bluuebunny/crossref_metadata_2025 huggingface dataset:
The Emerging Threats of Web Scrapping to Web Applications Security and Their Defense Mechanism
Authors: Ur Rahman Rizwan , Wadhwa Danish , Bali Aakash , Singh Tomar Deepak
Published: February 2020

Web scraping is the technique exploited to robotically obtain particular information from web applications instead of manually copying it. The purpose of a web scraper is to search for certain class of information, dig out, and aggregate it into new database. More precisely, web scrapers are used to transform unstructured web data and store them in structured databases. It is a continuing threat to web applications that aims to steal sensitive data from a victim or from web applications. The key objective of this article is to examine to what extent web scraping can cause a threat to web application security. This article explores the classification of web scraping such as content scraping, web scraping, price scraping, and database scraping in general and presents the most widely used scraping tools such as Web Content Extractor, and Screen Scrapper. Consequently, the aim of this article is to give evaluation of vulnerabilities, threats of web scraping associated with web application applications, and effective measures to counter them.
Occurrence and Impact of Emerging Contaminants in Nigeria's Freshwater Resources
Authors: Abosede Sinmi
Published: February 2020

The presence of emerging contaminants (ECs) in freshwater presents a major challenge as they pose serious threats to human life and ecosystems. It is essential that water is of good quality before it can be used by communities and benefit the environment. Nigeria is blessed with abundant water resources; however, the country lacks effective and efficient institutions to provide sanitation services to treat domestic waste and to monitor and regulate industries, helping them protect the environment by ensuring they treat their industrial waste before discharging to the water bodies. Various ECs have been detected in the nation's freshwater resources. They pose significant threat to the environment, and they have the potential to harm aquatic life and human health. Nigeria needs a comprehensive and integrated water resources management plan that gives priority to the monitoring, detection, and treatment of emerging contaminants to mitigate against the potential risks that occur when they are present in freshwater resources.
Use of Low Cost Materials to Remove Chemicals of Emerging Concern From Wastewater Effluents
Authors: Abosede Sinmi
Published: February 2020

The use and production of synthetic organic chemicals for use in households and various industries has led to an increase in the occurrence and concentration of chemicals of emerging concern (CEC) in wastewater effluents and consequently the environment. Due to the refractory nature of some CECs, conventional physicochemical and biological treatments are not able to provide adequate elimination of these compounds. It is beneficial that these pollutants are removed by other methods before they are discharged to the environment or before the effluent can be recycled for reuse. The use of low-cost materials for the removal of CECs is an unexploited opportunity in developing countries, as these compounds possess the necessary functionalities to make them an ideal choice for water and water treatment in countries with limited economic and technical resources. This chapter reviews the various treatment processes that has been used for the removal of CECs in literature with a particular emphasis on low-cost materials.
Preparing Critical Educators and Community-Engaged Scholars Through Participatory Action Research
Authors: Call-Cummings Meagan , Hauber-Özer Melissa , Rainey Jennifer
Published: February 2020

Participatory action research (PAR) is a community-based form of inquiry conducted with individuals affected by an issue or problem being studied rather than about them. Rather than a method of inquiry, PAR is an epistemological stance towards knowledge and knowledge creation that is rooted in critical, emancipatory pedagogy. Because it is an orientation, rather than a discrete method, PAR is difficult to teach. Here the authors explore the experiences of both undergraduate pre-service teachers and doctoral students as they seek to reconcile PAR principles and practice with their personal and professional backgrounds. The purpose is not to present the best approach for teaching PAR in the university classroom; rather, it is a reflective exploration of the experiences of the authors' participants, which reveals rich insights into what it feels like to become researchers within the ‘culture' of formal higher education in the United States.
Principles in Practice
Authors: Morton Mavis , Varghese Jeji , Jackson Elizabeth , Levac Leah
Published: February 2020

This chapter offers faculty and institutional leaders a set of principles and practical approaches for designing and supporting courses that develop and mentor emerging community engaged scholars at the undergraduate and graduate levels. The learning outcomes and design features of these courses provide students with opportunities to develop knowledge, skills, and values that are required for undertaking ethical sustainable critical community engaged scholarship (CCES). The chapter begins with an overview of the CCES framework that guides the authors' specific courses and thier commitments to supporting the development of community-engaged scholars more broadly. The chapter describes several courses that share the CCES framework but vary by size, disciplinary foundation, and engaged-learning approach. These courses are used to consider the development of students' capacities and values, the interplay between CCES and pedagogical best practices, and the role of institutional supports in enabling CCES and navigating institutional challenges to community-engaged teaching and learning.
“Rural Development” and the Search for an African Development Paradigm
Authors: Plaatjie Sebeka Richard
Published: February 2020

This chapter departs from the premise that African problems demand not African solutions but solutions founded on the principles of African culture and philosophy. The chapter analyzes hegemonic Euro-American-centric ideas of development and rural development from the perspective of the African philosophy of ubuntu. This chapter per the author dismisses the idea of “rural development” because it argues that “rural” is an oxymoron in African culture and philosophy and thus a discourse of a colonial heritage. The chapter understands “rural development” as a narrow Euro-American-centric construction founded on the principles of economism and classism of the Western philosophical ethic and which, according to the chapter, needs decolonization through ubuntu. The chapter further suggests pathways towards an African “rural development” paradigm.
Redressing Spatial Inequality in Rural Municipalities Through Service Delivery
Authors: Miya Wandile , Chipungu Lovemore , Magidimisha Hangwelani
Published: February 2020

Spatial inequality is a common challenge in some of South African municipalities. The level of service delivery is presented as one of the indicative factors, amongst South Africa's spatial history, using the case of Impendle Municipality. Using the qualitative methodology, the study investigated styles of governance as influential factors in spatial, inequality from three ages, being the colonial era, apartheid era, and the democratic era successively, with focus on rural areas as marginalised neighbourhoods. Subsequently, the study has identified possible factors which explain the continued backlog in service delivery in such areas, some being lack of coordination between tiers of governance, conflicts between municipal officials and the traditional authority, and lack of resources and capacity. Recommendations such as transformation of government relations and emphasized support amongst others were outlined as solutions to these matters.
POV in XR
Authors: Weston Eve
Published: February 2020

This chapter will introduce and explain the applications of a taxonomy for discussing point of view (POV) in XR. The simple designations of first, second, and third person that are used to categorize books, movies, and video games don't cover all the options and combinations available in immersive media. Accordingly, XR requires a new taxonomy that will allow for clear communication about content and experiences. This chapter will do three things: (1) present the four main POV tiers: narrative, visual, effectual, and experiential; (2) address less common tiers and how they might be incorporated and acknowledged in future XR experiences; and (3) show the taxonomy in action by using it to describe contemporary XR content.
Science Cartoons (SciToons)
Authors: Adetunji Oludurotimi , Levine Roger
Published: February 2020

The 21st century offers many technological advancements resulting from cutting-edge research being conducted by scientists and engineers at higher education institutions, industries, and national labs. As exciting scientific research is being conducted, the need to address the challenges of inspiring and engaging new learners in science, technology, engineering, and mathematics (STEM) fields continues to grow. The authors present the Science Cartoons (SciToons) program as a model for making science more accessible through the integration of the arts with STEM (STEAM). The SciToons model is based on a Multimedia Learning Theoretical Framework (MLTF), which facilitates co-creation of knowledge and takes into account the contributions of STEM and non-STEM experts. The SciToons model combines this knowledge and expertise with art, animation, high-quality multimedia, and storytelling in the development of science videos that are engaging to a broad audience.
The Effectiveness of Weblogs on Writing Tendency
Authors: Orhan-Karsak H. Gülhan
Published: February 2020

Writing, whether integrated technology or not, is an essential skill for today graduates. And motivating and improving students' life skills by Web 2.0 tools-integrated writing activities may be an effective way. Because of this, the aim of this chapter is to investigate the effect of weblog environment, which is used for writing, on writing tendency. A quantitative research design was used for this research. In this context, the “pretest-posttest control group design” was applied as an experimental research. Fourteen students who are at the fifth grade level in a public school participated in this research, seven in the experiment group and seven in the control group. While the experiment group worked on a weblog, the control group worked on a face-to-face environment. A writing tendency scale was applied as pre-test and post-test. The results are discussed in terms of findings.
Investigating the Adequacy of EFL Learners' L2 Digital Literacy Skills, Consistency of Self-Assessed Competence, and Actual Performance
Authors: Al Seghayer Khalid
Published: February 2020

This study was designed to investigate the adequacy of EFL learners' abilities in three major dimensions of digital literacy skills and whether self-assessments of competence were consistent with their actual performance. It also identified factors that affected learners' use of the selected digital literacy skills. To this end, 60 Saudi EFL learners (41 male and 19 female) responded to a five-part, cross-sectional questionnaire of 36 items categorized according to the three dimensions of digital literacy skills. They also engaged in 11 predetermined real-time Internet search tasks. The participants' on-screen online search activities were recorded and subjected to a search log analysis. Short, semi-structured post-search interviews were conducted to capture the participants' reflections on the search process. The data was analyzed with descriptive statistics and paired t-tests. The participants' success in searches was measured by the total number of tasks completed accurately. The results indicated that the participants were ill-equipped to efficiently handle the three key L2 digital literacy skills. Participants' low self-perceived ability to use them adequately was consistent with their actual poor online search performance. Further, the participants scored low in search accuracy, with the exception of search results interpretation skills and, to some extent, skills to evaluate a website's usefulness, and exhibited a wide range of areas for improvement and challenges in Web information search. The implications of the study and potential areas of future research are discussed.
HUNTINGTON, STORIA DI UN GENE ANTICO
Authors: Cattaneo Elena
Published: February 2020

Huntington is the gene that mutates in Huntingtonâ€™s Disease. Our laboratory is studying its physiological function during development and in adulthood and how its mutation causes the death of the striatal and cortical neurons with the ultimate goal of contributing toward the identification of a therapy.
Parents’ Perspectives: An Expanded View of Occupational and Co-Occupational Performance in the Neonatal Intensive Care Unit
Authors: Cardin Ashlea D.
Published: February 2020

Importance: One limitation of occupation-based neonatal practice is the lack of clarity surrounding what parent and infant occupations exist in the neonatal intensive care unit (NICU). Without clear definitions and examples of these constructs, occupational therapists may not recognize or value them as part of practice.

Objective: To explore concepts of occupational and co-occupational performance in the NICU and provide richly expanded descriptions of parent and infant occupations in this setting.

Design: Phenomenological study with convenience sampling. Participants engaged in semistructured interviews. Inductive content analysis, in vivo and process coding methods, and cross-case analysis were used. Member checking and expert review of emergent themes were used to ensure authenticity.

Setting: A metropolitan 48-bed Level 3 NICU with single-family rooms in the midwestern United States.

Participants: Fourteen parents (mean age = 29.7 yr; range = 19–37 yr) volunteered for the study.

Results: Five themes of active occupational engagement emerged: (1) perceiving “they” versus “I”; (2) maintaining proximity; (3) expressing emotions, values, and beliefs; (4) addressing health issues; and (5) analyzing. A matrix framework displayed emergent themes with definitions of parent occupations, infant occupations, and parent–infant co-occupations. Examples of both directly observable and hidden occupations were found at matrix intersections.

Conclusions and Relevance: Occupational performance prevalently reflected attempts to balance power differentials and pursue meaningful engagement through observable and hidden participation in caregiving. Findings suggest that beyond typical occupations (e.g., feeding, socializing), neonatal therapists can address the doing, being, and becoming occupations expressed by parents in this study.

What This Article Adds: Parents described five broad thematic categories of NICU-based occupation and co-occupation, which may be valuable to therapists seeking to strengthen the occupational focus of neonatal intervention. Neonatal therapists may need to advocate for service provision policy change to fully address the observable and nonobservable doing, being, and becoming occupational and co-occupational needs of parents and infants.
China's emission control strategies have suppressed unfavorable influences of climate on wintertime PM2.5 concentrations in Beijing since 2002
Authors: Gao Meng , Liu Zirui , Zheng Bo , Ji Dongsheng , Sherman Peter , Song Shaojie , Xin Jinyuan , Liu Cheng , Wang Yuesi , Zhang Qiang , Xing Jia , Jiang Jingkun , Wang Zifa , Carmichael Gregory R. , McElroy Michael B.
Published: February 2020

Abstract. Severe wintertime PM2.5 pollution in Beijing has been receiving
increasing worldwide attention, yet the decadal variations remain relatively
unexplored. Combining field measurements and model simulations, we
quantified the relative influences of anthropogenic emissions and
meteorological conditions on PM2.5 concentrations in Beijing over
the winters of 2002–2016. Between the winters of 2011 and 2016, stringent
emission control measures resulted in a 21 % decrease in mean mass
concentrations of PM2.5 in Beijing, with 7 fewer haze days per winter
on average. Given the overestimation of PM2.5 by the model, the
effectiveness of stringent emission control measures might have been
slightly overstated. With fixed emissions, meteorological conditions over
the study period would have led to an increase in haze in Beijing, but the
strict emission control measures have suppressed the unfavorable influences
of the recent climate. The unfavorable meteorological conditions are attributed
to the weakening of the East Asia winter monsoon associated particularly
with an increase in pressure associated with the Aleutian Low.
Size-segregated characteristics of organic carbon (OC), elemental carbon (EC) and organic matter in particulate matter (PM) emitted from different types of ships in China
Authors: Zhang Fan , Guo Hai , Chen Yingjun , Matthias Volker , Zhang Yan , Yang Xin , Chen Jianmin
Published: February 2020

Abstract. Studies of detailed chemical compositions in particles with different size
ranges emitted from ships are in serious shortage. In this study,
size-segregated distributions and characteristics of particle mass, organic
carbon (OC), elemental carbon (EC), 16 EPA polycyclic aromatic hydrocarbons (PAHs) and 25 n-alkanes measured aboard 12 different vessels in China are presented. The results showed
the following. (1) More than half of the total particle mass, OC, EC, PAHs and
n-alkanes were concentrated in fine particles with aerodynamic diameter
(Dp) < 1.1 µm for most of the tested ships. The relative
contributions of OC, EC, PAH and alkanes to the size-segregated particle
mass are decreasing with the increase in particle size. However, different
types of ships showed quite different particle-size-dependent chemical
compositions. (2) In fine particles, the OC and EC were the dominant
components, while in coarse particles, OC and EC only accounted for very
small proportions. With the increase in particle size, the OC / EC ratios
first decreased and then increased, having the lowest values for particle
sizes between 0.43 and 1.1 µm. (3) Out of the four OC fragments
and three EC fragments obtained in thermal–optical analysis, OC1, OC2 and
OC3 were the dominant OC fragments for all the tested ships, while EC1 and
EC2 were the main EC fragments for ships running on heavy fuel oil (HFO) and
marine-diesel fuel, respectively; different OC and EC fragments presented
different distributions in different particle sizes. (4) The four-stroke low-power
diesel fishing boat (4-LDF) had much higher PAH emission ratios than
the four-stroke high-power marine-diesel vessel (4-HMV) and two-stroke high-power
heavy-fuel-oil vessel (2-HHV) in fine particles, and 2-HHV had the lowest
values. (5) PAHs and n-alkanes showed different profile patterns for
different types of ships and also between different particle-size bins,
which meant that the particle size should be considered when source
apportionment is conducted. It is also noteworthy from the results in this
study that the smaller the particle size, the more toxic the particle was,
especially for the fishing boats in China.
Improved fuzzy logic method to distinguish between meteorological and non-meteorological echoes using C-band polarimetric radar data
Authors: Zhang Shuai , Huang Xingyou , Min Jinzhong , Chu Zhigang , Zhuang Xiaoran , Zhang Hengheng
Published: February 2020

Abstract. To obtain better performance of meteorological applications, it is necessary to distinguish radar echoes from meteorological and non-meteorological targets. After a comprehensive analysis of the computational efficiency and radar system characteristics, we propose a fuzzy logic method that is similar to the MetSignal algorithm; the performance of this method is improved significantly in weak-signal regions where polarimetric variables are severely affected by noise. In addition, post-processing is adjusted to prevent anomalous propagation at a far range from being misclassified as meteorological echo. Moreover, an additional fuzzy logic echo classifier is incorporated into post-processing to suppress misclassification in the melting layer. An independent test set is selected to evaluate algorithm performance, and the statistical results
show an improvement in the algorithm performance, especially with respect to
the classification of meteorological echoes in weak-signal regions.
Model representation of the coupling between evapotranspiration and soil water content at different depths
Authors: Qiu Jianxiu , Crow Wade T. , Dong Jianzhi , Nearing Grey S.
Published: February 2020

Abstract. Soil water content (θ) influences the climate
system by controlling the fraction of incoming solar and longwave energy
that is converted into evapotranspiration (ET). Therefore, investigating the
coupling strength between θ and ET is important for the study of
land surface–atmosphere interactions. Physical models are commonly tasked
with representing the coupling between θ and ET; however, few
studies have evaluated the accuracy of model-based estimates of θ ∕ ET
coupling (especially at multiple soil depths). To address this issue, we use
in situ AmeriFlux observations to evaluate θ ∕ ET coupling strength
estimates acquired from multiple land surface models (LSMs) and an ET
retrieval algorithm – the Global Land Evaporation Amsterdam Model (GLEAM).
For maximum robustness, coupling strength is represented using the sampled
normalized mutual information (NMI) between θ estimates acquired at
various vertical depths and surface evaporation flux expressed as a fraction
of potential evapotranspiration (fPET, the ratio of ET to potential ET).
Results indicate that LSMs and GLEAM are generally in agreement with
AmeriFlux measurements in that surface soil water content (θs)
contains slightly more NMI with fPET than vertically integrated soil water
content (θv). Overall, LSMs and GLEAM adequately capture
variations in NMI between fPET and θ estimates acquired at various
vertical depths. However, GLEAM significantly overestimates the NMI between
θ and ET, and the relative contribution of θs to total
ET. This bias appears attributable to differences in GLEAM's ET estimation
scheme relative to the other two LSMs considered here (i.e., the Noah model
with multi-parameterization options and the Catchment Land Surface Model, CLSM).
These results provide insight into improved LSM model structure and
parameter optimization for land surface–atmosphere coupling analyses.
A LANDMARK MATCHING ALGORITHM FOR THE GEOSTATIONARY SATELLITE IMAGES BASED ON MULTI-LEVEL GRIDS
Authors: Hou S. Y. , Qin Z. Y. , Niu L. , Zhang W. G. , Ai W. T.
Published: February 2020

Abstract. The resolution of geostationary satellite image is not high and the image is covered with clouds. At present, when the extracted feature points are unstable, there are some problems, such as low matching accuracy or even matching failure. In this paper, a landmark matching algorithm is proposed to directly establish the multi-level grids for the image coastline and the coastline template. Through the similarity measure of the multi-level grids, the landmark matching is realized layer by layer. First of all, we've finished cloud detection, establishment of landmark data set, and extraction of image coastline. Then we design and implement the landmark matching algorithm based on multi-level grids. Finally, through analysis from different levels of landmarks and different proportion of cloud cover, the advantages and applicable conditions of this algorithm are given. The experimental results show that: 1) with the increase of cloud cover, the correct rate of landmark matching decreases, but the decrease is small. It shows that the matching algorithm in this paper is stable. Correct matching rate could always be stable at about 75 percent in the fourth level. 2) when the proportion of cloud cover is less than 20 percent, the higher the matching level, the higher the matching accuracy. When the cloud cover is more than 20 percent, the matching accuracy in the fourth level is the highest. This algorithm provides a stable method for the landmark matching of geostationary satellite image.
Sleep in adolescence: sex matters?
Authors: Matos Margarida Gaspar de , Marques Adilson , Peralta Miguel , Gaspar Tânia , Simões Celeste , Pinto Helena Rebelo , Pinto Teresa Rebelo , Godeau Emmanuelle , Paiva Teresa
Published: February 2020

Objective Sleep is of upmost importance for everybody and especially for adolescents who face life and leisure challenges that may impair their sleep. This study aimed to verify if girls are at a higher risk to present sleep problems and if associations of a sleep perception are different between sexes even when accounting for biological maturation.

Methods Data is from the HBSC Portuguese survey 2014, all variables were self-reported. Participants were 3869 adolescents (2057 girls), mean age 14.8 years. Participants' socio-demographic characteristics included sex, age, school grade, father and mother education; besides participants were inquired about sleep duration and characteristics of their sleep quality.

Results Sleep deprivation was reported by 13.1% of the adolescents (girls 14.3%, boys 11.7%, p<0.05). The most prevalent characteristics of poor sleep quality were waking up tired (50.8%) and difficulties falling asleep (19.5%), for both girls presented higher prevalence than boys. Overall, girls presented a poorer sleep health with low quality and quantity of sleep. Furthermore, associations of an enough and good sleep were different between boys and girls, even when controlling for the impact of delayed pubertal maturity.

Discussion Together with screen time, substance use, poorer nutrition, sedentary behaviours and abuse of screen time, sleep is an issue that must be addressed by professionals, families and public policies with impact in family life and family routines. Modelling a health education in schools should include the sleep topic. In addition, yes, sex matters and must be included on board.
Derecho a no saber y privilegio terapéutico de menores de edad en patología de base genética
Authors: Vieito Villar Miguel
Published: February 2020

Analizaremos las figuras jurídicas “privilegio terapéutico” y “derecho a no saber”, circunscritas a la patología genética y a pacientes menores de edad. Para esto consideraremos, además de la normativa sobre consentimiento informado contenida en la Ley 41/2002 y sus normas complementarias, los recientes cambios legislativos relacionados con los menores y sus datos clínicos.

La aprobación de la Ley Orgánica 8/2015, de 22 de julio, de modificación del sistema de protección a la infancia y a la adolescencia; y de la Ley 26/2015, de 28 de julio, de idéntico rotulado; incrementan la autonomía de los menores y refuerzan la figura del "interés superior del menor". Así mismo, la aplicación del "Reglamento General de Protección de Datos"; y de la Ley Orgánica 3/2018, de 5 de diciembre, de Protección de Datos Personales y garantía de los derechos digitales, apuntalan la autodeterminación informativa, también de los pacientes, y también de los menores de edad.

El análisis de estas instituciones y su influencia en el contexto de la información clínica a los pacientes nos orientarán en la resolución de las eventuales colisiones de derechos y facultades, del menor por un lado y de sus representantes, en funciones de salvaguardia, por otro.

We intend to analyse the legal institutions of “therapeutic privilege” and “right not to know”, restricted to genetic diseases and minor patients. In order to achieve this, we will consider, beyond the law regarding informed consent (Law 41/2002), the most recent changes concerning minors and their clinical data.

The adoption of the Organic Law 8/2015, 22nd July, on amendment of the protection system for childhood and adolescence; and Law 26/2015, 28th July, with the same name; increases the minors autonomy and also strengthen the “best interest of the child”. Besides, the application of the “General Data Protection Regulation”; and Organic Law 3/2018, 5th December, of Personal Data Protection and guarantee of digital rights, reinforces the informational self-determination, regarding both patients and minors.

The analysis of these two institutions and their influence in the context of clinical information will guide us in dealing with eventual conflicts among minors rights and the safeguards of their legal representatives.
Comparison of routine hematological indicators of liver and kidney function, blood count and lipid profile in healthy people and stroke patients
Authors: Cui Xiaofang , Wei Wei , Qin Xiao , Hou Fei , Zhu Jin , Li Weiyang
Published: February 2020

Background and methods

Stroke has become a major public health problem worldwide. In this article, we carried out statistical analysis, correlation analysis and principal component analysis (PCA) to evaluate the clinical value of routine hematological indicators in early diagnosis of ischemic stroke using R language.

Results

For the full blood count comparisons, stroke patients had obvious differences in the distribution width of red blood cells (RDW-CV), average distribution width of red blood cells (RDW-SD), mean hemoglobin concentrations, platelet large cell ratio, mean platelet volume and lymphocytes. Patients with ischemic stroke also exhibited different degrees of abnormalities in liver function test. With respect to renal function, stroke patients had obvious changes in uric acid and urea levels. Finally, when comparing the lipid profile, triglyceride concentrations were increased and high-density lipoprotein cholesterol concentrations were reduced in stroke patients. In addition, correlation analysis among these clinical indicators indicated that there were both common characteristics and differences between patients and health controls. Furthermore, the results of PCA indicated that these clinical indicators could distinguish patients from the healthy controls.

Conclusion

Conventional hematological clinical indicators, such as liver function, renal function, full blood count and lipid concentration profiles highly correlated with the occurrence of ischemic stroke. Therefore, the detection and analyzation of these clinical indicators are of great significance for the prediction of ischemic stroke.
Structural and biophysical characterization of the type VII collagen vWFA2 subdomain leads to identification of two binding sites
Authors: Gebauer Jan M. , Flachsenberg Florian , Windler Cordula , Richer Barbara , Baumann Ulrich , Seeger Karsten
Published: February 2020

Type VII collagen is an extracellular matrix protein, which is important for skin stability; however, detailed information at the molecular level is scarce. The second vWFA (von Willebrand factor type A) domain of type VII collagen mediates important interactions, and immunization of mice induces skin blistering in certain strains. To understand vWFA2 function and the pathophysiological mechanisms leading to skin blistering, we structurally characterized this domain by X‐ray crystallography and NMR spectroscopy. Cell adhesion assays identified two new interactions: one with β1 integrin via its RGD motif and one with laminin‐332. The latter interaction was confirmed by surface plasmon resonance with a KD of about 1 mm. These data show that vWFA2 has additional functions in the extracellular matrix besides interacting with type I collagen.
ONDCP issues first ‘treatment plan’: Not part of Strategy
Authors: Knopf Alison
Published: February 2020

Last week, in a surprise move, the Office of National Drug Control Policy (ONDCP) issued its first National Treatment Plan for Substance Use Disorder, along with its National Drug Control Strategy. If anyone was expecting an additional windfall like the $1 billion annual State Opioid Response grant program, it's not there.
Research for the Safe Management of Nuclear Waste at Forschungszentrum Jülich: Materials Chemistry and Solid Solution Aspects
Authors: Bosbach Dirk , Brandt Felix , Bukaemskiy Andrey , Deissmann Guido , Kegler Philip , Klinkenberg Martina , Kowalski Piotr M. , Modolo Giuseppe , Niemeyer Irmgard , Neumeier Stefan , Vinograd Victor
Published: February 2020

The safe management of high‐level nuclear wastes, including their final disposal in a deep geological repository, requires a sound scientific understanding of the processes affecting the various materials present in the multibarrier system of the disposal facility, including the radioactive waste forms. Thus materials science aspects play an important role in the multidisciplinary and complex field of long‐term safety assessments. As many of these issues are related to mixed solid compounds, the aspect of structural radionuclide uptake by a host structure and subsequent solid solution formation is one of the key topics of the research related to nuclear waste management at Forschungszentrum Jülich. The adopted practice for deriving an in‐depth understanding of materials behavior by combining state‐of‐the‐art experimental and computational approaches is presented in the context of three examples: 1) corrosion of spent nuclear fuels, 2) radionuclide retention by secondary phases, and 3) innovative ceramic waste forms. New nano‐ and microanalytical tools, as well as advanced spectroscopic techniques and computational methods, further developed and tailored at Forschungszentrum Jülich, allowed for refined views on these materials.
Controlled n‐Doping in Air‐Stable CsPbI2Br Perovskite Solar Cells with a Record Efficiency of 16.79%
Authors: Han Yu , Zhao Huan , Duan Chenyang , Yang Shaomin , Yang Zhou , Liu Zhike , Liu Shengzhong (Frank)
Published: February 2020

Cesium‐based inorganic perovskites, such as CsPbI2Br, are promising candidates for photovoltaic applications owing to their exceptional optoelectronic properties and outstanding thermal stability. However, the power conversion efficiency of CsPbI2Br perovskite solar cells (PSCs) is still lower than those of hybrid PSCs and inorganic CsPbI3 PSCs. In this work, passivation and n‐type doping by adding CaCl2 to CsPbI2Br is demonstrated. The crystallinity of the CsPbI2Br perovskite film is enhanced, and the trap density is suppressed after adding CaCl2. In addition, the Fermi level of the CsPbI2Br is changed by the added CaCl2 to show heavy n‐type doping. As a result, the optimized CsPbI2Br PSC shows a highest open circuit voltage of 1.32 V and a record efficiency of 16.79%. Meanwhile, high air stability is demonstrated for a CsPbI2Br PSC with 90% of the initial efficiency remaining after more than 1000 h aging in air.
Hybridization of Triphenylamine and Salicylaldehyde: A Facile Strategy to Construct Aggregation‐Induced Emission Luminogens with Excited‐State Intramolecular Proton Transfer for Specific Lipid Droplets and Gram‐Positive Bacteria Imaging
Authors: Yin Wei , Li Yue , Li Nan , Yang Weiyao , An Hao , Gao Jinrui , Bi Yu , Zhao Na
Published: February 2020

Aggregation‐induced emission luminogens (AIEgens) with excited‐state intramolecular proton transfer (ESIPT) process have attracted significant attention in bioimaging applications owing to their high solid‐state emission efficiencies and large Stokes shifts. Herein, a series of simple AIEgens with ESIPT process, referred to as triphenylamine salicylaldehyde (TS) derivatives, are designed and synthesized by a rational hybridization of triphenylamine and salicylaldehyde units as the intramolecular rotor and ESIPT generator, respectively. Owing to the AIE and ESIPT effects, TS derivatives exhibit intense emission and large Stokes shifts (>140 nm) in the aggregated state. By altering the substituents in the triphenylamine units, their solid‐state emission varies from 490 to 590 nm. Owing to their excellent biocompatibilities and suitable lipophilicities, the TS derivatives are able to specifically and rapidly (<5 min) stain the lipid droplets in the cells in a wash‐free manner and successfully image the lipid‐rich tissue in vivo. Moreover, owing to their suitable hydrophilicity, TS and methoxyl substituted TS (TS‐OMe) are shown to stain gram‐positive bacteria with high selectivity.
Super‐Resolution Infrared Imaging of Polymorphic Amyloid Aggregates Directly in Neurons
Authors: Klementieva Oxana , Sandt Christophe , Martinsson Isak , Kansiz Mustafa , Gouras Gunnar K. , Borondics Ferenc
Published: February 2020

Loss of memory during Alzheimer's disease (AD), a fatal neurodegenerative disorder, is associated with neuronal loss and the aggregation of amyloid proteins into neurotoxic β‐sheet enriched structures. However, the mechanism of amyloid protein aggregation is still not well understood due to many challenges when studying the endogenous amyloid structures in neurons or in brain tissue. Available methods either require chemical processing of the sample or may affect the amyloid protein structure itself. Therefore, new approaches, which allow studying molecular structures directly in neurons, are urgently needed. A novel approach is tested, based on label‐free optical photothermal infrared super‐resolution microspectroscopy, to study AD‐related amyloid protein aggregation directly in the neuron at sub‐micrometer resolution. Using this approach, amyloid protein aggregates are detected at the subcellular level, along the neurites and strikingly, in dendritic spines, which has not been possible until now. Here, a polymorphic nature of amyloid structures that exist in AD transgenic neurons is reported. Based on the findings of this work, it is suggested that structural polymorphism of amyloid proteins that occur already in neurons may trigger different mechanisms of AD progression.
Deracemisierung durch Photokatalyse mit sichtbarem Licht
Authors: Shi Qinglong , Ye Juntao
Published: February 2020

Deracemisierung ist eine ideale, aber anspruchsvolle Strategie, um ein racemisches Gemisch in ein einzelnes Enantiomer umzuwandeln. Aktuelle Studien haben gezeigt, dass Photokatalyse mit sichtbarem Licht verwendet werden kann, um die selektive Deracemisierung von axial‐chiralen Allenen sowie von Cyclopropylchinolonen und cyclischen Harnstoffen mit zentraler Chiralität entweder durch einen Energietransfer oder durch eine Sequenz von Elektronen‐, Protonen‐ und Wasserstoffatomtransfer zu bewirken.
Chemical Synthesis of Interleukin‐2 and Disulfide Stabilizing Analogues
Authors: Murar Claudia E. , Ninomiya Mamiko , Shimura Satomi , Karakus Ufuk , Boyman Onur , Bode Jeffrey W.
Published: February 2020

Chemical protein synthesis allows the construction of well‐defined structural variations and facilitates the development of deeper understanding of protein structure–function relationships and new protein engineering strategies. Herein, we report the chemical synthesis of interleukin‐2 (IL‐2) variants on a multimilligram scale and the formation of non‐natural disulfide mimetics that improve stability against reduction. The synthesis was accomplished by convergent KAHA ligations; the acidic conditions of KAHA ligation proved to be valuable for the solubilization of the hydrophobic segments of IL‐2. The bioactivity of the synthetic IL‐2 and its analogues were shown to be equipotent to recombinant IL‐2 and exhibit improved stability against reducing agents.
Tumor Microenvironment‐Activated NIR‐II Nanotheranostic System for Precise Diagnosis and Treatment of Peritoneal Metastasis
Authors: Ling Sisi , Yang Xiaohu , Li Chunyan , Zhang Yejun , Yang Hongchao , Chen Guangcun , Wang Qiangbin
Published: February 2020

Activatable theranostic systems show potential for improved tumor diagnosis and therapy owing to high detection specificities, effective ablation, and minimal side‐effects. Herein, a tumor microenvironment (TME)‐activated NIR‐II nanotheranostic system (FEAD1) for precise diagnosis and treatment of peritoneal metastases is presented. FEAD1 was fabricated by self‐assembling the peptide Fmoc‐His, mercaptopropionic‐functionalized Ag2S quantum dots (MPA‐Ag2S QDs), the chemodrug doxorubicin (DOX), and NIR absorber A1094 into nanoparticles. We show that in healthy tissue, FEAD1 exists in an NIR‐II fluorescence “off” state, because of Ag2S QDs‐A1094 interactions, while DOX remains in stealth mode. Upon delivery of FEAD1 to the tumor, the acidic TME triggers its disassembly through breakage of the Fmoc‐His metal coordination and DOX hydrophobic interactions. Release of A1094 switches on Ag2S fluorescence, illuminating the tumor, accompanied by burst release of DOX within the tumor tissue, thereby achieving precise tumor theranostics. This TME‐activated theranostic strategy holds great promise for future clinical applications.
Deracemization Enabled by Visible‐Light Photocatalysis
Authors: Shi Qinglong , Ye Juntao
Published: February 2020

Deracemization is an ideal but challenging strategy for the conversion of a racemic mixture into a single enantiomer. Recent studies have demonstrated that visible‐light photocatalysis could be utilized to promote selective deracemization of axially chiral allenes as well as cyclopropylquinolones and cyclic ureas with central chirality either through energy transfer or through a sequence of electron, proton, and hydrogen‐atom transfer.
Amide Synthesis by Nickel/Photoredox‐Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides
Authors: Alandini Nurtalya , Buzzetti Luca , Favi Gianfranco , Schulte Tim , Candish Lisa , Collins Karl D. , Melchiorre Paolo
Published: February 2020

Herein, we report a one‐electron strategy for catalytic amide synthesis that enables the direct carbamoylation of (hetero)aryl bromides. This radical cross‐coupling approach, which is based on the combination of nickel and photoredox catalysis, proceeds at ambient temperature and uses readily available dihydropyridines as precursors of carbamoyl radicals. The method's mild reaction conditions make it tolerant of sensitive‐functional‐group‐containing substrates and allow the installation of an amide scaffold within biologically relevant heterocycles. In addition, we installed amide functionalities bearing electron‐poor and sterically hindered amine moieties, which would be difficult to prepare with classical dehydrative condensation methods.
Investigation of ring‐opening polymerization of 5‐[2‐{2‐(2‐methoxyethoxy)ethoxy}‐ethoxymethyl]‐5‐methyl‐1,3‐dioxa‐2‐one by organometallic catalysts
Authors: Chanthaset Nalinthip , Beckerle Klaus , Okuda Jun , Ajiro Hiroharu
Published: February 2020

To develop new polymer‐based materials, the design of aliphatic carbonate has received attention and become a well‐known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM‐MOE3OM, were typically prepared via ring‐opening polymerization (ROP) using amidine‐based catalysts such as 1,8‐diazabicyclo[5.4.0] undec‐7‐ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know‐how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)‐type cyclen chelating with a metal‐core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM‐MOE3OM upon steadily degree of polymerization.
Copper‐Catalyzed Enantioselective Synthesis of Oxazolines from Aminotriols via Asymmetric Desymmetrization
Authors: Yamamoto Kosuke , Tsuda Yutaro , Kuriyama Masami , Demizu Yosuke , Onomura Osamu
Published: February 2020

A copper‐catalyzed enantioselective transformation of tris(hydroxymethyl)aminomethane‐derived aminotriols was developed to provide multisubstituted oxazolines with a tetrasubstituted carbon center. The present transformation consisted of sequential reactions involving mono‐sulfonylation of aminotriols, subsequent intramolecular cyclization to afford prochiral oxazoline diols, and sulfonylative asymmetric desymmetrization of resultant oxazoline diols. In addition, the kinetic resolution process would be involved in the sulfonylative asymmetric desymmetrization step, which would amplify the enantiopurities of the desired products. Various aminotriols were tolerated in the present reaction, affording the desired oxazolines in good to high yields with excellent enantioselectivities. The synthetic utility of the present reaction was demonstrated by the transformation of the optically active oxazoline into a chiral α‐tertiary amine motif.
3 d Transition Metal‐Catalyzed Hydrogenation of Nitriles and Alkynes
Authors: Sharma Dipesh M. , Punji Benudhar
Published: February 2020

Selective hydrogenation of nitriles and alkynes is crucial considering the vast applications of reduced products in industries and in the synthesis of bioactive compounds. Particularly, the late 3d transition metal catalysts (manganese, iron, cobalt, nickel and copper) have shown promising activity for the hydrogenation of nitriles to primary amines, secondary amines and imines. Similarly, semihydrogenation of alkynes to E‐ and Z‐alkenes by 3d metals is adequately successful both via the transfer hydrogenation and by using molecular hydrogen. The emergence of 3d transition metals in the selective synthesis of industrially relevant amines, imines and alkenes makes this protocol more attractive. Herein, we provide a concise overview on the late 3d transition metal‐catalyzed hydrogenation of nitriles to amines and imines as well as semihydrogenation of alkynes to alkenes.
Hexaarylbutadiene: A Versatile Scaffold with Tunable Redox Properties towards Organic Near‐Infrared Electrochromic Material
Authors: Ishigaki Yusuke , Harimoto Takashi , Sugimoto Keisuke , Wu Luyan , Zeng Wenhui , Ye Deju , Suzuki Takanori
Published: February 2020

When the 1,1,4,4‐tetraanilinobutadiene skeleton is attached with two halogenated aryl units at the 2,3‐positions, they undergo facile two‐electron oxidation to give stable dicationic dyes which exhibit a near‐infrared (NIR) absorption whereas the neutral dienes show only pale color. Therefore, a distinct electrochromic response with an absorption change in the NIR region is achieved, which is attracting considerable recent attention from the viewpoint of bioimaging. Herein, we demonstrate that the redox potentials of the 1,1,4,4‐tetraanilinobutadiene can be precisely controlled by the donating properties of the amino group on the aniline unit as well as the number of halogen atoms on the aryl units at 2,3‐positions on the butadiene. In contrast, the NIR absorption bands mainly depend on the number of halogen atoms irrespective to the donating properties of aniline unit. Thus, the hexaarylbutadiene skeleton is proven to be a versatile scaffold to develop less‐explored organic NIR electrochromic materials, whose redox and spectroscopic properties can be finely tuned by modifying/attaching the proper substituents.