Future Oncology, Ahead of Print.
Thu May 28, 2020 14:48
Future Oncology, Ahead of Print.
Thu May 28, 2020 13:31
The role of sex-specific demography in hybridization and admixture of genetically diverged species and populations is essential to understand the mechanisms forming the genomic diversity of sexually reproducing organisms. In order to infer how sex-linked genetic loci have been differentiated undergoing frequent hybridization and admixture, we examined 17 whole-genome sequences of seven species of the genus Macaca, which shows frequent inter-specific hybridization and predominantly female philopatry....
Thu May 28, 2020 03:00
During range expansion, edge populations are expected to face increased genetic drift, which in turn can alter and potentially compromise adaptive dynamics, preventing the removal of deleterious mutations and slowing down adaptation. Here, we contrast populations of the European sub-species Arabidopsis lyrata ssp petraea, which expanded its Northern range after the last glaciation. We document a sharp decline in effective population size in the range-edge population and observe that non-synonymous...
Thu May 28, 2020 03:00
Cooperation plays a key role in advanced societies with human cooperation among kin being more prominent than cooperation among non-kin. However, little is known about the developmental roots of kin and non-kin cooperation in humans. Here, we show for the first time that children cooperated less successfully with siblings than with non-kin children, whether or not non-kin partners were friends. Furthermore, children with larger social networks cooperated better and the perception of friendship among...
Thu May 28, 2020 03:00
We introduce a simple test to infer mode of selection (STIMS) in metagenomic time series of evolving asexual populations. STIMS compares the tempo of molecular evolution for a gene set of interest against a null distribution that is bootstrapped on random gene sets. We test STIMS on metagenomic data spanning 62,750 generations of Lenskis long-term evolution experiment with E. coli (LTEE). Our method successfully recovers signals of purifying selection and positive selection on gold standard sets...
Thu May 28, 2020 03:00
While numerous studies have found horizontal transposon transfer (HTT) to be widespread across metazoans, few have focused on HTT in marine ecosystems. To investigate potential recent HTTs into marine species we searched for novel repetitive elements in sea snakes, a group of elapids which transitioned to a marine habitat at most 18 Mya. Our analysis uncovered repeated HTTs into sea snakes following their marine transition. Such major shifts in habitat should require significant genomic changes.The...
Thu May 28, 2020 03:00
Establishing reliable frameworks for predicting unknown outcomes from empirical observations is of great interest to ecologists and evolutionary biologists. Strong predictability in evolutionary responses has been previously demonstrated by the repeated observation of similar phenotypes or genotypes across multiple natural or experimental populations in analogous environments. However, the degree to which evolutionary outcomes can be predicted across environmental gradients, or in fluctuating environments,...
Thu May 28, 2020 03:00
Adaptation in new environments depends on the amount and type of genetic variation available for evolution, and the efficacy by which natural selection discriminates among this variation to favour the survival of the fittest. However, whether some environments systematically reveal more genetic variation in fitness, or impose stronger selection pressures than others, is typically not known. Here, we apply enzyme kinetic theory to show that rising global temperatures are predicted to intensify natural...
Thu May 28, 2020 03:00
Abstract Purpose We have previously demonstrated that dogs can be trained to distinguish the urine of patients with obstructive sleep apnea (OSA) from that of healthy controls based on olfaction. Encouraged by these promising results, we wanted to investigate if a detection dog could work as a screening tool for OSA. The objective of this study was to prospectively assess the dogs’ ability to identify sleep apnea in patients with OSA...
03:00
LaryngorhinootologieDOI: 10.1055/a-1174-0234Die SARS-CoV-2-Pandemie stellt das gesamte medizinische Versorgungssystem vor große Herausforderungen. Gerade in universitären Einrichtungen als Maximalversorger ist eine höhere Exposition zu potenziell infektiösen Patienten oder tatsächlichen COVID-19-Kranken zu erwarten. Es musste kurzfristig ein Betriebskonzept entwickelt werden, das den aktuellen Hygiene-Empfehlungen des Robert Koch-Instituts (RKI), den Empfehlungen der führenden Fachgesellschaften...
Thu May 28, 2020 02:00
Abstract The expression of programmed death-ligand 1 (PD-L1) is an established prerequisite for the administration of checkpoint inhibitor therapy and is of prognostic value in several cancer types. Data concerning the potential effect of PD-L1 on the prognosis of thyroid carcinoma are limited. Therefore, this study aimed to provide a systematic review of the published data on this topic. The literature was reviewed to gather and quantify evidence on the prognostic role of PD-L1...
03:00
Abstract Parathyroid gland excision specimens are common and sometimes underestimated cases that many surgical pathologists encounter regularly. In the vast majority of cases, these will be spot diagnoses of sporadic primary parathyroid adenomas or, perhaps, hyperplasias commonly in the setting of renal failure. However, a small but significant number of parathyroid gland excisions may be due to heritable disease. In most cases, hereditary disease is suspected by the referring...
Thu May 28, 2020 03:00
Correlative scanning probe microscopy of chemical identity, surface potential, and mechanical properties provides insight into structure‐functional relationships of nanomaterials. However, simultaneous measurement with comparable and high resolution is a challenge. Here, we seamlessly integrate nanoscale photothermal infrared imaging with Coulomb force detection to form Peak Force Infrared – Kelvin Probe Force Microscopy (PFIR‐KPFM), which enables simultaneous nano‐mapping of infrared absorption,...
Thu May 28, 2020 11:44
Li and Mn‐rich layered oxide (LMR‐NMC) is one of the most promising cathode materials for Li‐ion batteries with high theoretical energy density. Its practical application is, however, hampered by the capacity and voltage fade after long cycling. Herein, a finite difference method for near‐edge structure (FDMNES) code was combined with in‐situ X‐ray absorption spectroscopy (XAS) and transmission electron microscopy/electron energy loss spectroscopy (TEM/EELS) to investigate the evolution of transition...
Thu May 28, 2020 22:04
How to train your hydrides : Oxidation of a dicopper(I) acetonitrile complex with air results in the formation of a dicopper(II) bis(hydroxide) complex, which can in turn be reduced with silanes to form copper(I) hydrides. In the presence of Group 11 monocations, two equivalents of hydride reversibly form pentanuclear bow tie clusters. These hydride complexes are competent for catalytic dehydrogenation of formic acid. Abstract Reduction of a dicopper(II) bis(hydroxide) complex with silanes...
Thu May 28, 2020 22:00
In a high‐yield one‐pot synthesis, the reactions of [Cp*M(η 5 ‑P 5 )] (M = Fe ( 1 ), Ru ( 2 )) with I 2 resulted in the selective formation of [Cp*MP 6 I 6 ] + salts ( 3 , 4 ). The products comprise unprecedented all‐cis tripodal triphosphino‐cyclotriphosphine ligands. The iodination of [Cp*Fe(η 5 ‐As 5 )] ( 6 ) gave, in addition to [Fe(CH 3 CN) 6 ] 2+ salts of the rare [As 6 I 8 ] 2‐ (in 7 ) and [As 4 I 14 ] 2‐ (in 8 ) anions, the first di‐cationic Fe‐As triple decker complex...
Thu May 28, 2020 20:37
Highly effective photocatalysts for hydrogen‐evolution reaction was developed by conferring active copper centers to the linkers of NH 2 ‐MIL‐125(Ti), a metal organic framework (MOF) constructed from TiO x clusters and 2‐aminoterephthalic acid (linkers). This design enables effective transfer of electrons from the linkers to the transient Cu 2+ /Cu + centers, leading to 7000‐fold and 27‐fold increase of carrier density and lifetime of photogenerated charges, respectively, as well as high‐rate...
Thu May 28, 2020 20:33
Trifluoromethyl sulfoxides are a new class of trifluoromethylthiolating reagent. The sulfoxides engage in metal‐free C–H trifluoromethylthiolation with a range of (hetero)arenes. The method is also applicable to the functionalization of important compound classes, such as ligand derivatives and polyaromatics, and in the late‐stage trifluoromethylthiolation of medicines and agrochemicals. The isolation and characterization of a sulfonium salt intermediate supports an interrupted Pummerer reaction...
Thu May 28, 2020 20:09
Autocatalysis and self‐assembly are key processes in developmental biology and are involved in the emergence of life. In the last decade both features were extensively investigated by chemists with the final goal to design synthetic living systems. Herein, we describe the autonomous growth of a self‐assembled soft material, i.e. a supramolecular hydrogel, able to sustain its own formation through an autocatalytic mechanism not based on any template effect and emerging from a peptide (hydrogelator)...
Thu May 28, 2020 20:07
Coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in analogous manner via carbon‐carbon bond activation could greatly expand the tool‐box of the synthesis of aryl compounds due to the abundance of aryl ketones. Exploratory study of this approach is typically based on carbon‐carbon cleavage triggered by ring‐strain release and chelation assistance,...
Thu May 28, 2020 18:52
Electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance due to preferential catalyst‐H formation and the consequential hydrogen evolution reaction (HER). Herein, we electronically modify PtAu electrocatalyst d‐band structure using zeolitic‐imidazole framework (ZIF) to achieve a faradaic efficiency (FE) of >44% with high ammonia yield rate of >161 µg.mg cat ‐1 .h ‐1 at ambient conditions. Our strategy...
Thu May 28, 2020 18:52
Double deprotonation of the diamine 1,1′‐( t BuCH 2 NH)‐ferrocene ( 1 ‐H 2 ) by alkaline earth (Ae) or Eu(II) metal reagents gave the complexes 1 ‐Ae (Ae = Mg, Ca, Sr, Ba) and 1 ‐Eu. Complex 1 ‐Mg crystallized as a monomer with two THF ligands while the heavier complexes crystallized as dimers in which each metal is solvated by one ( 1 ‐Ca and 1 ‐Sr) or two ( 1 ‐Ba) THF ligands; 1 ‐Eu is isostructural to 1 ‐Sr. The Fe∙∙∙Mg distance in 1 ‐Mg (3.4255(6) Å) is too long for...
Thu May 28, 2020 16:05
Potentially explosive yet mild‐mannered ! The synthesis and reactivity of diamino‐substituted diborane(4) diazides, the first diborane(4) azides, is reported. Despite the presence of energetic and oxidizing azide groups and of reactive B−B bonds, they are astonishingly robust. The species do not decompose below 100 °C. Two diazides could be pyrolyzed in a controlled manner to diazadiboretidines, the dimerization product of transient iminoboranes. Abstract Herein we describe the first examples...
Thu May 28, 2020 14:53
Co‐Operation : An allied cooperation between cobalt catalysis and electrochemical synthesis enabled the mild catalytic carboxylation of allylic chlorides with atmospheric CO2. The resulting products are useful as versatile synthons of γ‐arylbutyrolactones. Abstract The chemical use of CO2 as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild...
Thu May 28, 2020 14:52
Light‐responsive nanomotors enabling NIR light‐driven drug release, photothermal therapy, and deep penetration into 3D tumors are proposed for cancer combination therapy. Systematic research and evaluation models including 2D cellular models, 3D multicellular tumor spheroids, and in vivo models were established for studies of the permeability of nanomotors. Abstract Limited tumor permeability of therapeutic agents is a great challenge faced by current cancer therapy methods. Herein, a kind...
Thu May 28, 2020 14:51
Two novel macrocyclic BODIPY derivatives possessing two and four BF2 units, respectively, display very high light‐capturing efficiency due to strong excitonic coupling within the constituent chromophoric units. Detailed photophysical analyses provided insight about their structure–property relationship. Abstract Two giant calix[n ]phyrin derivatives namely calix[8]‐ (4 ) and calix[16]phyrin (5 ), involving two and four BF2 units, respectively, were prepared through the condensation of the...
Thu May 28, 2020 14:50
The sulfone functional group has a strong capacity to direct the asymmetric transfer hydrogenation (ATH) of ketones by [(arene)Ru(TsDPEN)H] complexes by adopting a position distal to the η 6 ‐arene ring. This preference provides a means for the prediction of the sense of asymmetric reduction. The sulfone group also facilitates the formation of a range of reduction substrates and its ready removal provides a route to enantiomerically‐enriched alcohols which would otherwise be extremely difficult...
Thu May 28, 2020 14:05
A fine tuning of linker rotation and layer stacking in hydrolytically stable layered MOFs via metal substitution creates optimal expanded pore aperture and interlayer space coupled with multiple binding sites. It affords almost complete exclusion of C2‐C3 alkenes from alkynes with substantial alkyne uptake and record C3H4/C3H6 uptake ratios in a wide pressure range. Abstract C2‐C3 alkyne/alkene separation is of great importance; however, designing materials for an efficient molecular sieving...
Thu May 28, 2020 12:05
Ticking the right nanoboxes : A general strategy for the synthesis of amorphous metal sulfide nanoboxes has been developed. By using the multifunctional amorphous MoS3 nanoboxes with unsaturated Mo and catalysis as sulfur hosts, a high‐capacity and long‐life Li‐S battery can be realized. Abstract The practical implementation of lithium–sulfur batteries is obstructed by poor conductivity, sluggish redox kinetics, the shuttle effect, large volume variation, and low areal loading of sulfur electrodes....
Thu May 28, 2020 12:04
Transport tubes : A novel family of aromatic amide foldamer‐based helically folded organic nanotubes with a 2.8 nm length on average was efficiently made by a POCl3‐mediated one‐pot polymerization. Having a tubular cavity of a 2.8 Å diameter, these helical foldamer channels facilitate highly selective and superfast transport of both water molecules and protons, with a high rejection of both NaCl and KCl. Abstract Synthetic strategies that enable rapid construction of covalent organic nanotubes...
Thu May 28, 2020 11:13
The first enantioselective S−H insertion reaction of α‐carbonyl sulfoxonium ylides was developed under thiourea catalysis. Up to 95 % ee and 97 % isolated yields were obtained in 31 examples. Abstract The first example of enantioselective S−H insertion reactions of sulfoxonium ylides is reported. Under the influence of thiourea catalysis, excellent levels of enantiocontrol (up to 95 % ee ) and yields (up to 97 %) are achieved for 31 examples in S−H insertion reactions of aryl thiols and α‐carbonyl...
Thu May 28, 2020 11:12
Virtues we write in water : Cobalt‐catalyzed cycloisomerization occurs with efficiency in aqueous buffer at high dilution. A variety of putative metal hydride atom‐transfer (MHAT) reactions, including deallylation, proceed under these stringent conditions, even on DNA. Abstract Preparative reactions that occur efficiently under dilute, buffered, aqueous conditions in the presence of biomolecules find application in ligation, peptide synthesis, and polynucleotide synthesis and sequencing. However,...
Thu May 28, 2020 11:10
On the count of three : The first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 is reported. The assignments provide a benchmark for state‐of‐the‐art water potentials and dipole‐moment surfaces, especially with respect to three‐body interactions. Abstract Intermolecular interactions in bulk water are dominated by pairwise and non‐pairwise cooperative interactions. While accurate descriptions of the pairwise interactions are available and can be tested...
Thu May 28, 2020 11:10
Zooming into catalytic defects : By combining advanced synchrotron characterization tools and modeling, a more realistic picture is provided of the structure of catalytic palladium loaded into imine‐linked layered covalent organic frameworks. The occurrence of local defects plays a key role in both chemical modifications through metalation and catalytic activity in Suzuki–Miyaura cross‐couplings. Abstract Layered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and...
Thu May 28, 2020 11:08
What a boost : Undoped and Sb‐doped lead‐free 0D perovskites A2InCl5(H2O) (A=Rb, Cs) have been synthesized. Doping Sb3+ into Rb2InCl5(H2O) achieves a boost of PLQY from <2 % to 90 %. Sb‐doped A3InCl6 (A=Rb, Cs) are also synthesized and the effect of H2O coordination was studied. 0D rubidium indium chloride perovskites show excellent stability. Abstract Zero‐dimensional (0D) lead‐free perovskites have unique structures and optoelectronic properties. Undoped and Sb‐doped all inorganic, lead‐free,...
Thu May 28, 2020 11:08
Soft Janus nanoparticles (JNPs) assemble at a water–oil interface with corona chains spread out to cover the interface. The extent of chain stretching can be tailored by changing softness of JNPs and corporation with lithium ion in water to manipulate packing density of JNPs. Wrinkles were observed with compression, which later relax owing to reconfiguration of JNPs at the interface. Abstract Soft polymeric Janus nanoparticles (JNPs), made from polystyrene‐b ‐poly(butadiene)‐b ‐poly(methylmethacrylate),...
Wed May 27, 2020 22:00
MCOFs (metal–covalent organic frameworks) hold high promise in combining the advantages of MOFs (metal–organic frameworks) and COFs (covalent organic frameworks), thus realizing a balanced mix of crystallinity, porosity, stability, tunability, and functionality. This Minireview summarizes the recent progress of MCOFs regarding design strategy, synthesis, structural characterization, and their cutting‐edge applications. Abstract Many sophisticated chemical and physical properties of porous...
Wed May 27, 2020 13:49
CNGDY, HGDY, and MeGDY are prepared by a bottom‐to‐up synthesis strategy. The push–pull electron ability and size differences of groups play a key role on the partial property adjusting of as‐prepared graphdiyne (GDY) derivatives, such as energy gap, morphology, and affinity to alkali metals. Abstract The properties of graphdiyne (GDY), such as energy gap, morphology, and affinity to alkali metals, can be adjusted by including electron‐withdrawing/donating groups. The push–pull electron ability...
Wed May 27, 2020 13:48
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