A combined three-dimensional finite element and scattering matrix method for the analysis of plane wave diffraction by bi-periodic,multilayered structures

A three-dimensional finite element method (FEM) for the analysis of plane wave diffraction by a bi-periodic slab is described and implemented. A scattering matrix formalism based on the FEM allows the efficient treatment of light reflection and transmission by multilayer bi-periodic structures, and the computation of Bloch modes of three-dimensional arrays. Numerical simulations, which show the accuracy and flexibility of the FEM, are presented.     

Luminescent ‘On-Off’ CdSe/ZnS Quantum Dot Chemodosimeter for Hydroxide Based on Photoinduced Electron Transfer from a Carboxylate Moiety

A CdSe-ZnS quantum dot (QD) has been surface functionalised by a place exchange reaction with p-mercaptomethyl benzoate synthesized by a three-step procedure. The resulting lumophore-spacer-receptor QD-conjugate was characterized by IR, UV-visible and fluorescence spectroscopy. The emission profile of the QD reveals a narrow emission peak centred at 542 nm. Addition of hydroxide to the solution containing the QD-conjugate results in quenching of the original fluorescence, which is attributed to a photoinduced electron transfer reaction from the electron-rich benzoate moiety to the QD valence band. This is the first reported example of fluorescent quenching of a CdSe-ZnS QD luminescence by an aryl carboxylate moiety.     

Determining angular frequency from images of rotating objects via a generalized fast Fourier transform

In certain real-world applications, one needs to estimate the angular frequency of a spinning object. We consider the image processing problem of estimating this rate of rotation from a video of the object taken by a camera aligned with the axis of rotation. For many types of spinning objects, this problem can be addressed with existing techniques: simply register two consecutive video frames. We focus, however, on objects whose shape and intensity changes greatly from frame to frame, such as spinning plumes of plasma that emerge from a certain type of spacecraft thruster. To estimate the angular frequency of such objects, we introduce the Geometric Sum Transform (GST), a new rotation-based generalization of the discrete Fourier transform (DFT). Taking the GST of a given video produces a new sequence of images, the most coherent of which corresponds to the object’s true rate of rotation. After formally demonstrating this fact, we provide a fast algorithm for computing the GST which generalizes the decimation-in-frequency approach for performing a Fast Fourier Transform (FFT). We further show that computing a GST is, in fact, mathematically equivalent to computing a system of DFTs, provided one can decompose each video frame in terms of an eigenbasis of a rotation operator. We conclude with numerical experimentation.     

Composite Likelihood Inference in a Discrete Latent Variable Model for Two-Way “Clustering-by-Segmentation” Problems

We consider a discrete latent variable model for two-way data arrays, which allows one to simultaneously produce clusters along one of the data dimensions (e.g., exchangeable observational units or features) and contiguous groups, or segments, along the other (e.g., consecutively ordered times or locations). The model relies on a hidden Markov structure but, given its complexity, cannot be estimated by full maximum likelihood. Therefore, we introduce a composite likelihood methodology based on considering different subsets of the data. The proposed approach is illustrated by simulation, and with an application to genomic data.     

Enhancement of naringenin solution concentration by solid dispersion in cellulose derivative matrices

Naringenin (Nar) is an important bioactive flavonoid with poor organic solubility and oral bioavailability. It is highly promising for treatment of conditions including diabetes, hyperlipidemia, and hepatitis C infection. Amorphous solid dispersion (ASD) of Nar is an appealing way to enhance its solubility, and carboxylated cellulose esters are attractive polymers for this purpose because of their ability to stabilize drugs against crystallization in both solid and solution phases, while restricting drug release to the pH of the small intestine (ca. 6.8). We demonstrate that ASDs of Nar can be formed using such carboxylated cellulose derivatives as cellulose acetate adipate propionate (CAAdP), carboxymethylcellulose acetate butyrate (CMCAB) and hydroxypropylmethylcellulose acetate succinate (HPMCAS). We compare Nar solution concentrations and release profiles from these cellulosic ASDs to those from pure crystalline Nar, and to Nar ASD in poly(vinylpyrrolidinone) (PVP). We show that all polymers in this study form ASDs with Nar, that the PVP ASDs release Nar at both gastric (1.2) and small intestine (6.8) pH, and that the cellulosic polymers release Nar selectively at neutral pH. Solution concentrations of Nar are significantly enhanced from these ASDs. These preliminary studies indicate that HPMCAS, CAAdP, and CMCAB are practical ASD polymers for Nar due to their ability to generate and stabilize high solution concentrations, and their pH-triggered drug release.     

Synthesis and evaluation of N6-substituted azide- and alkyne-bearing N-mustard analogs of S-adenosyl-l-methionine

The synthesis of a family of N-mustard analogs of S-adenosyl-l-methionine (SAM) containing azides and alkynes at the N6-position of the adenosine base has been accomplished from commercially available inosine. Further biochemical analysis of these analogs indicates successful modification of pUC19 plasmid DNA in an enzyme-dependent fashion with DNA methyltransferases M.TaqI and M.HhaI.     

Stereoselective Remote Functionalization via Palladium-Catalyzed Redox-Relay Heck Methodologies

Exploration of novel, three-dimensional chemical space is of growing interest in the drug discovery community and with this comes the challenge for synthetic chemists to devise new stereoselective methods to introduce chirality in a rapid and efficient manner. This Minireview provides a timely summary of the development of palladium-catalyzed asymmetric redox-relay Heck-type processes. These reactions represent an important class of transformation for the selective introduction of remote stereocenters, and have risen to prominence over the past decade. Within this Minireview, the vast scope of these transformations will be showcased, alongside applications to pharmaceutically relevant chiral building blocks and drug substances. To complement this overview, a mechanistic summary and discussion of the current limitations of the transformation are presented, followed by an outlook on future areas of investigation.     

Photo-induced ligand substitution at a remote site via electron transfer in a porphyrin-appended rhenium carbonyl supermolecule

The photochemical and electrochemical properties of a Zn-porphyrin appended rhenium(I) tricarbonyl bipyridine 3-Me-pyridine complex have been investigated; visible-light sensitisation of electron transfer results in ligand substitution at a site remote from the chromophore.