maior evento religioso do século XX.
PRÁTICAS RELIGIOSAS SOB O GOVERNO DAS TECNOLOGIAS DE CONTROLE DE POPULAÇÕES NO CEMITÉRIO MUNICIPAL DE INDAIAL/SC
Authors: Fochi Graciela Márcia , Souza Rogério Luiz Klaumann de
Published: August 2022

Em meio a estes processos, as relações entre Estado, instituições religiosas, sociedade e indivíduos nem sempre resultaram em consensos e aceitações unânimes, antes foram responsáveis por promover processos de recepção e assimilações distintas, intercalando tanto experiências de conciliação como de resistência, conflito, conciliação, bem como outros e novos arranjos entre as diferentes partes envolvidas.
Worldpiece Reflections: Student Reflections of Covid-19 from Around the World
Authors: Pollack Victoria , Consolee Marie , Khadka Sabita , Frencham Ashleigh , Henry Laura
Published: August 2022

We can learn so much from each other by taking stock of the challenges this pandemic creates for students and newly qualified midwives around the world. We unite and celebrate our collective voice, realising our universal calling, our passion to care for birthing people and families worldwide despite the challenges coronavirus creates. These reflections provide worldview insight and are testaments to the strength and bravery of you all.
TERRITÓRIO, SUBJETIVIDADE E RECEPÇÃO: A Festa do Coco criando espaço incorporado
Authors: Moraes Peticia Carvalho de
Published: August 2022

Este artigo é parte integrante de minha dissertação de mestrado realizada na Universidade de São Paulo (USP), no programa de Estudos Culturais na área da Filosofia. Ao longo do texto, discuto as negociações realizadas durante a Festa do Coco das comunidades quilombolas paraibanas Ipiranga e Gurugi que evidenciam maneiras de como ocorre a construção do espaço subjetivo da festa através das inter-relações entre as trajetórias humanas e não humanas e suas subjetividades. Chamo de construção do espaço subjetivo as outras linhas de vida estabelecidas no local da festa e que também organizam a construção de seu território, como o círculo, evidenciado na formação da roda de coco, e as pequenas linhas retas, produzidas pela ligação entre as duplas brincantes no centro da roda. Esta construção do espaço subjetivo da festa se dá juntamente com a linha retangular da arquitetura do local: o formato do barracão. Os estudos da Estética da Recepção me ajudaram a discutir a relação entre o público das festas, seus horizontes de expectativa e suas produções de subjetividade, ou seja, os processos de criação de subjetividades que ocorrem durante a festa e a brincadeira.
DANÇA E MÚSICA DE BLOCOS AFRO: fundamentos de uma poética e política negra
Authors: Conrado Amélia Vitória Souza , Conceição Sueli Santos
Published: August 2022

A abordagem sobre Dança e Música dos Blocos Afro na cidade de Salvador-Bahia enfatiza os princípios que orientam uma poética e política negra enquanto uma forma de organização social e estratégia do Movimento Negro contemporâneo. Identifica-se que as instituições da educação oficial, em todos os níveis, não vem contemplando os conhecimentos e saberes que as instituições artístico-culturais negras produzem, apesar das ações e políticas afirmativas do Movimento Negro Unificado junto ao Estado brasileiro para o reconhecimento e valorização da sua identidade cultural. Nesse sentido, alguns autores auxiliam a definir conceitos, articular pressupostos e chegar a algumas evidências, tais como Santos (2003), Santos (2015), Gomes (2017), Silva (2011), entre outros. Acredita-se que somente com uma mudança de pensamento e ação compartilhada, em que a arte permaneça atuando em um campo do sensível e das questões humanas, poderemos almejar transformações nas formas políticas de emancipação e, portanto, de luta antirracista.
POLÍTICA HABITACIONAL E LOCAÇÃO SOCIAL EM SALVADOR
Authors: Baltrusis Nelson , Nazem Mourad Laila
Published: August 2022

Este artigo tem como objetivo analisar o mercado imobiliário de locação em Salvador. Num primeiro momento, caracterizaremos o problema habitacional em Salvador, para o que nos apoiaremos nas diretrizes e ações previstas no Plano Municipal de Habitação de Interesse Social (PMHIS). Em seguida, trataremos das políticas implantadas pelos governos do estado e federal, destacando a experiência do Programa de Arrendamento Residencial (PAR) e incorporando algumas considerações sobre o Programa Minha Casa, Minha Vida. Também será abordada a questão do mercado de locação em Salvador a partir do perfil de moradores e da dinâmica do mercado. PALAVRAS-CHAVE: Aluguel social. Política de habitação. Instrumentos de planeamento urbano. HOUSING POLICY AND SOCIAL RENT IN SALVADOR, BRAZIL Nelson Baltrusis Laila Nazem Mourad This article seeks to analyze the real state rental market in Salvador, Brazil. Initially, we describe the housing problem in Salvador based on the guidelines and actions foreseen in the Municipal Plan for Social Interest Housing (PMHIS). Then we treat the policies implemented by state and federal administrations, emphasizing the experience of Social Leasehold Housing (PAR), and including a few considerations on My Home, My Life program. We also approach the issue of the rental market in Salvador based on the profile of dwellers and on the dynamics of the market. KEYWORDS: Social rent. Housing policy. Urban planning instruments. POLITIQUE DE L’HABITAT ET LOGEMENTS SOCIAUX À SALVADOR Nelson Baltrusis Laila Nazem Mourad L’objectif de cet article est d’analyser le marché de l’immobilier destiné à la location à Salvador. Dans un premier temps, et pour caractériser le problème du logement à Salvador, nous nous basons sur les directives et les actions prévues par le Plan Municipal des Logements Sociaux (PMHIS). Nous abordons ensuite les politiques mises en place par le gouvernement fédéral, mettons en évidence l’expérience du Programme de Bail Résidentiel (PAR) et nous y ajoutons quelques considérations concernant le Programme “Ma Maison, Ma Vie”. La question du marché locatif à Salvador est également traitée à partir du profil des habitants et de la dynamique du marché. MOTS-CLÉS: Location sociale. Politique de l’Habitat. Instruments de planification urbaine. Publicação Online do Caderno CRH no Scielo: http://www.scielo.br/ccrh  Publicação Online do Caderno CRH: http://www.cadernocrh.ufba.br
What Should the Goals Be for Diverse Recruitment in Alzheimer Clinical Trials?
Authors: Grill Joshua D. , Sperling Reisa A. , Raman Rema
Published: August 2022

This Viewpoint discusses why it’s important for Alzheimer clinical trials to be inclusive and enroll diverse populations that include underrepresented racial, ethnic, and sociocultural groups.
An Innovative Faculty Travel Award Program to Support Child, Elder, or Dependent Care
Authors: Fuentes-Afflick Elena , García Paul , Friedli Amy B. , Johnson Bonnie , Binder Renée
Published: August 2022

This study observes how a travel award program that supports child, elder, or dependent care affected university faculty members.
Genome‐Wide 3′‐UTR Single Nucleotide Polymorphism Association Study Identifies Significant Prostate Cancer Risk‐Associated Functional Loci at 8p21.2 in Chinese Population
Authors: Zhang Ning , Huang Da , Jiang Guangliang , Chen Siteng , Ruan Xiaohao , Chen Haitao , Huang Jingyi , Liu Ao , Zhang Wenhui , Lin Xiaoling , Wu Yishuo , Zhang Qin , Li Jing , Tsu James Hok‐Leung , Wei Gong‐Hong , Na Rong
Published: August 2022

MicroRNAs (miRNAs) are involved in the regulation of gene expression via incomplete base pairing to sequence motifs at the three prime untranslated regions (3′‐UTRs) of mRNAs and play critical roles in the etiology of cancers. Single nucleotide polymorphisms (SNPs) in the 3′‐UTR miRNA‐binding regions may influence the miRNA affinity. However, this biological mechanism in prostate cancer (PCa) remains unclear. Here, a three‐stage genome‐wide association study of 3′‐UTR SNPs (n=33 117) is performed in 5515 Chinese men. Three genome‐wide significant variants are discovered at 8p21.2 (rs1567669, rs4872176, and rs4872177), which are all located in a linkage disequilibrium region of the NKX3‐1 gene. Phenome‐wide association analysis using the FinnGen data reveals a specific association of rs1567669 with PCa over 2,264 disease endpoints. Expression quantitative trait locus analyses based on both Chinese PCa cohort and the GTEx database show that risk alleles of these SNPs are significantly associated with low expression of NKX3‐1. Based on the MirSNP database, dual‐luciferase reporter assays show that risk alleles of these SNPs downregulate the expression of NKX3‐1 via increased miRNA binding. These results indicate that the SNPs at the 3′‐UTR of NKX3‐1 significantly downregulate NKX3‐1 expression by influencing the affinity of miRNA and increase the PCa risk.
Optimum Differentiation of Frontotemporal Lobar Degeneration from Alzheimer Disease Achieved with Cross‐Sectional Tau Positron Emission Tomography
Authors: Josephs Keith A. , Tosakulwong Nirubol , Gatto Rodolfo G. , Weigand Stephen D. , Ali Farwa , Botha Hugo , Graff‐Radford Jonathan , Machulda Mary M. , Savica Rodolfo , Schwarz Christopher G. , Senjem Matthew L. , Boeve Bradley F. , Kantarci Kejal , Jones David T. , Ramanan Vijay K. , Fields Julie A. , Reichard Ross R. , Dickson Dennis W. , Petersen Ronald C. , Jack Clifford R. , Lowe Val J. , Whitwell Jennifer L.
Published: August 2022

Objective

This study was undertaken to assess cross‐sectional and longitudinal [18F]‐flortaucipir positron emission tomography (PET) uptake in pathologically confirmed frontotemporal lobar degeneration (FTLD) and to compare FTLD to cases with high and low levels of Alzheimer disease (AD) neuropathologic changes (ADNC).

Methods

One hundred forty‐three participants who had completed at least one flortaucipir PET and had autopsy‐confirmed FTLD (n = 52) or high (n = 58) or low ADNC (n = 33) based on Braak neurofibrillary tangle stages 0–IV versus V–VI were included. Flortaucipir standard uptake value ratios (SUVRs) were calculated for 9 regions of interest (ROIs): an FTLD meta‐ROI, midbrain, globus pallidum, an AD meta‐ROI, entorhinal, inferior temporal, orbitofrontal, precentral, and medial parietal. Linear mixed effects models were used to compare mean baseline SUVRs and annual rate of change in SUVR by group. Sensitivity and specificity to distinguish FTLD from high and low ADNC were calculated.

Results

Baseline uptake in the FTLD meta‐ROI, midbrain, and globus pallidus was greater in FTLD than high and low ADNC. No region showed a greater rate of flortaucipir accumulation in FTLD. Baseline uptake in the AD‐related regions and orbitofrontal and precentral cortices was greater in high ADNC, and all showed greater rates of accumulation compared to FTLD. Baseline differences were superior to longitudinal rates in differentiating FTLD from high and low ADNC. A simple baseline metric of midbrain/inferior temporal ratio of flortaucipir uptake provided good to excellent differentiation between FTLD and high and low ADNC (sensitivities/specificities = 94%/95% and 71%/70%).

Interpretation

There are cross‐sectional and longitudinal differences in flortaucipir uptake between FTLD and high and low ADNC. However, optimum differentiation between FTLD and ADNC was achieved with baseline uptake rather than longitudinal rates. ANN NEUROL 2022;92:1016–1029
P and Cu Dual Sites on Graphitic Carbon Nitride for Photocatalytic CO2Reduction to Hydrocarbon Fuels with High C2H6Evolution
Authors: Wang Gang , Chen Zhe , Wang Tao , Wang Dingsheng , Mao Junjie
Published: August 2022

The light‐driven CO2reduction to multi‐carbon products is especially meaningful, while the low efficiency of multi‐electron transfer and sluggish C−C coupling greatly hinder its development. Herein, we report a photocatalyst comprising of P and Cu dual sites anchored on graphitic carbon nitride (P/Cu SAs@CN), which achieves a high C2H6evolution rate of 616.6 μmol g−1 h−1in reducing CO2to hydrocarbons. The detailed spectroscopic characterizations identify the formation of charge‐enriched Cu sites, where the isolated P atoms serve as hole capture sites during photocatalysis. Theoretical simulations combined with in situ FTIR measurement reveal a kinetically feasible process for the formation of C−C coupling intermediate (*OC−COH) and confirm the favorable production of C2H6on the P/Cu SAs@CN photocatalyst. This work offers new insights into the photocatalyst design with atomic precision toward highly efficient photocatalytic CO2conversion to high value‐added carbon products.
Highly Efficient Electrosynthesis of Nitric Oxide for Biomedical Applications
Authors: Jin Jing , Mao Junjie , Wu Wenjie , Jiang Ying , Ma Wenjie , Yu Ping , Mao Lanqun
Published: August 2022

Nitric oxide (NO) constitutes one of the most versatile therapeutics for biomedical applications. The efficient and on‐demand NO generation essentially dictates its concentration dependent therapeutic activity. Here, we report an electrochemical system employing a rationally designed single‐iron atom based biomimetic catalyst (i.e., Fe SAC), for high‐efficient and controlled NO generation. The Fe SAC shows superior catalytic ability in electrochemical reduction of nitrite, with maximal NO generation rate achieving 2.1 μM (min μg)−1. Theoretical studies suggest the significant decrease of Gibbs‐free energy of NO2−adsorption on single‐iron atom accounts for its high catalytic efficiency. Moreover, ample amount of NO can be controllably generated in a potential dependent manner. For antibacterial application, the generated NO overwhelmingly disrupts both gram‐negative and gram‐positive strains, highlighting a great promise to expedite NO research in both basic and applied sciences.
Mechanistic aspects of the Pd(OAc)n (n = 1–3) catalyzed ethylene acetoxylation: A density functional theory study
Authors: Chen Yamin , Qiu Pengyuan , Sun Haoyang , Sun Li , Liu Zhen
Published: August 2022

Vinyl acetate is a valuable industrial material used in the production of various polymers. The homogeneous Pd(OAc)n (n = 1–3) can catalyze ethylene acetoxylation to produce vinyl acetate. However, the reaction mechanism of Pd‐catalyzed formation of vinyl acetate remains unclear, especially in recognizing the active valence states of the Pd center. The full catalytic cycle of Pd‐catalyzed vinyl acetate formation includes ethylene‐acetate coupling, β‐H elimination, and catalyst regeneration. Based on the Wacker mechanism, two pathways were proposed for the ethylene‐acetate coupling, including a six‐membered ring mechanism through the attack of carbonyl oxygen (O2) of acetate, and a four‐membered ring mechanism through the attack of acetoxy oxygen (O1) of acetate on the coordinated ethylene. Our density functional theory (DFT) calculation shows that PdOAc cannot catalyze the acetoxylation of ethylene to form vinyl acetate due to the presence of a high energetic span. Pd(OAc)2 catalyzed reaction via the six‐membered mechanism is preferred, and the β‐H elimination is the rate‐determining step. For Pd(OAc)3, the six‐membered mechanism is favored as well, and the ethylene‐acetate coupling is the rate‐determining step. Overall, Pd(OAc)2 showed high activity (path a) toward the formation of vinyl acetate with a calculated TOF of 349 h−1.
Spectroscopic studies of 7,8‐diacetoxy‐4‐methylcoumarin and 7,8‐dipentynoyl‐4‐methylcoumarin binding with calreticulin
Authors: Moss Patrice E. , Talanova Galina G. , Fang Yayin , Thomas Courtney
Published: August 2022

Calreticulin (CRT) is a protein found mainly in the endoplasmic reticulum (ER) that maintains calcium levels and controls protein folding, but has recently been found at the cell surface, cytoplasm, and in the extracellular matrix. CRT participates in multiple physiological processes such as gene expression, the immune response, and cancer. Calreticulin has been shown to autoacetylate with the binding of preferred ligand 7,8‐diacetoxy‐4‐methylcoumarin (DAMC). This project aims to develop a chemical biology approach to investigate importance of CRT acylating abilities on its nonendoplasmic reticulum functions by targeting the downstream substrates of CRT acetylation. Our goal was to use CRT to transfer a pentynoyl tag (using a novel ligand, DPeMC) to its substrates, which can then be used as a handle for protein identification.

Molecular modelling using available data in the literature was used to approximate the binding interface between CRT and the acylation ligands. Molecular Operating Environment (MOE) software was used to perform sequence alignment, simulated annealing, positional refinement, and blind docking of acylated coumarins with the CRT model. Docking studies pointed to the P domain as the most thermodynamically and sterically favourable region for acylated coumarin binding with tryptophan residue 200 within the active site on CRT. Absorption and fluorescence spectra of all coumarin compounds in ethanol:PBS (1:9 v/v) solution were investigated. Stern–Volmer quenching constant (KSV), binding constant (K), and number of binding sites (n) of each coumarin compound with CRT was determined. Our studies demonstrated that acyl coumarin compounds bind to CRT using a dynamic quenching mechanism, bind to a single binding site on the P domain, and that the protein–ligand interaction is spontaneous and exothermic.
College violated Title IX by not excusing student's pregnancy‐related absences
Authors: Lyerly Eric
Published: August 2022

A recent Office for Civil Rights letter is making waves in higher education. Indeed, the letter will likely have a major impact on institutions’ compliance efforts under Title IX, especially regarding pregnant students.
A network analysis of self‐reported psychoneurological symptoms in patients with head and neck cancer undergoing intensity‐modulated radiotherapy
Authors: Lin Yufen , Bruner Deborah W. , Paul Sudeshna , Miller Andrew H. , Saba Nabil F. , Higgins Kristin A. , Shin Dong M. , Zhang Wenhui , Miaskowski Christine , Xiao Canhua
Published: August 2022

Background

Patients with head and neck cancer experience psychoneurological symptoms (PNS) (i.e., depression, fatigue, sleep disturbance, pain, and cognitive dysfunction) during intensity‐modulated radiotherapy (IMRT) that decrease their functional status, quality of life, and survival rates. The purpose of this study was to examine and visualize the relationships among PNS within networks over time and evaluate for demographic and clinical characteristics associated with symptom networks.

Methods

A total of 172 patients (mean age, 59.8 ± 9.9 years; 73.8%, male; 79.4%, White) completed symptom questionnaires four times, namely, before IMRT (T1), 1 month (T2), 3 months (T3), and 12 months (T4) post IMRT. Network analysis was used to examine the symptom‐symptom relationships among PNS. Centrality indices, including strength, closeness, and betweenness, were used to describe the degrees of symptom network interconnections. Network comparison test was used to assess the differences between two symptom networks.

Results

Depression was associated with the other four symptoms, and fatigue was associated with the other three symptoms across the four assessments. Based on the centrality indices, depression (rstrength = 1.3–1.4, rcloseness = 0.06–0.08, rbetweeness = 4–10) was the core symptom in all symptom networks, followed by fatigue. Female gender, higher levels of stress, and no alcohol use were associated with stronger symptom networks in network global strength before IMRT.

Conclusion

Network analysis provides a novel approach to gain insights into the relationships among self‐reported PNS and identify the core symptoms and associated characteristics. Clinicians may use this information to develop symptom management interventions that target core symptoms and interconnections within a network.

Lay summary

This study describes the symptom–symptom relationships for five common symptoms in patients with head and neck cancer receiving radiotherapy.

Depression and fatigue appeared to be two core symptoms that were connected with sleep disturbance, pain, and cognitive dysfunction within a network.

Several characteristics (i.e., female, higher stress, no alcohol use) were associated with stronger symptom networks.
The new endocrine WHO classification: What does this mean for thyroid cytology?
Authors: Wong Kristine S. , Barletta Justine A.
Published: August 2022

The new World Health Organization classification of endocrine tumors will include many updates on thyroid pathology. This summary highlights the changes that are most relevant for cytopathologists.
Structural analysis of regional transcatheter aortic valve underexpansion and its implications for subclinical leaflet thrombosis
Authors: Qiu Dong , Azadani Ali N.
Published: August 2022

Subclinical leaflet thrombosis has been increasingly recognized following transcatheter aortic valve replacement (TAVR). Determining the risk factors is vital in preventing clinical leaflet thrombosis and ensuring long‐term value durability. Clinical data have indicated that regional stent under‐expansion of transcatheter aortic valves (TAVs), particularly self‐expanding devices, may be associated with an increased risk of subclinical leaflet thrombosis. This study aimed to determine the effects of regional TAV frame under‐expansion on leaflet kinematics, leaflet structural characteristics, and explore its impact on the likelihood of leaflet thrombosis. In this study, mild and moderate regional frame under‐expansion of a 26‐mm CoreValve were examined using experimental testing and computational simulations. The results indicated that regional TAV frame under‐expansion impairs leaflet kinematics and reduces the range of motion in leaflets with an angle less than 120°. The reduced range of motion can increase blood stasis on the surface of the TAV leaflets. The results also demonstrated that regional frame under‐expansion induced localized high‐stress regions in the leaflets close to the fixed boundary edge. The increased mechanical stress can lead to accelerated tissue degeneration. The study improves our understanding of the effects of regional stent under‐expansion in TAVR. Post‐procedural balloon dilatation of self‐expanding TAVs can potentially be advantageous in reducing leaflet distortion and normalizing leaflet stress distribution. Large‐scale, prospective, and well‐controlled studies are needed to further investigate regional TAV frame under‐expansion effects on subclinical leaflet thrombosis and long‐term valve durability.
Bidirectional converter based on boost/buck DC‐DC converter for microgrids energy storage systems interface
Authors: Nimitti Fabiano Gonzales , Andrade António Manuel Santos Spencer
Published: August 2022

In this paper, a new bidirectional nonisolated DC‐DC (direct current–direct current) converter to interface microgrid energy storage systems is proposed. This converter is based on the classical bidirectional boost/buck converter, the most used converter in microgrids and can operate both in step‐down and step‐up modes. Besides that, this converter presents low number of components, low voltage and current stress on components, simplicity of operation, low current ripple from low‐side power supply, and two different modes of operation: synchronous and asynchronous. In addition, in this paper, the modeling, control, and power losses estimate of the proposed converter are carried out and the performance of the converter in different aspects of the microgrid application is evaluated, such as step load, abrupt power flux change, and transient analysis. A prototype of 1 kW, 144 to 400 V, is developed in the laboratory to validate the theoretical evaluations of the proposed converter. Besides that, the proposed converter is also evaluated under different dynamic condition which illustrates the effectiveness of the converter. Finally, the maximum efficiency obtained is 97.1% for 500 W working in step‐down operation.
Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with PdII and PtII Aryl Isocyanide Complexes
Authors: Popov Roman A. , Mikherdov Alexander S. , Boyarskiy Vadim P.
Published: August 2022

A method for obtaining C,S‐cyclometalated deprotonated diaminocarbene complexes via the addition of a bifunctional N,S‐nucleophile's endocyclic nitrogen atom to a coordinated isocyanide has been extended to the reactions with pyridine‐2(1H)‐thione. The coupling of PdII‐ and PtII‐bis(arylisocyanide) complexes with pyridine‐2(1H)‐thione leads to the formation of mononuclear C,S‐cyclometalated deprotonated diaminocarbene complexes in 90–96 % yield. The reaction proceeds via the initial coordination of the thione sulfur atom to the metal center followed by the intramolecular nucleophilic addition of the heterocyclic nitrogen atom to the metal‐ligated isocyanide carbon. Using an excess of pyridine‐2(1H)‐thione in this reaction leads to the formation of a mono‐C,S‐cyclometalated complex with a pendant mercaptopyridine ligand which is involved in the reversible intramolecular nucleophilic addition of the pyridine nitrogen to the isocyano carbon. The obtained complexes were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopies, and single‐crystal X‐ray diffraction.
Mechanistic Insights into Lewis Acid‐Controlled Torquoselective Nazarov Cyclization of Activated Dienones Bearing a Chiral Sulfoxide
Authors: Grenet Erwann , Robidas Raphaël , van der Lee Arie , Legault Claude Y. , Salom‐Roig Xavier J.
Published: August 2022

This work provides a switchable strategy to access, through a Nazarov cyclization, two diastereomeric disubstituted 3,4,5,6‐tetrahydrocyclopenta[b]pyran‐7(2H)‐ones from an activated dienone bearing a chiral sulfoxide. The switch in the torquoselectivity is controlled by the nature of the Lewis acid used as promoter. From the four possible stereoisomers, only the two trans were observed. The Lewis acids employed were achiral and the diastereoselectivities were dictated by the sulfinyl auxiliary. Density functional theory investigations shed light on the reaction mechanism. The experimental torquoselectivities were very closely reproduced and their inversion could be linked back to a change in the binding mode of the substrate.
Lewis Acid‐Catalyzed (3+2) Cycloaddition of 2‐Indolylmethanols with β,γ‐Unsaturated α‐Ketoesters
Authors: Yang Shuang , Wang Hai‐Qing , Gao Jun‐Nan , Tan Wen‐Xin , Zhang Yu‐Chen , Shi Feng
Published: August 2022

A Lewis acid‐catalyzed (3+2) cycloaddition of 2‐indolylmethanols with β,γ‐unsaturated α‐ketoesters was established, which afforded a series of cyclopenta[b]indoles in overall high yields (up to 98 %) with excellent diastereoselectivities (up to >95 : 5 dr). This reaction not only represents the first C3‐nucleophilic (3+2) cycloaddition of 2‐indolylmethanols, but also provides a good example for (2+n) cycloaddition of β,γ‐unsaturated α‐ketoesters, which will add new contents to the chemistry of 2‐indolylmethanols. In addition, this approach provides an atom‐economic and useful method for the construction of biologically important cyclopenta[b]indole scaffold.
Tau as a biomarker of cognitive impairment and neuropsychiatric symptom in Alzheimer's disease
Authors: Dang Mingxi , Chen Qian , Zhao Xiaobin , Chen Kewei , Li Xin , Zhang Junying , Lu Jie , Ai Lin , Chen Yaojing , Zhang Zhanjun
Published: August 2022

The A/T/N research framework has been proposed for the diagnosis and prognosis of Alzheimer's disease (AD). However, the spatial distribution of ATN biomarkers and their relationship with cognitive impairment and neuropsychiatric symptoms (NPS) need further clarification in patients with AD. We scanned 83 AD patients and 38 cognitively normal controls who independently completed the mini‐mental state examination and Neuropsychiatric Inventory scales. Tau, Aβ, and hypometabolism spatial patterns were characterized using Statistical Parametric Mapping together with [18F]flortaucipir, [18F]florbetapir, and [18F]FDG positron emission tomography. Piecewise linear regression, two‐samplet‐tests, and support vector machine algorithms were used to explore the relationship between tau, Aβ, and hypometabolism and cognition, NPS, and AD diagnosis. The results showed that regions with tau deposition are region‐specific and mainly occurred in inferior temporal lobes in AD, which extensively overlaps with the hypometabolic regions. While the deposition regions of Aβ were unique and the regions affected by hypometabolism were widely distributed. Unlike Aβ, tau and hypometabolism build up monotonically with increasing cognitive impairment in the late stages of AD. In addition, NPS in AD were associated with tau deposition closely, followed by hypometabolism, but not with Aβ. Finally, hypometabolism and tau had higher accuracy in differentiating the AD patients from controls (accuracy = 0.88, accuracy = 0.85) than Aβ (accuracy = 0.81), and the combined three were the highest (accuracy = 0.95). These findings suggest tau pathology is superior over Aβ and glucose metabolism to identify cognitive impairment and NPS. Its results support tau accumulation can be used as a biomarker of clinical impairment in AD.
The intergenerational persistence of opioid dependence: Evidence from administrative data
Authors: Ahammer Alexander , Halla Martin
Published: August 2022

To address the opioid crisis, it is crucial to understand its origins. We provide descriptive evidence for the intergenerational persistence of opioid dependence. Our analysis is based on administrative data covering the universe of Austrian births from 1984 to 1990. We consider prescription opioids and a new proxy for addiction to illicit opioids. We find that, if at least one parent is using illicit opioids, the likelihood of the child using increases from 1% to 7%. For prescription opioids, we observe an increase from 3.6% to 6.7%. Both associations are stable and do not change when controlling for environmental variables.
Relief and climate influence on isotopic composition of Atlantic‐Mediterranean karst spring waters (Andalusia, southern Spain)
Authors: Yanes José Luis , Moral Francisco
Published: August 2022

The geographic location of Andalusia, bordered by the Atlantic Ocean and the Mediterranean Sea, and its great topographic and climate diversity enable the analysis of different factors that condition the isotopic composition of precipitation and groundwater. A total of 42 karst springs representative of the main carbonate aquifers were selected in order to sample the base flow waters during the summer of 2020. Isotopic analyses revealed that groundwater δ18O was between −5.04 and −9.85‰ while that of δ2H was between −26.39 and −62.69‰. Weighted mean isotopic data for precipitation, from six IAEA stations in the study area, was between −4.67 and −9.06‰ for δ18O, and between −24.93 and −58.99 ‰ for δ2H. The results showed that diffuse flow groundwaters are lighter and have higher d‐excess than meteoric waters, which may be due to preferential recharge during winter months and the sub‐cloud evaporation effect. The spatial variation of d‐excess, with average values around 14 ‰ in the Atlantic watershed and 17 ‰ in the Mediterranean watershed, has showed for the first time the effect of the Atlantic‐Mediterranean divide on the isotopic composition of spring waters. Furthermore, a progressive decrease in δ18O towards the east of the study area seems to be related to the effects of continentality and altitude. This also allowed us to conclude that, in the areas with highest rainfall, springs drain waters with a relatively higher content of heavy isotopes than expected from the regional altitudinal gradient, while springs in drier areas discharge lighter waters. These differences can be attributed to a longer recharge period in the former, which extends in the warmer months or autumn and spring.
CO bonding in hexa‐ and pentacoordinate carboxy‐neuroglobin: A quantum mechanics/molecular mechanics and local vibrational mode study
Authors: Freindorf Marek , Delgado Alexis Antoinette Ann , Kraka Elfi
Published: August 2022

We present a comprehensive investigation on the different role of CO in carboxyneuroglobin (1) as ligand of the heme group in the active site forming a bond with the heme iron and (2) dissociated from the heme group but still trapped inside the active site, focusing on two specific orientations, one with CO perpendicular to the plane defined by the distal histidine of the enzyme (form A) and one with CO located parallel to that plane (form B). Our study includes wild type carboxy‐neuroglobin and nine known protein mutations. Considering that the distal histidine interacting with the heme group can adapt two different tautomeric forms and the two possible orientations of the dissociated CO, a total of 36 protein systems were analyzed in this study. Fully optimized geometries and vibrational frequencies were calculated at the QM/MM level, followed by the local mode analysis, to decode CO bond properties. The intrinsic bond strengths derived from the local mode analysis, complemented with NBO and QTAIM data, reveal that the strength of the CO bond, in the hexacoordinate (where CO is a ligand of the heme group) and pentacoordinate (where CO is dissociated from the heme group) scenarios, is dominated by through bond and through space charge transfer between CO and Fe, fine‐tuned by electrostatic and dispersion interactions with the side chain amino acids in the distal heme pocket. Suggestions are made as to advise on how protein modifications can influence the molecular properties of the coordinated or dissociated CO, which could serve the fine‐tuning of existing and the design of new neuroglobin models with specific FeC and CO bond strengths.
Connectivity preserving trees in k‐connected or k‐edge‐connected graphs
Authors: Hasunuma Toru
Published: August 2022

We show that for and any tree of order , every ‐connected (respectively, ‐edge‐connected) graph with minimum degree at least contains a subtree such that is ‐connected (respectively, ‐edge‐connected), where denotes the maximum degree of . We also show that for any and any tree of order , every ‐connected (respectively, ‐edge‐connected) graph of order with minimum degree at least where contains a subtree such that is ‐connected (respectively, ‐edge‐connected). The lower bound of on the minimum degree of can be improved to under several restrictions or assumptions.