bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anti‐Infective Application of Graphene‐Like Silicon Nanosheets via Membrane Destruction
Authors: Luo Yao , Ge Min , Lin Han , He Renke , Yuan Xiangwei , Yang Chao , Wang Wei , Zhang Xianlong 
Published: January 2020

AbstractThe increasing problem of bacterial resistance to the currently effective antibiotics has resulted in the need for increasingly potent therapeutics to eradicate pathogenic microorganisms. 2D nanomaterials (2D NMs) have unique physical and chemical properties that make them attractive candidates for biomedical applications. Recently, the application of 2D NMs as antibacterial agents has attracted significant attention. Herein, a novel 2D graphene‐like silicon nanosheet (GS NS) antimicrobial agent is fabricated from pristine silicon crystals by ultrasonication, which results in a highly exfoliated planar morphology and a significantly larger surface area as compared with bulk silicon. The GS NSs exhibit remarkable in vitro broad‐spectrum bactericidal activity against Gram (−) Escherichia coli and Gram (+) Staphylococcus aureus because of a close interaction with the bacteria, which leads to highly efficient membrane destruction. The in vivo studies demonstrate that the local administration of GS NSs effectively mitigates implant‐related infection by reducing the bacterial burden of the extracted samples and accelerating the remission of local inflammation. Based on these encouraging results, GS NSs are expected to be a useful new member of the 2D NMs family, with the potential of effectively killing pathogenic bacteria in clinical applications.
In Situ Investigation of Reversible Exsolution/Dissolution of CoFe Alloy Nanoparticles in a Co‐Doped Sr2Fe1.5Mo0.5O6−δ Cathode for CO2 Electrolysis
Authors: Lv Houfu , Lin Le , Zhang Xiaomin , Song Yuefeng , Matsumoto Hiroaki , Zeng Chaobin , Ta Na , Liu Wei , Gao Dunfeng , Wang Guoxiong , Bao Xinhe 
Published: January 2020

AbstractReversible exsolution and dissolution of metal nanoparticles in perovskite has been investigated as an efficient strategy to improve CO2 electrolysis performance. However, fundamental understanding with regard to the reversible exsolution and dissolution of metal nanoparticles in perovskite is still scarce. Herein, in situ exsolution and dissolution of CoFe alloy nanoparticles in Co‐doped Sr2Fe1.5Mo0.5O6–δ (SFMC) revealed by in situ X‐ray diffraction, scanning transmission electron microscopy, environmental scanning electron microscopy, and density functional theory calculations are reported. Under a reducing atmosphere, facile exsolution of Co promotes reduction of the Fe cation to generate CoFe alloy nanoparticles in SFMC, accompanied by structure transformation from double perovskite to layered perovskite at 800 °C. Under an oxidizing atmosphere, spherical CoFe alloy nanoparticles are first oxidized to flat CoFeOx nanosheets, and then dissolved into the bulk with structure evolution from layered perovskite back to double perovskite. Electrochemically, CO2 electrolysis performance can be retrieved during 12 redox cycles due to the regenerative ability of the CoFe alloy nanoparticles. The anchoring of the CoFe alloy nanoparticles in SFMC perovskite via reduction shows enhanced CO2 electrolysis performance and stability compared with the parent SFMC perovskite.
Synthesis of Pashinintide A, a Natural Cyclic Hexapeptide Supposedly Capable of Forming a Complex with Sucrose
Authors: Yin Xuejian , Li Wei , Yu Biao 
Published: January 2020

AbstractPashinintide A, a cyclic hexapeptide discovered from Pyrus pashia, has been synthesized in a linear sequence of 8 steps and 24% overall yield from N‐Boc glycine, featuring a convergent [3+3] fragment coupling strategy. Although the structure of the synthetic Pashinintide A was unambiguously confirmed by X‐ray diffraction analysis, its proposed complexation with sucrose cannot be validated.
Negativ geladene gelb emittierende 1‐Aminopyrene für reduktive Aminierung und Fluoreszenznachweis von Glykanen
Authors: Savicheva Elizaveta A. , Mitronova Guyzel Yu. , Thomas Laura , Böhm Marvin J. , Seikowski Jan , Belov Vladimir N. , Hell Stefan W. 
Published: January 2020

Abstract1‐Aminopyrene mit drei ω‐hydroxylierten N‐ Alkylsulfonamido‐ oder Alkylsulfonylgruppen an C‐3, C‐6 und C‐8 wurden hergestellt, O‐phosphoryliert und in der reduktiven Aminierung von Oligosacchariden eingesetzt. Diese Farbstoffe (ϵ≈20 000 m−1 cm−1) mit sechs negativen Ladungen (pH≥8) und niedrigen m/z‐Werten ermöglichen die Markierung, Elektrophorese und Detektion von reduzierenden Zuckern (Glykanen), welche die strukturell und funktionell vielfältigste Klasse von Naturprodukten darstellen. Bei Anregung mit einem 488‐nm‐Laser emittieren die neuen Glykokonjugate gelbes Licht von etwa 560 nm und weisen bessere Helligkeit und höhere elektrophoretische Mobilität als die entsprechenden APTS‐Derivate (Referenz mit grüner Emission) auf.
Kooperative Katalyse für die diastereo‐ und enantioselektive [4+3]‐Cycloanellierung von ortho‐Chinonmethiden und Carbonylyliden
Authors: Suneja Arun , Loui Henning Jakob , Schneider Christoph 
Published: January 2020

AbstractIm Rahmen dieser Arbeit wurde ein Verfahren zur diastereo‐ und enantioselektiven [4+3]‐Cycloanellierung von ortho‐Chinonmethiden und Carbonylyliden entwickelt, das funktionalisierte, sauerstoffverbrückte Dibenzooxazine in exzellenten Ausbeuten und Stereoselektivitäten innerhalb eines einzelnen Syntheseschrittes zugänglich macht. Die kooperative Katalyse von Rhodium und einer chiralen Brønsted‐Säure ermöglicht die in situ Erzeugung zweier hochreaktiver Intermediate, die zu komplexen, bicyclischen Produkten mit einem tertiären und zwei quartären Stereozentren reagieren. Diese wurden durch weitere Transformationen in wertvolle, enantiomerenangereicherte Synthesebausteine überführt.
Negatively Charged Yellow‐Emitting 1‐Aminopyrene Dyes for Reductive Amination and Fluorescence Detection of Glycans
Authors: Savicheva Elizaveta A. , Mitronova Guyzel Yu. , Thomas Laura , Böhm Marvin J. , Seikowski Jan , Belov Vladimir N. , Hell Stefan W. 
Published: January 2020

Abstract1‐Aminopyrenes with three ω‐hydroxylated N‐alkylsulfonamido or alkylsulfonyl residues in positions 3, 6, and 8 were prepared, O‐phosphorylated, and applied for reductive amination of oligosaccharides. The dyes (ϵ≈20 000 m−1 cm−1) with six negative charges (pH≥8) and low m/z ratios enable labeling and fluorescence detection of reducing sugars (glycans) related to the most structurally and functionally diverse class of natural products. Under excitation with a 488 nm laser, the new glycoconjugates emit yellow light of about 560 nm, outperforming (with respect to brightness and faster electrophoretic mobilities) the corresponding APTS derivatives (benchmark dye with green emission in conjugates).
Oxalyl‐CoA Decarboxylase Enables Nucleophilic One‐Carbon Extension of Aldehydes to Chiral α‐Hydroxy Acids
Authors: Burgener Simon , Cortina Niña Socorro , Erb Tobias J. 
Published: January 2020

AbstractThe synthesis of complex molecules from simple, renewable carbon units is the goal of a sustainable economy. Here we explored the biocatalytic potential of the thiamine‐diphosphate‐dependent (ThDP) oxalyl‐CoA decarboxylase (OXC)/2‐hydroxyacyl‐CoA lyase (HACL) superfamily that naturally catalyzes the shortening of acyl‐CoA thioester substrates through the release of the C1‐unit formyl‐CoA. We show that the OXC/HACL superfamily contains promiscuous members that can be reversed to perform nucleophilic C1‐extensions of various aldehydes to yield the corresponding 2‐hydroxyacyl‐CoA thioesters. We improved the catalytic properties of Methylorubrum extorquens OXC by rational enzyme engineering and combined it with two newly described enzymes—a specific oxalyl‐CoA synthetase and a 2‐hydroxyacyl‐CoA thioesterase. This enzymatic cascade enabled continuous conversion of oxalate and aromatic aldehydes into valuable (S)‐α‐hydroxy acids with enantiomeric excess up to 99 %.
Dichloroimidazolidinedione‐activated one‐pot Suzuki–Miyaura cross‐coupling of phenols
Authors: Madankar Kamelia , Mokhtari Javad , Mirjafary Zohreh 
Published: January 2020

AbstractThe first general method for the Suzuki‐type cross‐coupling of phenols with aryl boronic acids using dichloroimidazolidinedione (DCID) as a new reagent is presented. In the presence of DCID and Pd/metal–organic framework (MOF), coupling of aryl boronic acids with a wide range of phenols, was carried out smoothly in tetrahydrofuran (THF) at reflux conditions to afford the cross‐coupling products in good to excellent yields. The structures of all compounds were corroborated by 1H‐ and 13C‐NMR. A plausible mechanism for this type of reaction is proposed.
Benefits of crop diversification in Fiji's sugarcane farming
Authors: Singh Amar 
Published: January 2020

AbstractThe sugar industry has shaped the development of Fiji's economy for over a century; but, for the past 15 years, sugarcane production has been declining. A study was undertaken of over 300 sugarcane farmers in Fiji to determine the benefits of crop diversification and to compare the level of profitability for farmers fully dedicated to sugarcane farming and sugarcane farmers who have diversified. The findings demonstrate that a farmer in the latter group was able to achieve 45% higher profitability than one in the former. Fiji has the potential to increase farm output from diversification, but the relevant stakeholders need to help farmers secure markets and provide appropriate guidance and training.
Pharmacophore modeling, 3D‐QSAR, synthesis, and anti‐lung cancer evaluation of novel thieno[2,3‐d][1,2,3]triazines targeting EGFR
Authors: Elrayess Ranza , Abdel Aziz Yasmine M. , Elgawish Mohamed S. , Elewa Marwa , Elshihawy Hosam A. , Said Mohamed M. 
Published: January 2020

AbstractTwo series of thieno[2,3‐d][1,2,3]triazine derivatives were designed, synthesized, and biologically evaluated as potential epidermal growth factor receptor (EGFR) inhibitors targeting the non‐small‐cell lung cancer cell line H1299. Most of the synthesized compounds displayed IC50 values ranging from 25 to 58 nM against H1299, which are superior to that of gefitinib (40 µM). 3‐(5,6,7,8‐Tetrahydro‐7H‐cyclohexa[4:5]thieno[2,3‐d]‐1,2,3‐triazin‐4‐ylamino)benzene‐1,3‐diamine (6b) achieved the highest cytotoxic activity against H1299 with an IC50 value of 25 nM; it had the ability to decrease the EGFR concentration in H1299 cells from 7.22 to 2.67 pg/ml. In vitro, the IC50 value of compound 6b was 0.33 nM against EGFR, which is superior to that of gefitinib at 1.9 nM and erlotinib at 4 nM. The three‐dimensional quantitative structure–activity relationships and molecular modeling studies revealed comparable binding modes of compound 6b, gefitinib, and erlotinib in the EGFR active site. The in silico ADME (absorption, distribution, metabolism, and excretion) prediction parameters of this compound revealed promising pharmacokinetic and physicochemical properties. Moreover, DFT (density functional theory) calculations showed the high reactivity of compound 6b toward the EGFR compared with other compounds. The designed compound 6b might serve as an encouraging lead compound for the discovery of promising anti‐lung cancer agents targeting EGFR.
Advances in Protecting Groups for Oligosaccharide Synthesis
Authors: Ghosh Bhaswati , Kulkarni Suvarn S. 
Published: January 2020

AbstractCarbohydrates contain numerous hydroxyl groups and sometimes amine functionalities which lead to a variety of complex structures. In order to discriminate each hydroxyl group for the synthesis of complex oligosaccharides, protecting group manipulations are essential. Although the primary role of a protecting group is to temporarily mask a particular hydroxyl/amino group, it plays a greater role in tuning the reactivity of coupling partners as well as regioselectivity and stereoselectivity of glycosylations. Several protecting groups offer anchimeric assistance in glycosylation. They also alter the solubility of substrates and thereby influence the reaction outcome. Since oligosaccharides comprise branched structures, the glycosyl donors and acceptors need to be protected with orthogonal protected groups that can be selectively removed one at a time without affecting other groups. This minireview is therefore intended to provide a discussion on new protecting groups for amino and hydroxyl groups, which have been introduced over last ten years in the field of carbohydrate synthesis. These protecting groups are also useful for synthesizing non‐carbohydrate target molecules as well.
Intramuscular innervation patterns of the splenius capitis and splenius cervicis and their clinical implications for botulinum toxin injections
Authors: Kwon Hyun‐Jin , Yang Hun‐Mu , Won Sung‐Yoon 
Published: January 2020

AbstractIntroductionThe purpose of this study was to clearly characterize the intramuscular nerve distributions of the splenius capitis and splenius cervicis muscles that are both responsible for the onset of a chronic tension type headache and to use this information to identify the effective botulinum toxin (BoNT) injection sites.Materials and MethodsTen splenius capitis and splenius cervicis specimens were subjected to Sihler's staining to reveal intramuscular nerve arborization patterns and determined the optimal location for BoNT injection.ResultsNerve distribution patterns in the splenius capitis were identified as nerve pathways that travel down toward the origin point and others that travel up toward the insertion point. This neuromuscular innervation from the central (50%) point was distributed evenly in these two directions. The neural pathways of splenius cervicis traveled vertically from the insertion point to the origin point. If the length from the muscle origin point to the insertion point is normalized to 100%, motor neurons innervate the muscle from around the 30% to the 70% point.ConclusionsThe safest and most‐effective BoNT injection sites for the splenius capitis and splenius cervicis were found at around the 50% point and the 30% to the 70% point, respectively.
Location of the infraorbital foramen with reference to soft tissue landmarks for regional nerve blocks during midface surgery
Authors: Shin Kang‐Jae , Shin Hyun Jin , Lee Shin‐Hyo 
Published: January 2020

AbstractPurposeAn infraorbital nerve (ION) block is widely used to accomplish regional anesthesia during surgical procedures involving the midface region. This study aimed to elucidate the exact location of the infraorbital foramen (IOF) in relation to clinically useful soft‐tissue landmarks for achieving an effective ION block.MethodsForty‐three hemifaces from 23 embalmed Korean cadavers were dissected. The lateral canthus, peak of Cupid's bow, medial limbus, and midline were used as reference points. The distances from the IOF to the midline and the lateral canthus were measured.ResultsThe IOF was located approximately 25 mm below the lateral canthus and 27 mm lateral to the midline. In all cases, the IOF was situated within 9.0 mm of the crossing point of the oblique line connecting the lateral canthus to the peak of Cupid's bow and the vertical line through the medial limbus.ConclusionConsidering the spread of an anesthetic agent, injecting it into the crossing point of the oblique line through the lateral canthus to the peak of Cupid's bow and the vertical line through the medial limbus would successfully block the ION in most patients.
Morphology of ejaculatory ducts: A systematic review
Authors: Mathangasinghe Yasith , Samaranayake Udagedara M. J. E. , Dolapihilla Buddhini N , Anthony Dimonge J. , Malalasekera Ajith P. 
Published: January 2020

AbstractThe morphology of human ejaculatory ducts has not been well established. The objective of this study was to describe macroscopic and microscopic anatomy of ejaculatory ducts. We conducted a systematic review using MEDLINE, Scopus, PubMed, and Cochrane databases. Search terms were: “ejaculatory ducts,” “seminal colliculus,” “prostatic utricle,” “anatomy,” “histology,” “radiology,” and “embryology.” We only included studies assessing adult (>18 years) humans published before November 1, 2019. We excluded studies describing pathological ducts and case reports. Independent authors extracted data using predefined criteria. Fourteen studies were included in the qualitative synthesis. Usually, the ejaculatory ducts entered the prostate by piercing the central part of its base. Most studies identified an anteromedial curve of the ducts at the outset within the prostate, their subsequent course being a straight path towards the seminal colliculus, their terminal parts diverging immediately before joining the prostatic urethra. However, the morphology of the terminal part of the ducts was inconsistent. The mean length of the ducts ranged from 1.4 to 2.2 cm. In conclusion, the luminal diameter gradually decreased as the ducts traveled towards the seminal colliculus. Ejaculatory ducts angulate anteromedially at their onset within the prostate and travel straight towards the seminal colliculus. Their terminal parts diverge immediately before joining the prostatic urethra. However, the reported dimensions of the ducts differ among studies.
Integrating Reactors and Catalysts through Three‐Dimensional Printing: Efficiency and Reusability of an Impregnated Palladium on Silica Monolith in Sonogashira and Suzuki Reactions
Authors: Díaz‐Marta Antonio S. , Yañez Susana , Lasorsa Eliana , Pacheco Patricia , Tubío Carmen R. , Rivas José , Piñeiro Yolanda , Gómez Manuel A. Gonzalez , Amorín Manuel , Guitián Francisco , Coelho Alberto 
Published: January 2020

AbstractFor this work, an integrated system composed of a polypropylene reactor and a palladium on silica monolithic catalyst was designed and manufactured by 3D‐printing. These devices are able to perform solution phase chemistry in a robotic orbital shaker. The capped reactor was obtained in its entirety by 3D‐printing, using polypropylene and fused deposition modeling. The monolithic catalyst was also obtained by 3D‐printing ‐robocasting‐ of a silica support, sintering and subsequent palladium deposition through the wet impregnation method. The catalytic efficiency in Sonogashira or Suzuki reactions as well as the recyclability of the entire system – catalyst+reactor – were studied. The strong electrostatic adsorption (SEA) of the palladium on sintered silica and the reduced mechanical stress produced by the convenient adjustment of the catalyst into the polypropylene reactor makes the catalytic system reusable without significant loss of catalytic activity.
Phenomenological Rule from Correlations of Conduction/Valence Band Energies and Bandgap Energies in Semiconductor Photocatalysts: Calcium Bismuthates versus Strontium Bismuthates
Authors: Shtarev D. S. , Ryabchuk V. K. , Rudakova A. V. , Shtareva A. V. , Molokeev M. S. , Kirichenko E. A. , Serpone N. 
Published: January 2020

AbstractA number of calcium bismuthates were synthesized (25 to 50 mol% in Ca) and characterized by XRD, SEM, EDX, XPS and DRS techniques; the latter provided an estimate of the bandgap energies (Ebg=2.41 to 3.29 eV) via Tauc plots for indirect transitions, whereas XPS established the potentials (vs NHE) of their respective valence bands (and thus the conduction bands). Linear correlations existed between EVB/ECB and Ebg that when compared with those of strontium bismuthates (reported earlier) showed that differences in energies at Ebg=0 eV are related to the difference in the absolute electronegativities of Ca and Sr, from which the following empirical phenomenological rule is postulated: replacing one alkaline earth metal in bismuthates by another causes the points of intersection of the linear correlations ECB(Ebg) and EVB(Ebg) to be displaced by an amount equal to twice the difference in absolute electronegativities of these metals.
Au/Ta(110) and Au/Nb(110) as Highly Active, Stable, and Inexpensive Catalysts for Oxygen Reduction Reaction on Hydrogen Fuel Cell Cathodes: Prediction from First Principles
Authors: Campbell Tyler , Alcántara Ortigoza Marisol , Stolbov Sergey 
Published: January 2020

AbstractWe propose here structures – a gold monolayer on early transition metal surfaces – as a promising alternative to the prohibitively expensive platinum‐based electro‐catalysts for the oxygen reduction reaction (ORR), which occurs on hydrogen fuel cell cathodes. Based on existing knowledge and educated guesses, we preselect Au/Nb, Au/Ta, Au/Mo, and Au/W as potential catalysts. Our calculations show that these materials are stable and have very high dissolution potentials. A deviation from the linear scaling for the binding energy of ORR intermediates, revealed for Au/Nb and Au/Ta, has a desired impact on the ORR thermodynamics. We find it to be a result of hybridization of p‐electronic states of oxygen belonging the OOH‐radical and Au‐pz states. The calculated ORR free energy diagrams show that the ORR onset potentials for Au/Nb and Au/Ta are significantly higher than that for Pt. We thus predict two inexpensive, thermodynamically and electrochemically stable, and highly active ORR catalysts.
Relationship Between Sweat and Blood Lactate Levels During Exhaustive Physical Exercise
Authors: Karpova Elena V. , Laptev Aleksey I. , Andreev Egor A. , Karyakina Elena E. , Karyakin Arkady A. 
Published: January 2020

AbstractIn contrast to the generally accepted view, that sweat lactate is irrelevant to blood, we report on the suitability of sweat lactate for diagnostics. We demonstrate a significant increase in lactate concentration in sweat from the working muscle area simultaneously with the rise of blood lactate content during exhaustive physical exercise. The variation rates of lactate concentration in sweat from working and latent muscle areas correlate positively with blood lactate levels (r>0.8 and r=0.7, respectively), thus offering the prospect of a non‐invasive approach for the monitoring of sportsperson training. Moreover, sweat lactate, being the faster indicator of muscle metabolism, would be even more important for sports medicine than the nowadays‐used blood lactate.
Improving Gating Efficiency of Electron Transport through Redox‐Active Molecular Junctions with Conjugated Chains
Authors: Zhang Fan , Wu Xiao‐Hui , Zhou Yi‐Fan , Wang Ya‐Hao , Zhou Xiao‐Shun , Shao Yong , Li Jian‐Feng , Jin Shan , Zheng Ju‐Fang 
Published: January 2020

AbstractTuning the electron transport at the molecular scale is a key step in realizing functional electronic components for molecular electronics, and ongoing interest aims at achieving a higher modulation ratio for single‐molecular transistors. Here, a feasible strategy that connects the redox‐active moieties with conjugated chains is proposed to improve the electrochemical gating efficiency of molecular junctions in ionic liquid. Benefiting from the low energy barrier height between the Fermi level of the electrode and the frontier molecular orbitals, the conductance of C=C−Fc−Py is about one order of magnitude larger and the conductance on/off ratio shows 160 % improvement compared to that of C−C−Fc−Py at the equilibrium potential of Fc+/Fc. This work provides a new way to design high‐performance molecular devices.
One‐Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols
Authors: Ikawa Takashi , Masuda Shigeaki , Akai Shuji 
Published: January 2020

AbstractBenzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho‐ and meta‐substituted phenols produced meta‐substituted anilines exclusively, those of para‐substituted phenols provided ortho‐silylanilines.