A new and useful method for the macrocyclization of linear peptides

A new and useful procedure for the macrocyclization of linear peptides is described. The natural amino acid side chains of tyrosine (phenol), lysine (alkylamine), and histidine (imidazole) react in an intramolecular fashion with a pendent pyridine-N-oxide-carboxamide, which is selectively activated by the phosphonium salt, PyBroP. The reaction is mild, rapid, and efficient with a potentially large substrate scope. Multiple examples are provided with full characterization and analyses, including a novel aza-variant of the C-O-D ring system of vancomycin.     

Phonon-assisted optical absorption in silicon from first principles

The phonon-assisted interband optical absorption spectrum of silicon is calculated at the quasiparticle level entirely from first principles. We make use of the Wannier interpolation formalism to determine the quasiparticle energies, as well as the optical transition and electron-phonon coupling matrix elements, on fine grids in the Brillouin zone. The calculated spectrum near the onset of indirect absorption is in very good agreement with experimental measurements for a range of temperatures. Moreover, our method can accurately determine the optical absorption spectrum of silicon in the visible range, an important process for optoelectronic and photovoltaic applications that cannot be addressed with simple models. The computational formalism is quite general and can be used to understand the phonon-assisted absorption processes in general.     

Vibroacoustic characteristics of a gothic harp

The "gothic" style of harp was popular across most of Europe from the late medieval period to the Renaissance. These harps have a one-piece, longitudinally oriented hardwood soundboard, as opposed to the transverse-oriented bonded softwood structure on a modern instrument. In addition, the one-piece back is flexible, whereas the back of a modern instrument is a rigid molded shell. To study the gothic harp, one was constructed from plans created by the Boston Museum of Fine Arts from a late German model in their collection. The vibrational behaviors of the soundboard and soundbox were measured at various stages of construction. The completed instrument was subjected to modal analysis and radiativity measurements. The sound radiation is dominated by two breathing modes at 188 and 273 Hz, each with strong motion of the back, and modes around 350 Hz. Taken together, these modes function like the A0/T1 resonance pairs seen in the soundboxes of other instruments, and a comparison is made with the guitar. Also observed is that as the frequency increases, radiation is emitted from higher up the soundboard, and from higher soundholes. This feature has been observed in other harps, and is a consequence of the harp family's unique geometry.     

Graphene for energy harvesting/storage devices and printed electronics

Graphene-based materials are intriguing from the perspective of fundamental science and technology because they are non-toxic, chemically and thermally tolerant, and mechanically robust. Graphene exhibits superior electrical conductivity, high surface area and a broad electrochemical window that may be particularly advantageous for their applications in energy storage devices. In addition, graphene can be prepared in the form of a colloidal suspension with adjustable solubility and thus is suitable for printing applications and offers both transparency and good conductivity at the same time. In this review, applications of graphene in solar cells, batteries, supercapacitors and fuel cells are summarized with the latest developments. Furthermore, graphene as a conductive ink for printed electronics is also discussed.     

Assessing methodologies for calculating road traffic noise levels in Ireland - Converting CRTN indicators to the EU indicators (Lden, Lnight)

To comply with the EU Noise Directive 2002/49/EC, Member States are required to produce strategic noise maps for designated areas, including mapping road traffic noise from major roads. These maps must be presented using the EU indicators L_den and L_night. However, the most common noise indicator used in Ireland at present is the L_A10,18h indicator arising from the use of the Calculation of Road Traffic Noise (CRTN) prediction method. Therefore, a relationship needs to be established between L_A10,18h and L_den and L_night, separately. In addition to noise mapping these indicators are used for noise abatement purposes, so the proposed relationship must be accurate and robust. In 2002, the UK’s Transport Research Laboratory (TRL) published a paper describing mathematical procedures that could be used to convert values of L_A10 to L_den and L_night. These procedures were then adopted for use in Ireland. This paper examines the suitability of the TRL conversion methods 1 and 3 for use under Irish road conditions. Method 2 was not considered in this study, as it was a methodology not applicable in an Irish scenario. Studies concluded that where hourly traffic data are available, the conversion methodology outlined in TRL Method 1 is robust and reproducible. However, in the absence of hourly traffic data where daily traffic counts are used, the relevant conversion procedures produce variable results for both L_den and L_night when applied to Irish road conditions. To reduce the variability, new conversion procedures were developed, specifically for Irish road conditions.     

The use of calcination in exposing the entrapped Fe particles from multi-walled carbon nanotubes grown by chemical vapour deposition

Multi-walled carbon nanotubes (MWCNTs) were synthesized a by chemical vapour deposition method. The effect of calcination at temperatures ranging from 300 to 550°C in exposing the metal nanoparticles within the nanotube bundles was studied. The degree of degradation of the structural integrity of the MWCNTs during the thermal process was studied by Raman spectroscopy, X-ray diffraction analysis, field-emission scanning electron microscopy, and transmission electron microscopy. The thermal behaviour of the as-prepared and calcined samples was investigated by thermogravimetric analysis. Calcination in air, at 400°C for 1 h, was found to be an efficient and simple method to extract metallic impurities from the amorphous carbon shells with minimal damage to the tube walls and lengths. The nanotubes were observed to be damaged at temperatures higher than 450°C.     

The Structure of (SCN)x: A Study Using Molecular and Solid‐State Density Functional Theory Calculations

A riddle solved! Despite its simple formula, the structure of the (SCN)_x polymer has remained elusive since its first synthesis in 1929. From energetics as well as NMR chemical shifts, based on DFT calculations, we have strong evidence that it is indeed a tangle of linear chains, made up from N‐linked S₂C₂N five‐membered rings.

     

Planning sustainable community health schemes in rural areas of developing countries

In this research, we consider the planning of community health schemes by non-governmental or faith-based organisations in rural areas of developing countries, from both top-down and ground level viewpoints. We conclude that both types of planning approach are valid and necessary for sustainability of such developments. With top-down planning in mind, we describe our hierarchical models especially designed for location of community health facilities, with objectives pertaining to both efficiency and equity of provision. As an additional case study, we present modelling of the location of a maximal number of self-sustainable primary healthcare workers in a rural region of India.