Precise Fingerprint Determination of Vibrational Infrared Spectra in a Series of Co(II) Clathrochelates through Experimental and Theoretical Analyses.

The energetic demands of modern society for clean energy vectors, such as H, have caused a surge in research associated with homogeneous and immobilized electrocatalysts that may replace Pt. In particular, clathrochelates have shown excellent electrocatalytic properties for the hydrogen evolution reaction (HER). However, the actual mechanism for the HER catalyzed by these -metal complexes remains an open debate, which may be addressed via Operando spectroelectrochemistry.

Dramatic Effect of A Ring Size of Alicyclic α-Dioximate Ligand Synthons on Kinetics of the Template Synthesis and of the Acidic Decomposition of the Methylboron-Capped Iron(II) Clathrochelates.

Kinetics and thermodynamics of the template synthesis and of the acidic decomposition of the methylboron-capped iron(II) tris-1,2-dioximates-the clathrochelate derivatives of six (nioxime)- and eight (octoxime)-membered alicyclic ligand synthons-were compared. In the case of a macrobicyclic iron(II) tris-nioximate, the plausible pathway of its formation contains a rate-determining stage and includes a reversible formation of an almost trigonal-antiprismatic (TAP) protonated tris-complex, followed by its monodeprotonation and addition of CHB(OH). Thus, the formed TAP intermediate undergoes a multistep rate-determining stage of double cyclization with the elimination of two water molecules accompanied by a structural rearrangement, thus giving an almost trigonal-prismatic (TP) iron(II) semiclathrochelate.

Extension and functionalization of an encapsulating macrobicyclic ligand using palladium-catalyzed Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates with inherent halogen substituents.

A new approach for performing Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates, optimizing their reaction conditions (such as temperature, solvent and a palladium-containing catalyst) and the nature of other reagents (such as arylboron components) is elaborated. These palladium-catalyzed reactions are very sensitive to the nature of the macrobicyclic substrates. The reactivity of the leaving halogen atoms correlates with their ability to undergo an oxidative addition, decreasing in the order: I > Br > Cl, and iron(ii) diiodoclathrochelate underwent these C-C cross-couplings under their "classical" conditions.

Atlas-based shape analysis and classification of retinal optical coherence tomography images using the functional shape (fshape) framework.

We propose a novel approach for quantitative shape variability analysis in retinal optical coherence tomography images using the functional shape (fshape) framework. The fshape framework uses surface geometry together with functional measures, such as retinal layer thickness defined on the layer surface, for registration across anatomical shapes. This is used to generate a population mean template of the geometry-function measures from each individual.

Exact surface registration of retinal surfaces from 3-D optical coherence tomography images.

Nonrigid registration of optical coherence tomography (OCT) images is an important problem in studying eye diseases, evaluating the effect of pharmaceuticals in treating vision loss, and performing group-wise cross-sectional analysis. High dimensional nonrigid registration algorithms required for cross-sectional and longitudinal analysis are still being developed for accurate registration of OCT image volumes, with the speckle noise in images presenting a challenge for registration. Development of algorithms for segmentation of OCT images to generate surface models of retinal layers has advanced considerably and several algorithms are now available that can segment retinal OCT images into constituent retinal surfaces.