bluuebunny/crossref_metadata_2025 huggingface dataset:
Social Contract
Authors: Fabre Cécile
Published: June 2020

Contrast the following two political communities: one is governed by rulers who have not at any point elicited their subjects’ consent to their rulership; the other is governed by rulers who would not be in power were it not for the consent of those who are subject to their laws. According to social contract theory, the former rulers are illegitimate, precisely insofar as they do not govern with the consent of the governed, whereas the latter are legitimate, precisely insofar as they govern with such consent. The thought that the consent of the governed is a necessary condition for political legitimacy is the defining feature of social contract theory. In this entry, I first give a thematic overview of classical social contract theory as articulated in three seminal works: Hobbes'sLeviathan, Locke'sSecond Treatise of Government, and Rousseau'sThe Social Contract. I then sketch out the tradition's legacy in contemporary political philosophy, notably in the works of John Rawls.
Power
Authors: Patton Paul
Published: June 2020

A central concern for many fields of social, political, and moral inquiry, power is defined and described in different ways. This entry canvasses the primary sense of “power as capacity to do or to be something” before examining the distinction commonly drawn between “power to” and “power over.” It outlines differences between consensual and antagonistic approaches to power in society and discusses Lukes's influential definition of power in terms of action against the interests of agents. Criticisms of this approach lead to a consideration of recent definitions of power in normatively neutral terms of action upon the actions of others. Key theorists discussed include Arendt, Dahl, Forst, Foucault, Hobbes, Lukes, Macpherson, Wartenberg, and Weber.
Precautionary Principle
Authors: Munthe Christian
Published: June 2020

Ethical debate linking to the precautionary principle (PP) addresses underlying issues regarding the ethics of risk, uncertainty, and public policy. It has evolved quickly from an initial stage of skepticism and scorn, based on critique regarding unclarity, impracticality, and ethical unjustifiability. Nowadays, these points are incorporated into systematic debates on how to best understand and justify a precautionary approach to decision‐ and policy‐making. The general ethical idea behind PP says that in the face of an activity that may produce great harm, we (or society) have reason to ensure that the activity is not undertaken, unless it has been shown not to impose too serious risks. Recent debate has highlighted an epistemic perspective, dividing the debate into two main areas: (a) epistemic precaution, and (b) ethics of risk, which may be related to each other in different ways. With regard to these dimensions, an ethical theory of precaution needs to clarify what determines whether an activity may produce great harm (actualizing both (a) and (b)), what determines whether or not some risk is too serious (actualizing (b)), and what is required to show that too serious risks are not imposed (actualizing (a)). Several competing basic suggestions are in play regarding these issues, actualizing questions about the relationship between traditional ethical theory and the ethics of risk. All suggestions have wide applicability to contested moral and policy areas regarding the use of technology and environmental action, but much work remains to clarify what difference a sound PP makes for these.
Artificial Intelligence
Authors: Sparrow Robert
Published: June 2020

Artificial intelligences are machines that can perform tasks that are characteristically thought of as requiring intelligence. This entry distinguishes between four different types of artificial intelligence (AI): domain‐specific AI, artificial general intelligence (AGI), sentient AI, and “superintelligence.” Existing AI, which is domain‐specific, raises concerns about algorithmic bias, privacy, surveillance, and social impacts, including the possibility of mass unemployment. It is also vital that decisions reached by AI are available for public scrutiny and justification; the question of when we might be justified in trusting decisions reached by AI remains open. Military uses of AI are especially controversial. Should AGI be realized, these issues will become even more urgent and will be exacerbated by the possibility that political and economic questions might be handed over to artificial general intelligences. The idea of machine sentience raises the problem of other minds in an especially stark form. Questions would also arise as to whether sentient machines would have moral status or be moral persons. Might they even acquire more moral standing than human beings? The suggestion that AI might lead to the emergence of superintelligences, which might pose a threat to the human species, highlights an issue that is central to the ethics of all these sorts of AI: who has the right to make decisions about technologies that have the potential to radically the world we all share?
Development Ethics
Authors: Dower Nigel
Published: June 2020

Development ethics examines the ethical issues concerning the pursuit of socioeconomic development. The emergence of this as a subdiscipline over the past few decades sprung from earlier international debates about development in the second half of the twentieth century, particularly in relation to alleviating world poverty. Different models of development presuppose different concepts of well‐being and of justice which inform them. A development ethic can also be used to critique, if it is seen as unsatisfactory, what is done in the “name” of development by others. One significant disagreement is between those who focus on economic growth and those who argue for more expansive conceptions of well‐being and justice and put stress on factors such as environmental constraints on development. Development ethics is located within the wider framework of global ethics, which informs both the responsibilities of individuals as global citizens and the international responsibilities of nation‐states and business corporations to promote and not impede development.
Fair Trade
Authors: Goff Sarah C.
Published: June 2020

In general, an argument for fairness must specify the grounds of the argument, the relevant claimant(s) and duty‐bearer(s), and the contested goods. Arguments for fair trade are grounded in at least one of the following two reasons. First, trade is a particular kind of relationship with valuable goods at stake, and it is appropriate for the participants in this kind of relationship to have duties of fairness to one another. Second, fairness in a trading relationship is valuable in virtue of its consequences, including its impact beyond the scope of the relationship. Both justifications raise important questions that must be addressed in order to complete an argument for fair trade. Who are the participants in trade? What are the goods that trade produces? Some arguments about fair trade reference a description of trade as an economic relationship between individuals and groups based in different countries. Other arguments reference a description of trade as an economic relationship between nation‐states. A further set of arguments describe trade with reference to the subject of justice, which may consist in practices, dense associations, or institutions. The meaning of an argument for fair trade depends on its description of trade. For all descriptions, however, there is a common question about the appropriate method of ethical reasoning about trade. Should trade be described and evaluated as a distinct subject, so that it makes sense to distinguish between its “internal” fairness and its “external” consequences?
Ubuntu Ethics
Authors: Molefe Motsamai
Published: June 2020

This entry gives the reader some understanding of ubuntu as a moral theory. It begins by providing the reader with a brief exposition of an African metaphysical system informing ubuntu. It proceeds to familiarize the reader with the metaethical debate regarding ethical naturalism and supernaturalism in relation to ubuntu. Next, the four salient interpretations of ubuntu in the literature are considered. This entry also offers the reader a rough sense of applied ethics in the light of ubuntu. It concludes by considering some criticisms against ubuntu.
Engineering Mono‐Chalcogen Nanomaterials for Omnipotent Anticancer Applications: Progress and Challenges
Authors: Xing Chenyang , Yin Peng , Peng Zhengchun , Zhang Han
Published: June 2020

Belonging to the chalcogen group, the elements selenium (Se) and tellurium (Te) are located in Group VI‐A of the periodic table. Zero‐valent nanodimensioned Se (nano‐Se) and Te (nano‐Te) have displayed important biomedical applications in recent years. The past two decades have witnessed an explosion in novel cancer treatment strategies using nano‐Se and nano‐Te as aggressive weapons against tumors. Indeed, they are both inorganic nanomedicines that suppress tumor cell proliferation, diffusion, and metastasis. Abundant synthesis strategies for rational and precise surface decoration of nano‐Se and nano‐Te make them significant players in resisting cancers by means of powerful multi‐modal treatment methods. This review focuses on the design and engineering of nano‐Se‐ and nano‐Te‐based nanodelivery systems and their precise uses in cancer treatment. The corresponding anticancer molecular mechanisms of nano‐Se and nano‐Te are discussed in detail. Given their different photo‐induced behaviors, the presence or absence of near infrared illumination is used as a defining characteristic when describing the anticancer applications of nano‐Se and nano‐Te. Finally, the challenges and future prospects of nano‐Se and nano‐Te are summarized and highlighted.
Cellulose Nanomaterials in Interfacial Evaporators for Desalination: A “Natural” Choice
Authors: Cao Sisi , Rathi Priya , Wu Xuanhao , Ghim Deoukchen , Jun Young‐Shin , Singamaneni Srikanth
Published: June 2020

Herein, the recent advances in realizing highly efficient cellulose‐based solar evaporators for alleviating the global water crisis are summarized. Fresh water scarcity is one of the most threatening issues for sustainable development. Solar steam generation, which harnesses the abundant sunlight, has been recognized as a sustainable approach to harvest fresh water. In contrast to synthetic polymeric materials that can pose serious negative environmental impacts, cellulose‐based materials, owing to their biocompatibility, renewability, and sustainability, are highly attractive for realizing solar steam generators. The molecular and macromolecular features of cellulose and the physicochemical properties of extracted cellulose nanoparticles (cellulose nanocrystals and cellulose nanofibrils (CNF)) and natural cellulose materials (wood and bacterial nanocellulose (BNC)) that make them attractive as supporting substrate materials in solar steam generators are briefly discussed. Recent progress in designing highly efficient cellulose‐based solar evaporators, including utilizing extracted cellulose nanoparticles via bottom‐up assembly CNF, natural cellulose materials with intrinsic hierarchical structure (wood and BNC), and commercial planar cellulose substrates (air‐laid paper, cellulose paper, and cotton fabric) is reviewed. The outstanding challenges that need to be addressed for these materials and devices to be utilized in the real‐world and in overcoming global water crisis are also briefly highlighted.
Controllable Singlet–Triplet Energy Splitting of Graphene Quantum Dots through Oxidation: From Phosphorescence to TADF
Authors: Park Minsu , Kim Hyung Suk , Yoon Hyewon , Kim Jin , Lee Sukki , Yoo Seunghyup , Jeon Seokwoo
Published: June 2020

Long‐lived afterglow emissions, such as room‐temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF), are beneficial in the fields of displays, bioimaging, and data security. However, it is challenging to realize a single material that simultaneously exhibits both RTP and TADF properties with their relative strengths varied in a controlled manner. Herein, a new design approach is reported to control singlet–triplet energy splitting (∆EST) in graphene quantum dots (GQD)/graphene oxide quantum dots (GOQDs) by varying the ratio of oxygenated carbon to sp2 carbon (γOC). It is demonstrated that ∆EST decreases from 0.365 to 0.123 eV as γOC increases from 4.63% to 59.6%, which in turn induces a dramatic transition from RTP to TADF. Matrix‐assisted stabilization of triplet excited states provides ultralong lifetimes to both RTP and TADF. Embedded in boron oxynitride, the low oxidized (4.63%) GQD exhibits an RTP lifetime (τTavg) of 783 ms, and the highly oxidized (59.6%) GOQD exhibits a TADF lifetime (τDFavg) of 125 ms. Furthermore, the long‐lived RTP and TADF materials enable the first demonstration of anticounterfeiting and multilevel information security using GQD. These results will open up a new approach to the engineering of singlet–triplet splitting in GQD for controlled realization of smart multimodal afterglow materials.
Mesoporous PdAg Nanospheres for Stable Electrochemical CO2 Reduction to Formate
Authors: Zhou Yuan , Zhou Rui , Zhu Xiaorong , Han Na , Song Bin , Liu Tongchao , Hu Guangzhi , Li Yafei , Lu Jun , Li Yanguang
Published: June 2020

Palladium is a promising material for electrochemical CO2 reduction to formate with high Faradaic efficiency near the equilibrium potential. It unfortunately suffers from problematic operation stability due to CO poisoning on surface. Here, it is demonstrated that alloying is an effective strategy to alleviate this problem. Mesoporous PdAg nanospheres with uniform size and composition are prepared from the co‐reduction of palladium and silver precursors in aqueous solution using dioctadecyldimethylammonium chloride as the structure‐directing agent. The best candidate can initiate CO2 reduction at zero overpotential and achieve high formate selectivity close to 100% and great stability even at <‐0.2 V versus reversible hydrogen electrode. The high selectivity and stability are believed to result from the electronic coupling between Pd and Ag, which lowers the d‐band center of Pd and thereby significantly enhances its CO tolerance, as evidenced by both electrochemical analysis and theoretical simulations.
Changes of Structure and Bonding with Thickness in Chalcogenide Thin Films
Authors: Ronneberger Ider , Zanolli Zeila , Wuttig Matthias , Mazzarello Riccardo
Published: June 2020

Extreme miniaturization is known to be detrimental for certain properties, such as ferroelectricity in perovskite oxide films below a critical thickness. Remarkably, few‐layer crystalline films of monochalcogenides display robust in‐plane ferroelectricity with potential applications in nanoelectronics. These applications critically depend on the electronic properties and the nature of bonding in the 2D limit. A fundamental open question is thus to what extent bulk properties persist in thin films. Here, this question is addressed by a first‐principles study of the structural, electronic, and ferroelectric properties of selected monochalcogenides (GeSe, GeTe, SnSe, and SnTe) as a function of film thickness up to 18 bilayers. While in selenides a few bilayers are sufficient to recover the bulk behavior, the Te‐based compounds deviate strongly from the bulk, irrespective of the slab thickness. These results are explained in terms of depolarizing fields in Te‐based slabs and the different nature of the chemical bond in selenides and tellurides. It is shown that GeTe and SnTe slabs inherit metavalent bonding of the bulk phase, despite structural and electronic properties being strongly modified in thin films. This understanding of the nature of bonding in few‐layers structures offers a powerful tool to tune materials properties for applications in information technology.
Lipid‐Bilayer‐Supported 3D Printing of Human Cerebral Cortex Cells Reveals Developmental Interactions
Authors: Zhou Linna , Wolfes Anne C. , Li Yichen , Chan Danny C. W. , Ko Ho , Szele Francis G. , Bayley Hagan
Published: June 2020

Current understanding of human brain development is rudimentary due to suboptimal in vitro and animal models. In particular, how initial cell positions impact subsequent human cortical development is unclear because experimental spatial control of cortical cell arrangement is technically challenging. 3D cell printing provides a rapid customized approach for patterning. However, it has relied on materials that do not represent the extracellular matrix (ECM) of brain tissue. Therefore, in the present work, a lipid‐bilayer‐supported printing technique is developed to 3D print human cortical cells in the soft, biocompatible ECM, Matrigel. Printed human neural stem cells (hNSCs) show high viability, neural differentiation, and the formation of functional, stimulus‐responsive neural networks. By using prepatterned arrangements of neurons and astrocytes, it is found that hNSC process outgrowth and migration into cell‐free matrix and into astrocyte‐containing matrix are similar in extent. However, astrocytes enhance the later developmental event of axon bundling. Both young and mature neurons migrate into compartments containing astrocytes; in contrast, astrocytes do not migrate into neuronal domains signifying nonreciprocal chemorepulsion. Therefore, precise prepatterning by 3D printing allows the construction of natural and unnatural patterns that yield important insights into human cerebral cortex development.
Fully Inkjet‐Printed, Ultrathin and Conformable Organic Photovoltaics as Power Source Based on Cross‐Linked PEDOT:PSS Electrodes
Authors: Bihar Eloïse , Corzo Daniel , Hidalgo Tania C. , Rosas‐Villalva Diego , Salama Khaled N. , Inal Sahika , Baran Derya
Published: June 2020

Ultra‐lightweight solar cells have attracted enormous attention due to their ultra‐conformability, flexibility, and compatibility with applications including electronic skin or miniaturized electronics for biological applications. With the latest advancements in printing technologies, printing ultrathin electronics is becoming now a reality. This work offers an easy path to fabricate indium tin oxide (ITO)‐free ultra‐lightweight organic solar cells through inkjet‐printing while preserving high efficiencies. A method consisting of the modification of a poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) ink with a methoxysilane‐based cross‐linker (3‐glycidyloxypropyl)trimethoxysilane (GOPS)) is presented to chemically modify the structure of the electrode layer. Combined with plasma and solvent post‐treatments, this approach prevents shunts and ensures precise patterning of solar cells. By using poly(3‐hexylthiophene) along rhodanine‐benzothiadiazole‐coupled indacenodithiophene (P3HT:O‐IDTBR), the power conversion efficiency (PCE) of the fully printed solar cells is boosted up to 4.73% and fill factors approaching 65%. All inkjet‐printed ultrathin solar cells on a 1.7 µm thick biocompatible parylene substrate are fabricated with PCE reaching up to 3.6% and high power‐per‐weight values of 6.3 W g−1. After encapsulation, the cells retain their performance after being exposed for 6 h to aqueous environments such as water, seawater, or phosphate buffered saline, paving the way for their integration in more complex circuits for biological systems.
Selective and Sensitive Photon Sieve Based on III–V Semiconductor Nanowire Forest Fabricated by Lithography‐Free Process
Authors: Lee Gil Ju , Park Kwangwook , Kim Min Seok , Chang Sehui , Seok Tae Joon , Park Hong‐Gyu , Ju Gunwu , Kim Kyujung , Song Young Min
Published: June 2020

Vertically oriented semiconductor nanowires (NWs) have been intensely studied in macroscopic perspective due to their attractive applications such as optical filters, photodiodes, and solar cells. However, microscopic photonic phenomena of dense and random NWs have been rarely, and their promising applications have not been explored. Therefore, this article theoretically and experimentally investigates the microscopic photonic event of dense and random NWs using highly selective and sensitive photon sieve (SSPS), which employs highly populated III/V semiconductor NW forests fabricated with a lithography‐free self‐catalyzed growth method. Theoretical analyses reveal that diameter‐dependent and selective photon absorption occurs even for a dense and disordered NW distribution. The engineered growth process affords highly populated NW forests (mean shortest interval = 192.4 nm) comprising NWs with a high aspect ratio (mean aspect ratio = 34.3) and a sufficiently broad diameter distribution to span the visible spectrum and decompose it (mean diameter = 94 nm, standard deviation = 49 nm). Moreover, the SSPS exhibits unique spectral responses to monochromatic light of different wavelengths (correlation coefficients < 0.03) and a high sensitivity with a highest absorptivity of 92.4%. This work indicates SSPSs can be utilized for various applications of artificial photoreceptor, physically unclonable function, and high efficient optoelectronics.
Dual‐Function Fluorescent Covalent Organic Frameworks: HCl Sensing and Photocatalytic H2 Evolution from Water
Authors: EL‐Mahdy Ahmed F. M. , Elewa Ahmed M. , Huang Sheng‐Wen , Chou Ho‐Hsiu , Kuo Shiao‐Wei
Published: June 2020

Two ultrastable luminescent covalent organic frameworks (COFs), PyTA‐BC and PyTA‐BC‐Ph, are synthesized through polycondensations of 4,4′,4″,4′″‐pyrene‐1,3,6,8‐tetrayl)tetraaniline (PyTA‐4NH2) with two carbazole‐based derivatives having different degrees of conjugation. The PyTA‐BC and PyTA‐BC‐Ph COFs exhibit ultrahigh thermal stabilities (up to 421 °C), excellent crystallinity, and high Brunauer–Emmett–Teller surface areas (up to 1445 m2 g−1). These COFs display strong fluorescence emissions in various solvents, with their emission maxima gradually red‐shifting upon increasing the polarity of the solvent (solvatochromism). Upon exposure to HCl, they respond very rapidly and sensitively in terms of changing their colors and fluorescence emission maxima. In the presence of a sacrificial electron donor, these COFs mediate the highly efficient photocatalytic evolution of H2 from water. In the absence of a noble metal cocatalyst, the COFs and ascorbic acid provide a photocatalytic H2 production of up to 1183 µmol g−1 h−1 (λ ≥ 420 nm); this value is the highest reported to date for a COF. Such COFs appear to be potentially useful as chemosensors for the naked‐eye and sensitive spectroscopic detection of HCl and as cocatalysts for the sustainable photocatalytic production of H2 from water.
Reversible Emitting Anti‐Counterfeiting Ink Prepared by Anthraquinone‐Modified β‐Cyclodextrin Supramolecular Polymer
Authors: Chen Lei , Chen Yong , Fu Hong‐Guang , Liu Yu
Published: June 2020

Intelligent fluorescent materials have been paid more and more attention due to their wide application in information encryption and anti‐counterfeiting materials. Herein, a supramolecular polymer is constructed through the host–guest interaction of anthraquinone‐modified β‐cyclodextrin (AQ‐β‐CD) in aqueous solution. Thanks to the hydrophobic microenvironment of the cyclodextrin cavity and the shielding effect on oxygen molecules, the anthraquinone group, as the guest molecule, can rapidly produce 9,10‐anthracenediol (QH2) with strong fluorescence by photoreduction. Interestingly, the generated anthracenediol group is still sensitive to oxygen and can be converted to anthraquinone by oxygen. Significantly, aqueous solution of AQ‐β‐CD supermolecular polymer is used as emitting ink, which decrypts the information by ultraviolet light and encrypts the information in the air.
Axially Chiral Biphenyl Compound‐Based Thermally Activated Delayed Fluorescent Materials for High‐Performance Circularly Polarized Organic Light‐Emitting Diodes
Authors: Tu Zhen‐Long , Yan Zhi‐Ping , Liang Xiao , Chen Lei , Wu Zheng‐Guang , Wang Yi , Zheng You‐Xuan , Zuo Jing‐Lin , Pan Yi
Published: June 2020

To boost intrinsic circularly polarized luminescence (CPL) properties of chiral emitters, an axially chiral biphenyl unit is inlaid in thermally activated delayed fluorescent (TADF) skeleton, urging the participation of chiral source in frontier molecular orbital distributions. A pair of enantiomers, (R)‐BPPOACZ and (S)‐BPPOACZ, containing the cyano as electron‐withdrawing moieties and carbazole and phenoxazine as electron‐donating units are synthesized and separated. The circularly polarized TADF enantiomers exhibit both high photoluminescence quantum yield of 86.10% and excellent CPL activities with maximum dissymmetry factor |gPL| values of almost 10−2 in solution and 1.8 × 10−2 in doped film, which are among the best values of previously reported small chiral organic materials. Moreover, the circularly polarized organic light‐emitting diodes based on the TADF enantiomers achieve the maximum external quantum efficiency of 16.6% with extremely low efficiency roll‐off. Obvious circularly polarized electroluminescence signals with |gEL| values of 4 × 10−3 are also recorded.
Development and Applications of Water‐based Extraction Methods in Natural Products Isolation Chemistry
Authors: Deans Bianca J. , Just Jeremy , Smith Jason A. , Bissember Alex C.
Published: June 2020

This minireview presents and discusses natural product isolation studies that have been facilitated using predominately water‐based extraction methods over the past twenty years. The development and applications of new techniques for enabling natural products chemistry are examined. This includes techniques such as accelerated solvent extraction (ASE) and pressurised hot water extraction (PHWE). The latter, in particular, arguably represents an emerging approach that can allow for the rapid, efficient, and practical extraction of natural products by more environmentally‐benign approaches.
Activity‐Based Genetically Encoded Fluorescent and Luminescent Probes for Detecting Formaldehyde in Living Cells
Authors: Zhang Yuqing , Du Yimeng , Li Manjia , Zhang Dong , Xiang Zheng , Peng Tao
Published: June 2020

Formaldehyde (FA) is endogenously produced in living systems through a variety of biological processes and has been implicated in many pathological conditions. Detection tools for biological FA are therefore of great interest. Reported here are novel activity‐based genetically encoded fluorescent and luminescent probes for detecting FA in aqueous solutions and living mammalian cells. A FA‐reactive lysine analogue, PrAK, was site‐specifically incorporated into the essential lysine sites of enhanced green fluorescent protein (EGFP) and firefly luciferase (fLuc) to afford fluorescent and luminescent FA probes, respectively. FA selectively reacts with PrAK residues on EGFP and fLuc through a 2‐aza‐Cope rearrangement, resulting in fluorescence and luminescence turn‐on responses, respectively, to FA selectively over potentially interfering reactive species in aqueous buffer. Moreover, the genetically encoded probes are capable of visualizing FA at physiologically relevant levels in living mammalian cells by fluorescence and luminescence imaging, demonstrating their potential as new tools to explore FA biology.
Benetzungsvorgänge und ihr Einfluss auf die elektrochemischen Eigenschaften von oberflächenangepassten Lithium‐Metall‐Elektroden in Kontakt mit quervernetzten Polymer‐Elektrolyten
Authors: Zhang Mengyi , Becking Jens , Stan Marian Cristian , Lenoch Arthur , Bieker Peter , Kolek Martin , Winter Martin
Published: June 2020

Lithium‐Metall‐Batterien (LMBs) auf Basis von vernetzten Polymer‐Elektrolyten (PEs) sind vielversprechende Kandidaten für Batterien der nächsten Generation. Das Benetzungsverhalten von PEs auf unebenen Lithium‐Metall‐Oberflächen wurde jedoch in den meisten Studien bisher vernachlässigt. Hier wird gezeigt, dass mikroskalige Defektstellen mit gekrümmten Kanten eine entscheidende Rolle bei der benetzungsabhängigen, elektrochemischen Abscheidung von Lithium (Li) spielen. Die Benetzbarkeit und die viskoelastischen Eigenschaften von PEs werden in Zusammenhang gebracht und es wird der Einfluss der Benetzbarkeit auf die Keimbildung und Diffusion in der Nähe der Li|PE‐Grenzfläche untersucht. Es wird festgestellt, dass die Krümmung der Kanten an Li‐Defektstellen ein entscheidender Einflussfaktor für die Untersuchung von Benetzungsphänomenen ist. Das Auftreten von mikroskaligen Defekten und partieller Phasenseparation werden als Kernpunkte für unregelmäßige Nukleation identifiziert. Es wird betont, dass für eine stabile und beständige Langzeit‐Zyklenstabilität von PE‐basierten LMBs ein tieferes Verständnis des “weichen Festkörper”‐Festkörper‐Kontakts zwischen PEs und intrinsisch rauen Li‐Metall‐Oberflächen erforderlich ist.
Dual Role of Silver Moieties Coupled with Ordered Mesoporous Cobalt Oxide towards Electrocatalytic Oxygen Evolution Reaction
Authors: Yu Mingquan , Moon Gun‐hee , Castillo Rebeca G. , DeBeer Serena , Weidenthaler Claudia , Tüysüz Harun
Published: June 2020

Herein, we show that the performance of mesostructured cobalt oxide electrocatalyst for oxygen evolution reaction (OER) can be significantly enhanced by coupling of silver species. Various analysis techniques including pair distribution function and Rietveld refinement, X‐ray absorption spectroscopy at synchrotron as well as advanced electron microscopy revealed that silver exists as metallic Ag particles and well‐dispersed Ag2O nanoclusters within the mesostructure. The benefits of this synergy are twofold for OER: highly conductive metallic Ag improves the charge transfer ability of the electrocatalysts while ultra‐small Ag2O clusters provide the centers that can uptake Fe impurities from KOH electrolyte and boost the catalytic efficiency of Co–Ag oxides. The current density of mesostructured Co3O4 at 1.7 VRHE is increased from 102 to 211 mA cm−2 with incorporation of silver spices. This work presents the dual role of silver moieties and demonstrates a simple method to increase the OER activity of Co3O4.
Sensitive Morphological Characterization of Oriented High‐Density Lipoprotein Nanoparticles Using 31P NMR Spectroscopy
Authors: Lau Sophie , Middleton David A.
Published: June 2020

The biological function of high‐density lipoprotein (HDL) nanoparticles, the so‐called good cholesterol that is associated with a low risk of heart disease, depends on their composition, morphology, and size. The morphology of HDL particles composed of apolipoproteins, lipids and cholesterol is routinely visualised by transmission electron microscopy (TEM), but higher‐resolution tools are needed to observe more subtle structural differences between particles of different composition. Here, reconstituted HDL formulations are oriented on glass substrates and solid‐state 31P NMR spectroscopy is shown to be highly sensitive to the surface curvature of the lipid headgroups. The spectra report potentially functionally important differences in the morphology of different HDL preparations that are not detected by TEM. This method provides new morphological insights into HDL comprising a naturally occurring apolipoprotein A‐I mutant, which may be linked to its atheroprotective properties, and holds promise as a future research tool in the clinical analysis of plasma HDL.
Highly Conducting and Flexible Radical Crystals
Authors: Kwon Taeyeon , Koo Jin Young , Choi Hee Cheul
Published: June 2020

Together with high conductivity, high flexibility is an important property required for next generation organic electronic components. Both properties are difficult to achieve together especially when the components are crystalline because of the intrinsic high brittleness of organic molecular crystals. We report an organic radical crystal system that has both high flexibility and high conductivity. The crystal consists of 9,10‐bis(phenylethynyl)anthracene radical cation (BPEA.+) units, and shows flexibility under pressure with high conductivity in ambient condition exhibiting average conductivity of 2.68 S cm−1 when normal linear shape, as well as 2.43 S cm−1 when bent. The structural analysis reveals that both a short π–π distance (3.290 Å) between BPEA.+ units that are aligned along the crystal length direction, and the presence of PF6− counter ions induce flexibility and high electrical conductivity.
TEAD–YAP Interaction Inhibitors and MDM2 Binders from DNA‐Encoded Indole‐Focused Ugi Peptidomimetics
Authors: Kunig Verena B. K. , Potowski Marco , Akbarzadeh Mohammad , Klika Škopić Mateja , dos Santos Smith Denise , Arendt Lukas , Dormuth Ina , Adihou Hélène , Andlovic Blaž , Karatas Hacer , Shaabani Shabnam , Zarganes‐Tzitzikas Tryfon , Neochoritis Constantinos G. , Zhang Ran , Groves Matthew , Guéret Stéphanie M. , Ottmann Christian , Rahnenführer Jörg , Fried Roland , Dömling Alexander , Brunschweiger Andreas
Published: June 2020

DNA‐encoded combinatorial synthesis provides efficient and dense coverage of chemical space around privileged molecular structures. The indole side chain of tryptophan plays a prominent role in key, or “hot spot”, regions of protein–protein interactions. A DNA‐encoded combinatorial peptoid library was designed based on the Ugi four‐component reaction by employing tryptophan‐mimetic indole side chains to probe the surface of target proteins. Several peptoids were synthesized on a chemically stable hexathymidine adapter oligonucleotide “hexT”, encoded by DNA sequences, and substituted by azide‐alkyne cycloaddition to yield a library of 8112 molecules. Selection experiments for the tumor‐relevant proteins MDM2 and TEAD4 yielded MDM2 binders and a novel class of TEAD‐YAP interaction inhibitors that perturbed the expression of a gene under the control of these Hippo pathway effectors.
Rational Design of the Metal‐Free KBe2BO3F2⋅(KBBF) Family Member C(NH2)3SO3F with Ultraviolet Optical Nonlinearity
Authors: Luo Min , Lin Chensheng , Lin Donghong , Ye Ning
Published: June 2020

The first fluorosulfonic ultraviolet (UV) nonlinear optical (NLO) material, C(NH2)3SO3F, is rationally designed by taking KBe2BO3F2 (KBBF) as the parent compound. C(NH2)3SO3F features similar topological layers as KBBF by replacing inorganic (BO3)3− with organic C(NH2)3+ trigonal units and BeO3F with SO3F− tetrahedra. Therefore, C(NH2)3SO3F is a metal‐free UV NLO crystal. Benefiting from the coplanar configuration of the C(NH2)3+ cationic groups, it possesses a large SHG response of 5×KDP and moderate birefringence of 0.133@1064 nm. Besides, it has a short UV cutoff edge of 200 nm. The calculated results reveal the shortest SHG phase‐matching wavelengths can reach 200 nm. These findings highlight the exploration of metal‐free compounds as nontoxic and low‐cost UV NLO materials as a new research area.
Nanostructured Micelle Nanotubes Self‐Assembled from Dinucleobase Monomers in Water
Authors: Aparicio Fátima , Chamorro Paula B. , Chamorro Raquel , Casado Santiago , González‐Rodríguez David
Published: June 2020

Despite the central importance of aqueous amphiphile assemblies in science and industry, the size and shape of these nano‐objects is often difficult to control with accuracy owing to the non‐directional nature of the hydrophobic interactions that sustain them. Here, using a bioinspired strategy that consists of programming an amphiphile with shielded directional Watson–Crick hydrogen‐bonding functions, its self‐assembly in water was guided toward a novel family of chiral micelle nanotubes with partially filled lipophilic pores of about 2 nm in diameter. Moreover, these tailored nanotubes are successfully demonstrated to extract and host molecules that are complementary in size and chemical affinity.
Probing the Activity of Iron Peroxo Porphyrin Intermediates in the Reaction Layer during the Electrochemical Reductive Activation of O2
Authors: Noel Jean‐Marc , Kostopoulos Nikolaos , Achaibou Célia , Fave Claire , Anxolabéhère‐Mallart Elodie , Kanoufi Frédéric
Published: June 2020

Herein we report the first example of using scanning electrochemical microscopy (SECM) to quantitatively analyze O2 reductive activation in organic media catalyzed by three different Fe porphyrins. For each porphyrin, SECM can provide in one single experiment the redox potential of various intermediates, the association constant of FeII with O2, and the pKa of the FeIII(OOH−)/ FeIII(OO2−) couple. The results obtained can contribute to a further understanding of the parameters controlling the catalytic efficiency of the Fe porphyrin towards O2 activation and reduction.
Cooperativity of Catechols and Amines in High‐Performance Dry/Wet Adhesives
Authors: Tiu Brylee David B. , Delparastan Peyman , Ney Max R. , Gerst Matthias , Messersmith Phillip B.
Published: June 2020

The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino‐catechol synergy, polymeric pressure‐sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel‐inspired lysine‐ and aromatic‐rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM‐assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance.
Mechanically Assisted Bioluminescence with Natural Luciferase
Authors: Schramm Stefan , Al‐Handawi Marieh B. , Karothu Durga Prasad , Kurlevskaya Anastasiya , Commins Patrick , Mitani Yasuo , Wu Chun , Ohmiya Yoshihiro , Naumov Panče
Published: June 2020

Mechanochemical analogues have recently been established for several enzymatic reactions, but they require periodic interruption of the reaction for sampling, dissolution, and (bio)chemical analysis to monitor their progress. By applying a mechanochemical procedure to induce bioluminescence analogous to that used by the marine ostracod Cypridina (Vargula) hilgendorfii, here we demonstrate that the light emitted by a bioluminescent reaction can be used to directly monitor the progress of a mechanoenzymatic reaction without sampling. Mechanical treatment of Cypridina luciferase with luciferin generates bright blue light which can be readily detected and analyzed spectroscopically. This mechanically assisted bioluminescence proceeds through a mechanism identical to that of bioluminescence in solution, but has higher activation energy due to being diffusion‐controlled in the viscous matrix. The results suggest that luciferases could be used as light‐emissive reporters of mechanoenzymatic reactions.
Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity
Authors: Abet Valentina , Szczypiński Filip T. , Little Marc A. , Santolini Valentina , Jones Christopher D. , Evans Robert , Wilson Craig , Wu Xiaofeng , Thorne Michael F. , Bennison Michael J. , Cui Peng , Cooper Andrew I. , Jelfs Kim E. , Slater Anna G.
Published: June 2020

Many interesting target guest molecules have low symmetry, yet most methods for synthesising hosts result in highly symmetrical capsules. Methods of generating lower symmetry pores are thus required to maximise the binding affinity in host–guest complexes. Herein, we use mixtures of tetraaldehyde building blocks with cyclohexanediamine to access low‐symmetry imine cages. Whether a low‐energy cage is isolated can be correctly predicted from the thermodynamic preference observed in computational models. The stability of the observed structures depends on the geometrical match of the aldehyde building blocks. One bent aldehyde stands out as unable to assemble into high‐symmetry cages‐and the same aldehyde generates low‐symmetry socially self‐sorted cages when combined with a linear aldehyde. We exploit this finding to synthesise a family of low‐symmetry cages containing heteroatoms, illustrating that pores of varying geometries and surface chemistries may be reliably accessed through computational prediction and self‐sorting.
Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization, optical properties and photocatalytic activity
Authors: Said Mohamed I. , Aly Aref A.M. , El‐Said Asma I. , Abou‐Taleb Asia
Published: June 2020

A zinc coordination polymer derived from pyridine‐2,6‐dicarboxylate (PDC), {[Zn2(PDC)2]}n, was successfully prepared via conventional, sonication and microwave‐irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X‐ray diffraction and spectroscopic techniques. The so obtained CPs were heat‐treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere‐like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.
The peridural membrane of the spine has characteristics of synovium
Authors: Bosscher Hemmo A. , Grozdanov Petar N. , Warraich Irfan I. , MacDonald Clinton C. , Day Miles R.
Published: June 2020

The peridural membrane (PDM) is a well‐defined structure between dura mater and the wall of the spinal canal. The spine may be viewed as a multi‐segmented joint, with the epidural cavity and neural foramina as joint spaces and PDM as synovial lining. The objective of this investigation was to determine if PDM has histological characteristics of synovium. Samples of the PDM of the thoraco‐lumbar spine were taken from 23 human cadavers and analyzed with conventional light microscopy and confocal microscopy. Results were compared to reports on similar analyses of synovium in the literature. Histological distribution of areolar, fibrous, and adipose connective tissue in PDM was similar to synovium. The PDM has an intima and sub‐intima. No basement membrane was identified. CD68, a marker for macrophage‐like‐synoviocytes, and CD55, a marker for fibroblast‐like synoviocytes, were seen in the lining and sub‐lining of the PDM. Multifunctional hyaluronan receptor CD44 and hyaluronic acid synthetase 2 marker HAS2 were abundantly present throughout the membrane. Marked presence of CD44, CD55, and HAS2 in the well‐developed tunica muscularis of blood vessels and in the body of the PDM suggests a role in the maintenance and lubrication of the epidural cavity and neural foramina. Presence of CD68, CD55, and CD44 suggests a scavenging function and a role in the inflammatory response to noxious stimuli. Thus, the human PDM has histological and immunohistochemical characteristics of synovium. This suggests that the PDM may be important for the homeostasis of the flexible spine and the neural structures it contains.
Quinoline‐based promising anticancer and antibacterial agents, and some metabolic enzyme inhibitors
Authors: Ökten Salih , Aydın Ali , Koçyiğit Ümit M. , Çakmak Osman , Erkan Sultan , Andac Cenk A. , Taslimi Parham , Gülçin İlhami
Published: June 2020

A series of substituted quinolines was screened for their antiproliferative, cytotoxic, antibacterial activities, DNA/protein binding affinity, and anticholinergic properties by using the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide cell proliferation, lactate dehydrogenase cytotoxicity, and microdilution assays, the Wolfe–Shimmer equality method, the Ellman method, and the esterase assay, respectively. The results of the cytotoxic and anticancer activities of the compounds displayed that 6‐bromotetrahydroquinoline (2), 6,8‐dibromotetrahydroquinoline (3), 8‐bromo‐6‐cyanoquinoline (10), 5‐bromo‐6,8‐dimethoxyquinoline (12), the novel N‐nitrated 6,8‐dimethoxyquinoline (13), and 5,7‐dibromo‐8‐hydroxyquinoline (17) showed a significant antiproliferative potency against the A549, HeLa, HT29, Hep3B, and MCF7 cancer cell lines (IC50 = 2–50 μg/ml) and low cytotoxicity (∼7–35%) as the controls, 5‐fluorouracil and cisplatin. The compound–DNA linkages are hyperchromic or hypochromic, causing variations in their spectra. This situation shows that they can be bound to DNA with the groove‐binding mode, with Kb value in the range of 2.0 × 103–2.2 × 105 M–1. Studies on human Gram(+) and Gram(−) pathogenic bacteria showed that the substituted quinolines exhibited selective antimicrobial activities with MIC values of 62.50–250 μg/ml. All tested quinoline derivatives were found to be effective inhibitors of acetylcholinesterase (AChE) and the human carbonic anhydrase I and II isoforms (hCA I and II), with Ki values of 46.04–956.82 nM for hCA I, 54.95–976.93 nM for hCA II, and 5.51–155.22 nM for AChE. As a result, the preliminary data showed that substituted quinolines displayed effective pharmacological features. Molecular docking studies were performed to investigate the binding modes and interaction energies for compounds 2–17 with AChE (PDB ID: 4EY6), hCA I (PDB ID: 1BMZ), and hCA II (PDB ID: 2ABE).
Synthesis of Bifunctional Silsesquioxanes and Spherosilicates with Organogermyl Functionalities
Authors: Grzelak Magdalena , Marciniec Bogdan
Published: June 2020

In this paper we present the synthesis of mixed bifunctional compounds of T8H8 silsesquioxane and spherosilicate (HSiMe2O)8Si8O12 derivatives via platinum‐catalyzed hydrosilylation of alkenylgermanes and olefins. To the best of our knowledge, this is the first literature example of bifunctional compounds with organogermyl functionalities. Eleven mixed systems with a variety of substituents (Si−H, alkyl, germyl, epoxy, and hydroxy) were prepared and fully characterized by NMR spectroscopy. Additionally, our research includes a real‐time FT‐IR study of the synthesis of these bifunctional compounds of the general formula (R)8‐m(GeR’3(CH2)n+2R)mSi8O12. and (R’’(CH2)2R)8‐m(GeR’3(CH2)2R)mSi8O12 where m∼4.
Rapid and label‐free electrochemical DNA biosensor based on a facile one‐step electrochemical synthesis of rGO–PPy–(L‐Cys)–AuNPs nanocomposite for the HTLV‐1 oligonucleotide detection
Authors: Fani Mona , Rezayi Majid , Pourianfar Hamid R. , Meshkat Zahra , Makvandi Manoocher , Gholami Mehrdad , Rezaee Seyed Abdolrahim
Published: June 2020

Human T cell leukemia virus type 1 (HTLV‐1) as the first human retrovirus is currently a serious endemic health challenge. Despite the use of assorted molecular or serological assays for HTLV‐1 detection, there are several limitations due to the lack of a confirmatory test that may affect the accuracy of the results. Herein, a novel label‐free biosensor for the detection of HTLV‐1 Tax gene has been reported. An electrochemical facile ecofriendly synthesis method has been demonstrated based on a synthesis of nanocomposite of reduced graphene oxide, polypyrrole, and gold nanoparticles (rGO–PPy–(l‐Cys)–AuNPs) deposited on the surface of screen‐printed carbon electrode. Electrochemical techniques were used to characterize and study the electrochemical behavior of the rGO–PPy–(l‐Cys)–AuNPs, which exhibited a stable reference peak at 0.21 V associated with hybridization forms by applying the differential pulse voltammetry. The designed DNA biosensor presented a wide linear range from 0.1 fM to 100 µM and a low detection limit of 20 atto‐molar. The proposed biosensor presented in this study provides outstanding selectivity, sensitivity, repeatability, and reproducibility.