Abstract Purpose Recently, it has been reported that patients with acute vestibular syndrome (AVS) could present a marked enhancement of the semi-circular canals, involving mostly the superior semi-circular canals on delayed inner ear MRI. Methods We reported one patient having AVS and another one having superior semi-circular canal dehiscence syndrome (SCDS)...
Mark above section as read
Today's health care environment is shifting rapidly, driven by demographic change and high economic pressures on the system. Furthermore, modern precision medicine requires highly accurate and specific disease diagnostics in a short amount of time. Future imaging technology must adapt to these challenges. Demographic change necessitates scanner technologies tailored to the needs of an aging and increasingly multimorbid patient population. Accordingly, examination times have to be short enough...
Mark above section as read
Abstract Stretching in the plasma membranes of cells and lipid membranes of vesicles plays important roles in various physiological and physicochemical phenomena. Irreversible electroporation (IRE) is a minimally invasive non-thermal tumor ablation technique where a series of short electrical energy pulses with high frequency is applied to destabilize the cell membranes. IRE also induces lateral tension due to stretching in the membranes of giant unilamellar vesicles (GUVs). Here,...
Mark above section as read
Mark above section as read
Abstract Neurofibromatosis type 1 (NF1) is a genetic condition characterized by numerous somatic manifestations. The psychosocial burden in adults has rarely been studied. We examined the prevalence of self‐reported impairment of quality of life (QoL), symptoms of anxiety and depression and need for support, associated with disease severity and visibility. We conducted a nationwide cross‐sectional study of all 467 adults with NF1 diagnosed between 1977 and 2016 at one of the two national centers...
Abstract Fraser syndrome (FS) is a rare autosomal recessive multiple congenital malformation syndrome characterized by cryptophthalmos, cutaneous syndactyly, renal agenesis, ambiguous genitalia, and laryngotracheal anomalies. It is caused by biallelic mutations of FRAS1 , FREM2 , and GRIP1 genes, encoding components of a protein complex that mediates embryonic epithelial–mesenchymal interactions. Anecdotal reports have described abnormal orodental findings in FS, but no study has as yet addressed...
Mark above section as read
Background No screening is available for human papillomavirus (HPV)‐associated oropharyngeal cancers. The authors investigated whether cytology may be used as a screening tool and whether oral HPV infection is associated with cytologic abnormalities detected in oropharyngeal brushings and in oral rinse‐and‐gargle specimens from asymptomatic individuals at increased risk for oral HPV infection. Methods Specimens were collected from men who have sex with men at 6‐month intervals. Oropharyngeal...
Mark above section as read
Abstract Allergic reactions are a rare complication of anaesthesia and anaphylaxis is estimated to affect 1 in every 10,000 anaesthetics in the UK. Investigating reactions can be complex due to the frequent absence of validated skin tests to commonly implicated items, the large number of drugs given during surgery and the presence of non‐IgE mediated reactions.
Mark above section as read
Abstract Background Patients with Down Syndrome (DS) present functional and anatomical alterations that may negatively impact their health and quality of life. DS patients have been shown to have a high prevalence of temporomandibular disorder (TMD), but little is known about the diagnosis, treatment, and prevention in these individuals. Objective To evaluate the impact of a home‐based multidisciplinary program on muscular TMD in DS adults. Methods After being diagnosed with TMD‐related...
Mark above section as read
Abstract Adolescence is a challenging time for both patients and healthcare providers. Adolescent patients need to learn all the knowledge and skills required to competently and confidently self‐manage their allergy and asthma. They have to negotiate the challenging transition from being children, whose medical care is supervised by their parents, to independent expert adult patients. Although adolescent and young adult patients appear to be very robust, the reality is that they have often had a...
Abstract Severe asthma imposes a significant burden on patients, families and healthcare systems. Management is difficult, due to disease heterogeneity, comorbidities, complexity in care pathways and differences between national or regional healthcare systems. Better understanding of the mechanisms has enabled a stratified approach to the management of severe asthma, supporting the use of targeted treatments with biologicals. However, there are still many issues that require further clarification....
Mark above section as read
Treatment of [Ph3EMe][I] with [Na{N(SiMe3)2}] affords the ylides [Ph3E=CH2] (E = As, 1As; P, 1P). For 1As this overcomes prior difficulties in the synthesis of this classical arsonium‐ylide that have historically impeded its wider study. The structure of 1As has now been determined, 45 years after it was first convincingly isolated, and compared to 1P, confirming the long‐proposed hypothesis of increasing pyramidalisation of the ylide‐carbon, highlighting the increasing dominance of E+‐C‐ dipolar...
Potassium (K) cations are spontaneously formed upon thermal deposition of low‐coverage K onto an ultrathin CuO monolayer grown on Cu(110) and explored by low‐temperature scanning tunneling microscopy (STM) and X‐ray photoemission spectroscopy. The formed K cations are highly immobile and thermally stable. The local work function around an individual K cation decreases by 1.5 ± 0.3 eV, and a charging zone underneath it establishes within ~ 1.0 nm. The cationic and neutral states of the K atom...
Recently, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emissions through accurate structural design strategy considering the instability and low photoluminescence quantum yield (PLQY) of blue‐ emitting perovskites. Herein, by rationally introducing d 10 transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH 4 ) 2 ]CuPbBr...
Porous carbons are an important class of porous materials with many applications including gas separation, while N 2 adsorption isotherm at 77 K is the most widely used approach to characterize porosity. Conventionally, textual properties such as surface area and pore volumes are derived from the N 2 adsorption isotherm at 77 K via fitting to an adsorption theory and then correlated to gas separation performance (uptake and selectivity). Here we use the N 2 isotherm at 77 K directly as input...
Porous single crystals which combine ordered lattice structures and disordered inter‐connected pores would provide an alternative to create twisted surface in porous microstructures. Here we grow transition metal nitrides Nb4N5 and MoN single crystals at 2 cm scale to create well‐defined active structures at twisted surfaces and we present high catalytic activity and stability toward non‐oxidative dehydrogenation of ethane to ethylene. Unsaturated metal‐nitrogen coordination structures including...
High‐speed atomic force microscopy (HS‐AFM) is widely employed in the investigation of dynamic biomolecular processes at a single‐molecule level. However, it remains an open and somewhat controversial question, how these processes are affected by the rapidly scanned AFM tip. While tip effects are commonly believed to be of minor importance in strongly binding systems, weaker interactions may significantly be disturbed. Here, we quantitatively assess the role of tip effects in a strongly binding system...
Herein we report a facile, mild reaction protocol to form carbon‐carbon bonds in the absence of transition metal catalysts. We demonstrate the metal‐free alkenylation reactions of aryl esters with α‐diazoesters to give highly functionalized enyne products. Catalytic amounts of tris(pentafluorophenyl)borane (10–20 mol%) are employed to afford the C=C coupled products (31 examples) in good to excellent yields (36–87%). DFT studies have been undertaken to elucidate the mechanism for this alkenylation...
C7–H functionalized indoles are ubiquitous structural units of biological and pharmaceutical compounds for numerous antiviral agents against SARS‐CoV or HIV‐1. Thus, achieving site‐selective functionalizations of C7–H of indoles, while discriminating among other bonds, is highly demand. Herein, we disclose site‐selective C7–H activations of indoles accomplished by ruthenium(II)biscarboxylate catalysis under mild conditions. Base‐assisted internal electrophilic‐type substitution C–H ruthenation by...
Vinyl fluorides play an important role in drug development as bioisosteres for peptide bonds and are found in a range of bioactive molecules. The discovery of safe, general and practical procedures to prepare vinyl fluorides from readily available precursors remains a synthetic challenge. The metal‐free hydrofluorination of alkynes constitutes an attractive though elusive strategy for their preparation. Here we introduce an inexpensive and easily‐handled reagent that enabled the development of simple...
We report the two‐step hysteretic Fe(II) spin crossover (SCO) effect achieved in programmed layered Cs{[Fe(3‐CNpy)2] [Re(CN)8]}·H2O (1) assembly consisting of cyanido‐bridged FeII–ReV square grid sheets bonded by Cs+ ions. The presence of two non‐equivalent FeII sites and the conjunction of 2‐D bimetallic coordination network with non‐covalent interlayer interactions involving Cs+, [ReV(CN)8]3– ions, and 3‐CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity...
Reducing the amount of iridium in oxygen evolution electrocatalysts without compromising their catalytic performances is one of the major requirements in proton exchange membrane water electrolyzers. Here, with the help of theoretical studies, we show that anatase‐type TiO 2 ‐IrO 2 solid solutions possess more active iridium catalytic sites for the oxygen evolution reaction (OER) than IrO 2 , the benchmark OER catalyst. It is worth adding that the same is not observed for their rutile‐type...
Heteroatom‐doped polymers or carbon nanospheres have attracted a broad research interest because of their fascinating properties. However, rational synthesis of these nanospheres with controllable uniform morphologies, small particle sizes, and well‐designed functionalities is still a great challenge. Herein, we develop an approach to construct cross‐linked polyphosphazene nanospheres with tunable hollow structures via a facile template‐free one‐step method. As comonomers, hexachlorocyclotriphosphazene...
Photocatalytic hydrogenation of biomass‐derived organic molecules transforms solar energy to high‐energy‐density chemical bonds, and may enable the production of industrial building‐block chemicals with great economical values. Despite its great potential, photocatalytic hydrogenation remains poorly explored up to now. Existing researches are mostly based on broad bandgap inorganic semiconductors and require the assistance of noble metal based cocatalysts. Herein, we report the preparation of thiophene‐containing...
A supramolecular/synthetic method was devised to affix a sterically hindered substituent onto a fullerene guest encapsulated in a tubular host. A two‐wheeled complex of (C 59 N)–(C 59 N) with a tubular host was oxidatively bisected to afford the C 59 N + cation captured in the tube. The C 59 N + cation in the tube was then trapped by ethanol or water, which led to an oxy substituent pinned on the guest. The guest motions within the tube were modulated by the pinned substituent, and...
Designing cost‐effective and efficient electrocatalysts plays a pivotal role in advancing the development of electrochemical water splitting for hydrogen generation. Herein, multifunctional active‐center‐transferable heterostructured electrocatalysts, platinum/lithium cobalt oxide (Pt/LiCoO2) composites with Pt nanoparticles (Pt NPs) anchored on LiCoO2 nanosheets, are designed towards highly efficient water splitting. In this electrocatalyst system, the active center can be alternatively switched...
Let it be adaptive : A cobalt‐based molecular system capable of selectively reducing carbon dioxide either to the formic acid, formaldehyde, or methanol level has been developed. This approach shows that molecular control over product formation is possible with suitable catalysts that allow the reaction conditions to be adapted appropriately. Abstract The catalytic reduction of carbon dioxide (CO2) is considered a major pillar of future sustainable energy systems and chemical industries based...
Clusters : Enynes are an important functionality in organic chemistry. Reported here is the identification of the biosynthetic gene cluster and characterization of two crucial enzymes in the biosynthesis of asperpentyn (1 ). Notably, P450 monooxygenase was discovered to have a dual function, that is, to first catalyze dehydrogenation of the prenyl chain to generate a cis ‐diene intermediate, and then serve as an acetylenase to yield an alkyne moiety. Abstract The 1,3‐enyne moiety is commonly...
Identity dictates destiny : N2 activation has been investigated with anionic diniobium hydride complexes containing a series of alkali cations (Li+, Na+, and K+). In all cases, the μ‐η1:η2 N2 complexes are formed as an initial product upon exposure to N2. While the conversion of the N2 binding mode from μ‐η1:η2 to μ‐η1,η1 is observed with the Li+ countercation, N−N bond cleavage takes place for K+. The Na+ derivative reacts with Me3SiCl to give a nitride‐imide complex. Abstract We report the...
Visible‐light‐induced site‐selective trifluoromethylative pyridylation of unactivated alkenes has been achieved using pyridines and Tf2O. Intriguingly, the generated N‐triflylpyridinium salts serve as effective modular bifunctional reagents to install CF3 and pyridyl groups to olefins while controlling C4‐selectivity in radical addition to the pyridine core to provide C4‐alkylated pyridines and quinolines. Abstract A general strategy for visible‐light‐enabled site‐selective trifluoromethylative...
K[Al(NONDipp)] has been used to construct new C=C double bonds. The reaction with CS2 generates the ethenetetrathiolate [C2S4]4− containing product through a reductive coupling strategy. To obtain similar carbon–oxygen products, the alumoxane [K{Al(NONDipp)(O)}]2 was reacted with CO, affording a hitherto unknown ethenetetraolate [C2O4]4− ligand. DFT analysis indicates retention of a bimetallic species throughout the reaction with CO. Abstract [K{Al(NONDipp)}]2 (NONDipp=[O(SiMe2NDipp)2]2−,...
One way street : A photochemical deracemization provided—via sensitization by a chiral photocatalyst—access to a set of enantiomerically enriched allenes. Subsequent chirality transfer or ring opening enabled the synthesis of valuable chiral intermediates with >90 % ee . Abstract Trisubstituted allenes with a 3‐(1′‐alkenylidene)‐pyrrolidin‐2‐one motif were successfully deracemized (13 examples, 86–98 % ee ) employing visible light (λ =420 nm) and a chiral triplet sensitizer as the catalyst...
Branch out : A novel strategy for the synthesis of branched poly(monothiocarbonate)s is presented. Branched poly(monothiocarbonate)s are synthesized with tunable side‐chain lengths and densities by adjusting the reaction temperature. Abstract Topological polymers possess many advantages over linear polymers. However, when it comes to the poly(monothiocarbonate)s, no topological polymers have been reported. Described herein is a facile and efficient approach for synthesizing well‐defined branched...
The power of F : A high‐valent nickel–fluoride complex oxidizes hydrocarbons via a hydrogen atom transfer mechanism while also facilitating oxidative fluorination. The fluoride complex demonstrates a 103‐fold enhanced rate constant for hydrocarbon oxidation when compared to its chloride analogue, demonstrating that fluoride imbues a high driving force for oxidation. Abstract In the search for highly reactive oxidants we have identified high‐valent metal–fluorides as a potential potent oxidant....
Stiff‐stilbene is increasingly applied to reversibly control the properties and function of chemical as well as biological systems. In this Minireview an overview is provided of the basic properties of this promising photoswitch, which is followed by a survey of recent applications. Abstract Stiff‐stilbene, a sterically restricted fused ring analogue of stilbene, has been regularly used as a model compound in theoretical studies of stilbene photoisomerization. Lately, owing to its excellent...
Guanine oxidation produces two major tautomeric 2′‐deoxyguanosin‐yl radicals—dG(N2‐H). and dG(N1‐H).. dG(N2‐H). was independently generated from 1 . dG(N2‐H). reacts significantly more slowly with thiol reducing agents than alkyl radicals. Contrary to previous reports, there is no evidence that dG(N2‐H). rearranges to dG(N1‐H). on the sub‐millisecond timescale. Abstract Guanine radicals are important reactive intermediates in DNA damage. Hydroxyl radical (HO.) has long been believed to react...
A series of new bowl‐shaped N ‐hydroxyimide derivatives has been designed and used as selective organoradical catalysts. A number of these bowl‐shaped N ‐hydroxyimide derivatives exhibit excellent site‐selectivity in the amination of benzylic C(sp 3 )‐H bonds in aromatic hydrocarbon substrates.
In the present study, we investigated the biotransformation of the neonicotinoid pesticide sulfoxaflor and the metabolic responses in Sprague‐Dawley rats. Sulfoxaflor was catalyzed by cytochrome P450 while five phase I and four phase II metabolites were identified for the first time in vivo . The experimental results demonstrated that sulfoxaflor brought about the metabolic profiling disturbances in liver and bile. Exposure to sulfoxaflor caused dysregulation of bile acid synthesis and reabsorption...
Δεν υπάρχουν σχόλια:
Δημοσίευση σχολίου
Σημείωση: Μόνο ένα μέλος αυτού του ιστολογίου μπορεί να αναρτήσει σχόλιο.