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Πέμπτη 14 Μαΐου 2020


Performing Fuzzy DNA Strand Displacement Using Polymerases
Toehold‐mediated DNA strand displacement offers DNA nanostructures with dynamic response capability. However, the sequence designing complexity dramatically increases as the scale of networks becomes large. We attribute this problem to toehold‐mediated strand displacement is an Exact Strand Displacement (ESD), where one invader strand corresponds to one specific substrate. In this work, we propose the Fuzzy Strand Displacement (FSD), where one‐to‐many and many‐to‐one relationships are established...
Angewandte Chemie International Edition
Tue May 12, 2020 19:46
One‐Pot Domino Carbonylation Protocol for Aromatic Diimides toward n‐type Organic Semiconductors
Aromatic diimides are one of the most important chromophores in the construction of n‐type organic semiconductors, which lag far behind p‐type counterpart but is necessary for the ambipolar transistors, p–n junctions and organic complementary circuits. Herein, we establish a facile one‐pot domino synthetic protocol for aromatic diimides via palladium‐catalyzed carbonylation of tetrabromo aromatic precursors. Taking tetrabromocorannulene (TBrCor) and tetrabromo‐2,7‐di‐tert‐butylpyrene (TBrPy) as the...
Angewandte Chemie International Edition
Tue May 12, 2020 17:44
Azaruthena(II)‐bicyclo[3.2.0]heptadiene: Key Intermediate for Ruthenaelectro(II/III/I)‐catalyzed Alkyne Annulations
New mechanism: A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes delivers bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective C−H/N−H annulation without metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were identified as key intermediates. Mechanistic studies suggest an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime. Abstract A ruthenium‐catalyzed electrochemical dehydrogenative...
Angewandte Chemie International Edition
Tue May 12, 2020 17:34
Achieve Superior Electrocatalytic Performance by Surface Copper Vacancy Defects during Electrochemical Etching Process
Vacancy defect‐rich Pt‐Cu nanowire networks (VCu‐PtCu) exhibit superior electrocatalytic performance for the oxygen reduction reaction, in which the mass activity is 14.1 times higher than for commercial Pt/C (20 %.wt, JM), and is currently the best performance among unsupported Pt‐based nanomaterials. The Tafel plot shows that VCu‐PtCu delivers a mass activity (MA) 7.2 times higher than the 2020 target set by the US Department of Energy (DOE). Abstract Vacancy defects of catalysts have been...
Angewandte Chemie International Edition
Tue May 12, 2020 17:15
Equipping Natural Killer Cells with Specific Targeting and Checkpoint Blocking Aptamers for Enhanced Adoptive Immunotherapy in Solid Tumors
SUPER NK cells target cancer: An aptamer‐equipping strategy to generate specific, universal and permeable (SUPER) NK cells was reported for enhanced immunotherapy in solid tumors. SUPER NK cells were equipped with HepG2‐targeting and PDL1‐specific aptamers without genetic alteration, leading to effective homing to tumor sites, adaptation to the tumor microenvironment, and enhanced cytotoxicity. Abstract Herein, we propose an aptamer‐equipping strategy to generate specific, universal and permeable...
Angewandte Chemie International Edition
Tue May 12, 2020 17:14
Building an Air Stable and Lithium Deposition Regulable Garnet Interface from Moderate‐Temperature Conversion Chemistry
The detrimental contaminants on a garnet surface are converted into an air‐stable fluorinated interface by a facile chemical approach at moderate temperature (<180 °C). The modified interface shows a high electron tunneling barrier and a low energy barrier for Li+ surface diffusion, enabling a high critical current density of 1.4 mA cm−2. Abstract Garnet‐type electrolytes suffer from unstable chemistry against air exposure, which generates contaminants on electrolyte surface and accounts...
Angewandte Chemie International Edition
Tue May 12, 2020 17:14
A Chemically Soldered Polyoxometalate Single‐Molecule Transistor
Transistor al POModoro: An Anderson–Evans polyoxometalate functionalised with 4‐pyridyl termini has been used to fabricate single‐entity junctions in an electrochemical environment. As the charge state of the polyoxomolybdate is changed by the electrochemical potential, the fabricated devices show a tunnelling transistor behaviour, with OFF‐ON‐OFF conductance gating by more than one order of magnitude. Abstract Polyoxometalates have been proposed in the literature as nanoelectronic components,...
Angewandte Chemie International Edition
Tue May 12, 2020 17:14
Atomically Dispersed Nickel(I) on an Alloy‐Encapsulated Nitrogen‐Doped Carbon Nanotube Array for High‐Performance Electrochemical CO2 Reduction Reaction
If I had a nickel: An efficient NiI single‐atom electrode for the electrochemical CO2 reduction reaction is realized by combining the advantages of a single‐atom catalyst and a self‐standing nanoarray architecture. Abstract Single‐atom catalysts (SACs) show great promise for electrochemical CO2 reduction reaction (CRR), but the low density of active sites and the poor electrical conduction and mass transport of the single‐atom electrode greatly limit their performance. Herein, we prepared a...
Angewandte Chemie International Edition
Tue May 12, 2020 17:14
Chalcogen Bond Mediated Enhancement of Cooperative Ion‐Pair Recognition
Halogen bond and chalcogen bond ion‐pair heteroditopic receptors exhibit remarkable cooperative recognition of halide anions via sodium cation–benzo‐crown ether binding. The chalcogen bonding receptor displays the largest enhancement of halide binding strength of over two hundred‐fold. DFT calculations suggest sodium cation crown ether complexation induces a polarisation of the ChB and XB donor atoms as the source of cooperativity. Abstract A series of heteroditopic receptors containing halogen...
Angewandte Chemie International Edition
Tue May 12, 2020 17:13
Formation of Hierarchical FeCoS2–CoS2 Double‐Shelled Nanotubes with Enhanced Performance for Photocatalytic Reduction of CO2
The unique structure of hierarchical FeCoS2–CoS2 double‐shelled nanotubes constructed by ultrathin nanosheets can sufficiently inhibit recombination of electrons and holes by shortening diffusion length, exploit incident visible light by enhancing scattering in the cavity, and expose abundant active sites for redox reactions. Benefiting from these advantages, the obtained FeCoS2–CoS2 hybrid exhibits outstanding performance for CO2‐to‐CO conversion powered by solar light. Abstract Hierarchical...
Angewandte Chemie International Edition
Tue May 12, 2020 17:13
Optimal Configuration of N‐Doped Carbon Defects in 2D Turbostratic Carbon Nanomesh for Advanced Oxygen Reduction Electrocatalysis
Defects on purpose: A two‐dimensional porous turbostratic carbon nanomesh with abundant carbon defects coupled with N doping sites was developed by a novel molecular design strategy. This material displays exceptional oxygen reduction reaction electrocatalytic activity, which is attributed to the formation of highly exposed carbon edge defects doped with graphitic valley N atoms. Abstract The charge redistribution strategy driven by heteroatom doping or defect engineering has been developed...
Angewandte Chemie International Edition
Tue May 12, 2020 17:13
Key Intermediate Species Reveal the Copper(II)‐Exchange Pathway in Biorelevant ATCUN/NTS Complexes
ATCUN/NTS motifs participate in physiological CuII exchange. Using kinetic methods, spectroscopy, and electrochemistry, it was demonstrated that CuII binding to GGH, an ATCUN/NTS representative, proceeds via partially coordinated species. The 2N‐coordinated complex with t 1/2≈100 ms (pH 6.0) and CuII/CuI redox activity is the long‐sought reactive intermediate for extracellular copper delivery. Abstract The amino‐terminal copper and nickel/N‐terminal site (ATCUN/NTS) present in proteins and...
Angewandte Chemie International Edition
Tue May 12, 2020 17:12
Constructing Adaptive Photosensitizers via Supramolecular Modification Based on Pillararene Host–Guest Interactions
A supramolecular switch based on a host–guest complex containing a water‐soluble pillar[5]arene and an AIEgen photosensitizer was fabricated. Fluorescence and ROS generation of this switch can be switched on at pH 5.0. This work offers a new paradigm for the construction of adaptive photosensitizers based on supramolecular chemistry. Abstract In order to promote the development of photodynamic therapy (PDT), undesired side effects like low tumor specificity and the “always‐on” phenomenon should...
Angewandte Chemie International Edition
Tue May 12, 2020 17:11
Photon Equivalents as a Parameter for Scaling Photoredox Reactions in Flow: Translation of Photocatalytic C−N Cross‐Coupling from Lab Scale to Multikilogram Scale
Size matters: A predictive scaling parameter for photochemical reactions, absorbed photon equivalents, was established by a study of how a photoredox cross‐coupling reaction performed across multiple reactor sizes and types. The parameter could be employed in the successful scale‐up of this model reaction from the milligram scale in batch to the multi‐kilogram scale in flow. Abstract With the development of new photocatalytic methods over recent decades, the translation of these chemical reactions...
Angewandte Chemie International Edition
Tue May 12, 2020 17:05
A Predictive Model Towards Site‐Selective Metalations of Functionalized Heterocycles, Arenes, Olefins and Alkanes using TMPZnCl·LiCl
The development of a predictive model towards site‐selective deprotometalation reactions using TMPZnCl·LiCl is reported (TMP = 2,2,6,6‐tetramethylpiperidinyl). The p K a values of functionalized N ‐, S ‐, and O ‐heterocycles, arenes, alkenes or alkanes were calculated and compared to the experimental deprotonation sites. Large overlap (>80%) between the calculated and empirical deprotonation sites was observed, showing that thermodynamic factors strongly govern the metalation regioselectivity....
Angewandte Chemie International Edition
Tue May 12, 2020 16:56
Stabilization of highly efficient and stable phase‐pure FAPbI3 Perovskite Solar Cells by Molecularly Tailored 2D‐Overlayers
Due to their attractive optoelectronic properties, metal halide APbI3 perovskites employing formamidinum (FA+) as A cation are presently the focus of intense research, The superior chemical and thermal stability of FA+ cations renders α‐FAPbI3 more suitable for solar cell applications than methylammonium lead iodide (MAPbI3). However, its spontaneous conversion to the yellow non‐perovskite phase (δ‐FAPbI3) under ambient conditions poses a serious challenge for practical applications. Here, we report...
Angewandte Chemie International Edition
Tue May 12, 2020 16:55
Three‐dimensional Porous Organic Semiconductor Based on Fully sp2‐Hybridized Graphitic Polymer
Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three‐dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three‐dimensional organic polymers is challenging. Here, we report the synthesis of a  three‐dimensional  π ‐conjugated porous organic polymer (3D p‐POP) using catalyst‐free Diels−Alder cycloaddition polymerization  followed by acid‐promoted aromatization.  With a...
Angewandte Chemie International Edition
Tue May 12, 2020 16:55
Emerging concepts of nanobiotechnology in mRNA delivery
Introducing mRNA into cells has attracted intense interest for diverse applications, however success requires delivery solutions. Engineered nanomaterials have been applied as mRNA nanocarriers; their functions are designed mainly as delivery vehicles, but rarely in regulation of the protein translation. Recently, progress in nanobiotechnology has shifted the design principle of mRNA nanocarriers from simple delivery tools to translation modulators. Here, we review the emerging concepts of nanomaterials...
Angewandte Chemie International Edition
Tue May 12, 2020 16:53
Dual‐Functionalized Crescent Microgels for Selectively Capturing and Killing Cancer Cells
In cancer therapy, the selective targeting of cancer cells while avoiding side effects to normal cells is still full of challenges. Here, we developed dual‐functionalized crescent microgels, which selectively captured and killed lung cancer cells in situ without killing other cells. Crescent microgels with the inner surface of the cavity functionalized with antibody and containing glucose oxidase (GOX) in the gel matrix have been produced in a microfluidic device. These microgels presented high affinity...
Angewandte Chemie International Edition
Tue May 12, 2020 14:51
Ag2Au50(PET)36 Nanocluster: Dimeric Assembly of Au25(PET)18 Enabled by Silver Atoms
Assembly of atomically precise metal nanoclusters is now in the research spotlight, which offers exciting opportunities to gain fundamental insights into the hierarchical assembly of nanoparticles. However, it is still extremely challenging for controllable assembly of individual nanoclusters at a molecular‐ or atomic‐level. Herein we report the dimeric assembly of Au25(PET)18 (PET = 2‐phenylethanethiol), where two Au25(PET)18 monomers are bridged together by two Ag atoms to form the Ag2Au50(PET)36...
Angewandte Chemie International Edition
Tue May 12, 2020 14:50
DNA‐Edited Ligand Positioning on Red Blood Cells to Enable Optimized T Cell Activation for Adoptive Immunotherapy
Artificial antigen presenting cells (APCs) with surface‐anchored T cell activating ligands hold great potential in adoptive immunotherapy. However, it remains challenging to precisely control the ligand positioning on those platforms via conventional bioconjugation chemistry. Here, utilizing DNA‐assisted bottom‐up self‐assembly, we are able to precisely control both lateral and vertical distribution of T cell activation ligands on red blood cells (RBCs). It is found that the clustered lateral positioning...
Angewandte Chemie International Edition
Tue May 12, 2020 12:43
Localisation analysis of nerves in the mouse pancreas reveals the sites of highest nerve density and nociceptive innervation
Pancreatic cancer and chronic pancreatitis are characterized by a prominent pancreatic neuropathy and neuropathic pain. Mice are increasingly used for modelling neural alterations of pancreatic diseases; however, the numerous differences regarding the normal neuro‐anatomy and innervation between the mouse and human pancreas have so far been completely neglected. In the present study, we addressed this gap by introducing a standardized tissue harvesting and paraffin‐embedding technique that preserves...
The European Gastrointestinal Motility Society
Wed May 13, 2020 15:25
The clinical and economical impact of postoperative ileus in patients undergoing colorectal surgery
Analysis showing perioperative circulating CRP levels in patients with only postoperative ileus (POI) (n=38) against patients without complications (n=144) and in the total study population of patients with (n=66) and without (POI) (n=199), with other complications included, demonstrating the large contribution of POI in postoperative inflammation. Abstract Background Colorectal surgery is associated with postoperative ileus (POI). Despite its widespread manifestation, the influence of POI on...
The European Gastrointestinal Motility Society
Wed May 13, 2020 13:31
Anxiety‐related factors associated with symptom severity in irritable bowel syndrome
Gastrointestinal symptom‐specific anxiety may not be a key driver of symptom severity in irritable bowel syndrome (IBS). The visceral sensitivity index factors most overtly associated with fear and anxiety are not associated with IBS symptom severity on regression analysis. Abstract Background Gastrointestinal symptom‐specific anxiety and somatization have both been associated with higher symptom severity in patients with irritable bowel syndrome (IBS); however, this relationship has not been...
The European Gastrointestinal Motility Society
Tue May 12, 2020 16:32
Expanding criteria for slow colonic transit in patients being evaluated for chronic constipation by scintigraphy
Measurement of colonic transit by scintigraphy (upper left) identifies patients with slow transit at 24 and 48 hours, summarized as geometric center (lower left) (data points below dashed line in lower right), and also patients with slow progression of isotope through the colon (upper right) as shown by the low ΔGC48‐24h (lower right). Abstract Background Colonic transit measurement [geometric center (GC) at 24 and 48 hours] identifies slow transit constipation (STC) in patients with chronic...
The European Gastrointestinal Motility Society
Tue May 12, 2020 11:59
Mucocutaneous Manifestations of Scurvy
Figure 1.
The New England Journal of Medicine: Search Results in Dermatology
03:00
Prediagnostic Concentrations of Circulating Bile Acids and Hepatocellular Carcinoma Risk: REVEAL‐HBV and HCV Studies
Abstract Hepatocellular carcinoma (HCC) is the dominant histologic type of liver cancer, accounting for 75% of cases. Growing evidence suggests that the cross‐talk between the gut microbiome and metabolome (i.e., gut‐liver axis) are related to the development of hepatic inflammation, and ultimately, HCC. Bile acids are metabolites, derived from cholesterol and synthesized in the liver, which may have a critical role in regulation of the gut‐liver axis. We investigated whether prediagnostic circulating...
International Journal of Cancer
Wed May 13, 2020 20:20
The role of CDK6 in cancer
Abstract The regulation and function of cyclin dependent kinase 6 (CDK6)‐ and cyclin dependent kinase 4 (CDK4)‐cyclin complexes are commonly altered with enhanced kinase activity found in hematopoietic malignancies, breast cancer and melanoma making CDK4 and CDK6 attractive targets for therapeutic interference. Although dual CDK4/6 inhibitors have revolutionized treatment of breast cancer patients and reveal promising results in several solid tumors and hematological malignancies, there is a need...
International Journal of Cancer
Wed May 13, 2020 18:59
Molecular profiling of Chinese R‐CHOP treated DLBCL patients: identifying a high‐risk subgroup
Abstract Diffuse large B‐cell lymphoma (DLBCL) is a clinically aggressive and heterogenous disease. Although most patients can be cured by immunochemotherapy, 30‐40% patient will ultimately develop relapsed or refractory disease. Here, we investigated the molecular landscapes of patients with diverse responses to R‐CHOP. We performed capture‐based targeted sequencing on baseline samples of 105 DLBCL patients using a panel consisting of 112 lymphoma‐related genes. Subsequently, 81 treatment‐naïve...
International Journal of Cancer
Wed May 13, 2020 11:48
Association between inflammatory bowel disease and prostate cancer: A large‐scale, prospective, population‐based study
Abstract Inflammatory bowel disease (IBD) is an established risk factor for colorectal cancer. Recent reports suggesting IBD is also a risk factor for prostate cancer (PC) require further investigation. We studied 218,084 men in the population‐based UK Biobank cohort, aged 40‐69 at study entry between 2006 and 2010, with follow‐up through mid‐2015. We assessed the association between IBD and subsequent PC using multivariable Cox regression analyses, adjusting for age at assessment, ethnic group,...
International Journal of Cancer
Wed May 13, 2020 11:24
Erratum
International Journal of Cancer
Tue May 12, 2020 14:13
The State of Cannabis Research Legislation in 2020
As growing numbers of Americans use federally unregulated cannabis products and develop complications — such as psychosis, cannabis use disorder, and electronic-cigarette, or vaping, product use–associated lung injury (EVALI) — the need to facilitate research on the products that our patients…
The New England Journal of Medicine: Search Results in Health Policy and Reform
03:00
Inequity in Crisis Standards of Care
In Racism without Racists, Eduardo Bonilla-Silva articulates why "color blindness," an ethos based on the belief that race is no longer relevant, is contradictory and harmful. Color-blind policies, such as race-neutral mortgage practices and Medicare and Medicaid rules, have resulted in…
The New England Journal of Medicine: Search Results in Health Policy and Reform
Wed May 13, 2020 03:00
Preventing a Parallel Pandemic — A National Strategy to Protect Clinicians’ Well-Being
The Covid-19 pandemic, which had killed more than 60,000 Americans by May 1, has been compared with Pearl Harbor and September 11 — cataclysmic events that left indelible imprints on the U.S. national psyche. Like the volunteers who flooded into Manhattan after the World Trade Center attacks, the…
The New England Journal of Medicine: Search Results in Health Policy and Reform
Wed May 13, 2020 03:00
Systematic review and pooled analysis of survival rates, success, and outcomes of osseointegrated implants in a variety of composite free flaps
Abstract The aim of this review was to provide an update on survival rates of osseointegrated implants into common composite free flaps used for maxillary and mandibular reconstructions and identify factors affecting outcomes. PubMed, Medline, Embase, and Cochrane databases were searched. Included studies reported implant survival by flap type. Results were pooled and survival was estimated with the Kaplan‐Meier method. Variables affecting survival were assessed using Cox regression. Thirty‐two...
Head & Neck
Wed May 13, 2020 14:05
Modified technique of submandibular gland transfer followed by intensity modulated radiotherapy to reduce xerostomia in head and neck cancer patients
Abstract Background Xerostomia is one of the most common long‐term adverse effects of radiotherapy for head and neck cancer patients. Contralateral submandibular gland transfer (SMG‐T) before radiotherapy was shown to reduce xerostomia compared to pilocarpine. We sought to evaluate a modification of this surgery preserving the ipsilateral facial artery and vein to simplify the SMG‐T. Methods Eighteen patients planned for head and neck intensity modulated radiotherapy to both necks were...
Head & Neck
Wed May 13, 2020 14:00
Ethical framework for head and neck endocrine surgery in the COVID‐19 pandemic
Head & Neck
Wed May 13, 2020 13:44
Single‐session image‐guided robotic radiosurgery and quality of life for glomus jugulare tumors
Abstract Background Limited data are available on the efficacy and impact on the quality of life (Qol) of single‐session image‐guided robotic radiosurgery (RRS) for glomus jugulare tumors (GJTs). This study investigates the role of RRS in the management of GJTs and reviews the RRS literature. Methods We analyzed 53 GJT patients treated with RRS to evaluate the safety, local control, clinical outcome, and Qol assessed by the SF12v2. Results The local control was 98% at a median follow‐up...
Head & Neck
Tue May 12, 2020 22:37
Molecular skin changes in Cushing syndrome and the effects of treatment
Abstract Objective We investigated newly diagnosed patients with endogenous CS for molecular changes in skin by biopsy before and a year after treatment of CS. Patients and methods 26 Patients with CS and 23 healthy controls were included. All the patients were evaluated before and a year after treatment. Skin biopsies were obtained from abdominal...
Journal of Endocrinological Investigation
03:00

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