Synthesis and characterization of 1-methyl-1-silaindane and 1-methyl-1-germaindane

New synthetic routes to 1-methyl-1-silaindane (1b) and 1-methyl-1-germaindane (1b) were developed and the desired products were obtained in good isolated yield. Compounds 1a and 1b were fully characterized by mass spectroscopy, ¹H and ¹³C{¹H} NMR, and infrared spectroscopy.     

Highly selective olefin epoxidation with aqueous H2O2 over surface-modified TaSBA15 prepared via the TMP method

Trialkylsiloxy-modified Ta(v) centers on mesoporous silica exhibit excellent selectivity for epoxide formation (>98% after 2 h) in the oxidation of cyclohexene using aqueous H2O2 as the oxidant; the modified catalysts exhibit an increased lifetime, retaining high selectivity after 6 h of reaction (>95% epoxide).     

The classification and curvature of biquotients of the form Sp(3)/\!\!/Sp(1)^2

We show there are precisely \(15\) inhomogeneous biquotients of the form \(Sp(3)/\!\!/Sp(1)^2\) and show that at least \(8\) of them admit metrics of quasi-positive curvature.     

Elemental Composition Validation from Stored Waveform Inverse Fourier Transform (SWIFT) Isolation FT-ICR MS Isotopic Fine Structure

Elemental composition assignment confidence in mass spectrometry is typically assessed by monoisotopic mass accuracy. For a given mass accuracy, resolution and detection of other isotopologues can further narrow the number of possible elemental compositions. However, such measurements require ultrahigh resolving power and high dynamic range, particularly for compounds containing low numbers of nitrogen and oxygen (both ¹⁵N and ¹⁸O occur at less than 0.4 % natural abundance). Here, we demonstrate validation of molecular formula assignment from isotopic fine structure, based on ultrahigh resolution broadband Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Dynamic range is enhanced by external quadrupole and internal stored waveform inverse Fourier transform (SWIFT) isolation to facilitate detection of low abundance heavy atom isotopologues.

(N‐Phosphinoamidinate)cobalt‐Catalyzed Hydroboration: Alkene Isomerization Affords Terminal Selectivity

Herein we establish the utility of a three‐coordinate (N‐phosphinoamidinate)cobalt(amido) pre‐catalyst that is capable of effecting challenging alkene isomerization/hydroboration processes at room temperature, leading to the selective terminal addition of the boron group.     

Voice Handicap Index Results for Older Patients with Adductor Spasmodic Dysphonia

Adductor spasmodic dysphonia (ADSD) adversely affects a speaker's ability to effectively communicate. For many individuals suffering with ADSD, botulinum toxin (Botox) is the chosen treatment to remediate the symptoms. Although Botox's effects on symptom remediation have been examined before, patient perception of improvement post-Botox has been examined less frequently. Further, no studies have addressed the symptomatic changes in older adults that occur after Botox treatment. The Voice Handicap Index (VHI) was used as the instrument to assess older patient's (>65 years) perception of how ADSD impacts certain areas of their life pre- and post-Botox injection. The outcome of the VHI was related to a clinical judgment of voice severity. Participants also completed the Social Readjustment Rating Scale (SRRS) to examine overall stress level, and the outcome of the SRRS was correlated to postinjection VHI scores. Results indicated no significant correlation between VHI scores and voice severity or SRRS ratings. The current study suggests further study of voice outcomes with older adults with ADSD is needed.     

Kinetics and mechanism of olefin epoxidation with aqueous H2O2 and a highly selective surface-modified TaSBA15 heterogeneous catalyst

The reaction kinetics of cyclohexene epoxidation using aqueous H2O2 oxidant and the highly selective epoxidation catalyst Bu(cap)TaSBA15 were studied. The reaction was determined to be first-order in Ta(V) surface coverage. The reaction rate exhibited saturation with respect to increasing concentrations of cyclohexene and H2O2. An Eley-Rideal mechanism and rate equation may be used to describe the epoxidation kinetics, which are similar to those for Ti(IV)SiO2-catalyzed epoxidations. The observed kinetics may also be modeled by a double-displacement mechanism typically associated with saturation enzyme catalysts. In addition, (1)H NMR spectroscopy was employed to investigate H2O2 decomposition by Bu(cap)TaSBA15 and the unmodified TaSBA15 catalysts. Little decomposition occurred over the surface-modified material, but the unmodified material catalyzed a 30% conversion of H2O2 after 6 h. UV-visible absorbance and diffuse reflectance UV-visible (DRUV-vis) spectroscopy were used to investigate the structure of the Ta centers on the TaSBA15 catalysts. DRUV-vis spectroscopy was also used to identify a Ta(V)-based epoxidation intermediate, proposed to be a Ta(V)(eta(2)-O2) species, which forms upon reaction of the TaSBA15 and Bu(cap)TaSBA15 materials with H2O2.     

Stereoselective β-mannosylations and β-rhamnosylations from glycosyl hemiacetals mediated by lithium iodide

Stereoselective β-mannosylation is one of the most challenging problems in the synthesis of oligosaccharides. Herein, a highly selective synthesis of β-mannosides and β-rhamnosides from glycosyl hemi-acetals is reported, following a one-pot chlorination, iodination, glycosylation sequence employing cheap oxalyl chloride, phosphine oxide and LiI. The present protocol works excellently with a wide range of glycosyl acceptors and with armed glycosyl donors. The method doesn''t require conformationally restricted donors or directing groups; it is proposed that the high β-selectivities observed are achieved via an S_N2-type reaction of α-glycosyl iodide promoted by lithium iodide.

Breaking from the current paradigm, a highly selective synthesis of hard-to-make β-mannosides and β-rhamnosides from simple glycosyl hemi-acetals has been achieved without using conformational restrictions.     

Mathematical modelling of tongue deformation during swallow in patients with head and neck cancer

ABSTRACT

Cancer localized to the tongue is often characterized by increased stiffness in the affected region. This stiffness affects swallow in a manner that is difficult to quantify in patients. A biomechanical model was developed to simulate the spatio-temporal deformation of the tongue during the pharyngeal phase of swallow in patients with cancer of the tongue base. The model involves finite element analysis (FEA) of a three-dimensional (3D) model of the tongue reconstructed from magnetic resonance images (MRI). The tongue tissue is assumed to be hyper-elastic. In order to examine the effects of tissue change (increased stiffness) due to the presence of cancer localized to the tongue base, various sections of the 3D geometry are modified to exhibit different elastic properties. Three cases are considered, representing the normal tongue, a tongue with early-stage cancer, and tongue with late-stage cancer. Early- and late-stage cancers are differentiated by the degree of stiffness within the base of tongue tissue. Analysis of the model suggests that healthy tongue has a maximum deformation of 9.38 mm, whereas tongues having mild cancer and severe cancer have a maximum deformation of 8.65 and 6.17 mm, respectively. Biomechanical modelling is a useful tool to explain and estimate swallowing abnormalities associated with tongue cancer and post-treatment characteristics.