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Τρίτη 17 Σεπτεμβρίου 2019


Efficiency of arthrocentesis treatment for different temporomandibular joint disorders
This study was performed to determine whether arthrocentesis therapy has different outcomes in three groups of patients with different temporomandibular disorders (TMDs). A clinical trial was conducted including 45 patients with 45 unilaterally affected joints divided into three groups (n=15): osteoarthritis (OA), disc displacement with reduction (DDWR), and disc displacement without reduction (DDWoR). All patients underwent the same arthrocentesis treatment protocol. The outcome variables, including...
Oral & Maxillofacial Surgery
Tue Sep 17, 2019 03:00
Closed Reduction of a Fractured and Dislocated Ankle
The New England Journal of Medicine: Search Results in Primary Care\Hospitalist\Clinical Practice
Thu Sep 12, 2019 03:00
Efficacy of secondary closure technique after extraction of third molars: a meta-analysis
The purpose of this study was to assess the influence of two suture methods on the postoperative complications of extraction of mandibular third molars (M3M). We searched the MEDLINE (PubMed), Cochrane Library, and Web of Science databases until 18 May 2018 for randomised controlled trials (RCT) that evaluated the influence of any suture techniques on postoperative complications after the removal of impacted M3M. Pain, facial swelling, and trismus were measured for both the early stage (2–3 days)...
Oral and Maxillofacial Surgery
Tue Sep 17, 2019 03:00
Intrathoracic bifurcation of the left common carotid artery associated with rib fusion and Klippel–Feil syndrome
Abstract Common carotid artery usually bifurcates at the superior border of thyroid cartilage, corresponding to the C3–4 junction, however bifurcation level may vary. Common carotid bifurcation may have rare variations like separate origins of left internal and external carotid arteries from aortic arch, or bifurcation of common carotid artery within thoracic cavity. Intrathoracic carotid bifurcation is a rare variation with limited number of cases reported. The occurrence of a...
Surgical and Radiologic Anatomy
Tue Sep 17, 2019 03:00
Intestinal duplication in the tongue: embryological and radiological point of view
Abstract Intestinal duplication in the tongue is a rare entity. Occurrence in the anterior part of the tongue is exceptional. We report an intestinal duplication in the tongue causing eating difficulties and discuss the accuracy of embryologic and histopathology knowledge as radiology. A transoral complete resection of the lesion was performed, without postoperative complications. There was no recurrence with a follow-up of 15 years.
Surgical and Radiologic Anatomy
Tue Sep 17, 2019 03:00
Branches of ulnar artery in human fetuses: anatomical and morphometric study
Abstract Purpose This study was conducted to demonstrate morphological pattern of the ulnar artery and to evaluate morphometrically its anatomical branching pattern in human fetuses. Methods Branching pattern of ulnar artery was evaluated on 121 upper limbs of dissected 63 of formalin-fixed fetus cadavers with gestational age ranging from 17 to 40 weeks....
Surgical and Radiologic Anatomy
Tue Sep 17, 2019 03:00
Non-specific Lipid Transfer Protein allergy in United Kingdom
Non-specific lipid transfer proteins (nsLTPs) are a group of highly conserved, low-molecular-weight proteins that are found throughout the plant kingdom 1. nsLTPs are believed to have an important role in plant defence 2 and are concentrated in the skin of many fruits including those belonging to the Rosaceae family 1,3, of which the peach and it’s nsLTP Pru p 3 is the most well characterised 1. nsLTP allergy is a common type of food allergy in the Mediterranean, but it is thought to be uncommon...
Annals of Allergy, Asthma & Immunology
Tue Sep 17, 2019 03:00
Eosinophilic Gastrointestinal Disorders: The Journey to Diagnosis Remains Arduous
While great strides have been made in diagnosing eosinophilic esophagitis (EoE) over the past decade, the journey to diagnosis of eosinophilic gastrointestinal disorders (EGIDs) below the esophagus remains arduous. EGIDs are named after the location of the gastrointestinal tract that is infiltrated by eosinophils. These include eosinophilic gastritis, enteritis, gastroenteritis and colitis. While the prevalence of EGIDs is currently reported to be around 2-5/100,000, it is possible that it is underestimated...
Annals of Allergy, Asthma & Immunology
Tue Sep 17, 2019 03:00
Topographic map refinement and synaptic strengthening of a sound localization circuit require spontaneous peripheral activity
Key points •Loss of the calcium sensor otoferlin disrupts neurotransmission from inner hair cells. Central auditory nuclei are functionally denervated in Otof KOs via gene ablation confined to the periphery. •We employed juvenile and young‐adult Otof KO mice (postnatal days (P)10‐12 and P27‐49) as a model for lacking spontaneous activity and deafness, respectively. We studied the impact of peripheral activity on synaptic refinement in the sound localization circuit from the medial nucleus of...
The Journal of Physiology
Mon Sep 16, 2019 20:44
Measuring blood flow through intrapulmonary and intracardiac shunts: a technical labyrinth
The Journal of Physiology
Tue Sep 17, 2019 11:35
Early sinusoidal heart rate patterns and heart rate variability to assess hypoxia‐ischaemia in near‐term fetal sheep
Key points Therapeutic hypothermia needs to be started as early as possible in the first 6 hours after acute hypoxic‐ischaemic (HI) injury, but the severity and timing of HI are often unclear. In this study we evaluated whether measures of heart rate variability (HRV) might provide early biomarkers of HI. The duration but not magnitude of suppression of HRV power and conversely, increased sample entropy of the heart rate were associated with severity of HI, such that changes in the first 3 hours...
The Journal of Physiology
Tue Sep 17, 2019 17:13
Sex differences in fatigability and recovery relative to the intensity‐duration relationship
Key points Females demonstrate greater fatigue‐resistance than males during contractions at intensities relative to maximum force. However, previous studies haven't accounted for the influence of metabolic thresholds on fatigability. This study is the first to test whether sex differences in fatigability exist when exercise intensity is normalised relative to a metabolic threshold: the critical intensity derived from assessment of the intensity‐duration relationship during intermittent, isometric...
The Journal of Physiology
Tue Sep 17, 2019 17:56
Fear, anxiety, and their disorders from the perspective of psychophysiology
Abstract Psychophysiology is a central hub connecting neurobiological and behavioral domains with clinical science, thus providing ideal tools for increasing the understanding of mental disorders beyond the level of symptom reports. The present article provides an overview of how psychophysiological research can contribute toward efforts directed at an improved understanding of anxiety disorders. Starting with the behavioral domain, it is demonstrated that defensive behaviors are fundamental to...
Psychophysiology
Mon Sep 16, 2019 19:03
For distinguished contributions to psychophysiology: Julian F. Thayer
Psychophysiology
Tue Sep 17, 2019 14:19
Gut microbiotas and immune checkpoint inhibitor therapy response: a causal or coincidental relationship?
Journal Name: Clinical Chemistry and Laboratory Medicine (CCLM)Issue: Ahead of print
Clinical Chemistry and Laboratory Medicine (CCLM)
01:06
Validation of a liquid chromatography tandem mass spectrometry (LC-MS/MS) method to detect cannabinoids in whole blood and breath
Journal Name: Clinical Chemistry and Laboratory Medicine (CCLM)Issue: Ahead of print
Clinical Chemistry and Laboratory Medicine (CCLM)
01:06
Spatially Resolved Genetic Analysis of Tissue Sections Enabled by Microscale Flow Confinement Retrieval and Isotachophoretic Purification
Spatial sequencing: A method for spatially resolved genetic analysis of FFPE cell block and tissue sections is presented. This involves local sampling with hydrodynamic flow confinement of a lysis buffer, electrokinetic purification of nucleic acids from the lysate, and detection of single point mutations through amplification and sequencing. Abstract We have developed a method for spatially resolved genetic analysis of formalin‐fixed paraffin‐embedded (FFPE) cell block and tissue sections....
Angewandte Chemie International Edition
Mon Sep 16, 2019 21:50
Indeno[1,2‐b]carbazole as Methoxy‐Free Donor Group: Constructing Efficient and Stable Hole‐Transporting Materials for Perovskite Solar Cells
Balancing act: The indeno[1,2‐b]carbazole donor not only combines the characteristics of carbazole and fluorene, but also exhibits excellent thermal stability and high hole mobility as a result of the bulky planar structure. Hole‐transporting materials based on this methoxy‐free donor demonstrate a high efficiency and stability simultaneously, providing a promising strategy for developing efficient and stable perovskite‐based solar cells. Abstract With perovskite‐based solar cells (PSCs) now...
Angewandte Chemie International Edition
Mon Sep 16, 2019 21:54
Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated via Alkaline‐earth Metal Substitution by Tin
The excellent birefringent materials are needed urgently, and scientists have been looking for outstanding birefringent units until now. Here, we reported a new compound, the first tin borate chloride, Sn 2 B 5 O 9 Cl (SBOC) with a brilliant birefringence (0.168@546 nm) measured by the polarizing microscope. And its birefringence is 16 times that of isostructural Ba 2 B 5 O 9 Cl (BBOC) compound (0.010@546 nm). The research results show that the birefringence enhancement originates mainly...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:41
15‐Hydroperoxy‐PGE2 – A Novel Intermediate in Mammalian and Algal Prostaglandin Biosynthesis
Oxidized metabolites of C20 fatty acids are potent lipid mediators contributing to the initiation and resolution of inflammation in mammals. One important class are the arachidonic acid‐derived prostaglandins (PGs) with PGE2 playing a central role in inflammation and numerous immunological reactions. The enzymes of PGE2 biosynthesis are important pharmacological targets for anti‐inflammatory drugs. Besides mammals, certain edible marine algae possess a comprehensive repertoire of bioactive arachidonic...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:41
A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N–N Bond Cleavage
A novel method of trimethylsilyl diazomethane N‒N bond cleavage is reported for the synthesis of terminal nitride complexes. Using the lithium salt of trimethylsilyl diazomethane, a rare terminal nitrilimine transition metal complex with partially occu­pied d ‐orbitals was obtained. This iron complex 2 was charac­teri­zed by CHN combustion analysis, 1 H and 13 C NMR spectroscopic analysis, single‐crystal X‐ray crystallo­graphy, SQUID magnetometry, 57 Fe Mößbauer spectroscopy, and computational...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:42
Metal‐Organic Frameworks Based Electrocatalysts for the Oxygen Reduction Reaction
In view of the clean and sustainable energy, metal‐organic frameworks (MOF) based materials, including pristine MOFs, MOF composites, and their derivatives are emerging as unique electrocatalysts toward oxygen reduction reaction (ORR). Thanks to their tunable compositions and diverse structures, efficient MOF‐based materials provide new opportunities to accelerate the sluggish ORR at the cathode in fuel cells and metal‐air batteries. This mini‐Review first provides some introduction of ORR and MOFs,...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:42
Loading dependent Structural Model of Polymeric Micelles Encapsulating Curcumin by Solid‐State NMR Spectroscopy
Detailed insight into the internal structure of drug loaded polymeric micelles is scarce, but important for developing optimized delivery systems. We observed that an increase in curcumin loading of triblock copolymers based on poly(2‐oxazolines) and poly(2‐oxazines) results in poorer dissolution properties. Using solid‐state NMR and complementary tools we can propose a loading dependent structural model on the molecular level providing an explanation for these pronounced differences. Changes in...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:43
Metal‐Chelated Polymer Nanodiscs for NMR Studies
Paramagnetic relaxation enhancement (PRE) is commonly used to speed up spin lattice relaxation time (T 1 ) for rapid data acquisition in NMR structural studies. Consequently, there is significant interest in novel paramagnetic labels for enhanced NMR studies on biomolecules. Herein, we report the synthesis and characterization of a modified poly(styrene‐co‐maleic acid) polymer which forms nanodiscs while showing the ability to chelate metal ions. Cu 2+ ‐chelated nanodiscs are demonstrated to...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:43
Lead‐Free Na‐In Double Perovskite Nanocrystals Through Doping Ag+ for Bright Yellow Emission
Lead‐free halide perovskite nanocrystals (NCs) have drawn wide attention for solving the problem of lead perovskites toxicity and instability. Here, we successfully synthesize the direct band gap double perovskites undoped and Ag‐doped Cs2NaInCl6 NCs by variable temperature hot injection. The Cs2NaInCl6 NCs have little photoluminescence due to dark self‐trapped excitons (STEs). Interestingly, the dark STEs can be converted to bright STEs by doping Ag+ to produce a bright yellow emission, with the...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:43
Stereoselective Csp3‐Csp2 Cross‐Couplings of Chiral Secondary Alkylzinc Reagents with Alkenyl and Aryl Halides
We report palladium‐catalyzed cross‐coupling reactions of chiral secondary non‐stabilized dialkylzinc reagents ‐ prepared from readily available chiral secondary alkyl iodides ‐ with alkenyl and aryl halides. This method provided α‐chiral alkenes and arenes with very high retention of configuration (dr up to 98:2) and satisfactory overall yields (up to 76% for 3 reaction steps). The configurational stability of these chiral non‐stabilized dialkylzinc reagents was determined and exceeded several hours...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:43
Metal‐free acceptorless decarbonylation of formic acid enabled by a liquid chemical looping strategy
The selective decarbonylation of formic acid was achieved under metal‐free conditions. Using a liquid chemical looping strategy, the thermodynamically favored dehydrogenation of formic acid was shutdown, yielding a pure stream of CO, with no H2 or CO2 contamination. The transformation involves a two‐step sequence where methanol is used as a recyclable looping agent to yield methylformate, which is subsequently decomposed to carbon monoxide using transition metal‐free alkoxides as catalysts.
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:44
Halogen Vacancies Enable Ligand‐Assisted Self‐assembly of Perovskite Quantum Dots into Nanowires
Interest has been growing in defects of halide perovskites in view of their intimate connection with key material optoelectronic properties. In perovskite quantum dots (PQDs), the influence of defects is even more apparent than in their bulk counterparts. By combining experiment and theory, we report herein a halide‐vacancy‐driven, ligand‐directed self‐assembly process of CsPbBr3 PQDs. With the assistance of oleic acid and didodecyldimethylammonium sulfide, surface‐Br‐vacancy‐rich CsPbBr3 PQDs self‐assemble...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:46
Rational Design of pH‐Responsive DNA Motifs with General Sequence Compatibility
Reconfigurable molecular events are key to molecular machines. In response to external cues, molecular machines rearrange/change their structures to perform certain functions. Such machines exist in nature, e.g. cell surface receptors, and have been artificially engineered. To be able to build sophisticated, efficient, molecular machines for increasing range of applications, constant efforts have been devoted to developing new mechanisms of controllable, structural reconfiguration. Herein, we report...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:52
Lithium Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries
A new synthetic strategy for the synthesis of a covalent triazine framework (CTF‐1) was introduced based on the cyclotrimerization reaction of 1,4‐dicyanobenzene using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) under ionothermal conditions. LiTFSI not only served as a catalyst, but also facilitated the in‐situ generation and homogeneous distribution of LiF particles across the framework. Upon integration of CTF‐LiF onto an airlaid‐paper (AP), the resulting hierarchical structure offered...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:52
Peptide‐based molecular strategies to interfere with protein misfolding, aggregation, and cell degeneration
Protein misfolding into amyloid fibrils is linked to more than 40 yet incurable cell‐ and neurodegenerative diseases such as Alzheimer’s disease (AD), Parkinson’s disease (PD), and type 2 diabetes (T2D). So far, however, only one of the numerous anti‐amyloid molecules comprising highly promising antibodies, small molecules and peptides has reached the patient. Here we review molecular strategies and peptide chemistry “tools” to design, develop, and discover peptide‐based molecules as anti‐amyloid...
Angewandte Chemie International Edition
Tue Sep 17, 2019 11:54
Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites
Ab‐initio molecular dynamics simulations and transmission infrared spectroscopy are employed to characterize the structure of water networks in defect‐functionalized microporous zeolites. Thermodynamically stable phases of clustered water molecules are localized at some of the defects in zeolite Beta, which include catalytic sites such as framework Lewis acidic Sn atoms in closed and hydrolyzed‐open forms, as well as silanol nests. These water clusters compete with ideal gas‐like structures at low...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:01
Stochastic DNA Walkers in Droplets for Super‐Multiplexed Bacterial Phenotype Detection
Pathogen detection is important in the global health arena because of the high morbidity and mortality associated with bacterial infections. In their Communication (DOI: https://doi.org/10.1002/anie.20190643810.1002/anie.201906438), H. Pei and co‐workers present an autonomous nano‐machine made of DNA molecules for the high‐throughput detection of multiple bacteria phenotypes in blood samples.
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:01
4.5 V High‐Voltage Rechargeable Batteries Enabled by the Reduction of Polarization on the Lithium Metal Anode
The interface plays a critical role in the electrochemical performance of batteries. In their Communication (DOI: https://doi.org/10.1002/anie.20190887410.1002/anie.201908874), J.‐Q. Huang and co‐workers describe the interfacial behavior of the quasi‐solid‐state electrolyte layer Li3OCl with a three‐electrode setup. The electrolyte interface can remarkably reduce the over‐potential of the lithium anode and inhibit solvent decomposition, significantly extending the service life of high‐voltage (4.5...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:02
Enzyme‐Mediated Endogenous and Bioorthogonal Control of a DNAzyme Fluorescent Sensor for Imaging Metal Ions in Living Cells
Bioorthogonal control of metal ion sensors for imaging metal ions in living cells is important for better understanding of the distribution and fluctuation of metal ions. While bioorthogonal control using external stimuli such as light has been reported, these stimuli are not suitable for investigating many biological systems where light penetration is limited or quantum yield of activation is low. To overcome this limitation, we herein report the endogenous and bioorthogonal activation of a DNAzyme...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:18
Global Aromaticity and Antiaromaticity in Porphyrin Nanoring Anions
Negative isn't always bad: Reduction of a porphyrin nanoring by the addition of 4 or 6 electrons was found to result in global (anti)aromaticity (see picture), as revealed by 1H NMR spectroscopy and DFT calculations. Thus, the Hückel rules apply to huge macrocyclic anions, and the charge in these anions is fully delocalized. Abstract Doping, through oxidation or reduction, is often used to modify the properties of π‐conjugated oligomers. In most cases, the resulting charge distribution is difficult...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:39
Günther Laukien Prize 2019 / Friedrich Wilhelm Bessel Research Award for Huib Ovaa
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:39
Liang‐Qiu Lu
“My first experiment was to prepare a new chiral bifunctional organocatalyst which was designed by myself. Chemistry is fun because whatever you find, you will benefit by gaining new knowledge …” Find out more about Liang‐Qiu Lu in his Author Profile.
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:39
Phage Display: Simple Evolution in a Petri Dish (Nobel Lecture)
Playing with evolution: In his Nobel lecture, George P. Smith reconstructs the story of the phage‐display idea as he personally experienced it. The development of this technique is a case study in how a scientific advance emerges gradually in incremental steps within overlapping global scientific communities.
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:40

Harnessing Evolution to Make Medicines (Nobel Lecture)
Antibody libraries and phage display have provided the key elements for the creation of a fast evolutionary system for the generation of fully human antibody medicines. Important steps leading to this development are outlined by G. Winter in his Nobel lecture.
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:40
Observation and Kinetic Characterization of Transient Schiff Base Intermediates by CEST NMR Spectroscopy
Modified CEST NMR methodology allowed the detection of highly transient, very low populated Schiff base intermediates, not observable by conventional NMR, but key to product formation. Abstract In aqueous solution, many biochemical reaction pathways involve reaction of an aldehyde with an amine, which progresses through generally unstable, hydrated and dehydrated, Schiff base intermediates that often are unobservable by conventional NMR. There are 4 states in the relevant equilibrium: 1) gem‐diol,...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:40
Donor–Acceptor Nanocarbon Ensembles to Boost Metal‐Free All‐pH Hydrogen Evolution Catalysis by Combined Surface and Dual Electronic Modulation
An efficient and robust metal‐free all‐pH catalyst for hydrogen evolution reactions is realized by coupling inactive MOF‐derived N‐rich carbon (MHCF) with pure carbon nanotubes to induce combined intra‐/intermolecular electron transfer in the MHCF, followed by rational surface modulation of carboxyl‐group‐rich polymers to afford proton enrichment at pH 0 and enhanced water adsorption and activation at pH 7 and 14. Abstract A combined surface and dual electronic modulation strategy is used to...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:41
Molybdenum Alkylidyne Complexes with Tripodal Silanolate Ligands: The Next Generation of Alkyne Metathesis Catalysts
The canopy: Molybdenum alkylidyne complexes with triarylsilanolate ligands are privileged catalysts for alkyne metathesis, but tethering of the silyl groups seems to make things even better. Crystallographic data and a rare case study based on 95Mo NMR spectroscopy provide insights into why that is so. Abstract A new type of molybdenum alkylidyne catalysts for alkyne metathesis is described, which is distinguished by an unconventional podand topology. These structurally well‐defined complexes...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:41
Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks
Selective catalytic hydrogenation of propylene to propane at room temperature occurs in the gas phase at the metal nodes of a crystalline CuRh bimetallic metal–organic framework. The RhII ions are identified as the catalytically active sites. Abstract We report the first study of a gas‐phase reaction catalyzed by highly dispersed sites at the metal nodes of a crystalline metal–organic framework (MOF). Specifically, CuRhBTC (BTC3−=benzenetricarboxylate) exhibited hydrogenation activity, while...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:42
Development of Zinc‐Specific iCEST MRI as an Imaging Biomarker for Prostate Cancer
CEST for life: Normal prostate tissue has the highest zinc content in the body. Using TF‐BAPTA as a zinc‐specific iCEST MRI sensor for zinc depletion, a novel imaging biomarker has been developed that may find applications in the early detection of prostate cancer. Abstract The healthy prostate contains the highest concentration of mobile zinc in the body. As this level decreases dramatically during the initial development of prostate cancer, in vivo detection of prostate zinc content may be...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:42
Exploring Lead‐Free Hybrid Double Perovskite Crystals of (BA)2CsAgBiBr7 with Large Mobility‐Lifetime Product toward X‐Ray Detection
Finding X‐rays: Single crystals of a lead‐free hybrid double perovskite, (BA)2CsAgBiBr7 (BA+: n‐Butylammonium), adopting a unique 2D multilayered quantum‐confined motif, can serve as a potential X‐ray detecting material. This promise stems from the large μτ product of 1.21×10−3 cm2 V−1, high bulk resistivity, low trap density, and efficient X‐ray attenuation. Abstract Halide double perovskites have recently bloomed as the green candidates for optoelectronic applications, such as X‐ray detection....
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:42
Reprocessable thermoset soft actuators
To construct 3D soft actuators, the widely‐used traditional thermosets are good candidate due to their excellent stability, while it is generally acknowledged that they cannot be reprocessed. Here we show that the time‐temperature equivalence principle enables the reprocessing of traditional liquid crystalline epoxy thermosets (LCETs) into 3D soft actuators. Even though the transesterification reaction of LCETs is extremely slow, it is enough to induce a topology rearrangement and subsequent reprocessing...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:52
Uncovering the Neglected Similarities of Arynes and Donor‐Acceptor Cyclopropanes
Arynes and donor‐acceptor (D‐A) cyclopropanes are two classes of strained systems having the potential for numerous applications in organic synthesis. The last two decades have witnessed a renaissance of interest in the chemistry of these species primarily because of the mild and robust methods for their generation or activation. Commonly, arynes as easily polarizable systems result in 1,2‐disubstitution whereas D‐A cyclopropanes as polarized systems lead to 1,3‐bisfunctionalization thereby showing...
Angewandte Chemie International Edition
Tue Sep 17, 2019 12:52
Carboamination of Unactivated Alkenes via Three‐Component Radical Conjugate Addition
Two‐component Giese type radical additions are highly practical and established reactions. Herein, three‐component radical conjugate additions of unactivated alkenes to Michael acceptors are reported. Amidyl radicals, oxidatively generated from α‐amido oxy acids using redox catalysis, act as the third reaction component which add to the unactivated alkenes. The adduct radicals engage in Giese type additions to Michael acceptors to provide after reduction the three‐component products in an overall...
Angewandte Chemie International Edition
Tue Sep 17, 2019 13:24
6‐Methylenebicyclo[3.2.1]oct‐1‐en‐3‐one: Twisted Olefin as Diels–Alder Dienophile for Expedited Syntheses of Four Kaurane Diterpenoids
With a twist: 6‐Methylenebicyclo[3.2.1]oct‐1‐en‐3‐one, a twisted and highly reactive enone, was prepared for the first time by elimination of its bromide precursor. Its reactions as a dienophile with several dienes in Diels–Alder reactions proceeded smoothly to provide tricyclic and tetracyclic adducts, which allowed short syntheses (10–11 steps) of four kurane diterpenoids including 11β‐hydroxy‐16‐kaurene, 11α‐hydroxy‐16‐kaurene, liangshanin G, and gesneroidin B. Abstract 6‐Methylenebicyclo[3.2.1]oct‐1‐en‐3‐one,...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:17
Crystallographic Charge Density Study of the Partial Covalent Nature of Strong N⋅⋅⋅Br Halogen Bonds
Crystallographic charge density analysis of a strong N−Br⋅⋅⋅N halogen bond in a N‐bromosuccinimide and 3,5‐dimethylpyridine co‐crystal (NBS‐lut) reveals a partially covalent character. Comparisons with pure crystalline NBS and the covalent bond in a bis(3‐methylpyridine)bromonium cation suggest that there is a continuum of interactions between the intermolecular “non‐bonding” halogen bond and a three centre–two electron covalent bond. Abstract The covalent nature of strong N−Br⋅⋅⋅N halogen...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:18
Electrochemical Arylation of Electron‐Deficient Arenes through Reductive Activation
An electrochemical method was developed for arylation of electron‐deficient arenes through reductive activation. Various electron‐deficient arenes and aryldiazonium tetrafluoroborates were examined for the transformation within an undivided cell, furnishing the desired products with up to 92 % yield. Reduction of quinoxaline is a key step in the transformation. Abstract An electrochemical method has been developed to achieve arylation of electron‐deficient arenes through reductive activation....
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:18
Metastable Self‐Assembly of Theta‐Shaped Colloids and Twinning of Their Crystal Phases
Crystal clear: Metastable prone crystals and stable standing crystals form by self‐assembly of theta‐shaped colloids as a consequence of different self‐assembly paths. Twinning of the metastable crystals and two twinning mirror axes were found. A variety of complex twin crystals are formed by one or a combination of these two mirror axes. Abstract Anisotropic colloids self‐assemble into different crystal structures compared to spherical colloids. Exploring and understanding their self‐assembly...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:19
Stereoselective Synthesis of Trisubstituted Vinylboronates from Ketone Enolates Triggered by 1,3‐Metalate Rearrangement of Lithium Enolates
One to three: An unprecedented stereoselective synthesis of trisubstituted vinylboronates from the transition‐metal‐free borylation of lithium ketone enolates was developed. Carbonyl‐induced 1,3‐metalate rearrangement through a C‐bound boron enolate leads to the stereospecific C−O borylation of lithium enolates. A variety of stereospecific tri‐ and tetrasubstituted vinylboronates were easily obtained. Abstract An unprecedented stereoselective synthesis of trisubstituted vinylboronates is reported...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:19
Modification of Enzyme Activity by Vibrational Strong Coupling of Water
Quantum light‐matter strong coupling is currently emerging as non‐invasive method to alter chemical reactivity. Enzymatic activity can be modified by strongly coupling the vibrational stretching transitions of water. The activity of pepsin decreased 4.5‐fold when coupling the OH stretching vibration but remained unaltered when coupling the bending vibration. Abstract Vibrational strong coupling (VSC) has recently emerged as a completely new tool for influencing chemical reactivity. It harnesses...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:20
Scalable Rhodium(III)‐Catalyzed Aryl C−H Phosphorylation Enabled by Anodic Oxidation Induced Reductive Elimination
Electric cell: Reported herein is an electrochemically driven RhIII‐catalyzed aryl C−H phosphorylation reaction which proceeds through H2 evolution. The method is compatible with a variety of aryl C−H and P−H coupling partners and particularly useful for synthesizing triarylphosphine oxides from diarylphosphine oxides. Experimental results suggest that the mechanism responsible for the C−P bond formation involves an oxidation‐induced reductive elimination process. DG=directing group. Abstract...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:20
The Supramolecular Chemistry of Strained Carbon Nanohoops
Curvy rings: Recent progress in strained nanohoops as well as their host–guest chemistry, mechanical interlocking, and self‐assembly is summarized in this Minireview. Abstract Since 1996, a growing number of strained macrocycles, comprising only sp2‐ or sp‐hybridized carbon atoms within the ring, have become synthetically accessible, with the [n]cycloparaphenyleneacetylenes (CPPAs) and the [n]cycloparaphenylenes (CPPs) being the most prominent examples. Now that robust and relatively general...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:22
Bifunctional Metal Nanocrystals for Catalyzing and Reporting on Chemical Reactions
Bifunctional nanocrystals with integrated plasmonic and catalytic activities hold great promise for analyzing chemical reactions byin situsurface‐enhanced Raman spectroscopy. This review starts with a brief introduction to the general strategies for designing such nanocrystals, followed by the presentation of four typical examples, including their fabrication, characterization, and potential limitation. We then use the reduction of 4‐nitrothiophenol and oxidation of 4‐aminothiophenol as two model...
Angewandte Chemie International Edition
Tue Sep 17, 2019 17:45
Mechanoluminescence or Room Temperature Phosphorescence: Molecular Packing‐Dependent Emission Response
Mechanoluminescence (ML) and room‐temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivate with ortho‐substitution, respectively. This molecular packing‐dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing‐functions relationship. With the incorporation of solid state 13C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing...
Angewandte Chemie International Edition
Tue Sep 17, 2019 18:25

Synthesis of Head Group Labeled Gb3 Glycosphingolipids and Their Distribution in Phase‐Separated Giant Unilamellar Vesicles
The receptor lipid Gb3 is responsible for the specific internalization of Shiga toxin (STx) into cells. While the head group of Gb3 defines the specificity of STx binding, the ceramide backbone harboring different fatty acids is expected to influence its localization in membranes, which impacts membrane organization and protein internalization. To investigate the influence of the fatty acid of Gb3 on its distribution in membranes, a synthetic route towards a set of fluorescently labeled Gb3 glycosphingolipids...
Angewandte Chemie International Edition
Tue Sep 17, 2019 18:26
Photochemical C‐H Hydroxyalkylation of Quinolines and Isoquinolines
We report herein a visible light‐mediated C‐H hydroxyalkylation of quinolines and isoquinolines that proceeds via a radical path. The process exploits the excited‐state reactivity of 4‐acyl‐1,4‐dihydropyridines, which can readily generate acyl radicals upon blue light absorption. By avoiding the need for external oxidants, this radical‐generating strategy enables a departure from the classical, oxidative Minisci‐type pattern and unlocks a unique reactivity, leading to hydroxyalkylated heteroarenes....
Angewandte Chemie International Edition
Tue Sep 17, 2019 19:53
Tungsten‐Doped L10‐PtCo Ultrasmall Nanoparticles as a High‐Performance Fuel Cell Cathode
Transition‐metal‐doped 3 nm L10‐M‐PtCo nanoparticles (NPs) were synthesized using a core–shell Pt/CoOx precursor. The developed L10‐W‐PtCo NPs not only show enhanced ORR activity and stability at half‐cell test, but also demonstrate promising performance in a fuel‐cell test, with mass activity of 0.57 A mgPt−1 and negligible activity loss after 50 000 potential cycles. Abstract The commercialization of proton exchange membrane fuel cells (PEMFCs) relies on highly active and stable electrocatalysts...
Angewandte Chemie International Edition
Tue Sep 17, 2019 22:00

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