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Hemoglycin, a space polymer of glycine and iron, has been identified in the carbonaceous chondritic meteorites Allende, Acfer 086, Kaba, Sutters Mill and Orgueil. Its core form has a mass of 1494Da and is basically an antiparallel pair of polyglycine strands linked at each end by an iron atom. The polymer forms two- and three- dimensional lattices with an inter-vertex distance of 4.9nm. Here the extraction technique for meteorites is applied to a 2.1Gya fossil stromatolite to reveal the presence of hemoglycin by mass spectrometry. Intact ooids from a recent (3,000Ya) stromatolite exhibited the same visible hemoglycin fluorescence in response to x-rays as an intact crystal from the Orgueil meteorite. X-ray analysis confirmed the existence in ooids of an internal 3-dimensional lattice of 4.9nm inter-vertex spacing, matching the spacing of lattices in meteoritic crystals. FTIR measurements of acid-treated ooid and a Sutters Mill meteoritic crystal both show the presence, via the splitting of the Amide I band, of an extended anti-parallel beta sheet structure. It seems probable that the copious in-fall of carbonaceous meteoritic material, from Archaean times onward, has left traces of hemoglycin in sedimentary carbonates and potentially has influenced ooid formation., Comment: 45 pages 16 Figure 8 Tables

Herein we employed high-resolution spectroscopic techniques in combination with periodic ab initio density functional theory (DFT) calculations to establish the different polarization processes for a porous copper-based MOF, termed HKUST-1. We used alternating current measurements to determine its dielectric response between 4 Hz and 1.5 MHz where orientational polarization is predominant, while synchrotron infrared (IR) reflectance was used to probe the far-IR, mid-IR, and near-IR dielectric response across the 1.2 THz to 150 THz range (ca. 40 - 5000 cm^-1) where vibrational and optical polarizations are principal contributors to its dielectric permittivity. We demonstrate the role of pressure on the evolution of broadband dielectric response, where THz vibrations reveal distinct blue and red shifts of phonon modes from structural deformation of the copper paddle-wheel and the organic linker, respectively. We also investigated the effect of temperature on dielectric constants in the MHz region pertinent to microelectronics, to study temperature-dependent dielectric losses via dissipation in an alternating electric field. The DFT calculations offer insights into the physical mechanisms responsible for dielectric transitions observed in the experiments and enable us to explain the frequency shifts phenomenon detected under pressure. Together, the experiments and theory have enabled us to glimpse into the complex dielectric response and mechanisms underpinning a prototypical MOF subject to pressure, temperature, and vast frequencies., Comment: 20 pages, 6 figures, plus Supporting Information

We present the frequency-dependant (dynamic) dielectric response of a group of topical polycrystalline zeolitic imidazolate-based metal-organic framework (MOF) materials in the extended infrared spectral region. Using synchrotron-based FTIR spectroscopy in specular reflectance, in conjunction with density functional theory (DFT) calculations, we have revealed detailed structure-property trends linking the THz region dielectric response to framework porosity and structural density. The work demonstrates that MOFs are promising candidate materials not only for low-\k{appa} electronics applications but could also be pioneering for terahertz (THz) applications, such as next-generation broadband communications technologies., Comment: 6 pages, 5 figures

We have designed, constructed and optimized a novel cell for micro photoacoustic (microPA) spectroscopy (microPAS) as part of a collaboration between the Canadian Light Source and Natural Resources Canada. The cell allows inspection of micrometric samples under a visible light microscope, together with measurement of mid-infrared absorption spectra. Our goal is to introduce a methodology enabling mid-IR investigation of micrometric samples that are inaccessible by other measurement configurations; this includes opaque samples, as well as those that are prone to scattering or possess irregular topography. We have achieved this objective, building and testing a prototype PA spectromicroscopy cell using several different optical sources.

We show clear experimental evidence of co-operative terahertz (THz) dynamics observed below 3 THz (~100 cm-1), for a low-symmetry Zr-based metal-organic framework (MOF) structure, termed MIL-140A [ZrO(O2C-C6H4-CO2)]. Utilizing a combination of high-resolution inelastic neutron scattering and synchrotron radiation far-infrared spectroscopy, we measured low-energy vibrations originating from the hindered rotations of organic linkers, whose energy barriers and detailed dynamics have been elucidated via ab initio density functional theory (DFT) calculations. For completeness, we obtained Raman spectra and characterized the alterations to the complex pore architecture caused by the THz rotations. We discovered an array of soft modes with trampoline-like motions, which could potentially be the source of anomalous mechanical phenomena, such as negative linear compressibility and negative thermal expansion. Our results also demonstrate coordinated shear dynamics (~2.5 THz), a mechanism which we have shown to destabilize MOF crystals, in the exact crystallographic direction of the minimum shear modulus (Gmin)., Comment: 10 pages, 6 figures

We present the first use of in situ far-infrared spectroscopy to analyze the thermal amorphization of a zeolitic imidazolate framework material. We explain the nature of vibrational motion changes during the amorphization process and reveal new insights into the effect that temperature has on the Zn-N tetrahedra., Comment: 5 pages, 3 figures, 2 tables