bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phenyl Disulfide Additive for Solution‐Mediated Carbon Dioxide Utilization in Li–CO2 Batteries
Authors: Pipes Robert , Bhargav Amruth , Manthiram Arumugam 
Published: April 2019

AbstractPhenyl disulfide (PDS) is employed as an electrolyte additive in lithium–carbon dioxide (Li–CO2) batteries to allow for a solution‐mediated carbon dioxide reduction pathway. Thiophenolate anions, generated via electrochemical reduction of PDS, act as CO2 capture agents by forming the adduct S‐phenyl carbonothioate (SPC−) in solution. A mechanism of SPC−‐mediated CO2 capture and utilization is proposed and supported via carbon‐13 nuclear magnetic resonance spectroscopy and Fourier‐transform infrared spectroscopy. Reversible formation and decomposition of lithium carbonate and amorphous carbon during cycling, facilitated by the solution‐mediated pathway, are demonstrated with an array of characterization techniques. Li–CO2 batteries employing the PDS additive show vastly improved capacity, energy efficiency, and cycle life. The enhanced Li–CO2 battery performance offered by the proposed solution‐mediated reaction pathway offers a compelling step forward in the pursuit of reversible CO2 utilization.
Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth
Authors: Sturala Jiri , Sofer Zdenek , Pumera Martin 
Published: April 2019

AbstractMaterials with few layers have been subjected to extensive research for the last few decades owing to their remarkable properties as for example catalysts, optical and electrical devices, or sensors. The properties and electronic structure of these materials can be tailored by the introduction of substituents. In the case of more reactive species, the modification also can improve stability, which is also an important factor with respect to device fabrication. This review focuses on monoelemental layered materials of Group 15 elements (pnictogens) and in particular their modification, leading to better ambient stability and/or different properties by covalent and non‐covalent modifications. The future modification and application of pnictogens are outlined.
Mitochondria‐Targeting, Intracellular Delivery of Native Proteins Using Biodegradable Silica Nanoparticles
Authors: Yuan Peiyan , Mao Xin , Wu Xiaofeng , Liew Si Si , Li Lin , Yao Shao Q. 
Published: April 2019

AbstractMitochondria are key organelles in mammalian cells whose dysfunction is linked to various diseases. Drugs targeting mitochondrial proteins provide a highly promising strategy for potential therapeutics. Methods for the delivery of small‐molecule drugs to the mitochondria are available, but these are not suitable for macromolecules, such as proteins. Herein, we report the delivery of native proteins and antibodies to the mitochondria using biodegradable silica nanoparticles (BS–NPs). The modification of the nanoparticle surface with triphenylphosphonium (TPP) and cell‐penetrating poly(disulfide)s (CPD) facilitated their rapid intracellular uptake with minimal endolysosomal trapping, providing sufficient time for effective mitochondrial localization followed by glutathione‐triggered biodegradation and of native, functional proteins into the mitochondria.
β‐Selective Aroylation of Activated Alkenes by Photoredox Catalysis
Authors: Lei Zhen , Banerjee Arghya , Kusevska Elena , Rizzo Eric , Liu Peng , Ngai Ming‐Yu 
Published: April 2019

AbstractLate‐stage synthesis of α,β‐unsaturated aryl ketones remains an unmet challenge in organic synthesis. Reported herein is a photocatalytic non‐chain‐radical aroyl chlorination of alkenes by a 1,3‐chlorine atom shift to form β‐chloroketones as masked enones that liberate the desired enones upon workup. This strategy suppresses side reactions of the enone products. The reaction tolerates a wide array of functional groups and complex molecules including derivatives of peptides, sugars, natural products, nucleosides, and marketed drugs. Notably, addition of 2,6‐di‐tert‐butyl‐4‐methyl‐pyridine enhances the quantum yield and efficiency of the cross‐coupling reaction. Experimental and computational studies suggest a mechanism involving PCET, formation and reaction of an α‐chloro‐α‐hydroxy benzyl radical, and 1,3‐chlorine atom shift.
Optical Multiplexed Bioassays for Improved Biomedical Diagnostics
Authors: Fan Yong , Wang Shangfeng , Zhang Fan 
Published: April 2019

AbstractConventional analytical methods based on the detection of a single disease marker may not be sufficiently accurate because the progression of disease generally involves multiple chemicals and biomolecules. The drive for simultaneous analysis of multiple targets, which plays a key role in both basic biomedical research and clinical applications, demands the development of multiplexed bioassays with high‐throughput. In this minireview, we summarize the recent progress in optical multiplexed analytical techniques for improving biomedical diagnostics, in which fluorescence and surface enhanced Raman scattering (SERS) with distinctive optical features are chosen as the main readout signals. Focusing on multiplexed strategies in the biomedical field, a selection of recent contributions from biosensing of multiple analytes and multicolor cellular tracking to in vivo multiplexed bioimaging are highlighted. Finally, we frame the future challenges and opportunities for multiplexed bioanalysis.
Peptide‐Directed DNA‐Templated Protein Labelling for The Assembly of a Pseudo‐IgM
Authors: Nielsen Thorbjørn B. , Thomsen Rasmus P. , Mortensen Michael R. , Kjems Jørgen , Nielsen Per Franklin , Nielsen Thomas E. , Kodal Anne Louise B. , Cló Emiliano , Gothelf Kurt V. 
Published: April 2019

AbstractThe development of methods for conjugation of DNA to proteins is of high relevance for the integration of protein function and DNA structures. Here, we demonstrate that protein‐binding peptides can direct a DNA‐templated reaction, selectively furnishing DNA–protein conjugates with one DNA label. Quantitative conversion of oligonucleotides is achieved at low stoichiometries and the reaction can be performed in complex biological matrixes, such as cell lysates. Further, we have used a star‐like pentameric DNA nanostructure to assemble five DNA–Rituximab conjugates, made by our reported method, into a pseudo‐IgM antibody structure that was subsequently characterized by negative‐stain transmission electron microscopy (nsTEM) analysis.
Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu2O2 Complexes
Authors: Cutsail George E. , Gagnon Nicole L. , Spaeth Andrew D. , Tolman William B. , DeBeer Serena 
Published: April 2019

AbstractValence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [CuII2(μ‐η2:η2‐O2)]2+ core relative to its isomer with a cleaved O−O bond having a [CuIII2(μ‐O)2]2+ unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [CuII2(μ‐η2:η2‐O2)]2+ core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O−O bond activation in μ‐η2:η2‐O2 species and highlight the potential of this method for time‐resolved studies of reaction mechanisms.
Scalable Biosynthesis of the Seaweed Neurochemical, Kainic Acid
Authors: Chekan Jonathan R. , McKinnie Shaun M. K. , Moore Malia L. , Poplawski Shane G. , Michael Todd P. , Moore Bradley S. 
Published: April 2019

AbstractKainic acid, the flagship member of the kainoid family of natural neurochemicals, is a widely used neuropharmacological agent that helped unravel the key role of ionotropic glutamate receptors, including the kainate receptor, in the central nervous system. Worldwide shortages of this seaweed natural product in the year 2000 prompted numerous chemical syntheses, including scalable preparations with as few as six‐steps. Herein we report the discovery and characterization of the concise two‐enzyme biosynthetic pathway to kainic acid from l‐glutamic acid and dimethylallyl pyrophosphate in red macroalgae and show that the biosynthetic genes are co‐clustered in genomes of Digenea simplex and Palmaria palmata. Moreover, we applied a key biosynthetic α‐ketoglutarate‐dependent dioxygenase enzyme in a biotransformation methodology to efficiently construct kainic acid on the gram scale. This study establishes both the feasibility of mining seaweed genomes for their biotechnological prowess.
Oxygen Evolution Electrocatalysis of a Single MOF‐Derived Composite Nanoparticle on the Tip of a Nanoelectrode
Authors: Aiyappa Harshitha Barike , Wilde Patrick , Quast Thomas , Masa Justus , Andronescu Corina , Chen Yen‐Ting , Muhler Martin , Fischer Roland A. , Schuhmann Wolfgang 
Published: April 2019

AbstractDetermination of the intrinsic electrocatalytic activity of nanomaterials by means of macroelectrode techniques is compromised by ensemble and film effects. Here, a unique “particle on a stick” approach is used to grow a single metal–organic framework (MOF; ZIF‐67) nanoparticle on a nanoelectrode surface which is pyrolyzed to generate a cobalt/nitrogen‐doped carbon (CoN/C) composite nanoparticle that exhibits very high catalytic activity towards the oxygen evolution reaction (OER) with a current density of up to 230 mA cm−2 at 1.77 V (vs. RHE), and a high turnover frequency (TOF) of 29.7 s−1 at 540 mV overpotential. Identical location transmission electron microscopy (IL‐TEM) analysis substantiates the “self‐sacrificial” template nature of the MOF, while post‐electrocatalysis studies reveal agglomeration of Co centers within the CoN/C composite during the OER. “Single‐entity” electrochemical analysis allows for deriving the intrinsic electrocatalytic activity and furnishes insight into the transient behavior of the electrocatalyst under reaction conditions.
Asymmetric Synthesis of Alkyl Fluorides: Hydrogenation of Fluorinated Olefins
Authors: Ponra Sudipta , Yang Jianping , Kerdphon Sutthichat , Andersson Pher G. 
Published: April 2019

AbstractThe development of new general methods for the synthesis of chiral fluorine‐containing molecules is important for several scientific disciplines. We herein disclose a straightforward method for the preparation of chiral organofluorine molecules that is based on the iridium‐catalyzed asymmetric hydrogenation of trisubstituted alkenyl fluorides. This catalytic asymmetric process enables the synthesis of chiral fluorine molecules with or without carbonyl substitution. Owing to the tunable steric and electronic properties of the azabicyclo thiazole‐phosphine iridium catalyst, this stereoselective reaction could be optimized and was found to be compatible with various aromatic, aliphatic, and heterocyclic systems with a variety of functional groups, providing the highly desirable products in excellent yields and enantioselectivities.
Organic Photodynamic Nanoinhibitor for Synergistic Cancer Therapy
Authors: Jiang Yuyan , Li Jingchao , Zeng Ziling , Xie Chen , Lyu Yan , Pu Kanyi 
Published: April 2019

AbstractDespite its great potential in cancer treatment, photodynamic therapy (PDT) often exacerbates hypoxia and subsequently compromises its therapeutic efficacy. To overcome this issue, an organic photodynamic nanoinhibitor (OPNi) has been synthesized that has the additional ability to counteract carbonic anhydrase IX (CA‐IX), a molecular target in the hypoxia‐mediated signalling cascade. OPNi is composed of a metabolizable semiconducting polymer as the photosensitizer and a CA‐IX antagonist conjugated amphiphilic polymer as the matrix. This molecular structure allows OPNi not only to selectively bind CA‐IX positive cancer cells to facilitate its tumor accumulation but also to regulate the CA‐IX‐related pathway. The integration of CA‐IX inhibition into the targeted PDT process eventually has a synergistic effect, leading to superior antitumor efficacy over that of PDT alone, as well as the reduced probability of hypoxia‐induced cancer metastasis. This study thus proposes a molecular strategy to devise simple yet amplified photosensitizers to conquer the pitfalls of traditional PDT.
Induced Fit of C2H2 in a Flexible MOF Through Cooperative Action of Open Metal Sites
Authors: Zeng Heng , Xie Mo , Huang Yong‐Liang , Zhao Yifang , Xie Xiao‐Jing , Bai Jian‐Ping , Wan Meng‐Yan , Krishna Rajamani , Lu Weigang , Li Dan 
Published: April 2019

AbstractPorous materials that can undergo pore‐structure adjustment to better accommodate specific molecules are ideal for separation and purification. Here, we report a stable microporous metal‐organic framework, JNU‐1, featuring one‐dimensional diamond‐shaped channels with a high density of open metal sites arranged on the surface for the cooperative binding of acetylene. Together with its framework flexibility and appropriate pore geometry, JNU‐1 exhibits an induced‐fit behavior for acetylene. The specific binding sites and continuous framework adaptation upon increased acetylene pressure are validated by molecular modeling and in situ X‐ray diffraction study. This unique induced‐fit behavior endows JNU‐1 with an unprecedented increase in the acetylene binding affinity (adsorption enthalpy: up to 47.6 kJ mol−1 at ca. 2.0 mmol g−1 loading).
The extinction risk of New Zealand chondrichthyans
Authors: Finucci Brittany , Duffy Clinton A.J. , Francis Malcolm P. , Gibson Claudine , Kyne Peter M. 
Published: April 2019

Abstract

The national extinction risk of 103 New Zealand chondrichthyans (sharks, rays, and chimaeras), ~10% of the global chondrichthyan fauna, was evaluated for the first time using the International Union for Conservation of Nature Red List of Threatened Species Categories and Criteria. Across 32 families, 103 species were assessed.
New Zealand holds a high degree of species endemism (20%) with deepwater species dominating the fauna (77%). Sharks were the most speciose group with 68 species (66%), followed by 24 rays (23%), and 11 chimaeras (10%).
Most species were assessed as Least Concern (60%, 62 species) or Data Deficient (32%, 33 species), with four (3.8%) species listed as Near Threatened and four (3.8%) in a threatened category (Vulnerable, Endangered, Critically Endangered). Threatened species are all oceanic pelagic, of which two are only visitors to New Zealand waters, and their status the result of broader regional declines.
These results are in stark contrast to other recent regional assessments in Europe and the Arabian Sea and adjacent areas, where up to half of species were listed in a threatened category. However, given New Zealand's extensive deepwater fishing effort and rapid collapses of deepwater chondrichthyan fisheries elsewhere, it is possible that New Zealand populations of many deepwater species are the remnants of previously reduced populations that are now at a low, yet stable level. Ongoing species‐level catch monitoring will be required to ensure these species do not become threatened.
Recommendations for future research and conservation efforts include resolving taxonomic uncertainties, understanding habitat use, and increasing regional collaborations to better understand the effects of fishing on wider‐ranging species.
Pedro Ramón y Cajal: The Legacy of a Neurohistologist, a Medical Doctor, and a Pathologist
Authors: Ramón y Cajal Santiago , de Carlos Juan A. 
Published: April 2019

ABSTRACTThe work of Santiago Ramón y Cajal is difficult to understand without knowing the personalities of Justo, his father, and his brother Pedro. His father practically forced the two brothers to study medicine. Thanks to that, Santiago was able to combine his artistic talent with histology and wonderfully describe cerebral architecture. Pedro was a faithful brother and above all a friend of Santiago, and they worked together for years. Pedro was able to demonstrate the theories of his brother in nonmammalian amniotes, concluding that the basic elements of the nervous system are common to these animals and he provided images that served Santiago to formulate the theory of dynamic polarization. Pedro, who decided to remain in the shadow of his brother, was a very complete doctor, pathologist and gynecologist, who made interesting contributions in all these fields and above all was a great humanist who left an important personal and scientific legacy. Anat Rec, 2019. © 2019 The Authors. The Anatomical Record published by Wiley Periodicals, Inc. on behalf of American Association of Anatomists. Anat Rec, 303:1189–1202, 2020. © 2019 The Authors. The Anatomical Record published by Wiley Periodicals, Inc. on behalf of American Association of Anatomists.
Identification of dehydroxy isoquine and isotebuquine as promising antileishmanial agents
Authors: Romero Angel H. , Rodríguez Noris , López Simón E. , Oviedo Henry 
Published: April 2019

AbstractTraditional antimalarial drugs based on 4‐aminoquinolines have exhibited good antiproliferative activities against Leishmania parasites; however, their clinical use is currently limited. To identify new 4‐aminoquinolines to combat American cutaneous leishmaniasis, we carried out a full in vitro evaluation of a series of dehydroxy isoquines and isotebuquines against two Leishmania parasites such as Leishmania braziliensis and Leishmania mexicana. First, the antiproliferative activity of the quinolines was studied against the promastigote forms of L. braziliensis and L. mexicana parasites, finding that five of them exhibited good antileishmanial responses with micromolar IC50 values ranging from 3.84 to 10 μM. A structure‐activity relationship analysis gave evidence that a piperidine or a morpholine attached as N‐alkyamino terminal substituent as well as the inclusion of an extra phenyl ring attached at the aniline ring of the isotebuquine core constitute important pharmacophores to generate the most active derivatives, with antileishmanial responses by far superior to those found for the reference drug, glucantime. All compounds showed a relatively low toxicity on human dermis fibroblasts, with CC50 ranging from 69 to >250 μM. The five most active compounds displayed moderate to good antileishmanial activity against the intracellular amastigote form of L. braziliensis, compared to the reference drug. In particular, compound 2j was identified as the most potent agent against antimony‐resistant amastigotes of L. braziliensis with acceptable biological response and selectivity, emerging as a promising candidate for further in vivo antileishmanial evaluation. Diverse mechanism‐of‐action studies and molecular docking simulations were performed for the most active 4‐aminoquinoline.
Recent Advances in the Z/E Isomers of Tetraphenylethene Derivatives: Stereoselective Synthesis, AIE Mechanism, Photophysical Properties, and Application as Chemical Probes
Authors: Xie Yujun , Li Zhen 
Published: April 2019

AbstractFocused research on the Z/E isomers of tetraphenylethene (TPE) derivatives is scarce in comparison with the thousands of luminogens with AIE properties (AIEgens) that have been synthesized based on the TPE moiety. The similar chemical and physical properties of the Z/E isomers make them difficult to separate by using conventional chromatographic techniques. However, they can be isolated by introducing polar groups and the pure isomers exhibit very different photophysical properties, mechanochromism, and host–guest coordination, as well as assisting in deciphering the AIE mechanism. In this Minireview, we present an overview of the disagreement regarding the AIE mechanism between the restriction of intramolecular vibration and photoinduced Z/E isomerization. Then, we discuss the development of (Z)‐/(E)‐TPE derivatives, their use in host–guest detection, and their mechanoluminescence properties, with a focus on their photophysical characteristics. Finally, we explore the stereoselective synthesis of pure (Z)‐/(E)‐TPE derivatives.
Robust H∞ control for a class of quasi‐linear uncertain stochastic time‐varying delayed systems
Authors: Zhang Tianliang , Sun Pengxiang , Deng Feiqi , Zhang Weihai 
Published: April 2019

AbstractThis paper studies the H∞ control for a class of quasi‐linear uncertain stochastic time‐varying delayed systems. Firstly, by using the linear matrix inequality (LMI) method, a sufficient condition is obtained for the robustly stochastic stability. Secondly, the robust H∞ state feedback controller is designed, such that the considered system is not only internally stochastically stabilizable but also satisfies the robust H∞ performance. The desired robust H∞ controller is obtained via solving some LMIs. Finally, one example is provided to demonstrate the effectiveness of the proposed method.
Impact of the relative dose intensity on survival of patients with high‐risk myelodysplastic syndromes treated with Azacitidine
Authors: Laribi Kamel , Bolle Delphine , Alani Mustafa , Ghnaya Habib , Besançon Anne , Farhi Jonathan , Mheidly Kayane , Denizon Nathalie , Baugier de Materre Alix 
Published: April 2019

AbstractWe performed a retrospective analysis of 93 myelodysplastic syndromes (MDS) patients with intermediate 2 or high‐risk IPSS score to study the impact of Azacitidine (AZA) relative dose intensity (RDI) <80% on the overall survival (OS). There were 51.6% of patients who had full dose and 48.4% had dose reduction or delayed with a RDI <80%. Nineteen patients (20.4%) had RDI <80% before getting objective response. Overall and progression‐free survivals (OS, PFS) probabilities for the whole population were 58% (95% CI: 48‐69) and 47% (95% CI: 38‐58) at 1 year; 35% (95% CI: 26‐47) and 31% (95% CI: 23‐43) at two years, respectively. When analyzing the outcomes according to the response to AZA, median OS was 32 months (range: 26‐55) for responders and 8 months (range: 7‐12) for nonresponders, with a respective 1‐year and 2‐year OS probabilities of 91% vs 28% and 66% vs 6%, respectively (P < 0.001). Interestingly, there was no impact of dose reduction on OS nor on PFS, however, when analyzing the timing of dose reduction as time‐dependent variable, we found that patients who had dose reduction before achieving the objective response, had significantly lower OS (P = 0.02) and PFS (P = 0.01) compared to patients who had dose reduction after achieving the objective response. In multivariate analysis, acute myeloid leukemia with 21%‐30% blasts in BM and poor and very poor karyotype significantly impacted OS, (HR = 2.09, 95% CI: 1.27‐3.44, P = 0.004, and HR = 2.73, 95% CI: 1.6‐4.6, P < 0.001 respectively), as well as PFS (HR = 1.84, 95% CI: 1.07‐3.17, P = 0.028, and HR = 3.03, 95% CI: 1.7‐5.39, P < 0.001, respectively).