bluuebunny/crossref_metadata_2025_split huggingface dataset:
DNA Reaction–Diffusion Attractor Patterns
Authors: Dorsey Phillip James , Scalise Dominic , Schulman Rebecca 
Published: September 2020

AbstractLiving systems can form and recover complex chemical patterns with precisely sized features in the ranges of tens or hundreds of microns. We show how designed reaction–diffusion processes can likewise produce precise patterns, termed attractor patterns, that reform their precise shape after being perturbed. We use oligonucleotide reaction networks, photolithography, and microfluidic delivery to form precisely controlled attractor patterns and study the responses of these patterns to different localized perturbations. Linear and “hill”‐shaped patterns formed and stabilized into shapes and at time scales consistent with reaction–diffusion models. When patterns were perturbed in particular locations with UV light, they reliably reformed their steady‐state profiles. Recovery also occurred after repeated perturbations. By designing the far‐from‐equilibrium dynamics of a chemical system, this study shows how it is possible to design spatial patterns of molecules that are sustained and regenerated by continually evolving towards a specific steady state configuration.
Generation of Glycosyl Radicals from Glycosyl Sulfoxides and Its Use in the Synthesis ofC‐linked Glycoconjugates
Authors: Shang Weidong , Su Sheng‐Nan , Shi Rong , Mou Ze‐Dong , Yu Guo‐Qiang , Zhang Xia , Niu Dawen 
Published: September 2020

AbstractWe here report glycosyl sulfoxides appended with an aryl iodide moiety as readily available, air and moisture stable precursors to glycosyl radicals. These glycosyl sulfoxides could be converted to glycosyl radicals by way of a rapid and efficient intramolecular radical substitution event. The use of this type of precursors enabled the synthesis of various complexC‐linked glycoconjugates under mild conditions. This reaction could be performed in aqueous media and is amenable to the synthesis of glycopeptidomimetics and carbohydrate‐DNA conjugates.
Synthetisch biologisch getriebene Biosynthese von unnatürlichen Tropolon‐Sesquiterpenoiden
Authors: Schotte Carsten , Li Lei , Wibberg Daniel , Kalinowski Jörn , Cox Russell J. 
Published: September 2020

AbstractTropolon‐Sesquiterpenoide (TS) sind eine faszinierende Familie biologisch aktiver pilzlicher Meroterpenoide, die durch eine einzigartige intermolekulare Hetero‐Diels‐Alder (hDA)‐Reaktion zwischen Humulen und Tropolonen entstehen. Hier berichten wir über die kombinatorische Biosynthese einer Reihe beispielloser Analoga von Pycnidione 1 und Xenovulene A 2. In einem systematischen auf synthetischer Biologie basierendem Ansatz haben wir Gene aus drei Biosynthesegenclustern (Pycnidione 1, Xenovulene A 2 und Eupenifeldin 3) im pilzlichen Wirt Aspergillus oryzae NSAR1 rekombiniert. Das rationale Design der rekonstituierten Biosynthesewege ermöglichte die Kontrolle über die Anzahl der stattfindenden hDA‐Reaktionen, die chemische Natur der kondensierten Polyketideinheit (Tropolono‐ vs. Monobenzopyranyl) und den Hydroxylierungsgrad. Die Bildung unerwarteter Monobenzopyranylsesquiterpenoide wurde mithilfe von Isotopenfütterungsstudien untersucht und führte zur Entdeckung einer neuen und höchst ungewöhnlichen oxidativen Ringkontraktion.
Discovering the Elusive Global Minimum in a Ternary Chiral Cluster: Rotational Spectra of Propylene Oxide Trimer
Authors: Xie Fan , Fusè Marco , Hazrah Arsh S. , Jäger Wolfgang , Barone Vincenzo , Xu Yunjie 
Published: September 2020

AbstractThe chirality controlled conformational landscape of the trimer of propylene oxide (PO), a prototypical chiral molecule, was investigated using rotational spectroscopy and a range of theoretical tools for conformational searches and for evaluating vibrational contributions to effective structures. Two sets of homochiral (PO)3 rotational transitions were assigned and the associated conformers identified with theoretical support. One set of heterochiral (PO)3 transitions was assigned, but no structures generated by one of the latest, advanced conformational search codes could account for them. With the aid of a Python program, the carbon atom backbone and then the heterochiral (PO)3 structure were generated using 13C isotopic data. Excellent agreement between theoretical and experimental rotational constants and relative dipole moment components of all three conformers was achieved, especially after applying vibrational corrections to the rotational constants.
A Toroidal Zr70 Oxysulfate Cluster and Its Diverse Packing Structures
Authors: Øien‐Ødegaard Sigurd , Bazioti Calliope , Redekop Evgeniy A. , Prytz Øystein , Lillerud Karl Petter , Olsbye Unni 
Published: September 2020

AbstractHerein, we report the discovery of a toroidal inorganic cluster of zirconium(IV) oxysulfate of unprecedented size with the formula Zr70(SO4)58(O/OH)146⋅x(H2O) (Zr70), which displays different packing of ring units and thus several polymorphic crystal structures. The ring measures over 3 nm across, has an inner cavity of 1 nm and displays a pseudo‐10‐fold rotational symmetry of Zr6 octahedra bridged by an additional Zr in the outer rim of the ring. Depending on the co‐crystallizing species, the rings form various crystalline phases in which the torus units are connected in extended chain and network structures. One phase, in which the ring units are arranged in layers and form one‐dimensional channels, displays high permanent porosity (BET surface area: 241 m2 g−1), and thus demonstrates a functional property for potential use in, for example, adsorption or heterogeneous catalysis.
Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins
Authors: Gotico Philipp , Roupnel Loïc , Guillot Regis , Sircoglou Marie , Leibl Winfried , Halime Zakaria , Aukauloo Ally 
Published: September 2020

AbstractThe manipulation of the second coordination sphere for improving the electrocatalytic CO2 reduction has led to breakthroughs with hydrogen bonding, local proton source, or electrostatic effects. We have developed two atropisomers of an iron porphyrin complex with two urea functions acting as multiple hydrogen‐bonding tweezers to lock the metal‐bound CO2 in a similar fashion found in the carbon monoxide dehydrogenase (CODH) enzyme. The αα topological isomer with the two urea groups on the same side of the porphyrin provides a stronger binding affinity to tether the incoming CO2 in comparison to the αβ disposition. However, the electrocatalytic activity of the αβ atropisomer outperforms its congener with one of the highest reported turnover frequencies at low overpotential. The strong H/D kinetic isotope effect (KIE) observed for the αα system indicates the existence of a tight water hydrogen‐bonding network for proton delivery which is disrupted by addition of an acid source. The small H/D KIE for the αβ isomer and the enhanced electrocatalytic performance on addition of stronger acid indicate the free access of protons to the bound CO2 on the opposite side of the urea arm.
Tailoring Crystal Facets of Metal–Organic Layers to Enhance Photocatalytic Activity for CO2 Reduction
Authors: Yang Wei , Wang Hong‐Juan , Liu Rui‐Rui , Wang Jia‐Wei , Zhang Chao , Li Chao , Zhong Di‐Chang , Lu Tong‐Bu 
Published: September 2020

AbstractIt is common that different crystal facets in metal and metal oxide nanocrystals display different catalytic performances, whereas such phenomena have been rarely documented in metal–organic frameworks (MOFs). Herein, we demonstrate for the first time that a nickel metal–organic layer (MOL) exposing rich (100) crystal facets (Ni‐MOL‐100) shows a much higher photocatalytic CO2‐to‐CO activity than the one exposing rich (010) crystal facets (Ni‐MOL‐010) and its bulky counterpart (bulky Ni‐MOF), with a catalytic activity up to 2.5 and 4.6 times more active than Ni‐MOL‐010 and bulky Ni‐MOF, respectively. Theoretical studies reveal that the two coordinatively unsaturated NiII ions with a close distance of 3.50 Å on the surface of Ni‐MOL‐100 enables synergistic catalysis, leading to more favorable energetics in CO2 reduction than that of Ni‐MOL‐010.
Enantioselective Total Synthesis of Andrographolide and 14‐Hydroxy‐Colladonin: Carbonyl Reductive Coupling and trans‐Decalin Formation by Hydrogen Transfer
Authors: Yang Lin , Wurm Thomas , Sharma Poudel Binit , Krische Michael J. 
Published: September 2020

AbstractAn enantioselective total synthesis of the labdane diterpene andrographolide, the bitter principle of the herb Andrographis paniculata (known as “King of Bitters”), was accomplished in 14 steps (LLS). Key transformations include iridium‐catalyzed carbonyl reductive coupling to form the quaternary C4 stereocenter, diastereoselective alkene reduction to establish the trans‐decalin ring, and carbonylative lactonization to install the α‐alkylidene‐β‐hydroxy‐γ‐butyrolactone.
Silver Single Atom in Carbon Nitride Catalyst for Highly Efficient Photocatalytic Hydrogen Evolution
Authors: Jiang Xun‐Heng , Zhang Long‐Shuai , Liu Hai‐Yan , Wu Dai‐She , Wu Fei‐Yao , Tian Lei , Liu Ling‐Ling , Zou Jian‐Ping , Luo Sheng‐Lian , Chen Bing‐Bing 
Published: September 2020

AbstractSingle atom catalysts (SACs) with the maximized metal atom efficiency have sparked great attention. However, it is challenging to obtain SACs with high metal loading, high catalytic activity, and good stability. Herein, we demonstrate a new strategy to develop a highly active and stable Ag single atom in carbon nitride (Ag‐N2C2/CN) catalyst with a unique coordination. The Ag atomic dispersion and Ag‐N2C2 configuration have been identified by aberration‐correction high‐angle‐annular‐dark‐field scanning transmission electron microscopy (AC‐HAADF‐STEM) and extended X‐ray absorption. Experiments and DFT calculations further verify that Ag‐N2C2 can reduce the H2 evolution barrier, expand the light absorption range, and improve the charge transfer of CN. As a result, the Ag‐N2C2/CN catalyst exhibits much better H2 evolution activity than the N‐coordinated Ag single atom in CN (Ag‐N4/CN), and is even superior to the Pt nanoparticle‐loaded CN (PtNP/CN). This work provides a new idea for the design and synthesis of SACs with novel configurations and excellent catalytic activity and durability.
Chromophore‐Assisted Proximity Labeling of DNA Reveals Chromosomal Organization in Living Cells
Authors: Ding Tao , Zhu Liyuan , Fang Yuxin , Liu Yangluorong , Tang Wei , Zou Peng 
Published: September 2020

AbstractThe spatial arrangement of chromosome within the nucleus is linked to genome function and gene expression regulation. Existing genome‐wide mapping methods often rely on chemically crosslinking DNA with protein baits, which raises concerns of artifacts being introduced during cell fixation. By genetically targeting a photosensitizer protein to specific subnuclear locations, we achieved blue‐light‐activated labeling of local DNA with a bioorthogonal functional handle for affinity purification and sequence identification through next‐generation sequencing. When applied to the nuclear lamina in human embryonic kidney 293T cells, it revealed lamina‐associated domains (LADs) that cover 37.6 % of the genome. These LADs overlap with heterochromatin hallmarks and are depleted with CpG islands. This simple labeling method avoids the harsh treatment of chemical crosslinking and is generally applicable to the genome‐wide high‐resolution mapping of the spatial chromosome organization in living cells.
Cross‐Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate‐Determining Deprotonation of Bound Hydrazine
Authors: Wang Justin Y. , Choi Kyoungmin , Zuend Stephan J. , Borate Kailaskumar , Shinde Harish , Goetz Roland , Hartwig John F. 
Published: September 2020

AbstractReported here is the Pd‐catalyzed C–N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride. These compounds are present in two interconnected catalytic cycles and react with hydrazine and base or hydrazine alone to give the product. The selectivity of the hydroxide complex with hydrazine to form aryl over diaryl hydrazine was lower than that of the chloride complex, as well as the catalytic reaction. In contrast, the selectivity of the chloride complex closely matched that of the catalytic reaction, indicating that the aryl hydrazine is derived from this complex. Kinetic studies showed that the coupling process occurs by rate‐limiting deprotonation of a hydrazine‐bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.
Synthesis and Properties of a Cyclohexa‐2,7‐anthrylene Ethynylene Derivative
Authors: Matsuki Hironori , Okubo Keisuke , Takaki Yuta , Niihori Yoshiki , Mitsui Masaaki , Kayahara Eiichi , Yamago Shigeru , Kobayashi Kenji 
Published: September 2020

AbstractThe synthesis of a cyclohexa‐2,7‐(4,5‐diaryl)anthrylene ethynylene (1) was achieved for the first time by using 1,8‐diaryl‐3,6‐diborylanthracene and 1,8‐diaryl‐3,6‐diiodoanthracene as key synthetic intermediates. Macrocycle 1 possesses a planar conformation of approximately D6h symmetry, because of the triple‐bond linker between the anthracene units at the 2,7‐positions. It was confirmed that macrocycle 1, bearing bulky substituents at the outer peripheral positions, behaves as a monomeric form in solution without π‐stacking self‐association. Macrocycle 1 has an inner‐cavity size that allows specific inclusion of [9]cycloparaphenylene ([9]CPP), but not [8]CPP or [10]CPP, through an aromatic edge‐to‐face CH‐π interaction.
Construction of inter‐chain polymers and the investigation into Friedel–Crafts alkylation of styrene–acrylonitrile copolymers with chloroprene rubber and characterization
Authors: Wei Xuefeng , Zhang Pengcheng , Cui Shen , Che Wei , Zhao Jiruo , Feng Ying 
Published: September 2020

AbstractIn this study, the Friedel–Crafts alkylation was realized in a solvent free processing of styrene–acrylonitrile copolymers/chloroprene rubber (SAN/CR) molten blending which contributes the formation of SAN‐co‐CR co‐polymers and improved compatibility between SAN and CR. The properties of several Lewis acid compounds were tested as catalysts among which AlCl3 was the most efficient. The effects of blending temperature and time on the co‐polymer formation in situ were also investigated. The methodology of weighing and Fourier transform infrared analyses indicated that the reaction degree increases with increasing blending temperature and time in the ranges of this study. The micro‐structures and reaction mechanisms of the resulted SAN‐co‐CR polymers and morphological structures of SAN/CR/AlCl3 blends were characterized as well by differential scanning calorimetry, FT‐IR spectra, GPC and scanning electron microscopy. The results showed that the inter‐facial reactions between SAN and CR have been effectively improved. Moreover, the inter‐chain structure of SAN‐co‐CR co‐polymers was proposed which is different from general grafting or blocking co‐polymers.
Synthesis and characterization of polypropylene glycol‐based novel organogels as effective materials for the recovery of organic solvents
Authors: Erdem Ahmet 
Published: September 2020

AbstractIn this study, novel hydrophobic organogels were successfully prepared via the aza‐Michael addition reaction method using diamino terminated polypropylene glycol and diphenylmethane bismaleimide as monomers, in the presence of a tri‐amino functional polypropylene glycol as a crosslinking agent. The chemical structures, surface morphology, and thermal stability of the synthesized organogels were analyzed using Fourier transform infrared spectroscopy and solid‐state CPMAS 13C‐NMR, scanning electron microscope, and thermal gravimetric analysis technique, respectively. The effects of various parameters, such as the monomer ratio, amount of crosslinker, and as well as swelling properties of organogels by solvent absorption tests were studied. According to obtained results, the solvent uptake capacity increased with decreasing crosslinker ratio up to 30 wt%. The maximum solvent absorbency of the synthesized organogels were determined as 730%, 504%, 271%, 224%, 95%, and 17% for dichloromethane, tetrahydrofuran, benzene, acetone, gasoline and diesel oil, under optimum conditions, respectively. In addition, reusability of the organogels was evaluated for 10 cycles, depicting no significant loss in absorbance capacity. The fabricated organogels showed high solvent absorption efficiency with prospects as suitable material for the recovery of a wide range of organic solvents.
Dreams, djinn, and the evil eye: Interpreting the supernatural idiom of Yemenite Jewish immigration
Authors: Buse William 
Published: September 2020

AbstractThe lived experiences of immigration and transitional identity increasingly emerge as social challenges that urgently require greater understanding. With the mass emigration of Yemenite Jews out of Yemen to Israel undertaken 70 years ago, we now have an opportunity to assess the long‐term effects of this social phenomenon. A focus on the idiosyncratic supernatural productions of a representative sample of this population enable an innovative analysis through the application of tools from anthropology, psychology, and psychoanalysis. The proposed methods are a necessary supplement, and corrective, to those research projects that are solely dependent on the conscious, cognitively oriented participation of informants.
Development of novel indole‐linked pyrazoles as anticonvulsant agents: A molecular hybridization approach
Authors: Kerzare Deweshri R. , Menghani Sunil S. , Rarokar Nilesh R. , Khedekar Pramod B. 
Published: September 2020

AbstractA series of 3‐{2‐[1‐acetyl‐5‐(substitutedphenyl)‐4,5‐dihydropyrazol‐3‐yl]hydrazinylidene}‐1,3‐dihydro‐2H‐indol‐2‐ones 24–43 was synthesized using an appropriate synthetic route and evaluated experimentally by the maximal electroshock test. These compounds were evaluated for antidepressant and antianxiety activities. The most active compound, 3‐{2‐[1‐acetyl‐5‐(4‐chlorophenyl)‐4,5‐dihydropyrazol‐3‐yl]hydrazinylidene}‐1,3‐dihydro‐2H‐indol‐2‐one 25, exhibited an ED50 of 13.19 mmol/kg, a TD50 of 43.49 mmol/kg, and a high protective index of 3.29, compared with the standard drug diazepam. To get insights into the intermolecular interactions, molecular docking studies were performed at the active site of the GABAA receptor and the MAO‐A enzyme. Molecular docking studies are also in agreement with the pharmacological evaluation with potent compounds, exhibiting docking scores of −1.5180 and 0.7458 for the GABAA receptor and MAO‐A, respectively. The 3D‐QSAR analysis was carried out by Vlife MDS engine 4.3.1, and a statistically reliable model with good predictive power (r2 = 0.7523, q2 = 0.3773) was achieved. The 3D‐QSAR plots gave insights into the structure–activity relationship of these compounds, which may aid in the design of potent benzopyrrole derivatives as anticonvulsant agents. So, our research can make a great impact on those medicinal chemists who work on the development of anticonvulsant agents.
Isolated AGNs NGC 5347, ESO 438‐009, MCG‐02‐04‐090, and J11366‐6002: Swift and NuSTAR joined view1
Authors: Vasylenko Anatoliy A. , Vavilova Irina B. , Pulatova Nadiia G. 
Published: September 2020

AbstractWe present the spectral analysis with the Nuclear Spectroscopic Telescope Array (NuSTAR) of four isolated galaxies with active galactic nuclei selected from the 2MIG catalogue: NGC 5347, ESO 438‐009, MCG‐02‐09‐040, and IGR J11366‐6002. We also used the Swift/Burst Alert Telescope (BAT) data up to ∼150 keV for MCG 02‐09‐040, ESO 438‐009, and IGR J11366‐6002 as well as the Swift/XRT data in 0.3–10 keV energy band for NGC 5347, ESO 438‐009, and IGR J11366‐6002. All the sources appear to have the reflected spectrum component with different reflection fractions in addition to the primary power‐law continuum. We found that power‐law indices for these sources lie between 1.6 and 1.8. The spectra of two sources, NGC 5347 and MCG‐02‐09‐040, show the Fe Kα emission line. For both of these sources, the Fe Kα lines have a significant value of EW ∼1 keV. The X‐ray spectrum of NGC 5347 is best fitted by a pure reflection model with Ecut ∼ 117 keV and without the presence of any additional primary power‐law component. We also found that the X‐ray spectrum of MCG‐02‐09‐040 shows the presence of heavy neutral obscuration of NH ∼ 1024 cm−2. However, this provides a non‐physical value of reflection in the case with fitting by a simple reflection model. A more appropriate fit is obtained with adopting the physical Monte Carlo‐based model as BNTorus. It allowed us to determine the absorption value of NH ∼ 1.04 × 1024 cm−2 and reasonable power‐law index of Γ ≈ 1.63. Results for MCG‐02‐09‐040 are presented for the first time.
Anatomical guide for botulinum neurotoxin injection: Application to cosmetic shoulder contouring, pain syndromes, and cervical dystonia
Authors: Yi Kyu‐Ho , Lee Hyung‐Jin , Choi You‐Jin , Lee Kangwoo , Lee Ji‐Hyun , Kim Hee‐Jin 
Published: September 2020

AbstractIntroductionThis study proposes an ideal botulinum toxin injection point of the trapezius muscle for shoulder line contouring, pain management, and functional impairment. This study describes the intramuscular nerve branching in the trapezius muscle, providing essential information for botulinum neurotoxin injection.MethodA modified Sihler's method was performed on the trapezius muscles (16 specimens). The intramuscular arborization areas were elucidated regarding the external occipital protuberance superiorly, spinous process of the 12th thoracic vertebra inferiorly and acromion of the scapula.ResultThe intramuscular neural distribution for the superior, middle, and inferior regions of the trapezius muscle had the greatest arborized patterns in the horizontal 1/5–2/5 and vertical 2/10–4/10 sections, the horizontal 1/5–3/5 and vertical 4/10–5/10 sections, and the horizontal 1/5–2/5 and vertical 5/10–7/10 sections, respectively.DiscussionWe propose that BoNT treatments should be directed to the horizontal 1/5–2/5 and vertical 2/10–4/10 sections of the superior trapezius, the horizontal 1/5–3/5 and vertical 4/10–5/10 sections of the middle trapezius and the horizontal 1/5–2/5 and vertical 5/10–7/10 sections of the inferior trapezius. Additionally, injective treatment at the horizontal 2/5–3/5 and vertical 2/10–4/10 nerve entry points should be avoided to prevent nerve trunk damage causing paralysis. According to our guidelines, clinicians can ensure minimal dose injections and fewer adverse effects in botulinum neurotoxin injective treatment.
Giant laryngeal granuloma developed after a severely stressful life event
Authors: Ettori Jacopo , D'Onghia Alessandra , Pignataro Lorenzo , Cantarella Giovanna 
Published: September 2020

AbstractLaryngeal granulomas are ascribed to laryngopharyngeal reflux, voice abuse, and endotracheal intubation, but their pathogenesis is controversial. A recurrent giant granuloma causing dyspnea occurred after a severe psychological stress and was successfully treated by surgery, steroid injection, and psychotherapy. This case highlights the role of psychological stress in granulomas pathogenesis.