An improved approach to chiral cyclopentenone building blocks. Total synthesis of pentenomycin I and neplanocin A

An improved approach to enantiomerically pure hydroxylated cyclopentenones is reported here, which involves intramolecular nitrone cycloaddition of sugar-derived chiral pent-4-enals and hex-5-en-ones-2 followed by N-O bond cleavage, quaternization of the amine thus produced, and finally oxidative elimination of the amino group. Synthesis of pentenomycin I and neplanocin A is described following this methodology.     

The conformational analysis of aromatic methoxyl groups from carbon-13 chemical shifts and spin-lattice relaxation times

In a series of polymethoxy benzaldehydes and acetophenones it was found that diortho-substitution distorts the ArOCH₃ conformation. This distortion is accompanied by a downfield shift in the corresponding methoxyl ¹³C frequencies and an increase in their spin-lattice relaxation times.     

The natural hedge of a gas-fired power plant

Electricity industries worldwide have been restructured in order to introduce competition. As a result, decision makers are exposed to volatile electricity prices, which are positively correlated with those of natural gas in markets with price-setting gas-fired power plants. Consequently, gas-fired plants are said to enjoy a “natural hedge.” We explore the properties of such a built-in hedge for a gas-fired power plant via a stochastic programming approach, which enables characterisation of uncertainty in both electricity and gas prices in deriving optimal hedging and generation decisions. The producer engages in financial hedging by signing forward contracts at the beginning of the month while anticipating uncertainty in spot prices. Using UK energy price data from 2006 to 2011 and daily aggregated dispatch decisions of a typical gas-fired power plant, we find that such a producer does, in fact, enjoy a natural hedge, i.e., it is better off facing uncertain spot prices rather than locking in its generation cost. However, the natural hedge is not a perfect hedge, i.e., even modest risk aversion makes it optimal to use gas forwards partially. Furthermore, greater operational flexibility enhances this natural hedge as generation decisions provide a countervailing response to uncertainty. Conversely, higher energy-conversion efficiency reduces the natural hedge by decreasing the importance of natural gas price volatility and, thus, its correlation with the electricity price.     

Assembly of quantum dots on peptide nanostructures and their spectroscopic properties

We present a chemical process for the decoration of self-assembled two-dimensional peptide fibrils with two different sizes of CdSe@ZnS core–shell quantum dots (Qdots) capped with trioctylphosphine oxide molecules. The attachment of the semiconducting nanoparticles to the fibrils is directed via disulfide bond between the quantum dot and cysteine aminoacids that are deliberately impeded in the peptide structures. A significant red shift in the emission spectra of the quantum dots is observed and attributed to the synergistic interaction between adjacent nanoparticles arranged on peptide film templates extending over hundreds of nanometers.     

Computational techniques for the analysis and design of dielectric-loaded plasmonic circuitry

The finite element and the beam propagation method, two widely used methods in photonics, are utilized for the analysis of plasmonic components based on the dielectric-loaded plasmonic waveguide. Two components are chosen as examples and are subsequently numerically investigated by employing the aforementioned methods, in order to demonstrate their applicability in plasmonics. Specifically, a microring resonator add-drop filter and a Mach–Zehnder interferometric switch are analyzed by means of the finite element and the beam propagation method, respectively. The formulation adopted is clearly presented in both cases and the case-dependent implementation details are thoroughly discussed.     

A chiral phosphazane reagent strategy for the determination of enantiomeric excess of amines

Methods for measuring enantiomeric excess (ee) of organic molecules by NMR spectroscopy provide rapid analysis using a standard technique that is readily available. Commonly this is accomplished by chiral derivatisation of the detector molecule (producing a chiral derivatisation agent, CDA), which is reacted with the mixture of enantiomers under investigation. However, these CDAs have almost exclusively been based on carbon frameworks, which are generally costly and/or difficult to prepare. In this work, a methodology based on the readily prepared inorganic cyclodiphosph(iii)azane CDA ClP(μ-N^tBu)₂POBorn (Born = endo-(1S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl) is shown to be highly effective in the measurement of ee’s of chiral amines, involving in situ reaction of the chiral amines (R*NH₂) with the P–Cl bond of the CDA followed by quaternization of the phosphorus framework with methyl iodide. This results in sharp ³¹P NMR signals with distinct chemical shift differences between the diastereomers that are formed, which can be used to obtain the ee directly by integration. Spectroscopic, X-ray structural and DFT studies suggest that the NMR chemical shift differences between diastereomers is steric in origin, with the sharpness of these signals resulting from conformational locking of the bornyl group relative to the P₂N₂ ring induced by the presence of the P(v)-bonded amino group (R*NH). This study showcases cheap inorganic phosphazane CDAs as simple alternatives to organic variants for the rapid determination of ee.

The simple inorganic cyclodiphosph(iii)azane chiral derivatisation agent ClP(μ-^tBuN)₂POBorn (Born = endo-(1S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl) is shown to be effective in the measurement of ee’s of chiral amines using ³¹P NMR spectroscopy.     

Nonlinear constitutive force model selection,update and uncertainty quantification for periodically sequential impact applications

Nonlinear Dynamics - Contact–impact events frequently occur between solid contact interfaces in complex dynamic mechanical systems and engineering applications. Impact force models are used...     

Enhancing Magnetic Communication between Metal Centres: The Role of s-Tetrazine Based Radicals as Ligands

Although 1,2,4,5-tetrazines or s-tetrazines have been known in the literature for more than a century, their coordination chemistry has become increasingly popular in recent years due to their unique redox activity, multiple binding sites and their various applications. The electron-poor character of the ring and stabilization of the radical anion through all four nitrogen atoms in their metal complexes provide new aspects in molecular magnetism towards the synthesis of new high performing Single Molecule Magnets (SMMs). The scope of this review is to examine the role of s-tetrazine radical ligands in transition metal and lanthanide based SMMs and provide a critical overview of the progress thus far in this field. As well, general synthetic routes and new insights for the preparation of s-tetrazines are discussed, along with their redox activity and applications in various fields. Concluding remarks along with the limitations and perspectives of these ligands are discussed.     

Total synthesis of dimeric pyrrole-imidazole alkaloids: sceptrin, ageliferin, nagelamide e, oxysceptrin, nakamuric acid, and the axinellamine carbon skeleton

The dimeric pyrrole imidazole natural products are a growing class of alkaloids with exotic connectivity, unique topologies, high nitrogen content, and exciting bioactivities. This full account traces the evolution of a strategy that culminated in the first total syntheses of several members of this family, including sceptrin, ageliferin, nagelamide E, nakamuric acid (and its methyl ester), and oxysceptrin. Details on the fascinating conversion of sceptrin to ageliferin, which has been used to produce gram quantities of this sensitive natural product, are provided. In addition, the first enantioselective total synthesis of sceptrin and ageliferin are reported by programming the fragmentation of an oxaquadricyclane. A hallmark of our approach to this family of alkaloids is the minimal use of protecting groups despite the presence of 10 nitrogen atoms in the target compounds. Thus, the fundamental chemistry of the 2-aminoimidazole heterocycle was explored without masking its innate reactivity. Insights gained during these explorations led to total syntheses of oxysceptrin and nakamuric acid and a successful construction of the carbon skeleton of axinellamine.