Total Synthesis of (±)‐Phyllantidine: Development and Mechanistic Evaluation of a Ring Expansion for Installation of Embedded Nitrogen‐Oxygen Bonds

The development of a concise total synthesis of (±)‐phyllantidine ( 1 ), a member of the securinega family of alkaloids containing an unusual oxazabicyclo[3.3.1]nonane core, is described. The synthesis employs a unique synthetic strategy featuring the ring expansion of a substituted cyclopentanone to a cyclic hydroxamic acid as a key step that allows facile installation of the embedded nitrogen‐oxygen (N?O) bond. The optimization of this sequence to effect the desired regiochemical outcome and its mechanistic underpinnings were assessed both computationally and experimentally. This synthetic approach also features an early‐stage diastereoselective aldol reaction to assemble the substituted cyclopentanone, a mild reduction of an amide intermediate without N?O bond cleavage, and the rapid assembly of the butenolide found in ( 1 ) via use of the Bestmann ylide.     

Energy deposition during electron-induced dissociation

We report studies of the internal energy deposited during activation of mass-selected ions through electron-ion collisions. Characteristic fragmentations of the molecular ion of limonene and W(CO) ^n/+ (n = 1–6) indicate that electron-induced dissociation in a Fourier transform ion cyclotron resonance mass spectrometer proceeds via multiple collisions and that the average internal energy deposited during the activation process can be selected to be similar to that associated with electron-impact ionization. Control of the degree of ion excitation through selection of the electron energy, flux, and interaction time with the ions of interest is demonstrated, and advantages of this promising activation technique are discussed.     

The efficacy of tilted axial MRI of the CNS

The angle between the straight axial plane and the orbito-meatal line was measured in 156 consecutive magnetic resonance examinations. Inconsistent head positioning caused this angle to vary by as much as 44 degrees. Careful positioning of the patient by the technologist can minimize this variability, leading potentially to improved image interpretation. To assess the merit of a standardized orientation for MR examinations of the head, straight axial and tilted axial MR scans were compared in 34 patients. The tilted images were obtained parallel to the orbito-meatal line and were found to be superior for visualization of the cerebellum. When correlative x-ray CTs are available or when an abnormality in the posterior fossa is suspected, tilted axial MR scans should be employed.     

Silica aerogel–poly(ethylene‐co‐vinyl acetate) composite for transparent heat retention films

Poly(ethylene‐co‐vinyl acetate) (EVA) plastic films are widely used for solar coverings including photovoltaic modules and commercial greenhouse films, but are poor at controlling heat flow. In this work, silica aerogel (SA) nanogels were examined for preparing transparent heat retention EVA films that block far infrared spectra radiation to maintain heat, without compromising the optical performance of the films. SA nanogels were melt‐mixed using a mini twin‐screw extruder with EVA pellets to form SA/EVA composite, which were pressed into thin films with controlled thickness. The composite films were characterized in terms of optical properties using a variety of analytical methods including FTIR, UV–Vis spectroscopy, electron, confocal, and atomic force microscopy. Both thermicity and thermal conductivity of commercial and experimental SA/EVA films were measured. The results demonstrated that the SA/EVA films gave improved infrared retention compared to commercial thermal plastic films without compromising visible light transmission, showing the potential for this approach in next generation heat retention films. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 927–935     

Efficient Preparation of γ-Hydroxynitriles via Nitrile Enolate-Epoxide Reactions: Scope and Diastereoselectivity

The nucleophilic opening of epoxides by nitrile enolates using an efficient, convenient protocol is described. The diastereoselectivity of this reaction was explored and found to give syn:anti ratios ranging from 1.1:1.0 to 4.8:1.0.

     

The structure of linear codes of constant weight

In this paper we determine completely the structure of linear codes over of constant weight. Namely, we determine exactly which modules underlie linear codes of constant weight, and we describe the coordinate functionals involved. The weight functions considered are: Hamming weight, Lee weight, two forms of Euclidean weight, and pre-homogeneous weights. We prove a general uniqueness theorem for virtual linear codes of constant weight. Existence is settled on a case by case basis.