Synthetic studies toward the immunosuppressant FR901483. Facile construction of the azatricyclic skeleton

A concise synthesis of the azatricyclic core structure of FR901483, a potent immunosuppressant, has been accomplished. The key elements of the approach involve a nucleophilic addition to an acyl iminium ion, a ring closing metathesis and a lactone-lactam rearrangement to provide the tricyclic structure.     

Advanced Materials Processing by Adsorption Control

Precise control and knowledge of surface structures are essential inorder to meet the requirements of today's and future materials. One possiblegrowth technique capable of meeting the requirements is atomic layer epitaxy(ALE). ALE is based on sequentially applied saturated gas-solid reactions,which provide the means for adsorption controlled material deposition atatomic layer level. In this paper the potentiality of the use of porousmaterials in a detailed study of adsorption controlled growth is discussed.At the same time the study promotes the application of adsorption controlledmaterials processing for advanced catalysts manufacturing.     

One-pot synthesis of chiral azetidines from chloroaldehyde and chiral amines

A variety of chiral azetidinepiperidines have been synthesized utilizing an expedient one-pot union of piperidine chloroaldehyde with chiral amines. This two step one-pot procedure provides access to an interesting set of compounds that retain the chiral purity of the starting chiral amine.     

Isotopic pattern and accurate mass determination in urine drug screening by liquid chromatography/time-of-flight mass spectrometry

An efficient method was developed for toxicological drug screening in urine by liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry. The method relies on a large target database of exact monoisotopic masses representing the elemental formulae of reference drugs and their metabolites. Mass spectral identification is based on matching measured accurate mass and isotopic pattern (SigmaFit) of a sample component with those in the database. Data post-processing software was developed for automated reporting of findings in an easily interpretable form. The mean and median of SigmaFit for true-positive findings were 0.0066 and 0.0051, respectively. The mean and median of mass error absolute values for true-positive findings were 2.51 and 2.17 ppm, respectively, corresponding to 0.65 and 0.60 mTh. For routine screening practice, a SigmaFit tolerance of 0.03 and a mass tolerance of 10 ppm were chosen. Ion abundance differences from urine extracts did not affect the accuracy of the automatically acquired SigmaFit or mass values. The results show that isotopic pattern matching by SigmaFit is a powerful means of identification in addition to accurate mass measurement.     

Low-cost,solution processable carbon nanotube supercapacitors and their characterization

We report ecological and low-cost carbon nanotube (CNT) supercapacitors fabricated using a simple, scalable solution processing method, where the use of a highly porous and electrically conductive active material eliminates the need for a current collector. Electrodes were fabricated on a poly(ethylene terephthalate) substrate from a printable multi-wall CNT ink, where the CNTs are solubilized in water using xylan as a dispersion agent. The dispersion method facilitates a very high concentration of CNTs in the ink. Supercapacitors were assembled using a paper separator and an aqueous NaCl electrolyte and the devices were characterized with a galvanostatic discharge method defined by an industrial standard. The capacitance of the \(2\hbox { cm}^2\) devices was \(6\hbox { mF/cm}^2\)  (2.3 F/g) and equivalent series resistance \(80\,\Omega \) . Low-cost supercapacitors fabricated from safe and environmentally friendly materials have potential applications as energy storage devices in ubiquitous and autonomous intelligence as well as in disposable low-end products.     

Novel approach to the lundurine alkaloids: synthesis of the tetracyclic core

The tetracyclic core of the lundurine family of alkaloids has been synthesized by a novel approach that features a double ring-closing olefin metathesis to form the five-and eight-membered rings.     

Tidal Disruption Events

The majority of supermassive black holes in the Universe lie dormant and starved of fuel. These hidden beasts can be temporarily illuminated when an unlucky star passes close enough to be tidally disrupted and consumed by the black hole. Theorists first proposed in 1975 that tidal disruption events should be an inevitable consequence of supermassive black holes in galaxy nuclei and later argued that the resulting flare of radiation from the accretion of the stellar debris could be a unique signpost for the presence of a dormant black hole in the center of a normal galaxy. It was not until over two decades later that the first convincing tidal disruption event candidates emerged in the X-rays by the ROSAT All-Sky Survey. Since then, over a dozen total candidates have now emerged from searches across the electromagnetic spectrum, including the X-rays, the ultraviolet, and the optical. In the last couple of years, we have also witnessed a paradigm shift with the discovery of relativistic beamed emission associated with tidal disruption events. I review the census of observational candidates to date and discuss the exciting prospects for using large samples of tidal disruption events discovered with the next-generation of ground-based and space-based synoptic surveys to probe accretion disk and/or jet formation and black hole demographics.     

Nuclear spin optical rotation and Faraday effect in gaseous and liquid water

Nuclear spin optical rotation (NSOR) of linearly polarized light, due to the nuclear spins through the Faraday effect, provides a novel probe of molecular structure and could pave the way to optical detection of nuclear magnetization. We determine computationally the effects of the liquid medium on NSOR and the Verdet constant of Faraday rotation (arising from an external magnetic field) in water, using the recently developed theory applied on a first-principles molecular dynamics trajectory. The gas-to-liquid shifts of the relevant antisymmetric polarizability and, hence, NSOR magnitude are found to be -14% and -29% for (1)H and (17)O nuclei, respectively. On the other hand, medium effects both enhance the local electric field in water and, via bulk magnetization, the local magnetic field. Together these two effects partially cancel the solvation influence on the single-molecular property. We find a good agreement for the hydrogen NSOR with a recent pioneering experiment on H(2)O(l).     

Modular Architecture of Protein Binding Units for Designing Properties of Cellulose Nanomaterials

Molecular biomimetic models suggest that proteins in the soft matrix of nanocomposites have a multimodular architecture. Engineered proteins were used together with nanofibrillated cellulose (NFC) to show how this type of architecture leads to function. The proteins consist of two cellulose‐binding modules (CBM) separated by 12‐, 24‐, or 48‐mer linkers. Engineering the linkers has a considerable effects on the interaction between protein and NFC in both wet colloidal state and a dry film. The protein optionally incorporates a multimerizing hydrophobin (HFB) domain connected by another linker. The modular structure explains effects in the hydrated gel state, as well as the deformation of composite materials through stress distribution and crosslinking. Based on this work, strategies can be suggested for tuning the mechanical properties of materials through the coupling of protein modules and their interlinking architectures.