bluuebunny/crossref_metadata_2025 huggingface dataset:
Rationalizing the Thermal Response of Dual‐Center Molecular Thermometers: The Example of an Eu/Tb Coordination Complex
Authors: Carneiro Neto Albano N. , Mamontova Ekaterina , Botas Alexandre M. P. , Brites Carlos D. S. , Ferreira Rute A. S. , Rouquette Jérôme , Guari Yannick , Larionova Joulia , Long Jérôme , Carlos Luís D.
Published: December 2021

Luminescence thermometry allows the remote monitoring of the temperature and holds the promise to drive the next generation of future nano or micrometric devices. Materials able to sense the temperature are usually based on one or several lanthanide ions allowing a ratiometric measurement. Optimizing the thermometric features is usually achieved through a serendipity approach, but it still appears difficult to accurately predict the sensing performance. Through a combination of experiment and theoretical calculations, the first example of an energy‐driven luminescent molecular thermometer [Tb0.94Eu0.06(bpy)2(NO3)3] (bpy = 2,2′‐bipydine) displaying an exceptional thermal cyclability around room temperature is reported, for which the thermal properties could be theoretically forecasted. This work provides comprehensive guidelines that can be easily extended for any dual‐center thermometer in which energy transfer drives the thermometric performance opening the avenue for the smart engineering of sensing devices.
Tailoring Transition Dipole Moment in Colloidal Nanocrystal Thin Film on Nanocomposite Materials
Authors: Lee Kwang Jin , Kim Gahyeon , Lim Joonhyung , Nah Sanghee , Jeong Kwang Seob , Cho Minhaeng
Published: December 2021

Controlling the transition dipole moment is extremely important for various photophysical characteristics in semiconductors. Especially, suppression of Auger recombination in quantum dots (QDs) is essential for the development of novel applications, including bioimaging, lasing, and optoelectronic devices. To date, most of the studies on the Auger process are conducted on the basis of manipulating the material property such as wavefunction of electron and hole, energy band, and confinement potential. However, a new way of tuning the Auger process using nanocomposite materials is not reported. In this work, the biexciton Auger recombination (BAR) process in CdSe/CdS(1 ML) nanocrystal thin‐film is successfully controlled by introducing nanocomposite materials. Performing pump intensity‐dependent transient absorption experiments, a significant reduction (up to 30%) of BAR rate is observed in the presence of nanocomposite structures. This notable suppression effect is attributed to the modulation of the net transition dipole moment. These findings will provide further insight into the rational design of QDs combining with a nanostructure that efficiently suppresses Auger recombination rates.
In‐Plane Field‐Driven Excitonic Electro‐Optic Modulation in Monolayer Semiconductor
Authors: Vella Daniele , Barbosa Marcelo B. , Trevisanutto Paolo E. , Verzhbitskiy Ivan , Zhou Justin Yong , Watanabe Kenji , Taniguchi Takashi , Kajikawa Kotaro , Eda Goki
Published: December 2021

2D semiconductors are attractive candidates for on‐chip electro‐optic modulators due to their ease of integration and rich exciton‐mediated phenomena. While electrostatic doping and out‐of‐plane field effect have been extensively studied, in‐plane field‐induced phenomena remain largely unexplored. Here electro‐optic response of monolayer WSe2 subject to modulating in‐plane electric fields probed by electroabsorption and electroreflectance spectroscopy is reported. The devices are found to exhibit spatially varying response near exciton resonance, which cannot be explained by predicted effects such as Pockels and excitonic Stark effect. It is shown that the modulation signal is dominated by exciton linewidth broadening and narrowing associated with local accumulation and depletion of free holes. The field and frequency dependence of the devices is distinct from those of charge modulation devices. The observed behavior is ascribed to elastic scattering of excitons with field‐driven intrinsic free carriers.
High‐Efficiency Phase and Polarization Modulation Metasurfaces
Authors: Zhao Huan , Wang Xinke , Quan Baogang , Liu Shutian , Zhang Yan
Published: December 2021

Use of metasurfaces to control the characteristics of electromagnetic waves is an emerging trend at present. Multifunctional metasurfaces, which can modulate multiple wave parameters, greatly reduce the complexity and enrich the functionality of optical systems. Herein, a high‐efficiency multifunctional metasurface for operation in the terahertz band is proposed and demonstrated. Use of a trilayer structure allows the working efficiency to reach 85% at the designed operating frequency. The phase and polarization states of the transmitted waves are modulated individually via subtle adjustment of the geometric parameters of each layer. Two terahertz‐band vector beam generators are demonstrated based on the proposed metasurface. The two devices individually generate radial and azimuthal terahertz vortex beams that can carry arbitrary orbital angular momentum. The experimental results demonstrate the validity of the proposed approach. This method represents a route toward easy fabrication of high‐performance phase and polarization modulation metasurfaces that can improve the information‐carrying capabilities of terahertz systems and offers benefits for structured light generation, optical information security, and optical communication applications.
Remarkable Color Gamut Enhancement of Dye Lacquers Using Corrugated Surfaces
Authors: Mader Sebastian , Martin Olivier J. F.
Published: December 2021

The visual appearance of any colorized object is usually determined by the spectral absorption of either pigments or dyes. One can however also colorize objects with structural colors that typically have an iridescent appearance, as seen on many beetles. The former colorization mechanism is based on the chemical absorption of the used pigments or dye, while the latter mechanism exploits optical/physical effects such as interference, diffraction, or scattering. Both mechanisms are usually engineered separately and by different specialists. Actually, they can be combined synergistically and it is shown that absorption of three different dye lacquers is significantly enhanced when applied on a corrugated metal surface. Inspired by works on emission enhancement for molecules on top of grating surfaces, these dye lacquers are applied conformally on metallic crossed gratings. We vary thickness and extinction coefficient of the dye lacquers and find that absorption can be enhanced locally by more than a factor of 20. Simulations reveal the underlying mechanisms of this enhancement and the huge color gamut that can be realized by combining otherwise colorless dye lacquers with a corrugated surface is revealed. This approach has potential for applications in sensing with focus on visual inspection like the pregnancy test.
2.56 W Single‐Frequency All‐Fiber Oscillator at 1720 nm
Authors: Zhang Junxiang , Sheng Quan , Zhang Lu , Shi Chaodu , Sun Shuai , Shi Wei , Yao Jianquan
Published: December 2021

The saturable absorption effect of unpumped, rare earth‐doped fiber can be used as a method of achieving single‐frequency operation in fiber lasers. This effect in thulium‐doped fiber is used to achieve single‐frequency operation from an all‐fiber oscillator centered at 1720 nm. The characteristics of the saturable absorption effect are carefully studied and numerous operating regimes are identified wherein the oscillating state and frequency output characteristics of the laser can be manipulated via the injection of auxiliary pump light to the saturable absorber. A record single‐frequency output power of 2.56 W at 1720 nm is obtained; the slope efficiency is 44% and the laser linewidth is 3.3 kHz. The power scaling of the laser is only limited by the available power of the single‐mode 1570 nm pump source. Herein, new insights into methods of generating high‐power, single‐frequency emission from all‐fiber oscillators are offered.
Anti‐MicroRNA‐21 Oligonucleotide Loaded Spermine‐Modified Acetalated Dextran Nanoparticles for B1 Receptor‐Targeted Gene Therapy and Antiangiogenesis Therapy
Authors: Zheng Tao , Wang Wentao , Mohammadniaei Mohsen , Ashley Jon , Zhang Ming , Zhou Ninglin , Shen Jian , Sun Yi
Published: December 2021

The use of nanoparticles (NPs) to deliver small inhibiting microRNAs (miRNAs) has shown great promise for treating cancer. However, constructing a miRNA delivery system that targets brain cancers, such as glioblastoma multiforme (GBM), remains technically challenging due to the existence of the blood‐tumor barrier (BTB). In this work, a novel targeted antisense miRNA‐21 oligonucleotide (ATMO‐21) delivery system is developed for GBM treatment. Bradykinin ligand agonist‐decorated spermine‐modified acetalated dextran NPs (SpAcDex NPs) could temporarily open the BTB by activating G‐protein‐coupled receptors that are expressed in tumor blood vessels and tumor cells, which increase transportation to and accumulation in tumor sites. ATMO‐21 achieves high loading in the SpAcDex NPs (over 90%) and undergoes gradual controlled release with the degradation of the NPs in acidic lysosomal compartments. This allows for cell apoptosis and inhibition of the expression of vascular endothelial growth factor by downregulating hypoxia‐inducible factor (HIF‐1α) protein. An in vivo orthotopic U87MG glioma model confirms that the released ATMO‐21 shows significant therapeutic efficacy in inhibiting tumor growth and angiogenesis, demonstrating that agonist‐modified SpAcDex NPs represent a promising strategy for GBM treatment combining targeted gene therapy and antiangiogenic therapy.
3D‐Printed Strong Dental Crown with Multi‐Scale Ordered Architecture, High‐Precision, and Bioactivity
Authors: Zhao Menglu , Yang Danlei , Fan Suna , Yao Xiang , Wang Jiexin , Zhu Meifang , Zhang Yaopeng
Published: December 2021

Mimicking the multi‐scale highly ordered hydroxyapatite (HAp) nanocrystal structure of the natural tooth enamel remains a great challenge. Herein, a bottom‐up step‐by‐step strategy is developed using extrusion‐based 3D printing technology to achieve a high‐precision dental crown with multi‐scale highly ordered HAp structure. In this study, hybrid resin‐based composites (RBCs) with “supergravity +” HAp nanorods can be printed smoothly via direct ink writing (DIW) 3D printing, induced by shear force through a custom‐built nozzle with a gradually shrinking channel. The theoretical simulation results of finite element method are consistent with the experimental results. The HAp nanorods are first highly oriented along a programmable printing direction in a single printed fiber, then arranged in a layer by adjusting the printing path, and finally 3D printed into a highly ordered and complex crown structure. The printed samples with criss‐crossed layers by interrupting crack propagation exhibit a flexural strength of 134.1 ± 3.9 MPa and a compressive strength of 361.6 ± 8.9 MPa, which are superior to the corresponding values of traditional molding counterparts. The HAp‐monodispersed RBCs are successfully used to print strong and bioactive dental crowns with a printing accuracy of 95%. This new approach can help provide customized components for the clinical restoration of teeth.
Photoinduced Multistable Resonance Frequency Switching of Phase Change Microstring at Room Temperature
Authors: Bukhari Syed A. , McGee Ryan , Mahdavi Amirhossein , Bensebaa Farid , Zhou Liang , Chung Hyun‐Joong , Thundat Thomas , Goswami Ankur
Published: December 2021

Vanadium dioxide (VO2), a promising phase change material, exhibits insulator to metal transition at 68 °C, manifests a drastic change in multiple physical properties, such as electrical resistance, mechanical modulus, lattice parameters, etc. From technological perspective, the transition temperature can be reduced by precise strain engineering. Here a noncontact, all‐optical, and highly energy efficient platform is demonstrated to study macroscopic dynamics related to the localized structural rearrangements at room temperature. A thin layer (≈25 nm) of polycrystalline VO2 deposited on a platinum coated silicon nitride microstring resonator shows a fast controlled mechanical resonance frequency response upon variations in optical power and wavelength. It is shown multiple stable frequencies of the resonator, designated as different equilibrium states, can be activated at different optical powers (≈200 µW) and wavelength, i.e., 450, 520, and 635 nm. The observed multiple resonance states of the microstring are explained because of the generation of stress due to the interplay between thermal expansion and the temperature‐induced phase change of VO2. It is believed this change in frequency states under the controlled external optical excitation can have potential applications in ultrafast optical switching, intelligent temperature sensors, and neuromorphic devices operated at room temperature.
Graphene Acid for Lithium‐Ion Batteries—Carboxylation Boosts Storage Capacity in Graphene
Authors: Obraztsov Ievgen , Bakandritsos Aristides , Šedajová Veronika , Langer Rostislav , Jakubec Petr , Zoppellaro Giorgio , Pykal Martin , Presser Volker , Otyepka Michal , Zbořil Radek
Published: December 2021

Environmentally sustainable, low‐cost, flexible, and lightweight energy storage technologies require advancement in materials design in order to obtain more efficient organic metal‐ion batteries. Synthetically tailored organic molecules, which react reversibly with lithium, may address the need for cost‐effective and eco‐friendly anodes used for organic/lithium battery technologies. Among them, carboxylic group‐bearing molecules act as high‐energy content anodes. Although organic molecules offer rich chemistry, allowing a high content of carboxyl groups to be installed on aromatic rings, they suffer from low conductivity and leakage to the electrolytes, which restricts their actual capacity, the charging/discharging rate, and eventually their application potential. Here, a densely carboxylated but conducting graphene derivative (graphene acid (GA)) is designed to circumvent these critical limitations, enabling effective operation without compromising the mechanical or chemical stability of the electrode. Experiments including operando Raman measurements and theoretical calculations reveal the excellent charge transport, redox activity, and lithium intercalation properties of the GA anode at the single‐layer level, outperforming all reported organic anodes, including commercial monolayer graphene and graphene nanoplatelets. The practical capacity and rate capability of 800 mAh g−1 at 0.05 A g−1 and 174 mAh g−1 at 2.0 A g−1 demonstrate the true potential of GA anodes in advanced lithium‐ion batteries.
Unveiling the Synergy of O‐Vacancy and Heterostructure over MoO3‐x/MXene for N2 Electroreduction to NH3
Authors: Chu Ke , Luo Yaojing , Shen Peng , Li Xingchuan , Li Qingqing , Guo Yali
Published: December 2021

The electrochemical N2 reduction reaction (NRR) offers a promising approach for sustainable NH3 production, and modulating the structural/electronic configurations of the catalyst materials with optimized electrocatalytic properties is pivotal for achieving high‐efficiency NRR electrocatalysis. Herein, vacancy and heterostructure engineering are rationally integrated to explore O‐vacancy‐rich MoO3‐x anchored on Ti3C2Tx‐MXene (MoO3‐x/MXene) as a highly active and selective NRR electrocatalyst, achieving an exceptional NRR activity with an NH3 yield of 95.8 µg h−1 mg−1 (−0.4 V) and a Faradaic efficiency of 22.3% (−0.3 V). A combination of in situ spectroscopy, molecular dynamics simulations and density functional theory computations is employed to unveil the synergistic effect of O‐vacancies and heterostructures for the NRR, which demonstrates that O‐vacancies on MoO3‐x serve as the active sites for N2 chemisorption and activation, while the MXene substrate can further regulate the O‐vacancy sites to break the scaling relation to effectively stabilize *N2/*N2H while destabilizing *NH2/*NH3, resulting in more optimized binding affinity of NRR intermediates toward reduced energy barriers and an enhanced NRR activity for MoO3‐x/MXene.
Effects of Polymer Coating Mechanics at Solid‐Electrolyte Interphase for Stabilizing Lithium Metal Anodes
Authors: Huang Zhuojun , Choudhury Snehashis , Paul Neelima , Thienenkamp Johannes Helmut , Lennartz Peter , Gong Huaxin , Müller‐Buschbaum Peter , Brunklaus Gunther , Gilles Ralph , Bao Zhenan
Published: December 2021

Lithium metal batteries are next‐generation energy storage devices that rely on the stable electrodeposition of lithium metal during the charging process. The major challenge associated with this battery chemistry is related to the uneven deposition that leads to dendritic growth and poor coulombic efficiency (CE). A promising strategy for addressing this challenge is utilizing a polymer coating on the anodic surface. While several works in the past have evaluated polymer coatings, the requirements for polymer design are still unclear. In this work, the effect of polymer dynamics on lithium metal deposition is specifically investigated. Electrolyte (solvent) blocking perfluoropolyether polymer networks with evenly spaced H‐bonding sites of various strengths are designed, resulting in significant differences in the molecular ordering, as analyzed by X‐ray scattering measurements. The differences in the H‐bonding strength directly impact the mechanical properties of these materials, thus providing a controlled set of samples with a range of polymer dynamics for electrodeposition studies. Finally, a systematic evaluation of the lithium metal electrodeposition quality with these polymers as anodic coating shows that polymers with flowability or faster polymer dynamics exhibit higher CE. These experimental findings provide rational design principles for soft polymer coatings on lithium metal anodes.
Fine‐Tuning Batch Factors of Polymer Acceptors Enables a Binary All‐Polymer Solar Cell with High Efficiency of 16.11%
Authors: Jia Jianchao , Huang Qiri , Jia Tao , Zhang Kai , Zhang Jie , Miao Jingsheng , Huang Fei , Yang Chuluo
Published: December 2021

Random conjugated polymers, such as typical polymerized small molecular acceptors (PSMAs), concurrently suffer from the dual batch factors of molecular weights (MWs) and regioregularity, which seriously interfere with the study of the relationship between batch factors and polymer properties. Here, four isomer‐free PSMAs, PA‐5 and three members of a PA‐6 series with low (L), medium (M), and high (H) MWs, in which 5 and 6 define linkage position throughout conjugated backbone, are designed and synthesized to clearly investigate polymer batch effects. These studies reveal that PA‐6‐L and PA‐6‐M have ignorable batch differences within deviations, which deliver comparable maximum efficiencies of 14.81% and 14.99%, respectively. The PA‐6‐H based cell is processed from chlorobenzene with its high boiling point, due to the limited solubility in other common solvents, leading to large‐size phase separation during prolonged film drying process, and thereby inferior performance. In contrast, PA‐5 possesses diverse absorption characteristics, and ordered crystallization, which prompts higher short‐circuit current density and fill factor in the cell. As a result, the corresponding device realizes a photovoltaic performance of 16.11%, which is one of the best binary all‐polymer solar cells in the reported literature to date. This study provides a new insight into complicated batch effects of PSMAs on device performance while avoiding cross‐talk between them.
Liquid Metal Interdigitated Capacitive Strain Sensor with Normal Stress Insensitivity
Authors: Zhang Dongguang , Zhang Jie , Wu Yali , Xiong Xiaoyan , Yang Jiayi , Dickey Michael D.
Published: December 2021

Soft and stretchable sensors of strain are important for human–machine interfaces, soft robotics, and electronic skins. However, soft strain sensors generally cannot distinguish in‐plane strain from normal stress. For example, stretching a sensor often gives a similar signal to pressing the sensor. To solve this problem, a liquid metal (LM)‐interdigitated capacitive strain sensor that is insensitive to normal stress is introduced. The sensor contains LM‐interdigitated electrodes prepared by vacuum filling of LM into lithographically defined microchannels. The capacitance between the LM electrodes decreases with increasing strain due to geometric changes. Because of the liquid nature of the electrodes, the sensor exhibits high stretchability (100% strain) and repeatability with gauge factor of −0.3. Due to the elasticity of the device, the sensor has low hysteresis (<1%) and no crosstalk between strain and normal stress sensing. These types of soft sensors may find use in wearable devices.
Remembering where we're from: Community‐ and individual‐level predictors of college students' White privilege awareness
Authors: Blevins Emily J. , Todd Nathan R.
Published: December 2021

Scholars in the field of community psychology have called for more research dedicated to examining White privilege as part of a system of White supremacy in the United States. One branch of this work focuses on awareness of White privilege, yet to date, this research has typically investigated awareness of White privilege at individual levels of analysis instead of also focusing on neighborhoods, schools, and other levels of analysis beyond the individual. In this study, we combine survey and U.S. Census data to explore both individual‐ and community‐level predictors of White privilege awareness. With a sample of 1285 White college students, we found that gender, modern racism, social dominance orientation, and subjective socioeconomic status (SES) significantly predicted White privilege awareness. After accounting for these individual‐level variables, we found that characteristics of students' hometowns (defined by zip code) predicted White privilege awareness. Specifically, greater income inequality was associated with higher White privilege awareness, while greater White racial homogeneity was marginally associated with lower White privilege awareness. There was a significant interaction between community‐level White racial homogeneity and individual‐level subjective SES, such that students with high subjective SES and low White racial homogeneity had the highest White privilege awareness. This study highlights the importance of examining different facets of ecological context in relation to White Americans' racial attitudes.
Synthesis of Benzylidenesuccinates through Rhodium(III)‐Catalyzed C‐H Alkenylation with Itaconate
Authors: Ochiai Shiho , Yoshimoto Risa , Usuki Yoshinosuke , Satoh Tetsuya
Published: December 2021

The dehydrogenative coupling of aromatic amides with dimethyl itaconate proceeds smoothly under rhodium catalysis through ortho C−H bond cleavage directed by their amide group to produce benzylidenesuccinates. Aromatic carboxylic acids including benzoic and phthalic acids also couple with the itaconate to give 1 : 2 coupling products predominantly. Benzylidenesuccinic acid derivatives have been known to show various biological activities. These reactions provide easy access to the important structures.
Clinical reporting following the quantification of cerebrospinal fluid biomarkers in Alzheimer's disease: An international overview
Authors: Delaby Constance , Teunissen Charlotte E. , Blennow Kaj , Alcolea Daniel , Arisi Ivan , Amar Elodie Bouaziz , Beaume Anne , Bedel Aurélie , Bellomo Giovanni , Bigot‐Corbel Edith , Bjerke Maria , Blanc‐Quintin Marie‐Céline , Boada Mercè , Bousiges Olivier , Chapman Miles D , DeMarco Mari L. , D'Onofrio Mara , Dumurgier Julien , Dufour‐Rainfray Diane , Engelborghs Sebastiaan , Esselmann Hermann , Fogli Anne , Gabelle Audrey , Galloni Elisabetta , Gondolf Clémentine , Grandhomme Frédérique , Grau‐Rivera Oriol , Hart Melanie , Ikeuchi Takeshi , Jeromin Andreas , Kasuga Kensaku , Keshavan Ashvini , Khalil Michael , Körtvelyessy Peter , Kulczynska‐Przybik Agnieszka , Laplanche Jean‐Louis , Lewczuk Piotr , Li Qiao‐Xin , Lleó Alberto , Malaplate Catherine , Marquié Marta , Masters Colin L. , Mroczko Barbara , Nogueira Léonor , Orellana Adelina , Otto Markus , Oudart Jean‐Baptiste , Paquet Claire , Paoletti Federico Paolini , Parnetti Lucilla , Perret‐Liaudet Armand , Peoc'h Katell , Poesen Koen , Puig‐Pijoan Albert , Quadrio Isabelle , Quillard‐Muraine Muriel , Rucheton Benoit , Schraen Susanna , Schott Jonathan M. , Shaw Leslie M. , Suárez‐Calvet Marc , Tsolaki Magda , Tumani Hayrettin , Udeh‐Momoh Chinedu T , Vaudran Lucie , Verbeek Marcel M , Verde Federico , Vermunt Lisa , Vogelgsang Jonathan , Wiltfang Jens , Zetterberg Henrik , Lehmann Sylvain
Published: December 2021

Introduction

The current practice of quantifying cerebrospinal fluid (CSF) biomarkers as an aid in the diagnosis of Alzheimer's disease (AD) varies from center to center. For a same biochemical profile, interpretation and reporting of results may differ, which can lead to misunderstandings and raises questions about the commutability of tests.

Methods

We obtained a description of (pre‐)analytical protocols and sample reports from 40 centers worldwide. A consensus approach allowed us to propose harmonized comments corresponding to the different CSF biomarker profiles observed in patients.

Results

The (pre‐)analytical procedures were similar between centers. There was considerable heterogeneity in cutoff definitions and report comments. We therefore identified and selected by consensus the most accurate and informative comments regarding the interpretation of CSF biomarkers in the context of AD diagnosis.

Discussion

This is the first time that harmonized reports are proposed across worldwide specialized laboratories involved in the biochemical diagnosis of AD.
Nickel‐Mediated Enantioselective Photoredox Allylation of Aldehydes with Visible Light
Authors: Calogero Francesco , Potenti Simone , Bassan Elena , Fermi Andrea , Gualandi Andrea , Monaldi Jacopo , Dereli Busra , Maity Bholanath , Cavallo Luigi , Ceroni Paola , Cozzi Pier Giorgio
Published: December 2021

Here we report a practical, highly enantioselective photoredox allylation of aldehydes mediated by chiral nickel complexes with commercially available allyl acetate as the allylating agent. The methodology allows the clean stereoselective allylation of aldehydes in good to excellent yields and up to 93 % e.e. using a catalytic amount of NiCl2(glyme) in the presence of the chiral aminoindanol‐derived bis(oxazoline) as the chiral ligand. The photoredox system is constituted by the organic dye 3DPAFIPN and a Hantzsch's ester as the sacrificial reductant. The reaction proceeds under visible‐light irradiation (blue LEDs, 456 nm) at 8–12 °C. Compared to other published procedures, no metal reductants (such as Zn or Mn), additives (e.g. CuI) or air‐sensitive Ni(COD)2 are necessary for this reaction. Accurate DFT calculations and photophysical experiments have clarified the mechanistic picture of this stereoselective allylation reaction.
Tuning Exciton Coupling of Merocyanine Nucleoside Dimers by RNA, DNA and GNA Double Helix Conformations
Authors: Dietzsch Julia , Bialas David , Bandorf Johannes , Würthner Frank , Höbartner Claudia
Published: December 2021

Exciton coupling between two or more chromophores in a specific environment is a key mechanism associated with color tuning and modulation of absorption energies. This concept is well exemplified by natural photosynthetic proteins, and can also be achieved in synthetic nucleic acid nanostructures. Here we report the coupling of barbituric acid merocyanine (BAM) nucleoside analogues and show that exciton coupling can be tuned by the double helix conformation. BAM is a nucleobase mimic that was incorporated in the phosphodiester backbone of RNA, DNA and GNA oligonucleotides. Duplexes with different backbone constitutions and geometries afforded different mutual dye arrangements, leading to distinct optical signatures due to competing modes of chromophore organization via electrostatic, dipolar, π–π‐stacking and hydrogen‐bonding interactions. The realized supramolecular motifs include hydrogen‐bonded BAM–adenine base pairs and antiparallel as well as rotationally stacked BAM dimer aggregates with distinct absorption, CD and fluorescence properties.
Nano‐synthesis, solid‐state structural characterization, and antimicrobial and anticancer assessment of new sulfafurazole azo dye‐based metal complexes for further pharmacological applications
Authors: Khedr Abdalla M. , El‐Ghamry Hoda A. , El‐Sayed Yusif S.
Published: December 2021

A new azo dye ligand (abbreviated as H3L) derived from coupling of sulfafurazole diazonium salt with 2,4‐dihydroxybenzaldehyde was prepared and characterized applying different spectroscopic and analytical techniques. The novel nanosized trivalent Cr and Fe alongside with divalent Mn, Co, Ni, and Cd complexes with H3L have been synthesized for further promising pharmaceutical uses. All complexes were totally characterized by investigating various analytical and spectral tools such as microanalysis, FT‐IR, 1H NMR, UV‐Vis, powder XRD, and TEM spectra as well as magnetic moment and molar conductance measurements. Microanalysis, TGA, and conductance studies confirmed the formation of all metal complexes in 1:1 (L: M) molar ratio with covalent mode. The FT‐IR and 1H NMR investigation asserted the chelation of H3L to different metal ions through azo nitrogen and phenolic deprotonated hydroxy oxygen in the o‐position. UV‐Vis, ESR, and magnetic moment studies revealed octahedral geometry around Cr and Fe ions, whereas Mn, Co, Ni, and Cd complexes displayed tetrahedral configurations. XRD patterns and TEM images proved homogeneous distribution over the chelates surfaces and nanometric size of complexes particles. Molecular modeling was used to optimize the complexes' geometric structure showing good harmonity with the experimental results. The antifungal and antibacterial efficiencies were strongly enhanced upon complex formation. Cr(III) and Ni(II) complexes showed the strongest and promising anticancer activities (IC50 = 7.64 and 6.99 μg/ml) among the tested compounds, whereas Cd(II) complex showed moderate anticancer efficiency (IC50 = 12.10 μg/ml), compared with the 5‐fluorouracil (applied standard drug) with IC50 = 6.44 μg/ ml.
Inhibition of adhesion of CaCO3 scale by polydopamine/polytetrafluoroethylene coating with stability and anticorrosion properties
Authors: Wang Bing‐Bing , Wang Xin , Xu Zhi‐Ming , Zhao Qi , Wang Xiao‐Dong
Published: December 2021

Reduction of calcium carbonate (CaCO3) scale formation on the equipment surface is essential in a wide variety of industrial fields. In this work, polydopamine/polytetrafluoroethylene (PDA/PTFE) coating prepared by the simple immersion on stainless steel (SS) surfaces was developed to suppress the CaCO3 scale adhesion. The PDA/PTFE‐coated surface showed the higher hydrophobicity (water contact angle = 133.50°) and lower surface free energy (11.92 mN/m) than the stainless‐steel surface. The scale inhibiting rate of the coated surface was up to 76.8% after 12‐hour immersion in the CaCO3 solution in comparison with the untreated SS. More bubbles were observed on the PDA/PTFE‐coated surfaces, and the number of bubbles increased with increasing solution temperature leading to less area for the scale adhesion. As a result, the PDA/PTFE coated surfaces have the higher antiscale ability at the higher solution temperature. Furthermore, the stripping and electrochemical corrosion tests demonstrated that the PDA/PTFE coating has the better stability and anticorrosion ability. The PDA/PTFE coating with the superior properties has potential application for the long‐lasting reduction of the scale formation.
Observer‐based finite‐time congestion control for TCP/AQM network system with time‐varying delays and UDP flows
Authors: Shen Jindong , Jing Yuanwei , Ren Tao , Bai Yun
Published: December 2021

In this paper, the problem of observer‐based finite‐time congestion control for transmission control protocol (TCP)/active queue management (AQM) network systems with time‐varying delay and nonresponsive flows such as UDP is studied. The congestion control problem of TCP/AQM network system with time delay and external disturbances observer‐based finite‐time control is solved for the first time, and a theorem proved by the Lyapunov function of TCP/AQM network systems finite‐time bounded is given to ensure that the closed‐loop system is finite‐time bounded. Finally, the control gain and observer gain are obtained by linear matrix inequality (LMI) technique. Simulation results show the effectiveness and superiority of the proposed method.
Comparison of metabolic kinetics during high and low solids anaerobic digestion of fecal sludge
Authors: Kinyua Maureen , Stuart Kara
Published: December 2021

High solids anaerobic digestion (HS‐AD) is an attractive energy‐producing technology; however, high total solids (TS) content may inhibit methanogens due to high volatile fatty acid (VFA) and total ammonia nitrogen concentrations. The objective of this paper is to quantify rate‐limiting metabolic kinetic parameters to determine the influence of TS content during anaerobic digestion of fecal sludge. Two TS content: 11% and 17% microcosms were analyzed. Good performance was observed in both systems, with volatile solid (VS) removal greater than 50%, CH4 yield between 0.44 and 0.56 m3 CH4/g VS added and cumulative CH4 production between 1.78 and 2.03 m3 CH4/m3 digester‐day. At 11% TS VFA consumption and VS removal had a positive correlation to CH4 production while the 17% TS microcosm had a negative correlation with both. This is the first study to determine the kinetic parameters for hydrolysis, VFA consumption, and methanogenesis during digestion of fecal sludge. These kinetic parameters are necessary in the design and operation of anaerobic digestion systems treating fecal sludge.
Fast Feet Forward: Early intervention protocol using bilateral movements to reduce stress and increase positive cognitions in adopted children with complex trauma presentation
Authors: Draper Ana , Marcellino Elisa , Ogbonnaya Comfort
Published: December 2021

Adopted children are a vulnerable group that have often experienced multiple traumatic events such as maltreatment, neglect and the perpetuation of abuse. These early traumatic experiences can result in compromised resilience which impacts both psychological and biological development (Cicchetti & Banny, 2014). This study used the systemic model approach, method and technique to gain an understanding of the complexity of presentation and formulation being made (Harris & Burnham, 1985). It also expanded on an early intervention sports protocol, named fast feet forward, that was previously used with unaccompanied asylum‐seeking minors with significant results. The use of running as a bilateral stimulus resulted in a rise in VOC (validity of cognition) and a reduction in SUD (subjective units of distress) scores, both after a single session and after 12 sessions. The data reported from this study replicated the previous findings of Draper et al., 2020) and showed the benefits of using fast feet forward with adopted children. The results further evidence the potential efficacy of this protocol for adopted children displaying complex trauma and show promising results for future enquiry. Future research should aim to replicate these findings with a larger sample size.
Phytochemical Composition and Anti‐Aging Activity of Butanol Extract of Hedyotis diffusa in Caenorhabditis elegans
Authors: Li Jing , Liu Di , Li Danqing , Guo Yujie , Du Hongzhi , Cao Yan
Published: December 2021

Hedyotis diffusa Willd. (H. diffusa), a kind of traditional Chinese medicine, has been evaluated to potential display antioxidant and anti‐aging effects in vitro experiments. In this work, we investigated the effects on lifespan and stress resistance of the butanol extract from H. diffusa (NHD) in vivo using a Caenorhabditis elegans (C. elegans) model. The phytochemicals of NHD were identified by UPLC‐ESI‐qTOF‐MS/MS method. NHD‐treated wild‐type N2 worms showed an increase in survival time under both normal and stress conditions. Meanwhile, NHD promoted the healthspan of nematodes by stimulating growth and development, reducing the deposition of age pigment, increasing the activities of superoxide dismutase (SOD) and glutathione peroxidase dismutase (GSH‐Px), and decreasing the level of ROS without impairing fertility. Moreover, the upregulating of the expression of daf‐16, gst‐4, sod‐3, hsp12.6 genes and the downregulating of the expression of daf‐2 were involved in the NHD‐mediated lifespan extension. Finally, the increasing of the expression of GST‐4::GFP in CL2166 transgenic nematodes and the life‐span‐extending activity of NHD was completely abolished in daf‐2 and daf‐16 mutants further revealed that the potential roles for these genes in NHD‐induced longevity in C. elegans. Collectively, our findings suggest that NHD may have an active effect in healthy aging and age‐related diseases.
A novel nonsense variant in MED12 associated with malformations in a female fetus
Authors: Faergeman Soren Lejsted , Becher Naja , Andreasen Lotte , Christiansen Marianne , Frost Lise , Vogel Ida
Published: December 2021

Pathogenic variants in the MED12 gene located on the X‐chromosome have primarily been reported in males with Lujan‐Fryns syndrome, Ohdo syndrome and the Opits‐Kaveggia syndrome. However, earlier reports of female patients and female mice suggest that MED12 deficiency causes severe malformations. We report a novel example of a MED12 de novo nonsense variant in a female fetus with severe malformations identified by trio‐exome sequencing. This finding further expands the clinical spectrum of MED12‐related disorders, which is vital for prenatal diagnosis and genetic counselling of couples.
Chemoenzymatic Cascades Enabled by Combining Catalytically Active Emulsions and Biocatalysts
Authors: Sun Zhiyong , Zhao Qingcai , Haag Rainer , Wu Changzhu
Published: December 2021

The compartmentalization of chemo‐ and enzymatic reactions is an elegant strategy for one‐pot synthesis while avoiding reaction incompatibility issues. However, chemoenzymatic compartments developed to date are limited to complicated preparation. Herein, a simple, catalytically active polymer that stabilizes diverse types of emulsions for the encapsulation of active enzymes is presented. This design combines two distinct catalysts for cascade reaction while creating separate micro‐environments with a large interfacial area for high reactivity. Moreover, the system is developed for solvent‐free reactions, benefiting the “green” synthesis.
Molecular dynamics of CH4/CO2 on calcite for enhancing gas recovery
Authors: Carchini Giuliano , Al‐Marri Mohammed J. , Hussein Ibnelwaleed , Shawabkeh Reyad , Mahmoud Mohamed , Aparicio Santiago
Published: December 2021

The effect of temperature and pressure on the adsorption of CO2 and CH4 gases on calcite (104) has been studied by means of classical molecular dynamics. The results show that carbon dioxide greatly improves methane desorption in the 323–373 K range, even at low CO2 concentrations. However, this effect is less pronounced for very high temperatures (423 K), where most of the methane is desorbed and CO2 tends to desorb in large quantities. Radial distribution function (RDF) analysis reveals two distinct peaks for CO2 (0.36 and 0.47 nm) and two for methane (0.87 and 0.57 nm) and the intensities of these peaks tend to decrease with increasing temperature. Such peaks are always clearly visible for CO2, while the methane profile gets very broad already for mild conditions of temperature and CO2 concentration. These results highlight how the CO2 geometry of adsorption is well defined and characterized by strong interaction, while methane adsorption is quite loose and depicts a very dynamic picture. Focusing on the effect of pressure, RDF peaks intensities increase, although this effect is limited to the 1–5 MPa range. Moreover, the high CO2 presence further decreases the effect of pressure on methane adsorption. In fact, from pure methane to 20/80 CO2/CH4, methane adsorption increases linearly with pressure. For gas mixtures with a CO2 concentration higher than 40%, higher pressure has less impact on methane adsorption. Overall, the results obtained yield important details to tune the gas composition and conditions for efficient and enhanced natural gas recovery and sequestration of CO2.
Hydrodynamic collisions involving bubbles and mineral particles
Authors: Manica Rogerio , Liu Bo , Li Mingda , Chen Zhixiang , Liu Qingxia
Published: December 2021

The movement of bubbles inside a liquid and their interaction with other bubbles, solid particles, or surfaces has been a topic of intense research due to its importance to understand natural phenomena and improve industrial applications such as mineral flotation. For a long time, the mobility at the air–water interface was suggested to affect the flotation recovery, and this understanding was further advanced in the past few years with the development of experimental techniques. In this study, we review the recent experimental and theoretical understanding of the boundary conditions at the air–liquid interface, and how the surface mobility affects the rising speed of a single bubble and the coalescence of bubbles. Consequently, the flotation efficiency can be affected by the surface mobility by altering the probability of collision, attachment, and detachment between the bubble and valuable mineral particles. Recent works also show that the surface mobility is affected by the solution chemistry, the aging of the air–water interface, and the hydrodynamic flow. Therefore, it can be speculated that future techniques for mineral flotation can be developed by the controlled manipulation of surface mobility at the bubble surface. A freshly formed bubble has a mobile interface, but the presence of impurities or added surfactants at different concentrations can accelerate the immobilization of the air bubbles.
Intra‐cluster aggregation aware routing for distributed training in wireless sensor networks
Authors: Chen Zhaohong , Long Xin , Chen Long , Wu Yalan , Wu Jigang , Liu Shuangyin
Published: December 2021

In wireless sensor networks (WSNs), wireless sensor nodes can be equipped with deep neural network accelerators to deal with the computation challenges in distributed training. However, the communication overhead of distributed training and the limited battery capacity of sensor nodes still impedes the broad deployment of distributed training applications. This article investigates the distributed training in WSNs by formulating an aggregation‐aware routing problem into a non‐linear integer programming problem. The objective of the formulated problem is to reduce the training time using data aggregation‐aware routing under the constraints of memory size and energy cost. Meanwhile, the NP‐Hardness of the formulated problem is proved in this article. Then, an intra‐cluster aggregation‐aware routing algorithm is proposed. The proposed algorithm accelerates the transmission of the data packet by integrating the K‐Means clustering and shortest path routing to choose the aggregators and the route paths. Extensive experiments demonstrate that the proposed algorithm outperforms two classical clustering routing algorithms UC‐LEACH and K‐Means by 29% and 37% in terms of average training time, and reducing the energy consumption by 21% and 15%, respectively.
A Microporous Metal‐Organic Framework with Channels Constructed from Nonpolar Aromatic Rings for the Selective Separation of Ethane/Ethylene Mixtures
Authors: Liu Lizhen , Bo Yiyang , Zhuang Weitang , Xie Zhixuan , Yang Yisi , Lin Quanjie , Chen Dinggui , Yao Zizhu , Xiang Shengchang
Published: December 2021

The separation of ethane and ethylene is an important segment in the purification of chemical raw materials in industrial production. However, due to their similar physical and chemical properties, the separation of C2H6/C2H4 is challenging. Herein, we report the selective adsorption of ethane over ethylene by a microporous metal‐organic framework with nonpolar aromatic rings constructed channels, [Co1.5(TATB)(H2O)0.5] ⋅ 5DMA ⋅ 3H2O (Co‐TATB, H3TATB=4,4’,4’’‐(s‐triazine‐2,4,6‐triyl) tribenzoic acid). This compound showed a higher ethane capacity than that of ethylene, and a low adsorption enthalpy of ethane only of 19.4 kJ mol−1. Further, the dynamic breakthrough experimental confirmed that Co‐TATB can selectively adsorb ethane from ethane/ethylene separation.
Clinical, Cellular, and Molecular Effects of Corticosteroids on the Response to Intradermal Lipopolysaccharide Administration in Healthy Volunteers
Authors: Buters Thomas P. , Hameeteman Pieter W. , Jansen Iris M.E. , van Hindevoort Floris C. , ten Voorde Wouter , Grievink Hendrika W. , Schoonakker Mascha , de Kam Marieke L. , Gilroy Derek W. , Feiss Gary , Rissmann Robert , Jansen Manon A.A. , Burggraaf Jacobus , Moerland Matthijs
Published: December 2021

The intradermal lipopolysaccharide (LPS) challenge in healthy volunteers has proven to be a valuable tool to study local inflammation in vivo. In the current study the inhibitory effects of oral and topical corticosteroid treatment on intradermal LPS responses were evaluated to benchmark the challenge for future investigational drugs. Twenty‐four healthy male volunteers received a two‐and‐a‐half‐day twice daily (b.i.d.) pretreatment with topical clobetasol propionate 0.05% and six healthy volunteers received a two‐and‐a‐half‐day b.i.d. pretreatment with oral prednisolone at 0.25 mg/kg body weight per administration. Participants received one injection regimen of either 0, 2, or 4 intradermal LPS injections (5 ng LPS in 50 µL 0.9% sodium chloride solution). The LPS response was evaluated by noninvasive (perfusion, skin temperature, and erythema) and invasive assessments (cellular and cytokine responses) in suction blister exudate. Both corticosteroids significantly suppressed the clinical inflammatory response (erythema P = 0.0001 for clobetasol and P = 0.0016 for prednisolone; heat P = 0.0245 for clobetasol, perfusion P < 0.0001 for clobetasol and P = 0.0036 for prednisolone). Clobetasol also significantly reduced the number of monocytes subsets, dendritic cells, natural killer cells, and T cells in blister exudate. A similar effect was observed for prednisolone. No relevant corticosteroid effects were observed on the cytokine response to LPS. We successfully demonstrated that the anti‐inflammatory effects of corticosteroids can be detected using our intradermal LPS challenge model, validating it for evaluation of future investigational drugs, as an initial assessment of the anti‐inflammatory effects of such compounds in a minimally invasive manner.