bluuebunny/crossref_metadata_2025 huggingface dataset:
Graphene‐Assisted Synthesis of 2D Polyglycerols as Innovative Platforms for Multivalent Virus Interactions
Authors: Mohammadifar Ehsan , Ahmadi Vahid , Gholami Mohammad Fardin , Oehrl Alexander , Kolyvushko Oleksandr , Nie Chuanxiong , Donskyi Ievgen S. , Herziger Svenja , Radnik Jörg , Ludwig Kai , Böttcher Christoph , Rabe Jürgen P. , Osterrieder Klaus , Azab Walid , Haag Rainer , Adeli Mohsen
Published: March 2021

2D nanomaterials have garnered widespread attention in biomedicine and bioengineering due to their unique physicochemical properties. However, poor functionality, low solubility, intrinsic toxicity, and nonspecific interactions at biointerfaces have hampered their application in vivo. Here, biocompatible polyglycerol units are crosslinked in two dimensions using a graphene‐assisted strategy leading to highly functional and water‐soluble polyglycerols nanosheets with 263 ± 53 nm and 2.7 ± 0.2 nm average lateral size and thickness, respectively. A single‐layer hyperbranched polyglycerol containing azide functional groups is covalently conjugated to the surface of a functional graphene template through pH‐sensitive linkers. Then, lateral crosslinking of polyglycerol units is carried out by loading tripropargylamine on the surface of graphene followed by lifting off this reagent for an on‐face click reaction. Subsequently, the polyglycerol nanosheets are detached from the surface of graphene by slight acidification and centrifugation and is sulfated to mimic heparin sulfate proteoglycans. To highlight the impact of the two‐dimensionality of the synthesized polyglycerol sulfate nanosheets at nanobiointerfaces, their efficiency with respect to herpes simplex virus type 1 and severe acute respiratory syndrome corona virus 2 inhibition is compared to their 3D nanogel analogs. Four times stronger in virus inhibition suggests that 2D polyglycerols are superior to their current 3D counterparts.
Printed Capacitive Sensors Based on Ionic Liquid/Metal‐Organic Framework Composites for Volatile Organic Compounds Detection
Authors: Fernandez Eduardo , G. Saiz Paula , Peřinka Nikola , Wuttke Stefan , Fernández de Luis Roberto
Published: March 2021

In this paper, the potential of 2D printing technologies to create thin film gas sensors from ionic liquid (IL)/metal–organic framework (MOF) composites is evaluated. To accomplish this, the MOF is synthesized solvothermally, and impregnated with the IL. The structure and basic properties of the IL/MOF composites are characterized using thermal, spectroscopic, and X‐ray diffraction techniques, and the resultant sensing capacity of the bulk material is evaluated by impedance spectroscopy. The IL/MOF systems are then integrated into a 2D printed silver capacitive circuit by spray and tested on a custom‐made gas flow apparatus. Exposure of the IL/MOF based sensors to water, acetone, and ethanol induces a repetitive variation of the capacitance (from 0.05 to 7 pF) that is dependent on the nature of the gas. IL/MOF based sensors can detect changes in concentrations in the range of 10k–100k ppm in less than a second. The conclusions of this work are the first steps towards the development of 2D printed sensors based on IL/MOF materials. Such materials offer countless possibilities to tailor the porosity, chemistry, selectivity, and electrical response to make the sensor suitable to detect the desired analyte.
Stack‐and‐Draw Applied to the Engineering of Multi‐Material Fibers with Non‐Cylindrical Profiles
Authors: Strutynski Clément , Meza Ricardo Alvarado , Teulé‐Gay Lionel , El‐Dib Georges , Poulon‐Quintin Angeline , Salvetat Jean‐Paul , Vellutini Luc , Dussauze Marc , Cardinal Thierry , Danto Sylvain
Published: March 2021

Here, it is demonstrated that the stack‐and‐draw approach can be expanded to unusual materials association and profile geometries to generate fiber assemblies with unprecedented functionalities. This approach relies on the stacking of flat oxide glass slides into a preform, which is then thermally elongated into tens‐of‐meters‐long ribbon fibers with preserved cross‐section ratio. Fabrication methodology is introduced. In order to illustrate the versatility of the method, a panel of fibers with diverse geometries and functions is exposed, including glass‐only exposed‐core fibers for chemical sensing and, upon the insertion of metal electrodes, H‐shaped multi‐cavity structures and compact, glass‐metal fiber optical detectors applied to a gas analysis by means of fiber‐tip plasma spectroscopy. It is believed this new approach will offer an attractive, straightforward solution for designing innovative, complex multimaterial fiber platforms with enhanced functionalities.
Single Cell Bioprinting with Ultrashort Laser Pulses
Authors: Zhang Jun , Byers Patrick , Erben Amelie , Frank Christine , Schulte‐Spechtel Levin , Heymann Michael , Docheva Denitsa , Huber Heinz P. , Sudhop Stefanie , Clausen‐Schaumann Hauke
Published: March 2021

Tissue engineering requires the precise positioning of mammalian cells and biomaterials on substrate surfaces or in preprocessed scaffolds. Although the development of 2D and 3D bioprinting technologies has made substantial progress in recent years, precise, cell‐friendly, easy to use, and fast technologies for selecting and positioning mammalian cells with single cell precision are still in need. A new laser‐based bioprinting approach is therefore presented, which allows the selection of individual cells from complex cell mixtures based on morphology or fluorescence and their transfer onto a 2D target substrate or a preprocessed 3D scaffold with single cell precision and high cell viability (93–99% cell survival, depending on cell type and substrate). In addition to precise cell positioning, this approach can also be used for the generation of 3D structures by transferring and depositing multiple hydrogel droplets. By further automating and combining this approach with other 3D printing technologies, such as two‐photon stereolithography, it has a high potential of becoming a fast and versatile technology for the 2D and 3D bioprinting of mammalian cells with single cell resolution.
Two‐Dimensional Material‐Enhanced Flexible and Self‐Healable Photodetector for Large‐Area Photodetection
Authors: An Chunhua , Nie Fengmin , Zhang Rongjie , Ma Xinli , Wu Dahao , Sun Yang , Hu Xiaodong , Sun Dong , Pan Li , Liu Jing
Published: March 2021

Flexible photodetectors are fundamental elements to develop flexible/wearable systems, which can be widely used for in situ health and environmental monitoring, human–machine interacting, flexible displaying, etc. However, the degraded performance or even malfunction under severe mechanical deformation and/or damage remains a key challenge for current flexible photodetectors. In this article, a flexible photodetector is developed with strong self‐healing capability and stable performance under large deformation. This photodetector is made of the 2D material self‐healing film by mixing 2D materials homogenously with the self‐healing polymer of imidazolium‐based norbornene polymerized with ionic liquids and counterions. The 2D material self‐healing films show enhanced light absorption, and thus, decent photoresponse as compared to the pure self‐healing film. The achieved photoresponse remains stable and even increases under small tensile strain within 150%, while decreases slightly under large tensile strain up to 1000%. Moreover, the photodetector not only can be fully recovered from repeated mechanical cuttings, but also presents excellent long‐term stability in ambient condition for 500 days without showing any obvious degraded performance. Furthermore, a large‐area 2D material self‐healing photodetection array is designed with adjustable pixel size, which successfully recognizes the patterns of “T”, “J”, and “U”.
A Wearable Body Condition Sensor System with Wireless Feedback Alarm Functions
Authors: Xu Kaichen , Fujita Yusuke , Lu Yuyao , Honda Satoko , Shiomi Mao , Arie Takayuki , Akita Seiji , Takei Kuniharu
Published: March 2021

Emerging feedback systems based on tracking body conditions can save human lives. In particular, vulnerable populations such as disabled people, elderly, and infants often require special care. For example, the high global mortality of infants primarily owing to sudden infant death syndrome while sleeping makes request for extraordinary attentions in neonatal intensive care units or daily lives. Here, a versatile laser‐induced graphene (LIG)‐based integrated flexible sensor system, which can wirelessly monitor the sleeping postures, respiration rate, and diaper moisture with feedback alarm notifications, is reported. A tilt sensor based on confining a liquid metal droplet inside a cavity can track at least 18 slanting orientations. A rapid and scalable laser direct writing method realizes LIG patterning in both the in‐plane and out‐of‐plane configurations as well as the formation of nonstick conductive structures to the liquid metal. By rationally merging the LIG‐based tilt, strain, and humidity sensors on a thin flexible film, the multimodal sensor device is applied to a diaper as a real‐time feedback tracking system of the sleeping posture, respiration, and wetness toward secure and comfortable lives. User‐friendly interfaces, which incorporate alarming functions, provide timely feedback for caregivers tending to vulnerable populations with limited self‐care capabilities.
Antibiofouling Thin‐Film Nanocomposite Membranes for Sustainable Water Purification
Authors: Pang Lijuan , Meier‐Haack Jochen , Huang Shaolong , Qi Lu , Cui Hongzhi , Ruan Shuangchen , Zeng Yu‐Jia
Published: March 2021

Membrane technology provides a reliable and powerful solution to combat the global water crisis by producing fresh water through sustainable desalination. However, the decline in system performance due to membrane biofouling is a limitation and significant efforts have been made to explore fouling control mechanisms and develop simple methods to inhibit or eliminate membrane fouling. Nanotechnology has increased the number of options for the development of antibiofouling membranes by incorporating nanoparticles within the polyamide layer to produce a thin‐film nanocomposite (TFN) structure. This review presents recent advances in the preparation of antifouling TFN membranes and incorporation of different nanoparticles into the design. The review also discusses the strategies and mechanisms for reducing membrane fouling and proposes a future outlook for the field.
Solvent‐Promoted Oxidation of Aromatic Alcohols/Aldehydes to Carboxylic Acids by a Laccase‐TEMPO System: Efficient Access to 2,5‐Furandicarboxylic Acid and 5‐Methyl‐2‐Pyrazinecarboxylic Acid
Authors: Cheng Ai‐Di , Zong Min‐Hua , Lu Guang‐Hui , Li Ning
Published: March 2021

Laccase coupled with 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO) is a well‐known catalytic system for the oxidation of alcohols to the carbonyl compounds. In this work, a simple yet effective solvent engineering strategy is developed to enable aromatic alcohols/aldehydes to be efficiently oxidized to carboxylic acids by a laccase‐TEMPO system. Citrate buffer (100–300 mm, pH 6) rather than the widely used acetate buffer (pH 4–5) proves to be optimal for this purpose. The roles of citrate are discussed in laccase‐TEMPO‐catalyzed synthesis of carboxylic acids. 5‐Hydroxymethylfurfural (HMF) of 200 mm is oxidized to 2,5‐furandicarboxylic acid (FDCA), a top‐value biobased chemical in the polymer industry, in 28 h with a yield of up to 97%. Of the 18 substrates examined, 11 alcohols are converted to target carboxylic acids with >90% yields by this method, with 2 alcohols giving >60% yields of carboxylic acids. Gram‐scale preparation of FDCA and 5‐methyl‐2‐pyrazinecarboxylic acid, an important drug intermediate, is demonstrated with total turnover numbers up to 110 000 for laccase and space‐time yields up to 1.0 g/(L•h). This chemoenzymatic approach may be a promising alternative to traditional chemical oxidations for the synthesis of carboxylic acids.
A Theoretical Evaluation of Possible N2 Reduction Mechanism on Mo2B2
Authors: Wang Jia , He Chaozheng , Huo Jinrong , Fu Ling , Zhao Chenxu
Published: March 2021

2D MBene has similar properties to MXene, and it has received widespread attention as an efficient ammonia synthesis catalyst. Herein, the catalytic effect of 2D Mo2B2 applied to the electrochemical nitrogen reduction reaction (NRR) by the first principles calculation is studied. It is found that 2D Mo2B2 can form different adsorption structures which have different electronic properties, and active N2 molecules effectively. These different structures have different catalytic mechanism on the NRR process. In addition, the possibility of NRR reactions on these structures is explored and it is found that when N2 adsorbed obliquely on 2D Mo2B2, it has the lowest overpotential (0.34 V). This work provides important reference for exploring more excellent NRR catalysis in experiments and expands the application of transition metal borides in catalysis.
Comparative Study on the Performance of Different Lead‐Based and Lead‐Free Perovskite Solar Cells
Authors: Jayan K. Deepthi , Sebastian Varkey
Published: March 2021

A comparative theoretical study on the performance of perovskite solar cells (PSCs) with methyl ammonium lead iodide (MAPbI3) and methyl ammonium germanium iodide (MAGeI3) as absorber layers is reported by modeling the solar cells for a number of electron transport materials (ETMs), hole transport materials, and back‐contact metals using solar cell capacitance simulator 1D tool. For MAPbI3 as the absorber layer, the best photovoltaic performance is observed for the configuration glass/fluorine‐doped tin oxide (FTO)/SnO2/MAPbI3/NiO/Au with a power conversion efficiency (PCE) of 20.58% and a fill factor (FF) of 68.34% and for MAGeI3, the configuration glass/FTO/SnO2/MAGeI3/CuO/Pd exhibits the best performance with a PCE of 13.12% and a FF of 68.29%. This study indicates that the low‐cost metal oxide SnO2 is a better substitute for the commonly used TiO2 as ETM, and the metal oxides like NiO and CuO provide a higher PCE for device configurations with MAPbI3 and MAGeI3, respectively, as the absorber layer. The low‐cost back‐contact metal Pd provides a better performance for MAGeI3‐based PSCs. This study also indicates that the nontoxic MAGeI3‐based PSCs can be used for commercial applications as they are more thermally stable than the MAPbI3‐based PSCs and provide an equally good quantum efficiency curve as that of MAPbI3‐based PSCs.
Visible‐light‐induced Reactions Driven by Photochemical Activity of Quinolinone and Coumarin Scaffolds
Authors: Vellakkaran Mari , Hong Sungwoo
Published: March 2021

Organic photocatalysis has garnered significant interest in the field of photochemistry because of its ability to generate active radical species under mild conditions via energy or electron transfer from the excited state of photosensitizers to organic molecules. Quinolinones and coumarins are privileged scaffolds that are widely distributed in natural products and pharmaceutical agents. Recently, quinolinones and coumarins have emerged as promising organic photosensitizers for a variety of chemical transformations. Significant advances in the development of synthetic methods via organic photocatalysis have elucidated their essential electronic properties, leading to the development of highly site‐selective synthetic methods. This mini‐review highlights recent innovative approaches to site‐selective C−H bond functionalization catalyzed by light‐absorbing quinolinone and coumarin scaffolds.
Nanogels as Antifungal‐Drug Delivery System Against Aspergillus Fumigatus
Authors: Horvat Sonja , Yu Yidong , Manz Hannah , Keller Thorsten , Beilhack Andreas , Groll Jürgen , Albrecht Krystyna
Published: March 2021

Aspergillus fumigatus is the opportunistic fungus responsible for a variety of serious and often lethal diseases of immunocompromised patients, such as invasive aspergillosis, aspergilloma, and allergic bronchopulmonary aspergillosis. Therapeutic options for such fungal infections are limited due to the high toxicity of currently available drugs. Herein, the potency of nanogels (NGs) is assessed for uptake and delivery of antifungal therapeutics. Therefore, poly(glycidol)‐based NGs are prepared by surfactant‐free inverse nanoprecipitation. Uptake studies conducted with fluorescently labeled particles demonstrate internalization by fungi in their hyphal form. In addition, loading with both amphiphilic and hydrophobic fluorescent dyes as model drugs show efficient delivery of the fluorescent dyes into the fungus. Finally, particles are loaded with the antifungal drug itraconazole by soaking lyophilized NGs in the drug solution (breathing‐in method). Efficient delivery of the drug by nanoprecipitated NGs, improved fungicidal activity, and reduced side effects as compared with the drug itself are shown.
Lokale Deuterierung ermöglicht NMR‐Messung von Methylgruppen in Proteinen aus eukaryotischen und Zell‐freien Expressionssystemen
Authors: Dubey Abhinav , Stoyanov Nikolay , Viennet Thibault , Chhabra Sandeep , Elter Shantha , Borggräfe Jan , Viegas Aldino , Nowak Radosław P. , Burdzhiev Nikola , Petrov Ognyan , Fischer Eric S. , Etzkorn Manuel , Gelev Vladimir , Arthanari Haribabu
Published: March 2021

GPCRs, Antikörper, Proteinkinasen und andere therapeutisch relevante Proteine stellen NMR‐Untersuchungen vor klare Herausforderungen, da die notwendige ortspezifische Isotopenmarkierung sowie Deuterierung in eukaryotischen Expressionsystemen stark limitiert ist. Wir beschreiben hier eine kostengünstige und einfache Methode, mit der Proteine mit markierten Leucin‐Methylgruppen in bakteriellen, eukaryotischen oder zell‐freien Expressionssystemen hergestellt werden können, ohne dass bestehende Expressionsprotokolle abgeändert werden müssen. Dafür werden Leucine stereo‐selektiv 13C‐markiert und deuteriert, was den Bedarf für eine Deuterierung des Restproteins abmildert. Die resultierenden verbesserten NMR‐spektroskopischen Eigenschaften werden detailliert mittels Forbidden Coherence Transfer (FTC)‐Experimenten und Simulationen beschrieben. Die Anwendung dieser Isotopenmarkierung wird anhand von zell‐freier Synthese von Bakteriorhodopsin und der Expression der RRM2‐Domäne von humanem RBM39 in Insektenzellen gezeigt.
Mechanochemical Prebiotic Peptide Bond Formation**
Authors: Stolar Tomislav , Grubešić Saša , Cindro Nikola , Meštrović Ernest , Užarević Krunoslav , Hernández José G.
Published: March 2021

The presence of amino acids on the prebiotic Earth, either stemming from endogenous chemical routes or delivered by meteorites, is consensually accepted. Prebiotically plausible pathways to peptides from inactivated amino acids are still unclear as most oligomerization approaches rely on thermodynamically disfavored reactions in solution. Now, a combination of prebiotically plausible minerals and mechanochemical activation enables the oligomerization of glycine at ambient temperature in the absence of water. Raising the reaction temperature increases the degree of oligomerization concomitantly with the formation of a commonly unwanted cyclic glycine dimer (DKP). However, DKP is a productive intermediate in the mechanochemical oligomerization of glycine. The findings of this research show that mechanochemical peptide bond formation is a dynamic process that provides alternative routes towards oligopeptides and establishes new synthetic approaches for prebiotic chemistry.
Stereoselektive gerichtete kationische Kaskaden ermöglicht durch molekulare Verankerung in Terpencyclasen
Authors: Schneider Andreas , Jegl Philipp , Hauer Bernhard
Published: March 2021

Kaskadenreaktionen haben sich als eine innovative Methode erwiesen, um den Aufbau komplexer Moleküle aus natürlich verfügbaren Vorläufern auf atom‐, zeit‐, arbeits‐ und kosteneffiziente Weise zu ermöglichen. In dieser Arbeit berichten wir über eine Strategie zur Kontrolle von kationischen Cyclisierungskaskaden, indem wir die Fähigkeit zur Verankerung von dynamischen Substraten im aktiven Zentrum von Terpencyclasen über designte Wasserstoffbrückenbindungen ausnutzen. Dadurch ist es möglich, “gerichtete” Cyclisierungen im Gegensatz zu bisher etablierten “Non‐Stop”‐Cyclisierungen (99:1) zu induzieren und die Termination der Kaskade an ansonsten katalytisch kaum zugänglichen Intermediaten zu prädestinieren. Mittels dieser Strategie sind wir in der Lage, einen effizienten Zugang zu natürlich weit verbreiteten Apocarotenoiden, wertvollen Aromen und Düften im Gramm‐Maßstab zu schaffen, wobei wir mehrstufige Syntheserouten durch einen einzigen Schritt mit herausragender Selektivität (>99.5 % ee) und hohen Ausbeuten (bis zu 89 %) ersetzen.
Unified Synthesis of Polycyclic Alkaloids by Complementary Carbonyl Activation**
Authors: He Guoli , List Benjamin , Christmann Mathias
Published: March 2021

A complementary dual carbonyl activation strategy for the synthesis of polycyclic alkaloids has been developed. Successful applications include the synthesis of tetracyclic alkaloids harmalanine and harmalacinine, pentacyclic indoloquinolizidine alkaloid nortetoyobyrine, and octacyclic β‐carboline alkaloid peganumine A. The latter synthesis features a protecting‐group‐free assembly and an asymmetric disulfonimide‐catalyzed cyclization. Furthermore, formal syntheses of hirsutine, deplancheine, 10‐desbromoarborescidine A, and oxindole alkaloids rhynchophylline and isorhynchophylline have been achieved. Finally, a concise synthesis of berberine alkaloid ilicifoline B was completed.
Protein–Antibody Conjugates (PACs): A Plug‐and‐Play Strategy for Covalent Conjugation and Targeted Intracellular Delivery of Pristine Proteins
Authors: Liu Bin , Singh Khushboo , Gong Shuai , Canakci Mine , Osborne Barbara A. , Thayumanavan S.
Published: March 2021

We report here on protein–antibody conjugates (PACs) that are used for antibody‐directed delivery of protein therapeutics to specific cells. PACs have the potential to judiciously combine the merits of two prolific therapeutic approaches—biologics and antibody–drug conjugates. We utilize spherical polymer brushes to construct PACs using the combination of two simple and efficient functionally orthogonal click chemistries. In addition to the synthesis and characterization of these nanoparticles, we demonstrate that PACs are indeed capable of specifically targeting cells based on the presence of target antigen on the cell surface to deliver proteins. The potentially broad adaptability of PACs opens up new opportunities for targeted biologics in therapeutics and sensing.
Genetic Engineering in Combination with Semi‐Synthesis Leads to a New Route for Gram‐Scale Production of the Immunosuppressive Natural Product Brasilicardin A
Authors: Botas Alma , Eitel Michael , Schwarz Paul N. , Buchmann Anina , Costales Paula , Núñez Luz Elena , Cortés Jesús , Morís Francisco , Krawiec Michał , Wolański Marcin , Gust Bertolt , Rodriguez Mirna , Fischer Wolf‐Nicolas , Jandeleit Bernd , Zakrzewska‐Czerwińska Jolanta , Wohlleben Wolfgang , Stegmann Evi , Koch Pierre , Méndez Carmen , Gross Harald
Published: March 2021

Brasilicardin A (1) consists of an unusual anti/syn/anti‐perhydrophenanthrene skeleton with a carbohydrate side chain and an amino acid moiety. It exhibits potent immunosuppressive activity, yet its mode of action differs from standard drugs that are currently in use. Further pre‐clinical evaluation of this promising, biologically active natural product is hampered by restricted access to the ready material, as its synthesis requires both a low‐yielding fermentation process using a pathogenic organism and an elaborate, multi‐step total synthesis. Our semi‐synthetic approach included a) the heterologous expression of the brasilicardin A gene cluster in different non‐pathogenic bacterial strains producing brasilicardin A aglycone (5) in excellent yield and b) the chemical transformation of the aglycone 5 into the trifluoroacetic acid salt of brasilicardin A (1 a) via a short and straightforward five‐steps synthetic route. Additionally, we report the first preclinical data for brasilicardin A.
Recombinant Spider Silk Gels Derived from Aqueous–Organic Solvents as Depots for Drugs
Authors: Neubauer Vanessa J. , Trossmann Vanessa T. , Jacobi Sofia , Döbl Annika , Scheibel Thomas
Published: March 2021

Hydrogels are widely used in various biomedical applications, as they cannot only serve as materials for biofabrication but also as depots for the administration of drugs. However, the possibilities of formulation of water‐insoluble drugs in hydrogels are rather limited. Herein, we assembled recombinant spider silk gels using a new processing route with aqueous–organic co‐solvents, and the properties of these gels could be controlled by the choice of the co‐solvent. The presence of the organic co‐solvent further enabled the incorporation of hydrophobic drugs as exemplarily shown for 6‐mercaptopurine. The developed gels showed shear‐thinning behaviour and could be easily injected to serve, for example, as drug depots, and they could even be 3D printed to serve as scaffolds for biofabrication. With this new processing route, the formulation of water‐insoluble drugs in spider silk‐based depots is possible, circumventing common pharmaceutical solubility issues.
Peroxopolyoxometalate nanoparticles blended PES membrane with improved hydrophilicity, anti‐fouling, permeability, and dye separation properties
Authors: Barzegar Hossein , Shahsavarifar Samaneh , Vatanpour Vahid , Masteri‐Farahani Majid
Published: March 2021

Poly(ethersulfone) (PES) is one of the polymers most widely used for the fabrication of ultrafiltration or nanofiltration membranes in various applications, but its membrane suffers from fouling. In this study, preparation, characterization, and performance of PES nanocomposite membrane comprising peroxopolyoxometalate nanoparticles was studied to provide improved permeability and anti‐fouling properties. The high oxygen ratio of the PW4 nanoparticles could enhance the hydrophilicity of the membranes. The PW4 nanoparticles were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), energy dispersive X‐ray (EDX), and X‐ray diffraction analyses. The mixed matrix membranes were fabricated using a non‐solvent induced phase‐separation method. The fabricated membranes were characterized using atomic force microscopy, attenuated total reflection, SEM, EDX mapping, total average porosity, thermogravimetric analyze, and water contact angle experiments. The dye flux and rejection, pure water permeability and anti‐fouling properties of the membranes were investigated. All of the membranes blended by different contents of the PW4 nanoparticles presented better performance compared to the unmodified membrane. The filtration performance of the membranes in reactive green 19 (RG19) and reactive yellow 160 (RY160) dye separation showed that all of the PW4 blended membranes possessed dye rejection greater than 86% and 96% for RY160 and RG19, respectively. The reusability test using bovine serum albumin (BSA) protein and RG19 dye solutions in five cycle experiments presented good reproductivity of the PW4 blended membranes. The PES membrane containing 1 wt% of PW4 nanoparticles showed the highest flux recovery ratio (75%) as well as reduced irreversible fouling ratio (8%) through BSA protein filtration.
Sex differentiation of brain structures in autism: Findings from a gray matter asymmetry study
Authors: Deng Zhizhou , Wang Suiping
Published: March 2021

Autism spectrum disorder (ASD) is diagnosed much more often in males than females. This male predominance has prompted a number of studies to examine how sex differences are related to the neural expression of ASD. Different theories, such as the “extreme male brain” theory, the “female protective effect” (FPE) theory, and the gender incoherence (GI) theory, provide different explanations for the mixed findings of sex‐related neural expression of ASD. This study sought to clarify whether either theory applies to the brain structure in individuals with ASD by analyzing a selective high‐quality data subset from an open data resource (Autism Brain Imaging Data Exchange I and II) including 35 males/35 females with ASD and 86 male/86 female typical‐controls (TCs). We examined the sex‐related changes in ASD in gray matter asymmetry measures (i.e., asymmetry index, AI) derived from voxel‐based morphometry using a 2 (diagnosis: ASD vs. TC) ×  2 (sex: female vs. male) factorial design. A diagnosis‐by‐sex interaction effect was identified in the planum temporale/Heschl's gyrus: (i) compared to females, males exhibited decreased AI (indicating more leftward brain asymmetry) in the TC group, whereas AI was greater (indicating less leftward brain asymmetry) for males than for females in the ASD group; and (ii) females with ASD showed reduced AI (indicating more leftward brain asymmetry) compared to female TCs, whereas there were no differences between ASDs and TCs in the male group. This interaction pattern supports the FPE theory in showing greater brain structure changes (masculinization) in females with ASD.

Lay Summary

To understand the neural mechanisms underlying male predominance in autism spectrum disorder (ASD), we investigated the sex differences in ASD‐related alterations in brain asymmetry. We found greater changes in females with ASD compared with males with ASD, revealing a female protective effect. These findings provide novel insights into the neurobiology of sex differences in ASD.
Enhancing erythrocyte–influenza virus specificity by glycan‐conjugated gold nanoparticle: Validation of hemagglutination by aptamer and neuraminidases
Authors: Ye Meiyi , Lin Lei , Yang Wei , Gopinath Subash C.B.
Published: March 2021

This study demonstrated the terminated sialo‐sugar chains (Neu5Acα2,6Gal and Neu5Acα2,3Gal)‐mediated specificity enhancement of influenza virus and chicken red blood cell (RBC) by hemagglutination assay. These glycan chains were immobilized on the gold nanoparticle (GNP) to withhold the higher numbers. With the preliminary optimization, a clear button formation with 0.5% RBC was visualized. On the other hand, intact B/Tokio/53/99 with 750 nM hemagglutinin (HA) displayed a nice hemagglutination. The interference on the specificity of RBC and influenza virus was observed by anti‐influenza aptamer at the concentration 31 nM; however, there is no hemagglutination prevention was noticed in the presence of complementary aptamer sequences. Spiking GNP‐conjugated Neu5Acα2,6Gal or Neu5Acα2,3Gal or a mixture of these two to the reaction promoted the hemagglutination to 63‐folds higher with 12 nM virus, whereas under the same condition the heat‐inactivated viruses were lost the hemagglutination. Neuraminidases from Clostridium perfringens and Arthrobacter ureafaciens at 0.0025 neuraminidase units are able to abolish the hemagglutination. Other enzymes, Glycopeptidase F (Elizabethkingia meningoseptica) and Endoglycosidase H (Streptomyces plicatus) did not show the changes with agglutination. Obviously, sialyl‐Gal‐terminated glycan‐conjugated GNP amendment has enhanced the specificity of erythrocyte–influenza virus and able to be controlled by aptamer or neuraminidases.
Investigating antecedents of Islamophobia: The role of perceived control over terrorism, threat, meta‐dehumanization, and dehumanization
Authors: Pavetich Melissa , Stathi Sofia
Published: March 2021

Meta‐dehumanization contributes to a vicious cycle of hostility. This study extends the literature by investigating antecedents and outcomes of meta‐dehumanization in the context of Muslim–non‐Muslim relations. Specifically, control over terrorism (COT) and threat were tested as predictors of meta‐dehumanization among non‐Muslim British nationals (N = 313). The results revealed that lower perceptions of COT predicted increased threat, which in turn predicted meta‐dehumanization. Meta‐dehumanization, consequently, predicted Islamophobia via increased dehumanization of Muslim people. The results were significant while controlling for political orientation and intergroup contact. This research highlights the unsettling cycle of meta‐dehumanization and intergroup hostility. Theoretical and practical implications of this research are discussed. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Fluorinated Azobenzenes Switchable with Red Light
Authors: Leistner Anna‐Lena , Kirchner Susanne , Karcher Johannes , Bantle Tobias , Schulte Mariam L. , Gödtel Peter , Fengler Christian , Pianowski Zbigniew L.
Published: March 2021

Molecular photoswitches triggered with red or NIR light are optimal for photomodulation of complex biological systems, including efficient penetration of the human body for therapeutic purposes (“therapeutic window”). Yet, they are rarely reported, and even more rarely functional under aqueous conditions. In this work, fluorinated azobenzenes are shown to exhibit efficient E→Z photoisomerization with red light (PSS660nm >75 % Z) upon conjugation with unsaturated substituents. Initially demonstrated for aldehyde groups, this effect was also observed in a more complex structure by incorporating the chromophore into a cyclic dipeptide with propensity for self‐assembly. Under physiological conditions, the latter molecule formed a supramolecular material that reversibly changed its viscosity upon irradiation with red light. Our observation can lead to design of new photopharmacology agents or phototriggered materials for in vivo use.
3D Uranyl Organic Frameworks Supported by Rigid Octadentate Carboxylate Ligand: Synthesis, Structure Diversity, and Luminescence Properties
Authors: Wu Dai , Mo Xiu‐Fang , He Piao , Li Hai‐Ru , Yi Xiao‐Yi , Liu Chao
Published: March 2021

Seven three dimensional (3D) uranyl organic frameworks (UOFs), formulated as [NH4][(UO2)3(HTTDS)(H2O)] (1), [(UO2)4(HTTDS)2](HIM)6 (2, IM=imidazole), [(UO2)4(TTDS)(H2O)2(Phen)2] (3, Phen=1,10‐phenanthroline), [Zn(H2O)4]0.5[(UO2)3(HTTDS)(H2O)4] (4), and {(UO2)2[Zn(H2O)3]2(TTDS)} (5), {Zn(UO2)2(H2O)(Dib)0.5(HDib)(HTTDS)} (6, Dib=1,4‐di(1H‐imidazol‐1‐yl)benzene) and [Na]{(UO2)4[Cu3(u3‐OH)(H2O)7](TTDS)2} (7) have been hydrothermally prepared using a rigid octadentate carboxylate ligand, tetrakis(3,5‐dicarboxyphenyl)silicon(H8TTDS). These UOFs have different 3D self‐assembled structures as a function of co‐ligands, structure‐directing agents and transition metals. The structure of 1 has an infinite ribbon formed by the UO7 pentagonal bipyramid bridged by carboxylate groups. With further introduction of auxiliary N‐donor ligands, different structure of 2 and 3 are formed, in 2 the imidazole serves as space filler, while in 3 the Phen are bound to [UO2]2+ units as co‐ligands. The second metal centers were introduced in the syntheses of 4–7, and in all cases, they are part of the final structures, either as a counterion (4) or as a component of framework (5−7). Interesting, in 7, a rare polyoxometalate [Cu3(μ3‐OH)O7(O2CR)4] cluster was found in the structure. It acts as an inorganic building unit together with the dimer [(UO2)2(O2CR)4] unit. Those uranyl carboxylates were sufficiently determined by single crystal X‐ray diffraction, and their topological structures and luminescence properties were analyzed in detail.
Prediction and Validation of a Druggable Site on Virulence Factor of Drug Resistant Burkholderia cenocepacia**
Authors: Lal Kanhaya , Bermeo Rafael , Cramer Jonathan , Vasile Francesca , Ernst Beat , Imberty Anne , Bernardi Anna , Varrot Annabelle , Belvisi Laura
Published: March 2021

Burkholderia cenocepacia is an opportunistic Gram‐negative bacterium that causes infections in patients suffering from chronic granulomatous diseases and cystic fibrosis. It displays significant morbidity and mortality due to extreme resistance to almost all clinically useful antibiotics. The bacterial lectin BC2L‐C expressed in B. cenocepacia is an interesting drug target involved in bacterial adhesion and subsequent deadly infection to the host. We solved the first high resolution crystal structure of the apo form of the lectin N‐terminal domain (BC2L‐C‐nt) and compared it with the ones complexed with carbohydrate ligands. Virtual screening of a small fragment library identified potential hits predicted to bind in the vicinity of the fucose binding site. A series of biophysical techniques and X‐ray crystallographic screening were employed to validate the interaction of the hits with the protein domain. The X‐ray structure of BC2L‐C‐nt complexed with one of the identified active fragments confirmed the ability of the site computationally identified to host drug‐like fragments. The fragment affinity could be determined by titration microcalorimetry. These structure‐based strategies further provide an opportunity to elaborate the fragments into high affinity anti‐adhesive glycomimetics, as therapeutic agents against B. cenocepacia.
Synthesis of Desepoxy‐Tedanolide C
Authors: Lücke Daniel , Kalesse Markus
Published: March 2021

The synthesis of desepoxy‐tedanolide C was accomplished and provided experimental evidence on the configuration of tedanolide C. The reported chemical shifts and coupling constants point to a configuration different from the published structure and analogous to the structures of the other members of this family of natural products. The key step is a Kiyooka aldol protocol for the stereoselective synthesis of the tertiary alcohol flanked by three additional oxygenated carbon atoms. Furthermore, two additional aldol reactions and a Julia–Kocienski olefination were used to assemble the carbon framework.
Copper‐Catalyzed Synthesis of Tetrasubstituted Alkenes via Regio‐ and anti‐Selective Addition of Silylboronates to Internal Alkynes
Authors: Moniwa Hirokazu , Shintani Ryo
Published: March 2021

As a new and complementary method for the synthesis of structurally defined tetrasubstituted alkenes, a copper‐catalyzed regio‐ and anti‐selective addition of silylboronates to unsymmetric internal alkynes has been developed. A variety of unactivated alkynes can be employed with high selectivity under simple and mild conditions, and the resulting products have been further functionalized by utilizing silyl and boryl groups on the alkene.
The impact of underweight and obesity on outcomes in anticoagulated patients with atrial fibrillation: A systematic review and meta‐analysis on the obesity paradox
Authors: Grymonprez Maxim , Capiau Andreas , De Backer Tine L. , Steurbaut Stephane , Boussery Koen , Lahousse Lies
Published: March 2021

Although obesity is associated with the development and progression of atrial fibrillation (AF), an obesity paradox may be present, illustrated by seemingly protective effects of obesity on AF‐related outcomes. Body mass index (BMI) has an impact on outcomes in AF patients using oral anticoagulants. After searching Medline and Embase, meta‐analysis of results of four randomized and five observational studies demonstrated significantly lower risks of stroke or systemic embolism (RR 0.80, 95%CI [0.73–0.87]; RR 0.63, 95%CI [0.57–0.70]; and RR 0.42, 95%CI [0.31–0.57], respectively) and all‐cause mortality (RR 0.73, 95%CI [0.64–0.83]; RR 0.61, 95%CI [0.52–0.71]; and RR 0.56, 95%CI [0.47–0.66], respectively) in overweight, obese and morbidly obese anticoagulated AF patients (BMI 25 to <30, ≥30 and ≥40 kg/m2, respectively) compared to normal BMI anticoagulated AF patients (BMI 18.5 to <25 kg/m2). In contrast, thromboembolic (RR 1.92, 95%CI [1.28–2.90]) and mortality (RR 3.57, 95%CI [2.50–5.11]) risks were significantly increased in underweight anticoagulated AF patients (BMI <18.5 kg/m2). In overweight and obese anticoagulated AF patients, the risks of major bleeding (RR 0.86, 95%CI [0.76–0.99]; and RR 0.88, 95%CI [0.79–0.98], respectively) and intracranial bleeding (RR 0.75, 95%CI [0.58–0.97]; and RR 0.57, 95%CI [0.40–0.80], respectively) were also significantly lower compared to normal BMI patients, while similar risks were observed in underweight and morbidly obese patients. This meta‐analysis demonstrated lower thromboembolic and mortality risks with increasing BMI. However, as this paradox was driven by results from randomized studies, while observational studies rendered more conflicting results, these seemingly protective effects should still be interpreted with caution.
Halogen and Chalcogen Bonding Between the Triphenylphosphine Chalcogenides (Ph3P=E; E=O, S, Se) and Iodofluorobenzenes
Authors: Peloquin Andrew J. , McMillen Colin D. , Iacono Scott T. , Pennington William T.
Published: March 2021

A series of cocrystals of Ph3P=E (E=O, S, Se) with organoiodines were studied to understand the roles of noncovalent interactions including chalcogen (ChB) and halogen (XB) bonding in their formation. The structure of the cocrystal of Ph3P=S and 1,2‐diiodotetrafluorobezene was determined, which demonstrates a similar chalcogen⋅⋅⋅iodine XB pattern to the previously reported isomorphic Ph3P=Se structure. The cocrystalline structures resulting from the combination of 1,3‐diiodotetrafluorobenzene (1,3‐F4DIB), as well as iodopentafluorobenzene, with all three triphenylphosphine chalcogenides, were also determined. The (Ph3P=Se) ⋅ (1,3‐F4DIB) cocrystal presents a rare example of a selenium⋅⋅⋅organoiodine ChB. The observed ChB and XB interactions have normalized distance parameters (RXB) ranging from 0.80 to 0.98. The strength of the XB and ChB interactions were analyzed using natural bond orbital (NBO) theory, with calculated energies falling between 3.14 kcal/mol and 12.81 kcal/mol.
Triple full‐sibs: A method for estimating components of genetic variance and progeny selection in plants
Authors: Chaves Lázaro José
Published: March 2021

Quantifying the genetic variability present in plant populations is crucial for the success of selection plans. The partitioning of genetic variance into its components allows inferences about the inheritance of quantitative traits and prediction of the gain from selection. The present study aimed to present an alternative method to estimate components of genetic variance with applications in recurrent selection. The mating scheme is based on biparental cyclic crossing involving three parents in each chain, here called the triple full‐sibs (TFS) family, each of which is composed of three biparental progenies in which individuals are full‐sibs within each progeny and half‐sibs among progenies. The progenies are evaluated in experimental trials, and the total effect of progenies is hierarchically partitioned into the effects of TFS families and progenies within families. From the components of variance, additive and dominance variance, as well as the associated errors, can be estimated. Simulated data are used to illustrate the method of analysis and parameter estimation. The method combines the advantages of North Carolina Design I regarding estimation of variance components with the practicality of conventional full‐sib selection. The TFS method allows different selection strategies according to the selection unit and provides expected genetic gain equal to or greater than unrelated full‐sib selection. There is no further advantage to using more than three parents in each chain‐cross.
The evolution of hummock–depression micro‐topography in an alpine marshy wetland in Sanjiangyuan as inferred from vegetation and soil characteristics
Authors: Wu Guiling , Li Xilai , Gao Jay
Published: March 2021

The hummock–depression micro‐topography characteristics of the alpine marshy wetland in Sanjiangyuan are indicative of wetland degradation and the process by which healthy wetlands are transformed into flat grasslands. The aim of the present study was to examine changes in plant community structure and soil characteristics in a hummock–depression micro‐topography along a degradation gradient. We observed that: (a) the height and cover of dominant hydrophytes decreased gradually with an increase in degradation severity, leading to replacement by xerophytes; (b) with the transition from healthy to degraded wetlands, hummocks became sparser, shorter, and broader and became merged with nearby depressions; water reserves in the depressions shifted from perennial to seasonal, until they dried out completely; and (c) soil moisture content, porosity, hardness, and organic matter gradually decreased by 30.61%, 19.06%, 37.04%, and 73.27%, respectively, in hummocks and by 33.25%, 8.19%, 47.72%, and 76.79%, respectively, in depressions. Soil bulk density, soil electrical conductivity, and soil dry weight increased by 31%, 83.33%, and 105.44%, respectively, in hummocks, but by only 11.93%, 7.14%, and 97.72%, respectively, in depressions. The results show that hummock soils in healthy wetlands have strong water absorption properties, through which plant roots can penetrate easily. Wetland degradation reduces the water absorption capacity of hummock soil and soil saturation capacity of depressions, thus enhancing soil erosion potential and susceptibility to external factors. Soil moisture is a key environmental factor influencing wetland degradation, and grazing accelerates the process. Based on the changes observed in hummock morphology, vegetation, and soil properties along a degradation gradient, a conceptual model is proposed to illustrate the process of gradual degradation of marshy wetlands from healthy to transitional wetlands and finally to a degenerated state. Thus, our research provides insights into the degradation process of the alpine marshy wetland ecosystem in Sanjiangyuan.
Making the most of the old age: Autumn breeding as an extra reproductive investment in older seabirds
Authors: Ramírez Francisco , Chiaradia Andre , O'Leary Danielle A. , Reina Richard D.
Published: March 2021

The extrinsic and intrinsic factors affecting differing reproductive strategies among populations are central to understanding population and evolutionary ecology. To evaluate whether individual reproductive strategies responded to annual patterns in marine productivity and age‐related processes in a seabird we used a long term (2003–2013), a continuous dataset on nest occupancy and attendance at the colony by little penguins (Eudyptula minor) at Phillip Island (Victoria, Australia). We found that concurrent with a secondary annual peak of marine productivity, a secondary peak in colony attendance and nest occupancy was observed in Autumn (out of the regular breeding season in spring/summer) with individuals showing mating‐like behavior. Individuals attending this autumn peak averaged 2.5 years older than those individuals that exclusively bred during spring/summer. Rather than being a naïve response by younger and inexperienced birds misreading environmental cues, our data indicate that the autumn peak attendance is an earlier attempt to breed by older and more experienced penguins. Therefore, we provide strong support for the fundamental prediction of the life‐history theory of increasing investment in reproduction with age to maximize lifetime fitness as future survival prospects diminish and experience increases.