bluuebunny/crossref_metadata_2025 huggingface dataset:
Manifestations and impact of the COVID‐19 pandemic in neuroinflammatory diseases
Authors: Levin Seth N. , Venkatesh Shruthi , Nelson Katie E. , Li Yi , Aguerre Ines , Zhu Wen , Masown Karman , Rimmer Kathryn T. , Diaconu Claudiu I. , Onomichi Kaho B. , Leavitt Victoria M. , Levine Libby L. , Strauss‐Farber Rebecca , Vargas Wendy S. , Banwell Brenda , Bar‐Or Amit , Berger Joseph R. , Goodman Andrew D. , Longbrake Erin E. , Oh Jiwon , Weinstock‐Guttman Bianca , Thakur Kiran T. , Edwards Keith R. , Riley Claire S. , Xia Zongqi , De Jager Philip L. ,   Multiple Sclerosis Resilience to COVID‐19 (MSReCOV) Collaborative
Published: February 2021

Objective

To report initial results of a planned multicenter year‐long prospective study examining the risk and impact of COVID‐19 among persons with neuroinflammatory disorders (NID), particularly multiple sclerosis (MS).

Methods

In April 2020, we deployed online questionnaires to individuals in their home environment to assess the prevalence and potential risk factors of suspected COVID‐19 in persons with NID (PwNID) and change in their neurological care.

Results

Our cohort included 1115 participants (630 NID, 98% MS; 485 reference) as of 30 April 2020. 202 (18%) participants, residing in areas with high COVID‐19 case prevalence, met the April 2020 CDC symptom criteria for suspected COVID‐19, but only 4% of all participants received testing given testing shortages. Among all participants, those with suspected COVID‐19 were younger, more racially diverse, and reported more depression and liver disease. PwNID had the same rate of suspected COVID‐19 as the reference group. Early changes in disease management included telemedicine visits in 21% and treatment changes in 9% of PwNID. After adjusting for potential confounders, increasing neurological disability was associated with a greater likelihood of suspected COVID‐19 (ORadj = 1.45, 1.17–1.84).

Interpretations

Our study of real‐time, patient‐reported experience during the COVID‐19 pandemic complements physician‐reported MS case registries which capture an excess of severe cases. Overall, PwNID seem to have a risk of suspected COVID‐19 similar to the reference population.
Photocrosslinked Bioreducible Polymeric Nanoparticles for Enhanced Systemic siRNA Delivery as Cancer Therapy
Authors: Karlsson Johan , Tzeng Stephany Y. , Hemmati Shayan , Luly Kathryn M. , Choi Olivia , Rui Yuan , Wilson David R. , Kozielski Kristen L. , Quiñones‐Hinojosa Alfredo , Green Jordan J.
Published: February 2021

Clinical translation of polymer‐based nanocarriers for systemic delivery of RNA has been limited due to poor colloidal stability in the blood stream and intracellular delivery of the RNA to the cytosol. To address these limitations, this study reports a new strategy incorporating photocrosslinking of bioreducible nanoparticles for improved stability extracellularly and rapid release of RNA intracellularly. In this design, the polymeric nanocarriers contain ester bonds for hydrolytic degradation and disulfide bonds for environmentally triggered small interfering RNA (siRNA) release in the cytosol. These photocrosslinked bioreducible nanoparticles (XbNPs) have a shielded surface charge, reduced adsorption of serum proteins, and enable superior siRNA‐mediated knockdown in both glioma and melanoma cells in high‐serum conditions compared to non‐crosslinked formulations. Mechanistically, XbNPs promote cellular uptake and the presence of secondary and tertiary amines enables efficient endosomal escape. Following systemic administration, XbNPs facilitate targeting of cancer cells and tissue‐mediated siRNA delivery beyond the liver, unlike conventional nanoparticle‐based delivery. These attributes of XbNPs facilitate robust siRNA‐mediated knockdown in vivo in melanoma tumors colonized in the lungs following systemic administration. Thus, biodegradable polymeric nanoparticles, via photocrosslinking, demonstrate extended colloidal stability and efficient delivery of RNA therapeutics under physiological conditions, and thereby potentially advance systemic delivery technologies for nucleic acid‐based therapeutics.
Preparation of Polycrystalline‐Mixed Graphene Film with Benzene Solution by Electromagnetic Induction for Application in Metal Corrosion Protection
Authors: Chen Wei , Wu Chaoxing , Guo Tailiang , Hu Hailong , Li Fushan
Published: February 2021

Metals used in the electronics, machinery manufacturing, and construction industry are often chemically reactive and corrosion‐prone, while barriers on a metal as a conventional method for anticorrosion always have negative effects including a toxic nature, thickness increase over time, and changes of electrical and optical properties after surface coating. This study employs a benzene solution to induce a rapid formation of a polycrystalline graphene film on copper foils or iron sheet substrates under atmospheric conditions by electromagnetic induction, which is non‐toxic and environment‐friendly and produces favorable anticorrosive effects. The microscopic analysis shows that the as‐grown film is a polycrystalline graphene complex of graphene crystallites. It is revealed that the copper foils or iron sheets with the graphene film is significantly resistant to strong corrosion, with the corrosion current density is one order of magnitude lower when compared with samples without the graphene films. The polycrystalline structure of the graphene film can prevent the electronic conduction of the surface, thereby reducing corrosion and local over‐corrosion phenomena when metals are situated in a long‐term exposure to corrosive environments.
Lubricant Depletion‐Resistant Slippery Liquid‐Infused Porous Surfaces via Capillary Rise Lubrication of Nanowire Array
Authors: Tran Hong‐Huy , Kim Youngjin , Ternon Céline , Langlet Michel , Riassetto David , Lee Daeyeon
Published: February 2021

Despite their promise in diverse applications, lubricant depletion over time presents an important challenge for slippery lubricant‐infused porous surfaces (SLIPS). The main source of lubricant depletion is the growth of a wetting ridge around a droplet of foreign liquid that removes the infused lubricant from the porous surface when the droplet slides off. This work describes the fabrication of liquid‐infused ZnO nanowire array by capillary rise lubrication and the effect of array morphology on suppressing wetting ridge formation. The orientation of nanowires strongly affects lubricant infiltration and the stability of SLIPS properties. The infiltrated lubricant in random ZnO nanowire arrays does not form a visible wetting ridge around a water droplet because of the strong capillarity that retains the lubricant confined in the nanoporous structure. The lack of wetting ridge gives rise to a stable SLIPS that exhibits self‐recovery of the infused lubricant. Such a structure retains lubricant under a strong centrifugal force, showing high stability. This study provides a straightforward, robust, and potentially scalable approach for making stable SLIPS that suppresses lubricant depletion by taking advantage of the unique morphology of the random nanowire arrays and capillary rise lubrication.
Rapid Fabrication of Superhydrophilic Micro/Nanostructured Nickel Foam Toward High‐Performance Glucose Sensor
Authors: Gao Xiaohui , Feng Wenshuai , Zhu Zhuo , Wu Zhipeng , Li Shi , Kan Shuting , Qiu Xiaoqing , Guo Aimin , Chen Wei , Yin Kai
Published: February 2021

Porous materials with micro/nanostructures have demonstrated intriguing performance in glucose sensor. However, current methods have been limited to complex, time‐consuming, and toxic manufacturing process or unsatisfactory performance, which hugely restricts its practical applications. Herein, for the first time, a fast, simple, and nonpollution femtosecond laser direct writing technology is proposed to fabricate high‐performance glucose sensor. The as‐prepared nickel foam exhibits micro/nanostructures with superhydrophilic property, resulting in superior electrochemical sensing performance toward glucose. The sensitivity is determined to be 13.822 mA cm−2 mM−1 with the detection limit of 1.9 × 10−6 m, outperforming the results from the most, previously reported works. Meanwhile, the excellent selectivity for glucose detection is also demonstrated in the presence of interferences. This work is an attractive candidate for fast fabrication and designing of high‐performance glucose sensor.
Synthesis of Gram‐Scale Ultrastable Mn‐Doped 2D Perovskites for Light‐Emitting Diodes
Authors: Hou Lu , Zhu Yihua , Zhu Jingrun , Li Xuyan , Zeng Feng , Yang Tingyu , Gong Yiqin , Shen Jianhua , Li Chunzhong
Published: February 2021

Mn‐doped 2D perovskites are emerging as good candidates for light‐emitting applications due to their excellent optical and electrical properties. Major synthetic routes, solid‐state grinding and high‐temperature solution synthesis, are extensively studied to prepare Mn‐doped 2D perovskites. However, complicated synthesis, small‐scale yields, and poor‐stability impede their widespread applications. Herein, a one‐step acid‐solution‐assisted method is exhibited for gram‐scale production of Mn‐doped 2D (C8H17NH2)2PbBr4 with a solid yield of 1.35 g products out of 3 mL solvent. After Mn‐doped 2D (C8H17NH2)2PbBr4 being stored in the air for 90 days, the photoluminescence (PL) quantum yield of powders has minor changes, showing good stability. Phosphor‐converted monochrome light‐emitting diodes (LEDs) are fabricated. After the LEDs work 6 h under a voltage of 3 V, their PL spectra have no obvious change, showing a great potential in optoelectronic devices. This study provides a new effective strategy for large‐scale synthesis of ultrastable Mn‐doped 2D perovskites, which is expected to provide inspiration for the industrial optoelectronic applications of perovskites.
Self‐Assembled Nanorods and Microspheres for Functional Photonics: Retroreflector Meets Microlens Array
Authors: Chu Guang , Chen Feng , Zhao Bin , Zhang Xue , Zussman Eyal , Rojas Orlando J.
Published: February 2021

Patterned micro/nanomaterials display efficient light management capabilities owing to their control of light propagation within multiscale periodic structures. Here a hierarchical photonic structure composed of polystyrene microspheres and cholesteric assembly of cellulose nanocrystals is described, acting as a polarization‐sensitive retroreflective coating and microlens array. Micropatterned photonic films are prepared by casting an aqueous cellulose nanocrystal suspension onto a monolayer of polystyrene microspheres substrate through evaporation‐assisted transfer imprinting lithography, integrating a bulk cholesteric matrix and patterned surface. By directing light at the as‐assembled polystyrene surface, an enhanced structural color develops from the circularly polarized light retroreflection. Whereas when light travelling across the photonic film, the transparent layer of polystyrene microspheres forms into plano‐convex microlens to converge the transmitted light into the focus plane and reduce centimeter‐scale illuminated image into a high‐fidelity miniaturized replica. This simple method, combining self‐assembly with imprinting lithography, is expected to pave the way for designing custom‐tailored optics with novel functions.
A 1,4‐Palladium Migration/Heck Sequence with Unactivated Alkenes: Stereoselective Synthesis of Trisubstituted 1,3‐Dienes
Authors: Xue Ze‐Jian , Li Meng‐Yao , Zhu Bin‐Bin , He Zhi‐Tao , Feng Chen‐Guo , Lin Guo‐Qiang
Published: February 2021

The palladium‐catalyzed cross‐coupling of ortho‐vinyl aromatic bromides and olefins was achieved through a controllable 1,4‐palladium migration/Heck cascade protocol. The reaction represents a mild, efficient and highly stereoselective method for the synthesis of trisubstituted 1,3‐dienes, especially for triaryl‐substituted ones.

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Drug Repurposing of Itraconazole and Estradiol Benzoate against COVID‐19 by Blocking SARS‐CoV‐2 Spike Protein‐Mediated Membrane Fusion
Authors: Yang Chan , Pan Xiaoyan , Huang Yuan , Cheng Chen , Xu Xinfeng , Wu Yan , Xu Yunxia , Shang Weijuan , Niu Xiaoge , Wan Yihong , Li Zhaofeng , Zhang Rong , Liu Shuwen , Xiao Gengfu , Xu Wei
Published: February 2021

SARS‐CoV‐2 caused the emerging epidemic of coronavirus disease in 2019 (COVID‐19). To date, there are more than 82.9 million confirmed cases worldwide, there is no clinically effective drug against SARS‐CoV‐2 infection. The conserved properties of the membrane fusion domain of the spike (S) protein across SARS‐CoV‐2 make it a promising target to develop pan‐CoV therapeutics. Herein, two clinically approved drugs, Itraconazole (ITZ) and Estradiol benzoate (EB), are found to inhibit viral entry by targeting the six‐helix (6‐HB) fusion core of SARS‐CoV‐2 S protein. Further studies shed light on the mechanism that ITZ and EB can interact with the heptad repeat 1 (HR1) region of the spike protein, to present anti‐SARS‐CoV‐2 infections in vitro, indicating they are novel potential therapeutic remedies for COVID‐19 treatment. Furthermore, ITZ shows broad‐spectrum activity targeting 6‐HB in the S2 subunit of SARS‐CoV and MERS‐CoV S protein, inspiring that ITZ have the potential for development as a pan‐coronavirus fusion inhibitor.
Regulation of ID4 In Vivo for Efficient Magnetothermal Therapy of Breast Cancer
Authors: Dai Penggao , Zhu Wenjing , Yan Bin , Miao Yuqing , Hu Shanshuang , Gao Xiao , Liu Xiaoli , Zhang Yifan , Li Galong , Zhang Tingbin , Zhang Huan , Fan Haiming
Published: February 2021

Magnetic nanoparticles (MNPs) mediated magnetothermal therapy (MTT) has been proven as a promising modality for tumor treatment. However, the low therapeutic efficacy presents a major obstacle to its mass adoption. The Authors proposed to increase the therapeutic efficacy of MTT through the manipulation of magnetothermal‐related gene expression. ID4, a member of inhibitors of differentiation (ID) protein family, is identified to be downregulated in intracellular MTT (in‐MTT)‐treated MCF‐7 breast cancer cells according to the whole transcriptome sequencing. Interestingly, this occurrence is not observed in the exogenous MTT‐treated cells. More importantly, ID4‐silenced tumor cells show significantly decreased cell viability after in‐MTT, whereas ID4‐overexpressed cells exhibit more resistance to the MTT. This effect is also observed in other malignant breast cells derived from the human mammary gland. Furthermore, ID4 siRNA‐loaded superparamagnetic iron oxide nanoparticles are developed and delivered them to breast cancer xenografted nude mice. It is found that the synergistic combination of ID4 gene silencing and in‐MTT greatly inhibited the tumor growth and the efficacy of tumor volume inhibition is > 98%. This study, for the first time, provides the possibility of the sensitization of breast cancer cells for efficient MTT via molecular manipulation of cell signaling.
Lytic Polyplex Vaccines Enhance Antigen‐Specific Cytotoxic T Cell Response through Induction of Local Cell Death
Authors: Peeler David J. , Yen Albert , Luera Nicholas , Stayton Patrick S. , Pun Suzie H.
Published: February 2021

Endosomolytic vaccine nanocarriers can potentiate cellular immune responses by enhancing cross‐presentation. A cationic polymer–lytic peptide conjugate (VIPER) that greatly improves endosomal escape and intracellular activity of nucleic acid cargoes is recently developed; furthermore, it is hypothesized that VIPER's unique mechanism of endosomal disruption can increase cytoplasmic delivery of other biomacromolecules (e.g., peptides). Herein, VIPER is formulated as a polyplex subunit vaccine composed of conjugated peptide antigens and electrostatically complexed poly(I:C) nucleic acid adjuvant and is evaluated to determine whether the presence of the lytic peptide melittin conjugated to the pH‐responsive micelle core improves vaccination outcomes. Although VIPER delivers peptide antigens intracellularly, disrupts endosomes in antigen‐presenting cells (APCs) in vitro, and generates strong antigen‐specific cytotoxic T cell responses in vivo, significantly enhanced cross‐presentation is only observed in conjunction with VIPER‐induced local cell death. While these results demonstrate that VIPER is a useful platform technology for the study of vaccine delivery, full elucidation of how endosomal disruption by VIPER improves vaccination outcomes will require decoupling of endosomolysis from cytotoxicity, as well as precise targeting of VIPER vaccine formulations to APC populations in vivo.
Superstructured Biomaterials Formed by Exchange Dynamics and Host–Guest Interactions in Supramolecular Polymers
Authors: Edelbrock Alexandra N. , Clemons Tristan D. , Chin Stacey M. , Roan Joshua J. W. , Bruckner Eric P. , Álvarez Zaida , Edelbrock Jack F. , Wek Kristen S. , Stupp Samuel I.
Published: February 2021

Dynamic and reversible assembly of molecules is ubiquitous in the hierarchical superstructures of living systems and plays a key role in cellular functions. Recent work from the laboratory reported on the reversible formation of such superstructures in systems of peptide amphiphiles conjugated to oligonucleotides and electrostatically complimentary peptide sequences. Here, a supramolecular system is reported upon where exchange dynamics and host–guest interactions between β‐cyclodextrin and adamantane on peptide amphiphiles lead to superstructure formation. Superstructure formation with bundled nanoribbons generates a mechanically robust hydrogel with a highly porous architecture that can be 3D printed. Functionalization of the porous superstructured material with a biological signal results in a matrix with significant in vitro bioactivity toward neurons that could be used as a supramolecular model to design novel biomaterials.
Electronic Structure Engineering of Honeycomb Layered Cathode Material for Sodium‐Ion Batteries
Authors: Voronina Natalia , Kim Hee Jae , Konarov Aishuak , Yaqoob Najma , Lee Kug‐Seung , Kaghazchi Payam , Guillon Olivier , Myung Seung‐Taek
Published: February 2021

In this work, the rational design of O′3‐type Na[Ni2/3−xCoxSb1/3]O2, a solid solution of Na[Ni2/3Sb1/3]O2–Na[Co2/3Sb1/3]O2, is introduced. Because of the difficulty of the Co3+/2+ redox reaction, the electronic structures of Na[Ni2/3−xCoxSb1/3]O2 compounds are engineered to build electroconducting networks in the oxide matrix through electrochemical oxidation of Co2+ to Co3+, after which the formed Co3+ does not participate in the electrochemical reaction but improves the electrical conductivity in the structure. Density functional theory calculations reveal a reduced bandgap energy after the formation of Co3+ during desodiation of Na1−y[Ni2/3−xCoxSb1/3]O2. Using the oxidized Co3+ species while improving the electrical conductivity, the Na[Ni2/3−xCoxSb1/3]O2 (x = 1/6) electrode exhibits excellent cyclability for 1000 cycles with ≈72.5% capacity retention at 2C (400 mA g−1) and activity even at 50C (10 A g−1) in Na cells. Operando X‐ray diffraction and ex situ X‐ray absorption near‐edge structure investigations reveal suppressed lattice variations upon charge and discharge compared with those of Na[Ni2/3Sb1/3]O2 achieved by the presence of the electrochemical‐driven Co3+ in the structure. These findings offer a new strategy for the development of cathode materials for sodium‐ion batteries, providing important insight into their structural transformations and the electronic nature of advanced cathode materials.
Injuries and illnesses to children in commercial fishing in Alaska: A brief report
Authors: Rudolphi Josie M. , Berg Richard L.
Published: February 2021

Background

Commercial fishing is the most hazardous occupation in the United States. While the epidemiology of adult injuries and fatalities are well documented, injuries to children (<18 years old) are not described. The purpose of this report was to describe the characteristics of nonfatal injuries to children involved in commercial fishing.

Methods

Nonfatal commercial fishing injuries to children were identified in the Alaska Fishermen's Fund. The Alaska Fishermen's Fund is an emergency fund payor of last resort. Data on nonfatal injuries to victims aged 17 or younger were analyzed. Descriptive statistics were used to characterize demographics and injury characteristics.

Results

Forty‐four nonfatal child injury claims were made between 2012 and 2016. The mean age at the time of claim was 15.6 years (SD = 1.8) and 84% were male. The most common types of injuries among children were sprains and strains and the most commonly injured body parts were upper extremities and the trunk. Most injuries occurred in salmon fisheries.

Conclusions

Children are participating in commercial fishing. Based on the results of this analysis, children are also experiencing occupational injuries. The results of this analysis underscore the need for additional safety and health information, guidance for supervisors, and intervention to prevent injuries to children participating in commercial fishing.
Case report of adrenocortical carcinoma associated with double germline mutations in MSH2 and RET
Authors: Raygada Margarita , Raffeld Mark , Bernstein Andrew , Miettinen Markku , Glod John , Hughes Marybeth S. , Reilly Karlyne , Widemann Brigitte , Del Rivero Jaydira
Published: February 2021

Adrenocortical carcinoma (ACC) is a rare aggressive malignancy that originates in the outer layer of the adrenal gland. Most ACCs are sporadic, but a small percentage of cases are due to hereditary cancer syndromes such as Li‐Fraumeni syndrome (LFS), Lynch syndrome (LS), and familial adenomatous polyposis (FAP). Multiple endocrine neoplasia type 2A (MEN2A) is an inherited disorder that predisposes to medullary thyroid cancer, pheochromocytoma, and parathyroid hyperplasia. We present here a case of ACC with both LS and MEN2A; the family and medical history were consistent with Lynch. This is, to our knowledge, the first report of a patient with ACC associated with germline mutations in RET and MSH2, and no phenotypical characteristics of MEN2A.
Human burials at the Kisese II rockshelter, Tanzania
Authors: Laird Myra F. , Sawchuk Elizabeth A. , Kwekason Amandus , Mabulla Audax Z. P. , Ndiema Emmanuel , Tryon Christian A. , Lewis Jason E. , Ranhorn Kathryn L.
Published: February 2021

Objectives

The Late Pleistocene and early Holocene in eastern Africa are associated with complex evolutionary and demographic processes that contributed to the population variability observed in the region today. However, there are relatively few human skeletal remains from this time period. Here we describe six individuals from the Kisese II rockshelter in Tanzania that were excavated in 1956, present a radiocarbon date for one of the individuals, and compare craniodental morphological diversity among eastern African populations.

Materials and Methods

This study used standard biometric analyses to assess the age, sex, and stature of the Kisese II individuals. Eastern African craniodental morphological variation was assessed using measures of dental size and a subset of Howells' cranial measurements for the Kisese II individuals as well as early Holocene, early pastoralist, Pastoral Neolithic, and modern African individuals.

Results

Our results suggest a minimum of six individuals from the Kisese II collections with two adults and four juveniles. While the dating for most of the burials is uncertain, one individual is directly radiocarbon dated to ~7.1 ka indicating that at least one burial is early Holocene in age. Craniodental metric comparisons indicate that the Kisese II individuals extend the amount of human morphological diversity among Holocene eastern Africans.

Conclusions

Our findings contribute to a growing body of evidence that Late Pleistocene and early Holocene eastern Africans exhibited relatively high amounts of morphological diversity. However, the Kisese II individuals suggest morphological similarity at localized sites potentially supporting increased regionalization during the early Holocene.
Chemical Reduction of a Nanosized [6]Cyclo‐2,7‐naphthylene Macrocycle
Authors: Zhou Zheng , Wei Zheng , Ikemoto Koki , Sato Sota , Isobe Hiroyuki , Petrukhina Marina A.
Published: February 2021

Chemical reduction of a naphthylene macrocycle, [6]cyclo‐2,7‐naphthylene ([6]CNAP, 1), with alkali metals, Li and K, revealed the accessibility of the doubly‐reduced state of 1. The macrocyclic 12− anion was isolated in different coordination environments and crystallographically characterized. The single‐crystal X‐ray diffraction confirmed the formation of contact‐ion complexes with one Li+ and two K+ ions in THF, and a “naked” dianion in the solvent‐separated ion product with K+ ions in the presence of 18‐crown‐6 ether. The detailed structural analysis of 12− showed that the π‐conjugation over the biaryl linkages between naphthylene panels were enhanced upon two‐fold reduction, which was rationally explained by theoretical calculations.
Stimulierung eines redoxinduzierten Elektronentransfers durch Interligand‐Wasserstoffbrücken in einem Cobaltkomplex mit redoxaktivem Guanidin‐Liganden
Authors: Lohmeyer Lukas , Schön Florian , Kaifer Elisabeth , Himmel Hans‐Jörg
Published: February 2021

Die ersten oktaedrisch koordinierten CoII‐Komplexe mit redoxaktivem Bisguanidin‐Liganden und acac‐Coliganden wurden synthetisiert und hinsichtlich ihrer Redoxchemie analysiert. Die N‐H‐Funktionen in einem Bisguanidin‐Liganden mit partiell alkylierten Guanidino‐Gruppen bilden N‐H⋅⋅⋅O‐Brücken zu den acac‐Coliganden und beeinflussen dadurch stark die Redoxchemie. Bei allen Komplexen ist die erste 1 e−‐Oxidation metallzentriert und führt zu CoIII‐Komplexen mit neutralen Bisguanidin‐Ligandeneinheiten. Die zweite 1 e−‐Oxidation ist im Falle von Cobalt‐Bisguanidin‐Komplexen mit vollständig alkylierten Guanidino‐Gruppen ligandenzentriert; es resultieren CoIII‐Komplexe mit radikal‐monokationischen Bisguanidin‐Liganden. Bei der Oxidation eines Cobalt‐Bisguanidin‐Komplexes mit teilalkylierten Guanidino‐Gruppen kommt es dagegen durch die Verstärkung der Wasserstoffbrücken zu einer Metallreduktion (CoIII→CoII) und zu einer 2 e−‐Oxidation des Guanidin‐Liganden, dem ersten Beispiel für das Auslösen eines redoxinduzierten Elektronentransfers durch Interligand‐Wasserstoffbrücken.
Controlled Ligand Exchange Between Ruthenium Organometallic Cofactor Precursors and a Naïve Protein Scaffold Generates Artificial Metalloenzymes Catalysing Transfer Hydrogenation
Authors: Biggs George S. , Klein Oskar James , Maslen Sarah L. , Skehel J. Mark , Rutherford Trevor J. , Freund Stefan M. V. , Hollfelder Florian , Boss Sally R. , Barker Paul D.
Published: February 2021

Many natural metalloenzymes assemble from proteins and biosynthesised complexes, generating potent catalysts by changing metal coordination. Here we adopt the same strategy to generate artificial metalloenzymes (ArMs) using ligand exchange to unmask catalytic activity. By systematically testing RuII(η6‐arene)(bipyridine) complexes designed to facilitate the displacement of functionalised bipyridines, we develop a fast and robust procedure for generating new enzymes via ligand exchange in a protein that has not evolved to bind such a complex. The resulting metal cofactors form peptidic coordination bonds but also retain a non‐biological ligand. Tandem mass spectrometry and 19F NMR spectroscopy were used to characterise the organometallic cofactors and identify the protein‐derived ligands. By introduction of ruthenium cofactors into a 4‐helical bundle, transfer hydrogenation catalysts were generated that displayed a 35‐fold rate increase when compared to the respective small molecule reaction in solution.
Au–Ag Bimetallic Catalysis: 3‐Alkynyl Benzofurans from Phenols via Tandem C−H Alkynylation/Oxy‐Alkynylation
Authors: Hu Long , Dietl Martin C. , Han Chunyu , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: February 2021

The development of new methodologies enabling a facile access to valuable heterocyclic frameworks still is an important subject of research. In this context, we describe a dual catalytic cycle merging C−H alkynylation of phenols and oxy‐alkynylation of the newly introduced triple bond by using a unique redox property and the carbophilic π acidity of gold. Mechanistic studies support the participation of a bimetallic gold–silver species. The one‐pot protocol offers a direct, simple, and regio‐specific approach to 3‐alkynyl benzofurans from readily available phenols. A broad range of substrates, including heterocycles, is transferred with excellent functional group tolerance. Thus, this methodology can be used for the late‐stage incorporation of benzofurans.
Making Waxy Salts in Water: Synthetic Control of Hydrophobicity for Anion‐Induced and Aggregation‐Enhanced Light Emission
Authors: Kim Soohyung , Kim Jongmin , Lee Dongwhan
Published: February 2021

We show that multipodal polycationic receptors function as anion‐responsive light‐emitters in water. Prevailing paradigms utilize rigid holes and cavities for ion recognition. We instead built open amphiphilic scaffolds that trigger polar‐to‐nonpolar environment transitions around cationic fluorophores upon anion complexation. This ion‐pairing and aggregation event produces a dramatic enhancement in the emission intensity, as demonstrated by perchlorate as a non‐spherical hydrophobic anion model. A synergetic interplay of C−H⋅⋅⋅anion hydrogen bonding and tight anion–π+contacts underpins this supramolecular phenomenon. By changing the aliphatic chain length, we demonstrate that the response profile and threshold of this signaling event can be controlled at the molecular level. With appropriate molecular design, inherently weak, ill‐defined, and non‐directional van der Waals interaction enables selective, sensitive, and tunable recognition in water.
Acetate ion augmented fluorescence sensing of Zn2+ by Salen‐based probe, AIE character, and application for picric acid detection
Authors: Das Bhriguram , Dolai Malay , Dhara Anamika , Mabhai Subhabrata , Jana Atanu , Dey Satyajit , Misra Ajay
Published: February 2021

Counter anion‐triggered metal ion detection has been rarely reported by fluorimetric method. To address this challenging issue, a fluorescent probe (H2L) has been synthesized from bromo‐salicylaldehyde and hydrazine hydrate, and structurally characterized by single crystal X‐ray diffraction. The probe shows very weak fluorescence itself. However, its emission intensity increases in the presence of Zn2+ over other metal ions. Surprisingly, the emission profile of this probe in presence of Zn2+ is augmented only when acetate anion (OAc¯) is present as counter anion, that allows for precise quantitative analysis by spectroscopic studies. The compositions and complexation among the probe, Zn2+ ion, and OAc¯ are supported by ESI‐MS, 1H‐NMR, and Job's plot. Based on these studies, it is confirmed that the binding ratio between probe: metal is 1:2 and the detection limit (LOD) for the Zn2+ is 2.18 µM. The probe is capable of recognizing Zn2+ ion in the wide range of pH∼6.5‐9.5, and it could be efficiently recycled by EDTA. Furthermore, the combinatorial molecular logic gate and memory device have been constructed from the fluorescent behavior of H2L with Zn2+, OAc¯, and EDTA input as based on NOT and AND gates. Interestingly, the aggregation‐induced emission (AIEE) phenomenon is also perceived with greater than 50% water content in organic water mixtures, which are then useful for the detection of picric acid often used as explosive.
Erdbebensicherheit von Stahlbeton‐Bestandstragwerken im Kontext der Eurocode‐8‐Anwendung
Authors: Akkermann Jan
Published: February 2021

Erdbeben stellen eine in Deutschland seltene, aber grundsätzlich mögliche Gefährdung für Gebäude und Teile davon dar. Mit Veröffentlichung neuester Erkenntnisse zur Erdbebengefährdung in Deutschland ging eine Neubewertung des Einwirkungsniveaus im Nationalen Anhang zum Eurocode 8 einher, die in vielen erdbebengefährdeten Regionen höhere Bemessungsbelastungen zur Folge hat. Seit Einführung normativer Vorgaben zur Erdbebenbemessung hat das Einwirkungsniveau zumeist kontinuierlich zugenommen. Für Bestandstragwerke aus Stahlbeton stellt sich aus Gründen der Verkehrssicherheit generell und bei Tragwerkseingriffen aufgrund von ressourcenschonenden Revitalisierungen im Speziellen die Frage nach der Verhältnismäßigkeit zwischen Bestandsschutz und Sicherungspflicht. Trotz grundsätzlich erdbebenkonformer Bauart mit duktilen Rahmen und Wandscheiben – insbesondere bei im Vergleich zur Vertikalbelastung geringem Horizontallastniveau – sind die vorhandenen Aussteifungssysteme zumeist nicht für die höheren Beanspruchungen nachzuweisen. Für den Bereich zwischen einer seismischen Mindestbeanspruchbarkeit und vollständigem Erdbebenwiderstand gegen aktuelle Einwirkungen wird eine risikobasierte Bewertung anhand von Erfüllungsfaktoren in Anlehnung an die schweizerische SIA 269/8 vorgeschlagen.
Accompanied anomalies in anal atresia or tracheo‐esophageal fistula: Comparison with or without VACTERL association
Authors: Ahn Ji Hyun , Choi Hee Joung
Published: February 2021

Purpose

We evaluated the various accompanied malformations in patients with anal atresia or tracheoesophageal fistula (TEF). Furthermore, we determined the prevalence of VACTERL association and compared the clinical findings with those of patients without VACTERL association.

Methods

We enrolled the patients with anal atresia or TEF with/without esophageal atresia. We collected the patient data pertaining to accompanied vertebral, cardiovascular, renal or limb anomalies, single umbilical artery, maternal diabetes mellitus or drug history, and gene research.

Results

A total 155 patients (65 boys and 90 girls) were enrolled with 147 cases of anal atresia, 3 cases of TEF, and 5 cases of anal atresia with TEF. The prevalence of accompanied anomalies was 67.1% in cardiovascular, 27.1% in renal, 9.7% in vertebral, 2.6% in limb anomalies, and 3.9% in single umbilical artery. Thirty‐six (23.2%) patients were diagnosed with VACTERL association. The patients with VACTERL association had a significantly higher number of male patients (58.3 vs. 37.0%, p = .033) and single umbilical artery (11.1 vs. 1.7%, p = .026), and had a significantly lower birth weight (2.8 vs. 3.1 kg, p = .033) than the patients without VACTERL association. Genetic studies were performed in 111 patients, and 8 (7.2%) had chromosomal abnormalities—3 in VACTERL and 5 in no VACTERL group.

Conclusion

We recommend a careful evaluation for VACTERL association in patients with anal atresia or TEF. It is particularly important to screen for a single umbilical artery for features of VACTERL association as well as for other congenital anomalies.
Correcting the bias of the net benefit estimator due to right‐censored observations
Authors: Péron Julien , Idlhaj Maryam , Maucort‐Boulch Delphine , Giai Joris , Roy Pascal , Collette Laurence , Buyse Marc , Ozenne Brice
Published: February 2021

Generalized pairwise comparisons (GPCs) are a statistical method used in randomized clinical trials to simultaneously analyze several prioritized outcomes. This procedure estimates the net benefit (Δ). Δ may be interpreted as the probability for a random patient in the treatment group to have a better overall outcome than a random patient in the control group, minus the probability of the opposite situation. However, the presence of right censoring introduces uninformative pairs that will typically bias the estimate of Δ toward 0. We propose a correction to GPCs that estimates the contribution of each uninformative pair based on the average contribution of the informative pairs. The correction can be applied to the analysis of several prioritized outcomes. We perform a simulation study to evaluate the bias associated with this correction. When only one time‐to‐event outcome was generated, the corrected estimates were unbiased except in the presence of very heavy censoring. The correction had no effect on the power or type‐1 error of the tests based on the Δ. Finally, we illustrate the impact of the correction using data from two randomized trials. The illustrative datasets showed that the correction had limited impact when the proportion of censored observations was around 20% and was most useful when this proportion was close to 70%. Overall, we propose an estimator for the net benefit that is minimally affected by censoring under the assumption that uninformative pairs are exchangeable with informative pairs.
Sub‐second heat inactivation of coronavirus using a betacoronavirus model
Authors: Jiang Yuqian , Zhang Han , Wippold Jose A. , Gupta Jyotsana , Dai Jing , de Figueiredo Paul , Leibowitz Julian L. , Han Arum
Published: February 2021

Heat treatment denatures viral proteins that comprise the virion, making the virus incapable of infecting a host. Coronavirus (CoV) virions contain single‐stranded RNA genomes with a lipid envelope and four proteins, three of which are associated with the lipid envelope and thus are thought to be easily denatured by heat or surfactant‐type chemicals. Prior studies have shown that a temperature as low as 75°C with a treatment duration of 15 min can effectively inactivate CoV. The degree of CoV heat inactivation greatly depends on the length of heat treatment time and the temperature applied. With the goal of finding whether sub‐second heat exposure of CoV can sufficiently inactivate CoV, we designed and developed a simple fluidic system that can measure sub‐second heat inactivation of CoV. The system is composed of a stainless‐steel capillary immersed in a temperature‐controlled oil bath followed by an ice bath, through which virus solution can flow at various speeds. Flowing virus solution at different speeds, along with temperature control and monitoring system, allows the virus to be exposed to the desired temperature and treatment durations with high accuracy. Using mouse hepatitis virus, a betacoronavirus, as a model CoV system, we identified that 71.8°C for 0.51 s exposure is sufficient to obtain >5 Log10reduction in viral titer (starting titer: 5 × 107PFU/ml), and that when exposed to 83.4°C for 1.03 s, the virus was completely inactivated (>6 Log10reduction).
Autonomy and authority: Homeless service users' empowering experiences in housing first and staircase services
Authors: O'Shaughnessy Branagh R. , Greenwood Ronni Michelle
Published: February 2021

Although Housing First (HF) has gained widespread support as a service model to end homelessness, staircase services (SS) continue to proliferate. Critics have argued that SS contribute to institutionalisation and neglect the structural causes of homelessness. However, HF employs an empowerment‐orientated approach which can reduce institutionalisation and enable service users to achieve their potential. In this study, we combined a conceptual framework of empowering service features with the capabilities approach to compare the experiences of service users in HF and SS in Ireland. We carried out four focus group discussions with service users in HF (n = 7) and SS (n = 8). Using thematic analysis, we identified three themes that represented participants' descriptions of services: support orientation, home is more than shelter and organisational and political participation. Autonomy‐orientated support and an emphasis on service user choice and housing afforded HF service users' empowering experiences. The authoritarian approach, and emphasis on housing readiness and provider expertise undermined SS service users' empowering experiences. Findings suggest how HF and SS service features shape service users' lived experiences and perceptions of services. Implications for policy and practice are discussed.
Protective Effects of 3,4‐Seco‐Lupane Triterpenes from Food Raw Materials of the Leaves of Eleutherococcus Senticosus and Eleutherococcus Sessiliflorus on Arrhythmia Induced by Barium Chloride
Authors: Zhao Yan , Wang Xu , Chen Chen , Shi Kun , Li Jianming , Du Rui
Published: February 2021

As a traditional wild vegetable and food raw material, the leaves of Eleutherococcus senticosus and Eleutherococcus sessiliflorus are rich in 3,4‐seco‐lupane triterpenes, including chiisanoside (CSS), divaroside (DVS), sessiloside‐A (SSA), and chiisanogenin (CSG). This study was conducted to evaluate the anti‐arrhythmic effects of these 3,4‐seco‐lupane triterpenes. Evaluation of the cytotoxicity of compounds was performed by measuring cell viability and apoptosis with the CCK‐8 assay. In vivo, arrhythmia was induced by rapid injection of BaCl2 via rat caudal vein. The occurrence time and duration of arrhythmias in rats were studied. The levels of SOD and MDA in serum, and Na+‐K+‐ATPase and Ca2+‐Mg2+‐ATPase in myocardial homogenate were detected by ELISA. The histopathological changes of rats myocardial were observed by HE staining. Changes in the expression of PKA and related proteins were detected by Western blot. The 3,4‐seco‐lupane triterpenes interactions with protein kinase A were analyzed by molecular docking. In the present study, we found that 3,4‐seco‐lupane triterpenes exhibited powerful anti‐arrhythmic activity, especially DVS completely relieved the ventricular arrhythmia induced by BaCl2. This study suggests that the leaves of E. senticosus and E. sessiliflorus might be used as functional food materials to prevent arrhythmia, and DVS can potentially be further developed as an anti‐arrhythmic drug.
Frontiers in Hybrid Ion Capacitors: A Review on Advanced Materials and Emerging Devices
Authors: Naskar Pappu , Kundu Debojyoti , Maiti Apurba , Chakraborty Priyanka , Biswas Biplab , Banerjee Anjan
Published: February 2021

Hybrid supercapacitors are the most desirable electrochemical energy storage devices, owing to their versatile and tunable performance characteristics, specifically in energy and power densities, towards applications in research and development. Construction‐wise, optimized assembly of batteries (energy devices) and supercapacitors (power devices) are the key for hybrid supercapacitors. Based on scientific advancements and technological achievements, hybrid ion capacitors are the most important segments in hybrid supercapacitors, as well as in the overall energy storage arena. Herein, opportunities and challenges of hybrid ion capacitors are intensively addressed in light of lithium‐ion, sodium‐ion, potassium‐ion, magnesium‐ion, calcium‐ion, zinc‐ion, and aluminum‐ion capacitors. The historical origins and their developmental pathways are identified for each type of capacitor. Possible classes of materials for every hybrid ion capacitor are discussed, and relevant mechanisms are demonstrated. These discussions reveal that a rich materials bank exists for lithium‐ion, sodium‐ion, and zinc‐ion capacitors, but the same is not applicable for potassium‐ion, magnesium‐ion, calcium‐ion, and aluminum‐ion capacitors. Consequently, such hybrid ion capacitors have not yet reached the level of commercial benchmarks like lithium‐ion, sodium‐ion, and zinc‐ion capacitors. However, this Review focuses on mostly full‐cell device data that synchronize the performances of practical scaled‐up systems. Several electrolytes based on solvent media (aqueous, organic, and ionic liquid), phase (liquid, gel, and solid), and redox activity (active and passive) are exemplified in different sections of hybrid ion capacitors. Various device constructions are elaborated upon, such as liquid‐electrolyte devices, polymeric gel devices, all‐solid‐state devices, flexible‐cum‐wearable devices, microdevices, solar‐charging devices, and so forth. The Review culminates with feasible future directions for the commercial success of hybrid ion capacitors, which are in the nascent stages of developments. To the best of our knowledge, it is the first holistic account of hybrid ion capacitors from their historical perspectives to present developments.
Time‐traveling colors: Artisanal dreams and digital fabrication
Authors: Kutlu Mete
Published: February 2021

In the 15th century, the miniaturists of the Timurid court in Herat conceive colors that seem to be made of pure light, without weight and volume. Their luminous colors synthesize a unique worldview from the anti‐materialistic teachings of Mani, the Sufi “world of imagination” and the alchemists' principles of transmutation. Five centuries later, our digital technologies seem to offer us such disembodied colors, which used to be the artistic dream of an artisanal culture. Pixels replace pigments, light‐colors replace matter‐colors. With the booming animation and game cultures, Tokyo becomes one of the first places that pixels invade in the 80s. A group of Japanese architects and artists seeks to express in their creations the ethereal dimension of the pixels' electronic light. Through a spatio‐temporal leap, the miniatures, as a historical reference point, reveals the emerging chromatic trends in contemporary architecture and visual culture. Could the invention of pixels be after all, stemming from an ancestral aspiration of mankind based on the sensorial and intelligible duality of his nature?
Classification of some chemical drugs by genetic algorithm and deep neural network hybrid method
Authors: Karakaplan Mustafa , Avcu Fatih Mehmet
Published: February 2021

Deep neural networks (DNN) and genetic algorithm (GA) are gaining importance quickly with many successful applications in the field of science and technology. They are indispensable tool for the numerical solution of difficult problems. It is possible to optimize DNNs using the GA and this combination can be used to classify data. In this article, some drugs are classified by Monte Carlo sampling with combination of GA and DNN due to stochastic nature of the domain, exponential number of variables and small number of chemical species. In addition to the values obtained from the databases of selected drugs, molecular dynamic and ab initio molecular mechanical calculation results were also used. The aim of this study is to generalize the molecular classification with the data obtained from chemical databases as well as molecular docking results by using the combination of deep learning and GA and its usability in drug design. The selected drugs are some agonist and antagonist drugs that bind to dopamine receptors, which are widely studied and well known in the literature. To train the DNN, input datasets were chosen by the GA framework written in pure Python named PyEvolve. Classification of drugs has been analyzed with the focus on orbital energies and docking results. It is possible to use this algorithm in many in silico calculations such as affinity and separation processes. The reliability of the algorithm was tested with the results given in the literature and the expected values were estimated at 93.8%.
Supramolecular Coordination Complexes as Optical Biosensors
Authors: Dey Nilanjan , Haynes Cally J. E.
Published: February 2021

In recent years, luminescent supramolecular coordination complexes (SCCs), including 2D‐metallacycles and 3D‐metallacages have been utilised for biomolecular analysis. Unlike small‐molecular probes, the dimensions, size, shape, and flexibility of these complexes can easily be tuned by combining ligands designed with particular geometries, symmetries and denticity with metal ions with strong geometrical binding preferences. The well‐defined cavities that result, in combination with the other non‐covalent interactions that can be programmed into the ligand design, facilitate great selectivity towards guest binding. In this Review we will discuss the application of luminescent metallacycles and cages in the binding and detection of a wide range of biomolecules, such as carbohydrates, proteins, amino acids, and biogenic amines. We aim to explore the effect of the structural diversity of SCCs on the extent of biomolecular sensing, expressed in terms of sensitivity, selectivity and detection range.