bluuebunny/crossref_metadata_2025 huggingface dataset:
A Workforce Development Systems Model for Unemployed Job Seekers
Authors: Holland Brian
Published: May 2018

Workforce development is a set of processes that govern the identification, recruitment, assessment and training of job seekers into employment as well as the maintenance and advancement of these persons in their careers. Given the complexity of what workforce development entails, a systems approach is illustrated to ensure that the broader goal of human capital investment is met. The paper identifies the foundational assumptions of systems thinking, classifies the key stakeholders in workforce development and provides brief case studies on where systems thinking has been deployed. The paper also enunciates an outcomes framework to give the metrics by which progress towards performance goals can be measured.
The Status of Continuing Higher Education at German Universities: A Metaphor Analysis
Authors: Franz Melanie , Feld Timm C.
Published: May 2018

Many European countries are currently witnessing an increased development and expansion of continuing higher education at universities. In Germany, this development has until now been rather modest in comparison to countries such as England, France, Finland and the United States. The status of continuing education still seems just as unclear as the actual management of the implementation processes, something that is evident not least in the language or linguistic expressions used by those responsible for implementing continuing higher education. Systematically analysing language, and in particular metaphors, allows us to illuminate how meaning is attributed, and the challenges faced, by those implementing continuing higher education at universities. Based on two case studies from Germany, this paper demonstrates which perspectives and problems can lie hidden behind metaphors, and which effects this can have on how the implementation of continuing higher education is perceived and shaped.
Widening the Participation into Higher Education: Examining Bourdieusian Theory in Relation to HE in the UK
Authors: Burnell Iona
Published: May 2018

Bourdieu's theories enable us to conceptualise and understand why some people participate in higher education and some do not. Focussing on the working class as the marginalised social group in HE, Bourdieu demonstrated how education perpetuates inequality and lack of opportunity. The theories, or ‘thinking tools' as he called them, provide an explanation for why the working class do not participate in HE on the same scale as the middle and upper classes. Habitus, for example, enables us to understand that we have ‘a sense of one's place which leads one to exclude oneself from places from which one is excluded’ (Bourdieu, 1984: 471). I examine the theories in the context of my own research and explore my participants' experiences of HE using Bourdieu's theoretical framework. However, my research findings do not support an uncritical application of Bourdieu's theories; rather that one's habitus can change to accommodate new practices, and once that change has occurred, it is socially reproduced. The findings of the research are based on interviews with ten participants, all of whom are or have been mature working class students in higher education.
Eumycetoma on histopathology presenting at unusual site: A rare entity.
Authors: Shah Rajan , Karki Smriti , Rai Ujawal , Kafle Shankar
Published: May 2018

Mycetoma, an uncommon chronic infection of skin and subcutaneous tissues commonly seen in tropical and subtropical countries. It is caused by true mycetes named eumycetoma and filamentous bacteria belonging to group actinomycetes. The incidence is more common in agricultural workers walking in bare foot. Foot is most commonly affected. Other less commonly affected sites includes hand, knee, chest and head and neck region. Both forms of mycetoma present as a progressive, subcutaneous multiple nodular swelling with discharging sinuses containing black colour granules. The treatment of these two etiologies is entirely different, a definite diagnosis after histopathological examination is mandatory. We here by present a case of eumycetoma affecting knee joint.
Hand hygiene: A self reported practice among health care workers in tertiary health institutions in Plateau State, Nige
Authors: Afolaranmi Tolulope , Zuwaira I Hassan , Enoch N Nianglong , Issac I Adem , Azi B Atsi , Kenneth I Onyedibe , Danjuma A Bello
Published: May 2018

Background: Effective hand hygiene is the simplest proven and most cost effective means of reducing hospital acquired infections both among the health care providers and the receipts of health care services.   Hospital acquired infections have currently been identified as one of the challenges of health care delivery worldwide in view of its contribution to morbidity and mortality. Hence, it became imperative to assess the knowledge and practices of hand hygiene as well as its determinant among frontline health care workers in tertiary health institutions in Jos Plateau state Nigeria.Methodology: This was a cross sectional study conducted among 236 health care workers in two tertiary health institutions using quantitative method of data collection. Epi info version 7 was used for data analysis, Chi square test was used with odds ratio as point estimates and 95% confidence interval as the interval estimate. A probability value of less than 0.05 was considered statistically significant.Results: The mean age of the respondents was 37.1 ± 7.2 years while 121 (51.3%) of the respondents had good knowledge of hand hygiene and self reported good hand hygiene practice found among 134 (56.8%) of the health care workers.Conclusion: This study has brought to light the unsatisfactory level of practice of hand hygiene among health workers and the need to urgently provide interventions to addressing it.
Occupational fatigue score and risk of preterm birth
Authors: Bansal Aditi , Surbhi Saini , Srivastava Ankita , Rajoria Lata , Shweta Gangal
Published: May 2018

The aim of this study was to determine the elements of fatigue in occupations which constitute possible risk factors for the course of a pregnancy, and, in particular, that could cause premature birth. A total of 400 women with singleton pregnancies at ≥ 28 weeks’ gestation were enrolled in the study conducted at the Labor room,  Zenana Hospital , Jaipur. Patients reported the number of hours worked per week and answered specific questions designed to determine the following 5 sources of occupational fatigue: posture, work with industrial machines, physical exertion, mental stress, and environmental stress. Fatigue was quantified (0-5 index) according to the number of these sources positively reported. Simple and Mantel-Haenszel χ2 tests were used to test the univariate association and hypothesis of a linear trend between sources of occupational fatigue and spontaneous preterm delivery. Covariables were considered by multivariate logistic regression analysis. Women who did not work outside the home were considered separately from those who worked but did not report any sources of occupational fatigue.Result: women with sternous activity had higher occurrence of preterm birth. 18 % preterm mothers had high occupational fatigue index as compared to 75% term mothers, with p value <0.1,which was significant.
Temporospatial induction of homeodomain gene cut dictates natural lineage reprogramming
Authors: Xu Ke , Liu Xiaodan , Wang Yuchun , Wong Chouin , Song Yan
Published: May 2018

Understanding how cellular identity naturally interconverts with high efficiency and temporospatial precision is crucial for regenerative medicine. Here, we revealed a natural midgut-to-renal lineage conversion event during Drosophila metamorphosis and identified the evolutionarily-conserved homeodomain protein Cut as a master switch in this process. A steep Wnt/Wingless morphogen gradient intersects with a pulse of steroid hormone ecdysone to induce cut expression in a subset of midgut progenitors and reprogram them into renal progenitors. Molecularly, ecdysone-induced temporal factor Broad physically interacts with cut enhancer-bound Wnt pathway effector TCF/β-catenin and likely bridges the distant enhancer and promoter region of cut through its self-association. Such long-range enhancer-promoter looping could subsequently trigger timely cut transcription. Our results therefore led us to propose an unexpected poising-and-bridging mechanism whereby spatial and temporal cues intersect, likely via chromatin looping, to turn on a master transcription factor and dictate efficient and precise lineage reprogramming.
Distinct chromatin functional states correlate with HIV latency reactivation in infected primary CD4+ T cells
Authors: Battivelli Emilie , Dahabieh Matthew S , Abdel-Mohsen Mohamed , Svensson J Peter , Tojal Da Silva Israel , Cohn Lillian B , Gramatica Andrea , Deeks Steven , Greene Warner C , Pillai Satish K , Verdin Eric
Published: May 2018

Human immunodeficiency virus (HIV) infection is currently incurable, due to the persistence of latently infected cells. The ‘shock and kill’ approach to a cure proposes to eliminate this reservoir via transcriptional activation of latent proviruses, enabling direct or indirect killing of infected cells. Currently available latency-reversing agents (LRAs) have however proven ineffective. To understand why, we used a novel HIV reporter strain in primary CD4+ T cells and determined which latently infected cells are reactivatable by current candidate LRAs. Remarkably, none of these agents reactivated more than 5% of cells carrying a latent provirus. Sequencing analysis of reactivatable vs. non-reactivatable populations revealed that the integration sites were distinguishable in terms of chromatin functional states. Our findings challenge the feasibility of ‘shock and kill’, and suggest the need to explore other strategies to control the latent HIV reservoir.
SET-9 and SET-26 are H3K4me3 readers and play critical roles in germline development and longevity
Authors: Wang Wenke , Chaturbedi Amaresh , Wang Minghui , An Serim , Santhi Velayudhan Satheeja , Lee Siu Sylvia
Published: May 2018

C. elegans SET-9 and SET-26 are highly homologous paralogs that share redundant functions in germline development, but SET-26 alone plays a key role in longevity and heat stress response. Whereas SET-26 is broadly expressed, SET-9 is only detectable in the germline, which likely accounts for their different biological roles. SET-9 and SET-26 bind to H3K4me3 with adjacent acetylation marks in vitro and in vivo. In the soma, SET-26 acts through DAF-16 to modulate longevity. In the germline, SET-9 and SET-26 restrict H3K4me3 domains around SET-9 and SET-26 binding sites, and regulate the expression of specific target genes, with critical consequence on germline development. SET-9 and SET-26 are highly conserved and our findings provide new insights into the functions of these H3K4me3 readers in germline development and longevity.
Is the future already here? The impact of climate change on the distribution of the eastern coral snake (Micrurus fulvius)
Authors: Archis Jennifer N. , Akcali Christopher , Stuart Bryan L. , Kikuchi David , Chunco Amanda J.
Published: May 2018

Anthropogenic climate change is a significant global driver of species distribution change. Although many species have undergone range expansion at their poleward limits, data on several taxonomic groups are still lacking. A common method for studying range shifts is using species distribution models to evaluate current, and predict future, distributions. Notably, many sources of ‘current’ climate data used in species distribution modeling use the years 1950–2000 to calculate climatic averages. However, this does not account for recent (post 2000) climate change. This study examines the influence of climate change on the eastern coral snake (Micrurus fulvius). Specifically, we: (1) identified the current range and suitable environment of M. fulvius in the Southeastern United States, (2) investigated the potential impacts of climate change on the distribution of M. fulvius, and (3) evaluated the utility of future models in predicting recent (2001–2015) records. We used the species distribution modeling program Maxent and compared both current (1950–2000) and future (2050) climate conditions. Future climate models showed a shift in the distribution of suitable habitat across a significant portion of the range; however, results also suggest that much of the Southeastern United States will be outside the range of current conditions, suggesting that there may be no-analog environments in the future. Most strikingly, future models were more effective than the current models at predicting recent records, suggesting that range shifts may already be occurring. These results have implications for both M. fulvius and its Batesian mimics. More broadly, we recommend future Maxent studies consider using future climate data along with current data to better estimate the current distribution.
Salt marsh sediment bacterial communities maintain original population structure after transplantation across a latitudinal gradient
Authors: Angermeyer Angus , Crosby Sarah C. , Huber Julie A.
Published: May 2018

Dispersal and environmental selection are two of the most important factors that govern the distributions of microbial communities in nature. While dispersal rates are often inferred by measuring the degree to which community similarity diminishes with increasing geographic distance, determining the extent to which environmental selection impacts the distribution of microbes is more complex. To address this knowledge gap, we performed a large reciprocal transplant experiment to simulate the dispersal of US East Coast salt marsh Spartina alterniflora rhizome-associated microbial sediment communities across a latitudinal gradient and determined if any shifts in microbial community composition occurred as a result of the transplantation. Using bacterial 16S rRNA gene sequencing, we did not observe large-scale changes in community composition over a five-month S. alterniflora summer growing season and found that transplanted communities more closely resembled their origin sites than their destination sites. Furthermore, transplanted communities grouped predominantly by region, with two sites from the north and three sites to the south hosting distinct bacterial taxa, suggesting that sediment communities transplanted from north to south tended to retain their northern microbial distributions, and south to north maintained a southern distribution. A small number of potential indicator 16S rRNA gene sequences had distributions that were strongly correlated to both temperature and nitrogen, indicating that some organisms are more sensitive to environmental factors than others. These results provide new insight into the microbial biogeography of salt marsh sediments and suggest that established bacterial communities in frequently-inundated environments may be both highly resistant to invasion and resilient to some environmental shifts. However, the extent to which environmental selection impacts these communities is taxon specific and variable, highlighting the complex interplay between dispersal and environmental selection for microbial communities in nature.
Implantação de Práticas de Ti Verde no Setor de Correios e Arquivos do Departamento de Suporte Administrativo da Polícia Militar do Estado de São Paulo
Authors: Penha Marcelo , Paschoalin Filho João Alexandre , De Faria Ana Cristina
Published: May 2018

Este trabalho tem por intuito relatar a implantação de ferramentas baseadas no conceito de TI Verde no Setor de Correios e Arquivos do Departamento de Suporte Administrativo do Comando Geral (DSACG) da Polícia Militar do Estado de São Paulo (PMESP), de forma a reduzir o consumo de insumos de impressão e os impactos ambientais decorrentes desta atividade. Esta pesquisa qualitativa, também pode ser classificada como exploratória, pois desenvolveu uma análise rotinas administrativas existentes no Setor de Correio e Arquivo do DSACG. Foi empregada neste trabalho a metodologia da Pesquisa-Ação, pelo fato de os pesquisadores e colaboradores da organização estarem envolvidos e interagirem de maneira cooperativa e participante na resolução do problema em estudo. Para cumprir os objetivos desta pesquisa, foi realizado um diagnóstico prévio do Setor, identificando seu funcionamento e rotinas. Em seguida, foi realizada capacitação dos colaboradores do setor no intuito de conscientizá-los acerca da importância da necessidade ambiental e financeira da redução do consumo de insumos de impressão. A seguir, foram implantadas ações de TI Verde, as quais foram monitoradas e avaliadas. Por meio dos resultados obtidos, foi possível verificar a significativa redução no consumo e custos de insumos de impressão, bem como a diminuição do impacto ambiental causado pelas rotinas administrativas do setor.
El presupuesto participativo de Madrid: luces y sombras
Authors: Nebot Carmen Pineda
Published: May 2018

Curiosamente cuando en Brasil, país origen del Presupuesto Participativo, surgen muchas dificultades para su continuidad en comparación con otras innovaciones democráticas, en España comienzan a ponerse en marcha nuevas experiencias. Los cambios de gobierno, producidos después de las elecciones municipales de 2015, han provocado que muchos ayuntamientos importantes, entre ellos el de Madrid, gobernados por coaliciones de izquierda hayan decidido, como se señalaba en sus programas electorales, incorporar el Presupuesto Participativo a su proyecto de gobierno. Esta comunicación tiene como objetivo analizar, desde el conocimiento adquirido en los 25 años de funcionamiento del Presupuesto Participativo, la nueva experiencia puesta en marcha en el Ayuntamiento de Madrid. Para ello se realizará un análisis documental tanto de la experiencia en sí como de los procesos pilotos realizados durante 2015 en algunos distritos de la ciudad y se analizarán los discursos y entrevistas con miembros del gobierno municipal y de lo demás partidos presentes en el ayuntamiento.
Dilemas Morais na Gestão Pública: o estado do conhecimento sobre o tema
Authors: Santos Laís Silveira , Serafim Mauricio C. , Lorenzi Larissa
Published: May 2018

Na tomada de decisão entre conjuntos de valores pode ocorrer a formação de dilemas morais que não aceitam todas as alternativas possíveis de ação para resolvê-los, que possuem difíceis saídas e o conflito como característica crucial. O objetivo do artigo é construir um estado do conhecimento sobre o tema dilemas morais, de modo a compreender como eles estão sendo estudados na gestão pública. Para tanto, foi realizada uma revisão sistemática de literatura, por meio do Portal da EBSCOhost que, após a aplicação de critérios de seleção, resultou em um total de 28 artigos para análise. Os estudos indicam que os dilemas podem existir não apenas entre valores no âmbito individual, mas também entre diferentes culturas e valores organizacionais. As motivações para o estudo dos dilemas morais estão associadas à necessidade do gestor de tomar uma decisão frente a um dilema, uma vez que a maioria deles precisa de mais informações para avaliar os caminhos de ação quando se envolve a tomada de decisão, principalmente quando relacionada a um assunto de interesse público. A liderança, a competência moral e o ensino de ética são apontados como aspectos relevantes no enfrentamento de dilemas que não podem ser respondidos somente a partir de critérios técnicos. Por fim, indica-se a necessidade de discutir quais são os dilemas vivenciados na gestão pública brasileira diante da complexidade de sua gestão. Entretanto, se utilizadas teorias e métodos internacionais de análise, é importante considerar a realização de uma ‘redução sociológica’ como método de assimilação crítica de teorias estrangeiras.
Narrativas de uma Bacharela sobre A Construção de Suas Práticas de Professora na Universidade Pública
Authors: Souza Rosalia Beber , Ribeiro Douglas Candido
Published: May 2018

Este estudo de caso objetiva traçar reflexões acerca da formação de professores, especificamente em uma universidade pública, com base nos relatos obtidos através das histórias pedagógicas de uma bacharela que se tornou professora. Constatou-se que a identidade profissional da participante foi construída calcada em seus modelos de professores durante a vida escolar bem como em métodos de ensino. Percebeu-se também que suas crenças a respeito de ensino e aprendizagem foram adquiridas e fortificadas ao longo do tempo. Mais precisamente, a ênfase de nossa análise é dada nas ligações significativas entre as experiências passadas e as práticas atuais desta profissional em uma universidade pública que não teve formação específica para atuar como professora durante sua graduação.
Produção sobre Educação Corporativa no Brasil: um estudo bibliométrico
Authors: Toledo Gustavo Sousa , Domingues Carlos Roberto
Published: May 2018

Este artigo tem como objetivo identificar e analisar a produção acadêmica sobre o tema “Educação Corporativa” nos últimos 20 anos. O procedimento metodológico utilizado foi a Pesquisa Bibliométrica. Para tanto foram pesquisados os trabalhos acadêmicos através das plataformas Portal Spell, Periódicos Capes e nos periódicos ligados a Anpad, como a BAR – Brazilian Administration Review, a RAC – Revista de Administração Contemporânea, a TAC – Tecnlogia de Administração e Contabilidade e a RAC Eletrônica. E, a partir da análise dos dados, pode-se afirmar que a pesquisa vai ao encontro com que os principais autores do tema Educação Corporativa e Gestão de Pessoas têm afirmado em suas obras contemporâneas. As áreas de Recursos Humanos dentro das organizações vêm deixando de ser meras coadjuvantes e desfrutadora de recursos financeiros, para finalmente terem seus valores estratégicos reconhecidos e assim serem trabalhadas como tais. Os estudos reforçam, cada vez mais, que a gestão de pessoas, desde que bem definido seu papel e alinhamento com a estratégia da organização, pode gerar uma elevada taxa de variação positiva de desempenho organizacional e produtividade.
Impact of a clinical pharmacist–managed clinic in primary care mental health integration at a Veterans Affairs health system
Authors: Herbert Christina , Winkler Holly
Published: May 2018

Introduction:

The demand for mental health (MH) services has increased as more veterans seek MH care. At the South Texas Veterans Health Care System, Primary Care Mental Health Integration (PCMHI) was developed to manage patients with uncomplicated MH conditions, including depression, anxiety, or posttraumatic stress disorder (PTSD), within an interdisciplinary primary care (PC) team that includes clinical pharmacy specialists (CPSs). Pharmacists have improved outcomes and access to care for many chronic medical conditions, but limited data demonstrate the impact of MH pharmacists within PC.

Methods:

This project evaluated the impact of a PCMHI CPS clinic on managing patients with recent antidepressant initiation and CPS clinic intake from September 2015 through December 2016, including follow-up through January 2017. Markers used to evaluate effectiveness of the service included the Patient Health Questionnaire-9 scores, antidepressant medication possession ratio, number of emergency department visits for MH-related concerns, patient engagement in concurrent psychotherapy, and referrals to specialty MH providers.

Results:

A total of 196 unique patients had intake with the PCMHI CPS in the time specified; 172 of these patients were included in analyses. There were 155 patients maintained in PC. Average Patient Health Questionnaire-9 scores decreased from 14.5 to 8.5, with 63 patients (46%) achieving response and 42 patients (31%) achieving remission. The average antidepressant medication possession ratio was 0.93 for all included patients.

Discussion:

A PCMHI CPS successfully manages and maintains patients with uncomplicated MH conditions in PC through evidence-based pharmacotherapy, as evidenced by symptom improvement, medication adherence, and low rate of specialty MH referrals.
Preliminary evaluation of the efficacy, safety, and costs associated with the treatment of chronic pain with medical cannabis
Authors: Bellnier Terrance , Brown Geoffrey W. , Ortega Tulio R.
Published: May 2018

Introduction:

Medical cannabis (MC) is commonly claimed to be an effective treatment for chronic or refractory pain. With interest in MC in the United States growing, as evidenced by the 29 states and 3 US districts that now have public MC programs, the need for clinical evidence supporting this claim has never been greater.

Methods:

This was a retrospective, mirror-image study that investigated MC's effectiveness in patients suffering from chronic pain associated with qualifying conditions for MC in New York State. The primary outcome was to compare European Quality of Life 5 Dimension Questionnaire (EQ-5D) and Pain Quality Assessment Scale (PQAS) scores at baseline and 3 months post-therapy. The secondary outcomes included comparisons of monthly analgesic prescription costs and opioid consumption pre- and post-therapy. Tolerability was assessed by side effect incidence.

Results:

This investigation included 29 subjects. Quality of life and pain improved, measured by change in EQ-5D (Pre 36 – Post 64, P < .0001) and change in PQAS paroxysmal (Pre 6.76 – Post 2.04, P < .0001), surface (Pre 4.20 – Post 1.30, P < .0001), deep (Pre 5.87 – Post 2.03, P < .0001), unpleasant (Pre “miserable” – Post “annoying”, P < .0001). Adverse effects were reported in 10% of subjects.

Discussion:

After 3 months treatment, MC improved quality of life, reduced pain and opioid use, and lead to cost savings. Large randomized clinical trials are warranted to further evaluate the role of MC in the treatment of chronic pain.
Antipsychotic discontinuation after the initiation of selective serotonin reuptake inhibitors therapy for the treatment of behavioral and psychological symptoms associated with dementia
Authors: Mathys Monica , Fang Steven , John Jini , Carter Jasmine
Published: May 2018

Introduction:

Antipsychotics are used off label to treat behavioral and psychological symptoms of dementia (BPSD). Due to the emerging data of selective serotonin reuptake inhibitors (SSRIs) for treatment of BPSD, clinicians may choose to use this medication class instead of antipsychotics when pharmacologic therapy is necessary. The objective of this study was to evaluate the prevalence of antipsychotic discontinuation 6 months after SSRI initiation for the treatment of BPSD.

Methods:

Patients with Alzheimer dementia who were prescribed an antipsychotic and later prescribed an SSRI for BPSD during January 1, 2009, through December 30, 2014, were studied. Exclusion criteria included (1) a dementia diagnosis besides Alzheimer; (2) scheduled benzodiazepines, mood stabilizers, or non-SSRI antidepressant use during the study period; (3) diagnoses of bipolar or psychotic disorders; and (4) diagnosis of delirium during the study period. Patients' age, sex, race, and functional assessment of staging for Alzheimer disease scores were collected. The names, doses, and stop dates of SSRIs and antipsychotics were also recorded.

Results:

Thirty-six patients were included in the analyses. Overall, antipsychotic use was reduced in 11 patients (30.6%). Ten patients (27.8%) discontinued the antipsychotic, and 1 additional patient had a reduction in dose. When comparing specific SSRIs, 8 (72%) responders were prescribed citalopram, and 15 (60%) nonresponders were prescribed sertraline.

Discussion:

Approximately 30% of patients with Alzheimer dementia who were prescribed antipsychotics for BPSD were able to discontinue the medication or had a dose reduction after starting SSRI therapy. Most SSRI responders were prescribed citalopram.
Políticas para culturas digitais no Brasil
Authors: Rubim Antonio Albino Canelas , Rubim Iuri Oliveira
Published: May 2018

Após uma breve introdução às configurações da sociabilidade e da cultura contemporâneas, o texto se debruça sobre as políticas desenvolvidas no Brasil para as culturas digitais, em especial no Governo Lula, nas gestões de Gilberto Gil e Juca Ferreira no Ministério da Cultura.
Disilylation of Palladacycles that were Generated through the C−H Activation of Aryl Halides
Authors: Ma Xiaotian , Lu Ailan , Ji Xiaoming , Shi Guangfa , Zhang Yanghui
Published: May 2018

The reactions of various C,C‐palladacycles that were generated through the C−H activation of aryl halides with disilanes have been studied. The reaction of arylnorbornyl palladacycles, which were generated through a Catellani reaction, with hexamethyldisilane proceeded very efficiently to afford disilylated products. Palladacycles that were obtained through the remote C−H activation of aryl halides that contained a styrene moiety with an ether linkage also underwent a disilylation reaction with hexamethyldisilane. Furthermore, the reactions of dibenzopalladacyclopentadienes, which were generated from 2‐iodobiphenyls, with diphenyltetramethyldisilane were also investigated and a range of 2‐iodobiphenyls were disilylated in moderate yields.
Supramolecular Reassembly of Self‐Exfoliated Ionic Covalent Organic Nanosheets for Label‐Free Detection of Double‐Stranded DNA
Authors: Mal Arindam , Mishra Rakesh K. , Praveen Vakayil K. , Khayum M. Abdul , Banerjee Rahul , Ajayaghosh Ayyappanpillai
Published: May 2018

Ionic covalent organic nanosheets (iCONs), a member of the two‐dimensional (2D) nanomaterials family, offer a unique functional platform for a wide range of applications. Herein, we explore the potential of an ethidium bromide (EB)‐based covalent organic framework (EB‐TFP) that self‐exfoliates in water resulting in 2D ionic covalent organic nanosheets (EB‐TFP‐iCONs) for the selective detection of double‐stranded DNA (dsDNA). In an aqueous medium, the self‐exfoliated EB‐TFP‐iCONs reassemble in the presence of dsDNA resulting in hybrid EB‐TFP‐iCONs‐DNA crystalline nanosheets with enhanced fluorescence at 600 nm. Detailed steady‐state and time‐resolved emission studies revealed that the reassembly phenomenon was highly selective for dsDNA when compared to single‐stranded DNA (ssDNA), which allowed us to use the EB‐TFP‐iCONs as a 2D fluorescent platform for the label‐free detection of complementary DNA strands.
Bifunctional Electrocatalysts for Overall Water Splitting from an Iron/Nickel‐Based Bimetallic Metal–Organic Framework/Dicyandiamide Composite
Authors: Zhao Xiaojia , Pachfule Pradip , Li Shuang , Simke Jan Ron Justin , Schmidt Johannes , Thomas Arne
Published: May 2018

Pyrolysis of a bimetallic metal–organic framework (MIL‐88‐Fe/Ni)‐dicyandiamide composite yield a Fe and Ni containing carbonaceous material, which is an efficient bifunctional electrocatalyst for overall water splitting. FeNi3 and NiFe2O4 are found as metallic and metal oxide compounds closely embedded in an N‐doped carbon–carbon nanotube matrix. This hybrid catalyst (Fe‐Ni@NC‐CNTs) significantly promotes the charge transfer efficiency and restrains the corrosion of the metallic catalysts, which is shown in a high OER and HER activity with an overpotential of 274 and 202 mV, respectively at 10 mA cm−2 in alkaline solution. When this bifunctional catalyst was further used for H2 and O2 production in an electrochemical water‐splitting unit, it can operate in ambient conditions with a competitive gas production rate of 1.15 and 0.57 μL s−1 for hydrogen and oxygen, respectively, showing its potential for practical applications.
Synthesis of 5‐Cyano‐Tryptophan as a Two‐Dimensional Infrared Spectroscopic Reporter of Structure
Authors: Chalyavi Farzaneh , Gilmartin Philip H. , Schmitz Andrew J. , Fennie Michael W. , Tucker Matthew J.
Published: May 2018

A concise synthesis of protected 5‐cyano‐l‐tryptophan (Trp5CN) has been developed for 2D IR spectroscopic investigations within either peptides or proteins. To assess the potential of differently substituted cyano‐tryptophans, several model cyano‐indole systems were characterized using IR spectroscopy. Upon assessment of their spectroscopic properties, Trp5CN was integrated into a model peptide sequence, Trp5CN‐Gly‐Phe4CN, to elucidate its structure. This peptide demonstrates the capability of this probe to capture structural information by 2D IR spectroscopy. The 2D IR spectrum of the peptide in water was simulated to reveal a unique spectral signature resulting from the presence of dipolar coupling. The coupling strength between cyano labels was determined to be 1.4 cm−1 by matching the slopes along the max contour for the simulated and experimental spectrum. Using transition dipole coupling, a distance between the two probes of 13 Å was calculated.
Synthesis of β‐Substituted γ‐Aminobutyric Acid Derivatives through Enantioselective Photoredox Catalysis
Authors: Ma Jiajia , Lin Jiahui , Zhao Lifang , Harms Klaus , Marsch Michael , Xie Xiulan , Meggers Eric
Published: May 2018

β‐Substituted chiral γ‐aminobutyric acids feature important biological activities and are valuable intermediates for the synthesis of pharmaceuticals. Herein, an efficient catalytic enantioselective approach for the synthesis of β‐substituted γ‐aminobutyric acid derivatives through visible‐light‐induced photocatalyst‐free asymmetric radical conjugate additions is reported. Various β‐substituted γ‐aminobutyric acid analogues, including previously inaccessible derivatives containing fluorinated quaternary stereocenters, were obtained in good yields (42–89 %) and with excellent enantioselectivity (90–97 % ee). Synthetically valuable applications were demonstrated by providing straightforward synthetic access to the pharmaceuticals or related bioactive compounds (S)‐pregabalin, (R)‐baclofen, (R)‐rolipram, and (S)‐nebracetam.
Synthesis of Renewable meta‐Xylylenediamine from Biomass‐Derived Furfural
Authors: Scodeller Ivan , Mansouri Samir , Morvan Didier , Muller Eric , de Oliveira Vigier Karine , Wischert Raphael , Jérôme François
Published: May 2018

We report the synthesis of biomass‐derived functionalized aromatic chemicals from furfural, a building block nowadays available in large scale from low‐cost biomass. The scientific strategy relies on a Diels–Alder/aromatization sequence. By controlling the rate of each step, it was possible to produce exclusively the meta aromatic isomer. In particular, through this route, we describe the synthesis of renewably sourced meta‐xylylenediamine (MXD). Transposition of this work to other furfural‐derived chemicals is also discussed and reveals that functionalized biomass‐derived aromatics (benzaldehyde, benzylamine, etc.) can be potentially produced, according to this route.
A Redox‐Active Bridging Ligand to Promote Spin Delocalization, High‐Spin Complexes, and Magnetic Multi‐Switchability
Authors: Ma Xiaozhou , Suturina Elizaveta A. , De Siddhartha , Négrier Philippe , Rouzières Mathieu , Clérac Rodolphe , Dechambenoit Pierre
Published: May 2018

A dinuclear CoII complex, [Co2(tphz)(tpy)2]n+ (n=4, 3 or 2; tphz: tetrapyridophenazine; tpy: terpyridine), has been assembled using the redox‐active and strongly complexing tphz bridging ligand. The magnetic properties of this complex can be tuned from spin‐crossover with T1/2≈470 K for the pristine compound (n=4) to single‐molecule magnet with an ST=5/2 spin ground state when once reduced (n=3) to finally a diamagnetic species when twice reduced (n=2). The two successive and reversible reductions are concomitant with an increase of the spin delocalization within the complex, promoting remarkably large magnetic exchange couplings and high‐spin species even at room temperature.
Experimental study of the combustion and NO emission behaviors during cofiring coal and biomass in O2/N2 and O2/H2O
Authors: Li Yuan , Zhou Hao , Li Ning , Tao Chengfei , Liu Zihua , Cen Kefa
Published: May 2018

Oxy‐H2O is considered to be a new generation of carbon capture and storage technology. The combustion and NO emission behaviors during co‐combustion in O2/N2 and O2/H2O were studied simultaneously in an isothermal thermogravimetric system, including the influence of blending ratio, coal type, biomass type, and oxygen concentration. The results show that replacing N2 by H2O accelerates the burning rate of a blend significantly and reduces the NO emission obviously. In O2/N2 and O2/H2O, blending biomass improves the burning rate and reduces the NO emission. The improvement of H2O on burning rate becomes weak with increasing blending ratio. There is an interactive effect on NO emission during co‐combustion in both atmospheres. For cofiring bituminous coal and poplar wood, the NO yield decreases with increasing blending ratio, whereas the NO conversion ratio increases in both atmospheres. As different coal ranks blend with a certain biomass, the blend with a higher coal rank results in a more obvious improvement of burning rate and a higher NO conversion ratio in both atmospheres. As a coal blends with different biofuels, a higher volatile biofuel leads to a higher burning rate in O2/N2, whereas this behavior is not obvious in O2/H2O. Blending coal with a higher nitrogen biofuel results in a lower NO conversion ratio in both atmospheres. In both atmospheres, the burning rate and NO conversion ratio of a blend both increase, as the oxygen concentration increases from 21% to 30%. The results provide direct guidance for the application of co‐combustion in O2/H2O.
Palladium‐Catalyzed Divergent Arylation of Triazolopyridines: A Computational Study
Authors: AbuSalim Deyaa I. , Hong Sungwoo , Baik Mu‐Hyun
Published: May 2018

The mechanisms for new palladium‐catalyzed divergent reactions of triazolopyridines were investigated by means of DFT calculations. Previously, it was observed experimentally that cross‐coupling at the C7‐position of triazolopyridines occurred when a strong base was used, whereas the reaction could be diverted to the C3‐position if a weak base was employed. Calculations suggest that a strong base, such as tert‐butoxide, can easily deprotonate C7−H, independent of the palladium metal, and deliver the preactivated substrate to palladium, which can reductively eliminate the final product. Without a strong base, the palladium(II) center reacts with the ring‐opened diazo imine isomer of triazolopyridine to initially form a palladium(II)–carbene intermediate, which undergoes migratory insertion followed by β‐hydride elimination to afford a 1,1‐disubstituted alkene.
Tetrafluorination of Aromatic Azide Yields a Highly Efficient Staudinger Reaction: Kinetics and Biolabeling
Authors: Xie Yonghui , Cheng Longhuai , Gao Yasi , Cai Xuekang , Yang Xing , Yi Long , Xi Zhen
Published: May 2018

The development of highly efficient bioorthogonal reactions is of paramount importance for the research fields of biomaterials and chemical biology. We found that the o,o′‐difluorinated aromatic azide was able to react with triphenylphosphine to produce water‐stable phosphanimine. To further improve the efficiency of this kind of nonhydrolysis Staudinger reaction, a tetrafluorinated aromatic azide was employed to develop a faster nonhydrolysis Staudinger reaction with a rate of up to 51 m−1 s−1, as revealed by high‐performance liquid chromatography (HPLC) analysis and fluorescence kinetics. As a proof‐of‐concept study, the highly efficient Staudinger reaction was successfully used for chemoselective fluorescence labeling of proteins and nucleic acids (DNA and RNA) as well as for protein polyethyleneglycol (PEG)ylation. We believe that this bioorthogonal reaction can provide a broadly useful tool for various bioconjugations.
Toward tunable dynamic repression using CRISPRi
Authors: Jang Sungyeon , Jang Sungho , Jung Gyoo Yeol
Published: May 2018

CRISPR interference (CRISPRi) is widely utilized for regulation of target gene expression by repressing transcription. Simple design rules for the single guide RNA (sgRNA) and multiplexity won this method immense popularity. However, quantitative control of the expression levels at varying degrees in a dynamic manner using CRISPRi has been regarded difficult. To deal with this limitation, Fontana et al. modulated the expression levels of the components of CRISPRi, the deactivated Cas9 (dCas9), and the sgRNAs, using various constitutive or inducible promoters (Fontana et al., Biotechnol. J. 2018, 13, 1800069). They found that the expression level of sgRNA is the key to controlling CRISPRi. Modulation of sgRNA expression levels enabled quantitative tuning of the CRISPRi‐regulated gene expression level. This approach is expected to be easily applied to diverse applications owing to its simplicity compared to the conventional approaches that modified target sequence or changed the expression level of dCas9.
Mixing Halogens To Assemble an All‐Inorganic Layered Perovskite with Warm White‐Light Emission
Authors: Li Xianfeng , Wang Sasa , Zhao Sangen , Li Lina , Li Yanqiang , Zhao Bingqing , Shen Yaoguo , Wu Zhenyue , Shan Pai , Luo Junhua
Published: May 2018

Most of single‐component white‐light‐emitting materials focus on organic–inorganic hybrid perovskites, metal–organic frameworks, as well as all‐inorganic semiconductors. In this work, we successfully assembled an all‐inorganic layered perovskite by mixing two halogens of distinct ionic radii, namely, Rb2CdCl2I2, which emits “warm” white light with a high color rendering index of 88. To date, Rb2CdCl2I2 is the first single‐component white‐light‐emitting material with an all‐inorganic layered perovskite structure. Furthermore, Rb2CdCl2I2 is thermally highly stable up to 575 K. A series of luminescence measurements show that the white‐light emission arises from the lattice deformation, which are closely related to the [CdCl4I2]2− octahedra with high distortion from the distinct ionic radii of Cl and I. The first‐principles calculations reveal that both the Cl and I components make significant contributions to the electronic band structures of Rb2CdCl2I2. These findings indicate that mixing halogens is an effective route to design and synthesize new single‐component white‐light‐emitting materials.
Incorporating Energetic Moieties into Four Oxadiazole Ring Systems for the Generation of High‐Performance Energetic Materials
Authors: Wang Bohan , Xiong Hualin , Cheng Guangbin , Yang Hongwei
Published: May 2018

The synthesis of three neutral 3,3′‐di(1,2,5‐oxadiazol‐3‐yl)‐5,5′‐bi(1,2,4‐oxadiazole) structures in combination with different energetic moieties such as nitramino, trinitroethylamino, and N‐nitrated trinitroethylamino is presented. In addition, a novel family of energetic salts based on 4,4′‐([5,5′‐bi(1,2,4‐oxadiazole)]‐3,3′‐diyl)‐bis(1,2,5‐oxadiazol‐3‐nitramide) is synthesized. The new compounds (4, 6–18) are characterized by IR and multinuclear NMR spectroscopy and elemental analysis. The structures of 4⋅2 C4H8O2, 9, 13, 15, and 16 are further confirmed by single‐crystal X‐ray diffraction studies. The thermal stabilities of 4 and 6–18 are determined by differential scanning calorimetry. Most of the new compounds have high densities (1.72–1.93 g cm−3) measured using a gas pycnometer (25 °C). Energetic evaluation indicates that they also have good detonation pressures and velocities (P: 26.4–41.9 GPa; D: 8218–9550 m s−1).
Potential‐Dependent, Switchable Ion Selectivity in Aqueous Media Using Titanium Disulfide
Authors: Srimuk Pattarachai , Lee Juhan , Fleischmann Simon , Aslan Mesut , Kim Choonsoo , Presser Volker
Published: May 2018

The selective removal of ions by an electrochemical process is a promising approach to enable various water‐treatment applications such as water softening or heavy‐metal removal. Ion intercalation materials have been investigated for their intrinsic ability to prefer one specific ion over others, showing a preference for (small) monovalent ions over multivalent species. In this work, we present a fundamentally different approach: tunable ion selectivity not by modifying the electrode material, but by changing the operational voltage. We used titanium disulfide, which shows distinctly different potentials for the intercalation of different cations and formed binder‐free composite electrodes with carbon nanotubes. Capitalizing on this potential difference, we demonstrated controllable cation selectivity by online monitoring the effluent stream during electrochemical operation by inductively coupled plasma optical emission spectrometry of aqueous 50 mm CsCl and MgCl2. We obtained a molar selectivity of Mg2+ over Cs+ of 31 (strong Mg preference) in the potential range between −396 mV and −220 mV versus Ag/AgCl. By adjusting the operational potential window from −219 mV to +26 mV versus Ag/AgCl, Cs+ was preferred over Mg2+ by 1.7 times (Cs preference).
Atmospheric deposition and exceedances of critical loads from 1800−2025 for the conterminous United States
Authors: Clark Christopher M. , Phelan Jennifer , Doraiswamy Prakash , Buckley John , Cajka James C. , Dennis Robin L. , Lynch Jason , Nolte Christopher G. , Spero Tanya L.
Published: May 2018

Atmospheric deposition of nitrogen (N) and sulfur (S) has increased dramatically over pre‐industrial levels, with many potential impacts on terrestrial and aquatic ecosystems. Quantitative thresholds, termed “critical loads” (CLs), have been developed to estimate the deposition rate above which damage is thought to occur. However, there remains no comprehensive comparison of when, where, and over what time periods individual CLs have been exceeded. We addressed this knowledge gap by combining several published data sources for historical and contemporary deposition, and overlaying these on six CL types from the National Critical Loads Database (NCLDv2.5; terrestrial acidification, aquatic acidification, lichen, nitrate leaching, plant community composition, and forest‐tree health) to examine exceedances from 1800 to 2011. We expressed CLs as the minimum, 10th, and 50th percentiles within 12‐km grid cells. Minimum CLs were relatively uniform across the country (200–400 eq·ha−1·yr−1), and have been exceeded for decades beginning in the early 20th century. The area exceeding minimum CLs peaked in the 1970s and 1980s, exposing 300,000 to 3 million km2 (depending on the CL type) to harmful levels of deposition, with a total area exceeded of 5.8 million km2 (~70% of the conterminous United States). Since then, deposition levels have dropped, especially for S, with modest reductions in exceedance by 2011 for all CL types, totaling 5.2 million km2 in exceedance. The 10th and 50th percentile CLs followed similar trends, but were not consistently available at the 12‐km grid scale. We also examined near‐term future deposition and exceedances in 2025 under current air quality regulations, and under various scenarios of climate change and additional nitrogen management controls. Current regulations were projected to reduce exceedances of any CL from 5.2 million km2 in 2011 to 4.8 million km2 in 2025. None of the additional N management or climate scenarios significantly affected areal exceedances, although exceedance severity declined. In total, it is clear that many CLs have been exceeded for decades, and are likely to remain so in the short term under current policies. Additionally, we suggest many areas for improvement to enhance our understanding of deposition and its effects to support informed decision making.