bluuebunny/crossref_metadata_2025 huggingface dataset:
O controle social e sua relação com a gestão social na administração pública brasileira: revisão sistemática da literatura
Authors: Brilhante Roberto Leopoldo Nogueira , Azevedo João Luiz Trindade de , Barbosa Flávia Lorenne Sampaio , Bizarria Fabiana Pinto de Almeida
Published: November 2022

Do paradigma do estadocêntrica, que prevaleceu até meados de 1980, para o sociocêntrico, observa-se ampliação do reconhecimento da sociedade civil como ator social e político. Nesse contexto, o processo participativo ganha maior relevo, estando presente em duas concepções estudadas no âmbito da administração pública, o controle social e a gestão social. O presente texto utiliza-se da técnica de revisão bibliográfica sistemática para fazer uma breve reflexão sobre a relação entre o controle social e a gestão social, buscando as semelhanças, diferenças e possíveis interseções entre os conceitos. A priori, considerou-se que o controle social poderia ser utilizado para o exercício da gestão social, como uma espécie de ferramenta. Após aprofundamento no assunto, verificou-se justamente o direcionamento contrário, que a gestão social, normalmente, é apontada como meio para concretização do controle social, este sendo compreendido, majoritariamente, como controle da sociedade sobre o Estado e aquele apenas como um modo da gestão participativo, mas que requer toda uma estrutura de não coação, incentivo à participação e solidariedade, tendo sido verificada uma ênfase associativa ao conceito de exercício da cidadania deliberativa.
Auditoria e gestão pública hospitalar: déficit de leitos no período de 2019 a 2021 no sistema único de saúde em Pernambuco
Authors: Cesar Junior Carlos Claudio Correa
Published: November 2022

O presente trabalho trará uma análise da medida governamental, que ocorreu no período de 2015 a 2020, no Estado de Pernambuco, onde o mesmo inicia uma parceria com a Rede Suplementar, tendo como objetivo a ampliação do número de vagas nas UTI’s em que visa alocar o paciente na Unidade de Saúde para a Rede Privada, pacientes estes que possuem um quadro clínico de Baixa Complexidade (Pacientes grave, porem estáveis, onde necessitam de um acompanhamento menos intenso oferecido pela Rede Suplementar) e também pacientes com maior grau de Complexidade (Pacientes graves, onde necessitam de um acompanhamento mais intenso oferecido pela Rede Suplementar). Apontar o déficit que ocorreu entre os anos 2019 e 2021 de leitos públicos dentro do Sistema Único de Saúde para atender à demanda existente e comparar os resultados com a recomendação do Ministério da Saúde. O dimensionamento adequado de leitos e sua transferência para hospitais privados devem considerar os motivos de limitações de acesso oportuno e a gestão do fluxo de pacientes em um cenário que associa priorização das solicitações. Num mundo globalizado e economicamente frenético, atualmente, está se vivenciando um grande acontecimento no âmbito da saúde, o apogeu de uma Pandemia chamada Coronavírus. Em todo mundo foram confirmados cerca xxx casos de infectados e xxxxx mortes pela COVID-19 (dados registrados até dezembro/2021), estando a Organização Pan-Americana da Saúde (OPAS) e a Organização Mundial de Saúde (OMS) por meio do Escritório que representa as duas instituições no Brasil (POHAS), prestando apoio técnico aos brasileiros, na resposta ao surto do Coronavírus. Neste contexto, os déficits de leitos ficaram ainda mais caóticos, necessitando de uma gestão hospitalar eficaz.
Percepção da escrituração contábil na concepção de microempreendedores individuais do município de Porto Velho (RO)
Authors: Souza Keliane Gonçalves de , Severino Josilene Duarte , Leal Matheus Lucas Maciel
Published: November 2022

O presente trabalho propõe uma análise quanto a percepção dos microempreendedores individuais, da cidade de Porto Velho (RO), sobre as práticas da escrituração contábil na organização como auxilio na gestão do negócio, bem como, medir a confiabilidade do pequeno empresário com relação ao profissional contábil. Para entender esta finalidade, foi utilizado o método de pesquisa quali-quantitativa, ao qual foi realizada através de uma pesquisa bibliográfica e entrevistas aplicada a gestores, constituídas de questões que permitiu identificar o perfil social e institucional, a organização contábil nas microempresas e a percepção dos microempreendedores sobre a escrituração contábil. Os resultados obtidos demonstram que os empreendedores têm experiência em gestão, visto que as empresas atuam no mercado a mais de 5 anos. Os gestores avaliaram os serviços realizados pelo contador, na qual a maioria das funções ligadas a apoio a gestão, planejamento, relatórios, com notas abaixo da média, fato que demonstra a desvalorização da contabilidade como ferramenta de apoio a gestão, por parte destes empreendedores. As empresas adotam procedimentos de controles internos por meios tecnológicos, mecânicos e manuais, tratando com grande importância a necessidade de manter a supervisão de suas receitas, despesas e estoque, todavia somente uma empresa conta com um profissional contábil para a execução dessas atividades. Quanto às projeções futuras das organizações, as perspectivas dos gestores giram em torno de um mesmo propósito: a expansão dos negócios, ao qual, acreditam que os principais fatores para atingir esses objetivos são: marketing e propaganda, não considerando a assessoria contábil importante. No que se refere a percepção dos gestores sobre a escrituração contábil, os resultados apontam que os respondentes não têm conhecimento quanto as principais informações desta técnica, como documentos, benefícios, riscos e ônus, além de não conseguir observar a sua utilidade dentro da organização. Fato justificado quando os gestores apresentam os serviços contábeis contratados/utilizados na empresa, sendo eles: folha de pagamento, orientação trabalhista e envio de declarações anuais, onde nenhum empresário faz uso da escrituração contábil. É necessário maior aprofundamento no conhecimento dos gestores em relação a escrituração contábil, por isso o profissional contábil é ausente dentro dessas organizações, estimulando resistência em utilizar os serviços contábeis no processo de gerenciamento e tomada de decisão.
Danskernes brug af medicinplanter
Authors: Kjellerup Hundahl Andreas , Isager Lotte , Theilade Ida
Published: November 2022

Danmark, og i særdeleshed Midt- og Vestjylland, har en veldokumenteret historisk tradition for brug af medicinplanter. Etnobotaniske studier af nutidig brug af medicinplanter i Danmark er til gengæld fåtallige. Formålet med dette studie var at kortlægge brugen af medicinplanter i Danmark. I alt 169 plantearter tilhørende 65 familier blev registreret som værdifulde i nutidig dansk urtemedicin. En sammenligning med historiske kilder fra 1800-tallets brug af medicinplanter viste 85 nye plantearter, mens anvendelsen af 71 arter var forsvundet. Lidt over halvdelen af de nye arter var ikke-hjemmehørende i Danmark. Kombinationen af ’nye’ og ’glemte’ arter indikerer, at nutidens urtekendskab er levende og dynamisk. I diskussionen forholder vi os ud fra kortlægningen af nutidens brug af medicinplanter i Danmark til spørgsmål om kontinuitet og forandring, dels i forhold til studier fra andre europæiske lande, dels i forhold til en dansk historisk tradition for viden og praksis om medicinplanter. En levende dansk etnobotanisk tradition kan være med til at styrke følelsen af identitet og forbundenhed med kulturhistorien og naturen.
A CIRCULAR ECONOMY INVESTIGATION INTO TREATMENT TECHNOLOGIES AVAILABLE FOR THE DISPOSAL OF SLAUGHTERHOUSE DERIVATIVES
Authors: van Zyl Minette , van Eeden Joubert
Published: November 2022

Two major problems challenge the world of food today: the constantly growing demand for meat products and dealing with the volumes of waste produced by the industry. The volume of slaughterhouse derivatives produced when generating meat products threatens the health of humans and the environment. The need to feed a growing population sustainably and to find more sustainable and circular alternative treatment technologies for handling and disposing of slaughtering derivatives undoubtedly creates opportunities for several role players. A comprehensive bibliometric analysis was undertaken to identify such processes, considering the different slaughterhouse derivatives generated by red meat and poultry slaughterhouse facilities. The literature search and refinement process identified 130 scientific documents for analysis. The results highlight an increase in the scientific literature on the sustainable recovery of slaughterhouse derivatives, and a diverse range of available treatment technologies to dispose of such derivatives.
EVALUATION OF BUDGETING METHODS FOR MAINTENANCE OF HERITAGE BUILDINGS
Authors: Lekarapa Martin , Grobbelaar Schalk
Published: November 2022

Heritage buildings have evolved into development catalysts that, when properly maintained, can improve their surrounding area’s liveability while sustaining productivity in an ever-changing global context. Unfortunately, the high uncertainty involved in preserving heritage buildings frequently leads to over-budget projects. This article evaluates the factors that contribute to projects being over budget and the methods used to develop project budgets. History-based budgeting methods, value-oriented budgeting methods, analytical budgeting methods, and budgeting by condition description are frequently used, while new artificial intelligence models are also emerging. In addition, the review considers the Monte Carlo method and compares it with artificial intelligence models. Considering the high uncertainty involved when maintaining heritage buildings, it is concluded that the Monte Carlo method could be a very effective tool. For this reason, it is recommended that its use be tested on heritage building projects. Keywords heritage buildings; budget; maintenance; conservation projects; Monte Carlo simulation
INFLUENCE OF Sn ON THE MICROSTRUCTURE AND MECHANICAL PROPERTIES OF Ti-Mo-Nb ALLOYS FOR ORTHOPAEDIC APPLICATIONS
Authors: Muchavi Noluntu , Ranganya Lerato , maChaka Ronald , Motsi Glenda , Makhatha Elizabeth
Published: November 2022

Metastable ß-Ti alloys intended for orthopaedic implants typically possess undesirable α′, α″, ω precipitates, which increase the elastic modulus. Non-toxic Sn was reported as an effective suppressor of α′, α″ and ω precipitates. Furthermore, increasing Sn content was reported to decrease the elastic modulus. In this study, the cluster plus glue atom (CPGA) model was used to develop structurally stable ß-Ti alloys through the addition of Sn. Arc melting was conducted to fabricate the alloys. The effect of substituting Mo atoms with 0.4 and 0.5 Sn atoms on the microstructure and mechanical properties of [(Mo,Sn)(Ti)14](Nb)1 alloys was investigated. The microstructure of the alloys exhibited large equiaxed beta grains with the [(Mo0.6Sn0.4)(Ti)14](Nb)1 and [(Mo0.5Sn0.5)(Ti)14](Nb)1 alloys showing substructures. The XRD results showed that the alloys consisted of the β phase; however, the presence of α” was observed in the [(Mo0.6Sn0.4)(Ti)14](Nb)1 alloy. The study showed that substitution of 0.5 Mo atoms with 0.5 atoms of Sn to form the [(Mo0.5Sn0.5)(Ti)14](Nb)1 cluster resulted in an elastic modulus of 49 GPa.
Challenges and Possibilities of Memory and Reconciliation: Empirical Evidence for Colombia
Authors: Arrieta-Flórez Rosaura , Marún Uparela Katleen , Torres-Pacheco Silvana
Published: November 2022

The signing of the peace agreement with the Revolutionary Armed Forces of Colombia-People’s Army (FARC-EP) deepened the debate on the reconstruction of memory as a right of the victims and a way to advance in the reconciliation of Colombian society. This article uses data from the 2019 Colombian Reconciliation Barometer of the Program of Alliances for Reconciliation of the United States Agency for International Development and ACDI/VOCA to analyze the individual and contextual factors that affect how individuals perceive the reconstruction of memory as a tool that contributes to reconciliation. We estimated a probabilistic model for which the dependent variable is the predisposition toward memory reconstruction as a predictor of reconciliation based on the context of the Colombian armed conflict, and a set of individual factors that capture the effects of community initiatives and state institutions and programs arising within the framework of transitional justice. We sought to verify whether the characteristics of individuals and their way of relating to each other in a community and municipal context shape the perception of the contribution of reconstructed memory to reconciliation. The results show that being a female victim of the armed conflict, developing empathy, residing in municipalities with the presence of Places of Memory, and trusting in the processes of transitional justice —such as clarifying the truth— increase an individual’s predisposition to consider that the reconstruction of memory contributes to reconciliation. In contrast, other policies and programs that emerged after the agreement, such as residing in municipalities with Territorially Focused Development Plans (PDET in Spanish) and the presence of Casas de Verdad (Truth Houses), operate in the opposite direction. This work suggests challenges for transitional justice by identifying the factors that condition positive outlooks toward the reconstruction of memory in reconciliation processes and opens the possibility of formulating actions with greater citizen acceptance.
A novel cis-regulatory element drives early expression of Nkx3.2 in the gnathostome primary jaw joint
Authors: Leyhr Jake , Waldmann Laura , Filipek-Górniok Beata , Zhang Hanqing , Allalou Amin , Haitina Tatjana
Published: November 2022

The acquisition of movable jaws was a major event during vertebrate evolution. The role of NK3 homeobox 2 (Nkx3.2) transcription factor in patterning the primary jaw joint of gnathostomes (jawed vertebrates) is well known, however knowledge about its regulatory mechanism is lacking. In this study, we report a proximal enhancer element of Nkx3.2 that is deeply conserved in most gnathostomes but undetectable in the jawless hagfish and lamprey. This enhancer is active in the developing jaw joint region of the zebrafish Danio rerio, and was thus designated as jaw joint regulatory sequence 1 (JRS1). We further show that JRS1 enhancer sequences from a range of gnathostome species, including a chondrichthyan and mammals, have the same activity in the jaw joint as the native zebrafish enhancer, indicating a high degree of functional conservation despite the divergence of cartilaginous and bony fish lineages or the transition of the primary jaw joint into the middle ear of mammals. Finally, we show that deletion of JRS1 from the zebrafish genome using CRISPR/Cas9 results in a significant reduction of early gene expression of nkx3.2 and leads to a transient jaw joint deformation and partial fusion. Emergence of this Nkx3.2 enhancer in early gnathostomes may have contributed to the origin and shaping of the articulating surfaces of vertebrate jaws.
A manager’s guide to using eDNA metabarcoding in marine ecosystems
Authors: Gold Zachary , Wall Adam R. , Schweizer Teia M. , Pentcheff N. Dean , Curd Emily E. , Barber Paul H. , Meyer Rachel S. , Wayne Robert , Stolzenbach Kevin , Prickett Kat , Luedy Justin , Wetzer Regina
Published: November 2022

Environmental DNA (eDNA) metabarcoding is a powerful tool that can enhance marine ecosystem/biodiversity monitoring programs. Here we outline five important steps managers and researchers should consider when developing eDNA monitoring program: (1) select genes and primers to target taxa; (2) assemble or develop comprehensive barcode reference databases; (3) apply rigorous site occupancy based decontamination pipelines; (4) conduct pilot studies to define spatial and temporal variance of eDNA; and (5) archive samples, extracts, and raw sequence data. We demonstrate the importance of each of these considerations using a case study of eDNA metabarcoding in the Ports of Los Angeles and Long Beach. eDNA metabarcoding approaches detected 94.1% (16/17) of species observed in paired trawl surveys while identifying an additional 55 native fishes, providing more comprehensive biodiversity inventories. Rigorous benchmarking of eDNA metabarcoding results improved ecological interpretation and confidence in species detections while providing archived genetic resources for future analyses. Well designed and validated eDNA metabarcoding approaches are ideally suited for biomonitoring applications that rely on the detection of species, including mapping invasive species fronts and endangered species habitats as well as tracking range shifts in response to climate change. Incorporating these considerations will enhance the utility and efficacy of eDNA metabarcoding for routine biomonitoring applications.
Effect of Benincasa hispida Fruit Dry Powder on Behaviour Changes and Antioxidants Levels in Adult Wistar Rats: An Experimental Study
Authors: Anbarasu Umamaheswari , Jayagowri K , Bhuvaneswari K
Published: November 2022

Introduction: Chronic stress has been implicated to be the important aetiological factor involved in several pathologies. Antioxidants play major roles in the maintenance of good health in the cellular level. Various studies have shown the anxiolytic, muscle relaxant, antidepressant, and antioxidant effects of Benincasa hispida (B.hispida) (white pumpkin). There is no available literature exploring the effects of this B.hispida dry powder on food intake, body weight, behavioural changes and antioxidant levels in whole animal model. Aim: This study aimed to understand the protective effects of the B.hispida dry powder in overcoming stress induction by analysing the pattern of food intake, behavioural changes and body weight and the change in blood levels of Superoxide Dismutase (SOD) and Malondialdehyde (MDA) in adult wister rats. Materials and Methods: This experimental study was conducted in the Department of Pharmacology, PSG Institute of Medical Sciences and Research, Tamil Nadu, India, for the duration of 3 weeks during the month of March 2020. Six male wister rats were obtained from the central animal house and assessed for baseline values of parameters including body weight, food intake, behaviour changes, blood levels of SOD and MDA and they were used as controls (without treatment) later. Then another 12 animals, matched for age and weight were selected and divided into two test groups (six in each). The animals in test groups 1 and 2 were pretreated with dry powder preparation of B.hispida at a dose of 250 mg/kg and 500 mg/kg orally and once daily respectively. The entire study population of 18 animals (control, group 1 and group 2) subjected to stress in a restrainer for 2 hours per day for 7 days. The study parameters were repeated at the end of 24 hours and at the end of 7 days. Results were analysed using Analysis of Variance (ANOVA) in Statistical Package for Social Sciences software version 24.0. Results: The results were 500 mg /kg dose of B.hispida helped in overcoming stress induction by giving the statistically significant (p-value<0.05) results of increase in body weight, food intake pattern and normalised general behaviour after 24 hrs and 7 days of repeated stress induction. But no significant changes were seen in blood levels of SOD (p-value>0.05) and MDA (p-value>0.05). Conclusion: Based on the previous literatures, it was stated as “sparing effect of the powder” that is, exogenous supplementation is likely to suppress its endogenous production of antioxidants. This mechanism could attribute to the potential beneficial effect of B.hispida on the outcomes, despite having no significant alterations in blood levels of SOD and MDA. Further studies are needed to confirm the effects B. hispida in overcoming stress induction.
Efficacy of 70% Glycolic Acid Peel versus 30% Salicylic Acid Peel in the Treatment of Mild to Moderate Acne Vulgaris: A Retrospective Study
Authors: Pavithra S , Gopalakrishnan K , Shanmugam Jeevithan
Published: November 2022

Introduction: Chemical peels have become a useful modality in the management of acne in addition to topical and systemic medications. Studies done to evaluate the effectiveness of peels have compared only lower concentration of Glycolic Acid (GA) (35%) and Salicylic Acid (SA) peels. Higher concentrations of glycolic acid i.e., (70%) are reported to be safe and more effective than lower concentrations. Despite reported advantages of higher concentration of glycolic acid peel, no published data is available regarding its efficacy, safety and tolerability in comparison with other peels. Aim: To compare the effectiveness of 70% GA peel with 30% SA peel in the management of mild to moderate acne. Materials and Methods: The present study was a cross-sectional retrospective study conducted from December 2021 to April 2022 in which, 60 participants were enrolled. They were diagnosed with mild to moderate acne, based on the Indian Acne Alliance (IAA) grading system and all of them underwent chemical peel treatment. Among them 30 had received 70% GA peel (group 1) and 30 had received 30% SA peel (group 2). The number of sittings and the individual lesional count at baseline and at each sitting were recorded. Acne lesional count (sum of comedones, papules, pustules, and nodules) was recorded at baseline, 2, 4, 6 and 8 weeks. Categorical variables were presented as frequency and percentages. Continuous variables were presented as Mean±Standard deviation. Results: There was a significantly greater decrease in mean acne lesional count in group 2 from the baseline of 25.73 to 13.83 at the end of 2nd weekin comparison to group 1 wherein the values reduced from 26.30 to 17.73 (p-value of 0.003). At the end of eight weeks, the mean acne lesional count of both groups (group 1- 2.17 and group 2-1.50, p-value of 0.097) were comparable. Conclusion: Higher concentration of GA (70%) has comparable effectiveness to 30% SA peel in management of mild to moderate acne. SA peel has an advantage of earlier decrease in lesional count.
Proportion and Pattern of Chromosomal Abnormalities in Primary Amenorrhea in Kerala- A Retrospective Study
Authors: Thankam Uma , Hariharan Sankar Vaikom , Sarojam Santhi , Syamala Remya , Alex Sherrin Thomas , Ratnamma Nandini V , Jacob Sujamol
Published: November 2022

Introduction: Primary amenorrhoea may be due to chromosomal abnormalities and identification of these abnormalities is important for counselling and management of these individuals. Aim: To identify the prevalence of chromosomal abnormalities in a cohort of primary amenorrhoea patients and to evaluate the various pattern of chromosomal abnormalities. Materials and Methods: This retrospective study was conducted at Government Medical College, Thiruvananthapuram, Kerala, India (serves as a referral centre for most of south Kerala and adjoining districts of Tamil Nadu), from January 2013 to December 2020. All phenotypically females, in the age group of 15-30 years, attending the Genetic Clinic with a diagnosis of primary amenorrhoea were evaluated with karyotype from peripheral blood as per the standard protocol. An abstraction proforma was used to collect the data from the master case sheet available in the genetic laboratory. Cytogenetic abnormalities were described as per the standard International System for Human Cytogenomic Nomenclature (ISCN). For statistical analysis, proportion of cases with chromosome abnormality in the cohort was described as percentage. Results: Chromosomal analysis revealed 25.5% (38 out of 149) with abnormal karyotype. Among the abnormalities, the most common abnormality was 45, X (12, 31.6%) Turners syndrome. Other abnormalities included sex reversal female (46, XY) in six (15.8%), isochromosome Turner syndrome in five (13.1%), partial deletion in X chromosome in three (7.8%) and various combination of mosaic pattern in nine (23.7%) cases. Hypergonadotropic hypogonadism was significantly associated with chromosomal abnormality. Conclusion: Cytogenetic abnormality is a cause for primary amenorrhoea in a significant proportion of cases and karyotype should be an integral part of evaluation in such cases. In resource limited settings, karyotype is having more clinical utility in cases with hypergonadotropic hypogonadism.
Catalytic Photodegradation of Cyclic Sulfur Compounds in a Model Fuel Using a Bench-scale Falling-film Reactor Irradiated by a Visible Light
Authors: Mousa Noor Edin , Mohammed Seba S. , Shnain Zainab Y. , Abid Mohammad F. , Alwasiti Asawer A. , Sukkar Khalid A.
Published: November 2022

A homemade N doped-TiO2 nanoparticle were used to degrade dibenzothiophene (DBT) in a model fuel flowing on a bench-scale glass-made falling film reactor irradiated by a xenon lamp that emitted visible light. The photocatalyst was immobilized on the glass sheet. EDS, SEM, and FT-IR techniques were utilized to identify the morphology of the N doped-TiO2 nanoparticles. Different operating parameters (e.g., N loading (0, 4, 5, and 6 wt%), light intensity (20, 40, and 60 W/m2), and pH (4, 7, and 10)) were investigated for their effect on the DBT degradation.  The effect of the N loading on the wettability of the nano-TiO2 particles was also investigated. Experimental results revealed that the N loading did not affect the wettability characteristics of the nano TiO2 particles. Moreover, results showed that DBT conversion positively depends on N loading, light intensity (hv), and pH increase. The estimated optimal operating parameters were 5 wt% N loading, pH = 10, and hv = 40 W/m2 to ensure the best photo-oxidation efficiency of 91.4% after 120 min of operation. The outcomes of the present work confirmed the effective efficiency of the N-doped TiO2 nanoparticles irradiated by visible light for DBT degradation. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).
The Sussicranistic Mind
Authors: O'Neill-Dean Richard
Published: November 2022

This paper presents a thought for a new diagnostic category equivalent to narcissism. Taking as its starting point Neville Symington's definition of narcissism, the paper puts forward the existence of a correlative state of mind, 'Sussicranism'. This state is descdbed and illustrated with clinical and day-to-day examples. The paper concludes with some comments on the relevance of sussicranism to the profession of psychotherapy.
Campaign Reform for US News and World Report Rankings
Authors: Daskivich Timothy J. , Gewertz Bruce L.
Published: November 2022

This Viewpoint discusses the perceived importance of US News and World Report hospital rankings and concerns with using specialty voting to dominate the assessment of process.
Ni Center Coordination Reconstructed Nanocorals for Efficient Water Splitting
Authors: Xu Tianyi , Jiao Dongxu , Liu Manman , Zhang Lei , Fan Xiaofeng , Zheng Lirong , Zheng Weitao , Cui Xiaoqiang
Published: November 2022

Efficient electrocatalytic reactions require a coordinated active center that may provide a properly reaction intermediates adsorption in water splitting. Herein, a Ni active center coordination reconstruction method achieved by multidimensional modulation of phase transition, iodine coordination, and vacancy defects is designed and implemented. This coordination reconstruction results in the successful synthesis of Ni5P4−xIx/Ni2P nanocorals that show outstanding bifunctional catalytic activity due to deep optimization of the adsorption energy. The overpotentials of hydrogen evolution reaction and oxygen evolution reaction at 10 mA cm−2 are 46 and 163 mV, respectively. Only 1.46 V is required to drive alkaline overall water splitting. Novel coordination environment is investigated by electron paramagnetic resonance spectroscopy and extended X‐ray absorption fine structure spectroscopy. A 4D integrated material design strategy of “thermodynamic stability‐electronic properties‐charge transfer‐adsorption energy” for water‐splitting catalysts is proposed. This coordination reconstruction concept and material design method provide new perspectives for the research of novel catalysts.
Genetic potential for changes in breeding systems: Predicted and observed trait changes during artificial selection for male and female allocation in a gynodioecious species
Authors: Campbell Diane R. , Sakai Ann K. , Weller Stephen G. , Culley Theresa M. , Dunbar‐Wallis Amy K. , Andres Allen M. , Wong Tiffany G. , Dang Tam , Au Bryan , Ku Mickey , Marcantonio Andrea R. , Ngo Paul J. , Nguyen Andrew A. , Tran My Hanh , Tran Quoc‐Phong
Published: November 2022

Premise

Evolution of separate sexes from hermaphroditism often proceeds through gynodioecy, but genetic constraints on this process are poorly understood. Genetic (co‐)variances and between‐sex genetic correlations were used to predict evolutionary responses of multiple reproductive traits in a sexually dimorphic gynodioecious species, and predictions were compared with observed responses to artificial selection.

Methods

Schiedea (Caryophyllaceae) is an endemic Hawaiian lineage with hermaphroditic, gynodioecious, subdioecious, and dioecious species. We measured genetic parameters of Schiedea salicaria and used them to predict evolutionary responses of 18 traits in hermaphrodites and females in response to artificial selection for increased male (stamen) biomass in hermaphrodites or increased female (carpel, capsule) biomass in females. Observed responses over two generations were compared with predictions in replicate lines of treatments and controls.

Results

In only two generations, both stamen biomass in hermaphrodites and female biomass in females responded markedly to direct selection, supporting a key assumption of models for evolution of dioecy. Other biomass traits, pollen and ovule numbers, and inflorescence characters important in wind pollination evolved indirectly in response to selection on sex allocation. Responses generally followed predictions from multivariate selection models, with some responses unexpectedly large due to increased genetic correlations as selection proceeded.

Conclusions

Results illustrate the power of artificial selection and utility of multivariate selection models incorporating sex differences. They further indicate that pollen and ovule numbers and inflorescence architecture could evolve in response to selection on biomass allocation to male versus female function, producing complex changes in plant phenotype as separate sexes evolve.
Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single‐Atom Catalysts throughp‐nJunction Rectification
Authors: Zhuang Zechao , Xia Lixue , Huang Jiazhao , Zhu Peng , Li Yong , Ye Chenliang , Xia Minggang , Yu Ruohan , Lang Zhiquan , Zhu Jiexin , Zheng Lirong , Wang Yu , Zhai Tianyou , Zhao Yan , Wei Shiqiang , Li Jun , Wang Dingsheng , Li Yadong
Published: November 2022

Fine‐tuning single‐atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploitp‐type semiconducting character of SACs having a metal center coordinated to nitrogen donors (MeNx) and rectify their local charge density by ann‐type semiconductor support. With iron phthalocyanine (FePc) as a model SAC, introducing ann‐type gallium monosulfide that features a low work function generates a space‐charged region across the junction interface, and causes distortion of the FeN4moiety and spin‐state transition in the FeIIcenter. This catalyst shows an over two‐fold higher specific oxygen‐reduction activity than that of pristine FePc. We further employ three othern‐type metal chalcogenides of varying work function as supports, and discover a linear correlation between the activities of the supported FeN4and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.
Visible‐Light‐Switchable Tellurium‐Based Chalcogen Bonding: Photocontrolled Anion Binding and Anion Abstraction Catalysis
Authors: Duan Hong‐Ying , Han Shi‐Tao , Zhan Tian‐Guang , Liu Li‐Juan , Zhang Kang‐Da
Published: November 2022

Exploring new noncovalent bonding motifs with reversibly tunable binding affinity is of fundamental importance in manipulating the properties and functions of supramolecular self‐assembly systems and materials. Herein, for the first time, we demonstrate a unique visible‐light‐switchable telluro‐triazole/triazolium‐based chalcogen bonding (ChB) system in which the Te moieties are connected by azobenzene cores. The binding strengths between these azo‐derived ChB receptors and the halide anions (Cl−, Br−) could be reversibly regulated upon irradiation by visible light of different wavelengths. Thecis‐bidentate ChB receptors exhibit enhanced halide anion binding ability compared to thetrans‐monodentate receptors. In particular, the telluro‐triazolium‐based ChB receptor can achieve both high and significantly photoswitchable binding affinities for halide anions, which enable it to serve as an efficient photocontrolled organocatalyst for ChB‐assisted halide abstraction in a Friedel–Crafts alkylation benchmark reaction.
Multi‐Dimensional Structure and Dynamics Landscape of Proteins in Mammalian Cells Revealed by In‐Cell NMR
Authors: Kadavath Harindranath , Cecilia Prymaczok Natalia , Eichmann Cédric , Riek Roland , Gerez Juan Atilio
Published: November 2022

Governing function, half‐life and subcellular localization, the 3D structure and dynamics of proteins are in nature constantly changing in a tightly regulated manner to fulfill the physiological and adaptive requirements of the cells. To find evidence for this hypothesis, we applied in‐cell NMR to three folded model proteins and propose that the splitting of cross peaks constitutes an atomic fingerprint of distinct structural states that arise from multiple target binding co‐existing inside mammalian cells. These structural states change upon protein loss of function or subcellular localisation into distinct cell compartments. In addition to peak splitting, we observed NMR signal intensity attenuations indicative of transient interactions with other molecules and dynamics on the microsecond to millisecond time scale.
Azaarenes: 13 Rings in a Row by Cyclopentannulation
Authors: Maier Steffen , Hippchen Nikolai , Jester Fabian , Dodds Marcus , Weber Michel , Skarjan Leon , Rominger Frank , Freudenberg Jan , Bunz Uwe H. F.
Published: November 2022

Cyclopentannulation was explored as a strategy to access large, stable azaarenes. Buchwald–Hartwig coupling of previously reported di‐ and tetrabrominated cyclopentannulatedN,N′‐dihydrotetraazapentacenes furnished stable azaarenes with up to 13 six‐membered rings in a row and a length of 3.1 nm. Their optoelectronic and semi‐conducting properties as well as their aromaticity were investigated.
Polyetheretherketone/Nano‐Ag‐TiO2 composite with mechanical properties and antibacterial activity
Authors: Ru Xiaona , Chu Minghui , Jiang Jiazhen , Yin Tong , Li Jiamin , Gao Shijun
Published: November 2022

Polyetheretherketone (PEEK) is of interest because of its excellent biocompatibility. However, the lack of antimicrobial activity of PEEK limits its use in clinical applications. Silver‐loaded nano titanium dioxide (Nano‐Ag‐TiO2)/PEEK composites with different mass fractions (1, 2, 3, and 4 wt%) were prepared by hot compression molding to achieve better mechanical and antimicrobial properties. The results of scanning electron microscopy (SEM) and energy dispersive spectrum (EDS) showed that Nano‐Ag‐TiO2 successfully modified PEEK. The contact angle of Nano‐Ag‐TiO2/PEEK increased compared to PEEK (p < 0.01). The flexural strength, compressive strength, and Vickers hardness of Nano‐Ag‐TiO2/PEEK composites first increased and then decreased. When the Nano‐Ag‐TiO2 content is 3 wt%, the flexural strength of Nano‐Ag‐TiO2/PEEK composite reaches its maximum, which is 171.19 MPa; the compressive strength reaches the maximum, which is 24.7% higher than that of pure PEEK specimens; the Vickers hardness of Nano‐Ag‐TiO2/PEEK composite reaches its maximum, which is 19.84% higher than that of pure PEEK specimens. The in vitro antibacterial evaluation reveals that all Nano‐Ag‐TiO2/PEEK samples exhibited good resistance and anti‐adhesive properties against Staphylococcus aureus (S. aureus). This finding suggests that the 3 wt% Nano‐Ag‐TiO2/PEEK composite has better mechanical properties and antimicrobial ability, which is promising for dental applications.
The Effects of Daily Prednisone and Tocilizumab on Hemoglobin A1c During the Treatment of Giant Cell Arteritis
Authors: Patel Naomi J. , Tozzo Veronica , Higgins John M. , Stone John H.
Published: November 2022

Objective

To study the longitudinal effects of both glucocorticoids and tocilizumab, an interleukin‐6 receptor inhibitor, on hemoglobin A1c (HbA1c) levels during glucocorticoid tapering.

Methods

We analyzed patients with complete data from the Giant Cell Arteritis Clinical Research Study (GiACTA) to investigate the impact of both glycemic and nonglycemic factors on changes in HbA1c levels over the 52‐week trial. Giant cell arteritis (GCA) patients were randomized to receive either tocilizumab or placebo in addition to glucocorticoids. We used a multivariable mixed‐effects model to evaluate associations of HbA1c level with daily glucocorticoid dose, randomization to receive tocilizumab, and red blood cell count in patients with and those without diabetes mellitus at baseline, over 52 weeks.

Results

In 209 patients, the median HbA1c level decreased by 0.50% (P < 0.01) in the group that received both tocilizumab and glucocorticoids (tocilizumab/glucocorticoid) and by 0.10% (P < 0.01) in the glucocorticoid‐only group. Randomization to tocilizumab/glucocorticoid was associated with lower HbA1c (β = −0.209% in those without diabetes, P < 0.01; β = −0.290% in those with diabetes, P = 0.23). These changes had a sizable impact on glucose tolerance classification: 42.5% of patients in the tocilizumab/glucocorticoid group improved from prediabetes status to normal, compared to only 12.5% of patients treated with glucocorticoids alone. Daily glucocorticoid dose was associated with HbA1c level in patients with baseline diabetes (β = 0.018%/mg, P < 0.01) and those without baseline diabetes (β = 0.005%/mg, P < 0.01).

Conclusion

Tocilizumab treatment was associated with a substantial reduction in HbA1c level, independent of glucocorticoid exposure, which may be achieved through a combination of glycemic and nonglycemic effects.
Synthesis, Structures, and Complexation with Phenolic Guests of Acridone‐Incorporated Arylene–Ethynylene Macrocyclic Compounds
Authors: Komori Takashi , Tsurumaki Eiji , Toyota Shinji
Published: November 2022

Acridone units were incorporated into the arylene–ethynylene structure as polar arene units. Cyclic trimers consisting of three acridone‐2,7‐diyl units and three 1,3‐phenylene units were synthesized by Sonogashira couplings via stepwise or direct route. X‐ray analysis revealed that the trimer had a nearly planar macrocyclic framework with a cavity surrounded by three carbonyl groups. In contrast, the corresponding tetramer had a nonplanar macrocyclic framework. 1H NMR measurements showed that the trimer formed a 1 : 1 complex as a macrocyclic host with dihydric phenol guests, and the association constants were determined to be ca. 1.0×103 L mol−1 for hydroquinone or resorcinol guests in CDCl3 at 298 K. The calculated structures of these complexes by the DFT method supported the presence of two sets of OH⋅⋅⋅O=C hydrogen bonds between the host and guest molecules. The spectroscopic data of the cyclic trimers and tetramers are compared with those of reference acridone compounds.
Randomized preclinical study of machine perfusion in vascularized composite allografts
Authors: Amin K R , Stone J P , Kerr J , Geraghty A , Joseph L , Montero-Fernandez A , Wong J K , Fildes J E
Published: November 2022

Background

Attempts to improve limb preservation for transplantation using ex vivo perfusion have yielded promising results. However, metabolic acidosis, aberrant perfusate biochemistry and significant perfusion-induced oedema are reported universally. Optimizing perfusion protocols is therefore essential for maintaining tissue health.

Methods

A randomized, two-stage open preclinical trial design was used to determine the optimal temperature and mean arterial pressure for machine perfusion. Conditions compared were: normothermic machine perfusion at 70 mmHg (NMP-70); subnormothermic perfusion (28°C) at 70 mmHg; subnormothermic (28°C) perfusion at 50 mmHg; and hypothermic perfusion (10°C) at 30 mmHg. Following this, a head-to-head experiment was undertaken comparing the optimal machine perfusion with static cold storage. Paired bilateral limbs (10 in total) were randomized to either 8 h of static cold storage, or 2 h of static cold storage and 6 h of optimal machine perfusion. Both groups of limbs were then reperfused on a circuit primed with matched blood from unrelated donors for 4 h without immunosuppression.

Results

NMP-70 resulted in less tissue injury and stable perfusion biochemistry. Assessing reperfusion outcomes, static cold storage resulted in acidosis with increased lactate and a worsening electrolyte profile, necessitating bolus infusions of bicarbonate to prevent graft loss. Conversely, NMP-70 was associated with haemodynamic and biochemical stability. Histologically, on reperfusion with allogeneic whole blood, limbs subjected to static cold storage exhibited multifocal ischaemic injury and increased inflammation, which was absent with NMP-70. Static cold storage also resulted in significant oedema compared with NMP-70.

Conclusion

Normothermic perfusion resulted in superior graft preservation and less reperfusion injury compared with the current static cold storage protocol.
Enabling Technologies in Carbohydrate Chemistry: Automated Glycan Assembly, Flow Chemistry and Data Science
Authors: Lin Mei‐Huei , Wolf Jakob B. , Sletten Eric T. , Cambié Dario , Danglad‐Flores José , Seeberger Peter H.
Published: November 2022

The synthesis of defined oligosaccharides is a complex task. Several enabling technologies have been introduced in the last two decades to facilitate synthetic access to these valuable biomolecules. In this concept, we describe the technological solutions that have advanced glycochemistry using automated glycan assembly, flow chemistry and data science as examples. We highlight how the synergies between these different technologies can further advance the field, with progress toward the realization of a self‐driving lab for glycan synthesis.
Coupling Value‐Added Anodic Reactions with Electrocatalytic CO2 Reduction
Authors: Xu Zikai , Peng Chen , Zheng Gengfeng
Published: November 2022

Electrocatalytic CO2 reduction features a promising approach to realize carbon neutrality. However, its competitiveness is limited by the sluggish oxygen evolution reaction (OER) at anode, which consumes a large portion of energy. Coupling value‐added anodic reactions with CO2 electroreduction has been emerging as a promising strategy in recent years to enhance the full‐cell energy efficiency and produce valuable chemicals at both cathode and anode of the electrolyzer. This review briefly summarizes recent progresses on the electrocatalytic CO2 reduction, and the economic feasibility of different CO2 electrolysis systems is discussed. Then a comprehensive summary of recent advances in the coupled electrolysis of CO2 and potential value‐added anodic reactions is provided, with special focus on the specific cell designs. Finally, current challenges and future opportunities for the coupled electrolysis systems are proposed, which are targeted to facilitate progress in this field and push the CO2 electrolyzers to a more practical level.
Magnetically Induced CO2 Methanation In Continuous Flow Over Supported Nickel Catalysts with Improved Energy Efficiency
Authors: Ghosh Sourav , Ourlin Thibault , Fazzini Pier‐Francesco , Lacroix Lise‐Marie , Tricard Simon , Esvan Jerome , Cayez Simon , Chaudret Bruno
Published: November 2022

A new selective and efficient catalytic system for magnetically induced catalytic CO2 methanation was developed, composed of an abundant iron‐based heating agent, namely a commercial iron wool, combined with supported Nickel nanoparticles (Ni NPs) as catalysts. The effect of metal oxide support was evaluated by preparing different 10 wt % Ni catalyst (TiO2, ZrO2, CeO2, and CeZrO2) via organometallic decomposition route. As‐prepared catalysts were thoroughly characterized using powder X‐ray diffraction, electron microscopy, elemental analysis, vibrating sample magnetometer, and X‐ray photoelectron spectroscopy techniques. High conversion and selectivity toward methane were observed at mid‐temperature range, hence improving energy efficiency of the process with respect to the previous results under magnetic heating conditions. To gain further insight into the catalytic system, the effects of the synthesis method and of 0.5 wt % Ru doping were evaluated. Finally, the dynamic nature of magnetically induced heating was demonstrated through fast stop‐and‐go experiments, proving the suitability of this technology for the storage of intermittent renewable energy through P2G process.
Catalytic Stereoselective Multicomponent Reactions for the Synthesis of Spiro Derivatives: Recent Progress
Authors: Patel Divyang M. , Patel Paras J. , Patel Hitendra M.
Published: November 2022

Spiro derivatives are important scaffolding substances found in many natural products and pharmaceuticals. In the last decade, numerous new approaches based on multicomponent reactions have been explored for the selective and efficient development of new spiro derivatives using various organocatalytic and transition metal‐based catalytic systems. This Review discusses pioneering advances in the field of catalytic stereoselective multicomponent reactions for the preparation of various spiro derivatives. These include stereoselective Michael cascade cyclization reactions, cycloadditions, diastereoselective reactions, and miscellaneous reactions for the synthesis of spiro‐hetero/carbocycles. Advances in the last decade have made it possible to synthesize various spiro compounds with good to excellent stereoselectivity under appropriate reaction conditions. However, achieving high regioselectivity in several described multicomponent reactions remains a challenge. Organocatalysts and transition‐metal‐based catalysts play a crucial role in achieving this milestone. Proposed catalytic mechanisms and supporting evidence are highlighted in this Review. The progress described in catalytic stereoselective approaches for spiro derivatives is immense. However, it is expected that new stereoselective synthetic methods will soon be developed that can be widely used for the preparation of spiro‐heterocycles/carbocycles.
Cross‐Dehydrogenative Homocoupling of 2‐Aryl‐N‐heterocycles and Application to the Synthesis of Phenylpyridine Borane Dimers
Authors: Gao Longhui , Feuillastre Sophie , Clavier Gilles , Pieters Grégory
Published: November 2022

A method for the synthesis of 2‐aryl‐N‐heterocyclic dimers via a cross‐dehydrogenative homocoupling (homo‐CDC) has been developed using commercially available Ruthenium on charcoal as catalyst and iron trichloride as oxidant. A large variety of heterocyclic scaffolds and functional groups are tolerated and a complete regioselectivity resulting from the activation of the less sterically hindered C−H bonds was observed for meta‐substituted substrates. Starting from several homocoupling products obtained, a series of pyridine‐borane complexes was synthesized and the impact of the dimerization on their photophysical properties was studied and rationalized using theoretical calculations.