Abstract Background We evaluated the long‐term efficacy and safety of carbon‐ion radiotherapy (C‐ion RT) for skull base chordoma, a rare neoplasm. Methods Thirty‐four patients with skull base chordoma who were treated with C‐ion RT were prospectively enrolled and analyzed retrospectively. C‐ion RT was delivered with 60.8 Gy (relative biological effectiveness [RBE]) in 16 fractions at four fractions per week. Results The median follow‐up period was 108 months. The 5‐ and 9‐year local...
Familial cancer risk in family members and spouses of patients with early‐onset head and neck cancer
Abstract Background Reported patterns of familial aggregation of head and neck cancer (HNC) vary greatly, with many studies hampered by the limited number of subjects. Methods Altogether 923 early‐onset (≤40 years old) HNC probands, their first‐degree relatives, spouses, and siblings' offspring were ascertained. Cumulative risk and standardized incidence ratios (SIRs) were estimated. Results Of all early‐onset HNC families, only 21 (2.3%) had familial HNC cancers at any age and less...
Abstract The COVID‐19 pandemic has had a significant impact on many aspects of head and neck cancer (HNC) care. The uncertainty and stress resulting from these changes has led many patients and caregivers to turn to HNC advocacy groups for guidance and support. Here we outline some of the issues being faced by patients with HNC during the current crisis and provide examples of programs being developed by advocacy groups to address them. We also highlight the increased utilization of these organizations...
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Rational Design of Cyclometalated Iridium(III) Complexes for Three‐Photon Phosphorescence Bioimaging
Compared to two‐photon excitation (2PE) microscopy, three‐photon excitation (3PE) microscopy has superior spatial resolution, deeper tissue penetration, and less defocused interference, and is, therefore, of great interest in the field of bioimaging. The design of suitable agents which can meet the various needs of the technology, such as large Stokes shift, good three‐photon absorption (3PA), subcellular targeting, and fluorescence lifetime imaging (FLIM) properties, is a formidable challenge. In...
Encapsulating transition metal nanoparticles inside carbon nanotubes (CNTs) or spheres has emerged as a novel strategy of designing highly‐durable non‐precious metal catalysts. The stable carbon layer protects the inner metal core from the destructive reaction environment and thus is vividly described as chainmail for catalysts. Electron transfer from the active metal core to the carbon layer stimulates unique catalytic activity on the carbon surface which has been extensively utilized in a variety...
In recent years, the non‐covalent interaction of halogen bonding (XB) has found increasing application in organocatalysis. However, reports of the activation of metal‐ligand bonds by XB have so far been limited to a few reactions with elemental iodine or bromine. Herein, we present the activation of metal‐halogen bonds by two classes of inert halogen bond donors and the use of the resulting activated complexes in homogenous gold catalysis. The only recently explored class of iodolium derivatives...
Perovskite solar cells (PSCs) are promising photovoltaic technology to sustainably drive stretchable applications, due to their flexible, light‐weight and low‐cost superiorities. However, fragility of crystals and poor crystallinity of perovskite on stretchable substrate afford an inevitable performance loss. In fact, the grain boundary defects are the Achilles’ heel for the optoelectronic and mechanical degradations. Herein, we incorporate a self‐healing polyurethane (s‐PU) with dynamic oxime−carbamate...
The counterions of polydiallyldimethylammonium (PDADMA) coatings were systematically altered by incubation in aqueous solutions of different types of electrolytes. Oil de‐wetting on the resulting polycationic surfaces upon water action exhibited a surprisingly straightforward connection with the Jones‐Dole viscosity B‐coefficient (Bη) sign of surface counter‐anions. Upon water action, surface counter‐anions with negative Bη render PDADMA coatings rather oil‐adhering, but those with positive Bη furnish...
A distannylated electron‐deficient bithiophene imide (BTI‐Tin) monomer was readily synthesized and polymerized with imide‐functionalized co‐units via Stille coupling to afford homopolymer PBTI and copolymer P(BTI‐BTI2), both featuring acceptor‐acceptor backbone with high molecular weight. Benefitting from their improved electronic property and increased molecular weight, both polymers exhibited excellent unipolar n‐type character in transistors with electron mobility up to 2.60 cm2 V‐1 s‐1. When...
Selective and sensitive molecular probes for hydrogen peroxide (H 2 O 2 ), which plays diverse roles in oxidative stress and redox signalling, are urgently needed to investigate the physiological and pathological effects of H 2 O 2 . A lack of reliable tools for in vivo imaging has hampered the development of H 2 O 2 mediated therapeutics. By combining a specific tandem Payne/Dakin reaction with a chemiluminescent scaffold, H 2 O 2 ‐CL‐510 was developed as a highly selective and...
We report on the impact of the central heteroatom on structural, electronic, and spectroscopic properties in a series of heterotriangulenes including a spirofluorene‐bridged triphenylamine, ‐phosphine, and ‐phosphine oxide and provide a detailed study on their aggregates. The in‐depth analysis of their molecular structure by NMR spectroscopy and X‐ray crystallography was complemented by density functional theory calculations to shed light on the electronic structure. This analysis was particularly...
The formation of spontaneously twisted crystals is a common but poorly understood growth phenomenon. Here, we analyze the formation of twisted crystals of a metastable benzamide polymorph (form II ) crystallizing from highly supersaturated aqueous and ethanol solutions. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently...
Low‐dimensional ns 2 ‐metal halide compounds have recently received immense attention for applications in solid‐state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb 2+ or unstable Sn 2+ , and a stable inorganic luminescent material has yet to be found. Herein we present the zero‐dimensional Rb 7 Sb 3 Cl 16 phase, which is comprised of isolated [SbCl 6 ] 3‐ octahedra and edge‐sharing...
Herein we report on the design of a programmable DNA ribbon using long‐chain DNA molecules with a user‐defined repetitive padlock sequence. The DNA ribbon can be further combined with gold nanoparticles (AuNPs) to create a composite nanomaterial that contains an AuNP core and a high‐density DNA crown carrying a cancer cell‐targeting DNA aptamer, a fluorescent tag for location tracking and a cell‐killing drug. This composite material can be efficiently internalized by cancer cells and its cellular...
This paper describes the modulation of tunneling probabilities in molecular junctions by switching one of two parallel intramolecular pathways. A linearly‐conjugated molecular wire provides a rigid framework that allows a second, cross‐conjugated pathway to be effectively switched on and off by protonation, affecting the total conductance of the junction. This approach works because a traversing electron interacts with the entire quantum‐mechanical circuit simultaneously; Kirchhoff's rules do not...
Enzymatic reactions have the potential to enable a greener production of chemicals and pharmaceuticals. Recent publications revealed the suitability of Metal‐Organic Frameworks (MOFs) as an enzyme immobilization matrix. However, the MOF separation and additional transport resistances are still challenging. We report the in‐situ biomineralization of glucose oxidase (GOD) into MOF crystals (ZIF‐8) via interfacial crystallization. This method proves to be effective for the selective coating of porous...
The rational synthesis of organometallic complexes of modified 26 π ‐conjugated hexaphyrins with third near‐infrared (NIR‐III) absorption and emission capabilities is described. Symmetry alteration of the frontier molecular orbitals of bis‐Pd(II) and bis‐Pt(II) complexes of hexaphyrin via N‐confusion modification led to substantial metal d π –p π interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO – LUMO energy gap. A remarkable long‐wavelength shift of the lowest...
We report here a general four‐component synthetic procedure for the preparation of β‐boryl ketones and β‐boryl vinyl esters. Joined catalyzed by palladium and copper catalysts, borocarbonylative reaction between vinylarenes, aryl halides/triflates, B 2 Pin 2 and carbon monoxide proceed successfully. A variety of synthetically useful β‐boryl ketones were synthesized in good to high yields by using aryl iodides as the substrates. It is noteworthy that, when applying aryl triflates as the starting...
Bulk up : A Pd‐catalyzed enantioselective β‐C(sp3)−H functionalization of thioamides has been developed using a chiral phosphoric acid (CPA) as the chiral auxiliary. Mass spectrometry studies and DFT analysis elucidate the role of the bulky CPA and the assistance of the thioamide ligand, which define a robust chiral cavity for achieving a high level of stereocontrol. Abstract A hybrid palladium catalyst assembled from a chiral phosphoric acid (CPA) and thioamide enables a highly efficient and...
The single‐molecule magnets (SMMs) [Cp′2Dy(μ ‐X)]2 (Cp′=cyclopentadienyltrimethylsilane anion; X=CH3−, Cl−, Br−, =I−) are investigated. For the first time, the magnetic easy axes of dysprosium metallocene SMMs are experimentally determined, confirming that they are oriented perpendicular to the equatorial plane which is made up of dysprosium and bridging atoms. Abstract We investigate a family of dinuclear dysprosium metallocene single‐molecule magnets (SMMs) bridged by methyl and halogen...
Peptide synthesis goes green : A water‐compatible 2,7‐disulfo‐9‐fluorenylmethoxycarbonyl (Smoc) protecting group has been developed that enables solid‐phase peptide synthesis under aqueous conditions as well as efficient postsynthetic purification of the peptides. This protecting group is fluorescent both when attached to an Nα atom and when cleaved and so also allows real‐time monitoring of building block coupling Abstract The growing interest in synthetic peptides has prompted the development...
The first systematic Kβ XES study for a second‐row transition metal, including a thorough analysis of the transitions responsible for Kβ2 (4p→1s) and valence‐to‐core (valence→1s) emission lines, is presented. Mo–Fe–S cubane clusters are also explored as a practical example of the efficiency of this technique for elucidating the nature of not only Mo but also any other second‐row TM center in biological systems. Abstract In recent years, X‐ray emission spectroscopy (XES) in the Kβ (3p‐1s) and...
Sulfur cycle meets pathogen . Sulfonium acids known from global sulfur cycles were elucidated as the biosynthetic origin of the cyclopropanol warhead of malleicyprols, virulence factors of human‐pathogenic bacteria. The pathway involves a specialized S ‐methyl transferase to form DMSP, which is activated by a zwitterion‐specific adenylation domain and transformed into the key intermediate gonyol. Abstract Pathogenic bacteria of the Burkholderia pseudomallei group cause severe infectious diseases...
Face the interface : Using 2D surface‐specific vibrational spectroscopy, the heterogeneity of water molecules at the CaF2/water interface is quantified and information about the sub‐picosecond vibrational‐energy‐relaxation dynamics is provided. Strongly oriented H‐bonded water molecules in the adsorbed layer can exchange vibrational energy very rapidly due to a strong collective dipole, compensating for a partially missing solvation shell. Abstract We investigate the dynamics of water in contact...
The isolation and characterization of the zwitterionic intermediate in 1,1‐carboboration reactions is reported. The highly reactive zwitterionic intermediates are generated from tris(pentafluorophenyl)borane and alkynes under reaction conditions of 1,1‐carboboration. Abstract The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1‐carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1‐Carboboration...
Photo–thermo catalytic oxidation of propane (C3H8) on Pt/TiO2‐WO3 catalyst proceeds with excellent activity at high O2/C3H8 ratios and low temperatures. An investigation of the apparent activation energy and reaction orders (relative to thermal catalysis) reveals that oxygen poisoning of the supported Pt catalyst is mitigated and performance is consequently enhanced. Abstract Photo–thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic...
With the advent of layered two‐dimensional crystals, surface dangling bonds‐free planar sheets provide one emergent type of growth substrates to explore the new possibilities of crystal synthesis. While graphene has been widely exploited as the buffered substrate in van der Waals epitaxy, the encapsulation by two sheets can lock liquid droplets in between and more importantly, experience a van der Waals pressure up to 1 GPa, producing a miniaturized high‐pressure container for the crystallization...
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Abstract Squamous cell carcinoma of the external auditory canal (SCC‐EAC) is rare and has a poor prognosis. SCC‐EAC cases with high‐grade tumor budding (TB) or poorly differentiated clusters (PDCs) are associated with shorter survival than those with low‐grade TB or PDCs. Emmprin is a protein expressed in tumor cells that stimulates the production of matrix metalloproteinase (MMP)‐2 by stromal fibroblasts to facilitate tumor invasion. Recently, we reported that emmprin forms a complex with CD73...
Clonal lineage from normal endometrium to ovarian clear cell carcinoma through ovarian endometriosis
Abstract Clear cell carcinoma of the ovary is thought to arise from endometriosis. Additionally, retrograde menstruation of shed endometrium is considered the origin of endometriosis. However, little evidence supports cellular continuity from uterine endometrium to clear cell carcinoma through endometriosis at the genomic level. Here, we performed multiregional whole‐exome sequencing to clarify clonal relationships among uterine endometrium, ovarian endometriosis, and ovarian clear cell carcinoma...
Abstract The hepatocellular carcinoma (HCC) is a highly heterogenous liver cancer with significant male‐biases in incidence, disease progression and outcomes. Previous studies suggested that genes on the Y‐chromosome could be expressed and exert various male‐specific functions in the oncogenic processes. In particular, the RNA‐binding motif on the Y chromosome (RBMY ) gene is frequently activated in HCC and postulated to promote hepatic oncogenesis in patients and animal models. In the present study,...
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ABSTRACT Since January 11th, when the first 40 cases of infection by SARS‐Cov‐2 (COVID‐19 disease) were communicated from Wuhan, in the Chinese province of Hubei, about 4.5 million confirmed cases have been reported worldwide. During this three‐month period, 80,000 new cases and 11,000 deaths were registered daily. Spain holds the sad privilege of leading the European raking of confirmed cases (>228,000) and deaths (>27,000) with no consensus on the actual figures.
ABSTRACT The COVID‐19 pandemic is a major public health crisis worldwide. Dental professionals are at high risk of contracting COVID‐19 due to occupational hazard associated with aerosol generating dental procedures (Ge et al., 2020). In this commentary, we share the perspectives of dentists practicing in private practice and clinician‐researchers in academic dental institutions. More specifically, we discuss about measures implemented to minimize risks of disease transmission, challenges in emergency...
Abstract Objective The aim of this systematic review and meta‐analysis was to evaluate the experience of dental caries in individuals pre or post‐liver transplant. Materials and Methods Searches in PubMed, Scopus, Web of Science, Ovid and Lilacs from databases’ inception date up to April 2020 were undertaken. Gray literature and manual searches were also conducted. Observational studies were eligible. The retrieved references were evaluated by two independent reviewers. Meta‐analysis and...
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Abstract Purpose The critical literature review investigates the extent to which the current evidence supports that three-dimensional printing (3DP) could play an important role in human anatomy education. Methods PubMed, ERIC, and Cochrane databases were searched for papers dealing with the outcomes of 3DP implementation in human undergraduate...
Abstract Introduction There are many craniometric measurements that are used in evaluating craniovertebral junction (CVJ) pathologies such as basilar invagination, atlantoaxial dislocation and platybasia. Therefore, it is important to determine the normal reference range of the craniometric measurements. This study aims to determine the morphometric reference values of the bony structures in the CVJ from cone-beam computed tomography...
Abstract We incidentally observed the occipital artery (OA) arising from the cervical internal carotid artery (ICA) at the level of the C2 vertebral body on magnetic resonance (MR) angiography in three patients. In the rare case in which the OA arises from the ICA, it is generally at its origin. The OA arises from the cervical ICA when all but the distal part of the anastomosis of the primitive proatlantal artery between the ICA and vertebral artery persists. Careful review...
Abstract Purpose The aim of this study was to investigate the morphometric properties of the fovea capitis femoris (FCF) and its localization on the femoral head, the shape types, and the relationship with the femoral head parameters. Methods This study was performed on 146 dry femora. The morphological and morphometric properties were evaluated on...
Abstract Purpose There is not a classification of azygos anterior cerebral artery (ACA) based on anatomical branching levels in the literature. In the present study, a classification of azygos ACA was made based on radiological imaging for a common terminology, and frequency, accompanying vascular anomalies and malformations were investigated. Methods ...
Abstract Orbital fat herniation is primarily in a subconjunctival location. However, herniation through the inferior orbital fissure (IOF) has been scantly reported. Here, we report a cadaveric case of herniation of orbital fat through the inferior orbital fissure and into the infratemporal fossa. The cadaver’s orbital anatomy and orbital fat herniation were found during routine dissection. The details of this case are reported. We also discuss anatomical variations of the inferior...
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