Rapid Discrimination of Crystal Handedness by X-ray Natural Circular Dichroism (XNCD) Mapping

An original method for determining the handedness of individual non-centrosymmetric crystals in a mixture using a tightly-focused, circularly polarized X-ray beam is presented. The X-ray natural circular dichroism (XNCD) spectra recorded at the metal K-edge on selected crystals of [Δ-M(en)₃](NO₃)₂ and [Λ-M(en)₃](NO₃)₂ (M=Co^II, Ni^II) show extrema at the metal pre-edge (7712 eV for Co, 8335 eV for Ni). A mapping of a collection of some 220 crystals was performed at the respective energies by using left and right circular polarizations. The difference in absorption for the two polarizations, being either negative or positive, directly yielded the handedness of the crystal volume probed by the beam. By using this technique, it was found that the addition of l -ascorbic acid during the synthesis of [Co(en)₃](NO₃)₂ resulted in an enantiomeric enrichment of the Λ-isomer of 67±13 %, whereas the Ni analogue was similarly, but conversely, enriched in the Δ-isomer (65±22 %).     

Mechanisms of graphene influence on cell differentiation

The graphene family of nanomaterials (GFN) have a common carbon lattice base structure but represent a diverse range of materials with distinct chemical and physical characteristics. These characteristics are determined by the fabrication method and impart each material with specific chemical properties which govern interaction with cells and biomolecules, and physical properties that give unique nanotopography, stiffness, and electrical properties. Remarkably, members of the GFN have been shown to promote tissue formation and influence cell differentiation in a variety of tissue types, including neural, bone, and cardiac muscle, making them of high interest to the biomedical field. The diverse range of materials and experimental setups in the literature make uncovering the mechanism of action challenging. Nevertheless, it is becoming clear that the ability of GFN to form non-covalent interactions (π-π, hydrogen bonding, electrostatic) with biomolecules may increase their bioavailability via sequestering/concentration/conformation protection to induce cell differentiation. In addition to the chemical properties, the stimulation of mechanosensing pathways, cytoskeletal rearrangement, and enhanced electrical activity of cells on GFN substrates demonstrates the importance of the physical properties in directing cell differentiation. The understanding of the mechanism behind the ability of GFN to enhance cell differentiation will allow the design and selection of materials with the desired properties for tissue repair and regeneration.     

Cyclobutane-based peptides/terpyridine conjugates: Their use in metal catalysis and as functional organogelators

Two new conjugates, hcptpyDP and hcptpyTP, of a terpyridine derivative incorporating artificial peptide moieties, have been synthesized and their use in the preparation of metal catalysts and organogelators has been investigated. Ru(II) complexes derived from these ligands showed electrochemical behavior and activity as catalysts in the epoxidation of olefins similar to that of Beller's catalyst. As organogelators, these conjugates were able to gelate a variety of solvents, from toluene to methanol, with satisfactory mgc (minimum gelation concentration) values. The presence of 4′-(4-carboxy)phenylterpyridine (hcptpy) moiety allows tuning the gelling properties and also influences the supramolecular self-assembling mode to produce chiral aggregates with respect to parent peptides DP and TP. In the case of the conjugates, π?π interactions provided by the aromatic moieties cooperate with inter-molecular hydrogen bonding between NH and CO in the amide groups. Further properties of peptide/terpyridine conjugates are under investigation in view of future applications.     

Unusual synthesis of azines and their oxidative degradation to carboxylic acid using iodobenzene diacetate

Reaction of 3-hydrazonobutan-2-one oxime with aromatic aldehydes resulted in the formation of 1,2-bis(arylidene)hydrazine commonly referred as azine as an unexpected product, instead of expected product 3-(aryl)methylenehydrazonobutan-2-one oxime, which were subsequently oxidized to corresponding aromatic acids with an ecofriendly oxidizing agent iodobenzene diacetate. Azines and carboxylic acids were characterized by IR and NMR (¹H, ¹³C, HMBC, and HMQC) studies.     

Tunable diode lasers and two-tone frequency modulation spectroscopy applied to atmospheric gas analysis

In this paper, we discuss the main features of a class of gas analyzers based on spectroscopic techniques with the aim of realizing fully automated systems which can be used for practical purposes. The technique we deal with is based on semiconductor diode laser as sources, emitting in the near infrared region of the electromagnetic spectrum, and the two-tone frequency modulation spectroscopy as the detection technique. We will describe the main features of a typical device and two particular apparata for industrial and biological applications.     

Determination of strain and stress distribution on shearwalls by using the speckle photography technique

Speckle photography (SP) is a powerful tool that is adequate to determine small displacements in micrometer range. This information shows other characteristics of structure deformation under loads and can be determined as stress and strain distribution. In this paper we present the results of the application of the SP technique used to study the behaviour of discontinuities in a shearwall model. These structural elements are very important to the stability of buildings. The displacement whole field around the discontinuities and loading points was determined using the pointwise method. This allows us to determine stress distribution at the point of interest by means of the suitable equations. We also present the stress distribution obtained through the finite element method in order to compare the results obtained by means of these two techniques. Good correspondence was found between the displacements determined by both techniques (r=0.982) and also between the stress values we obtained.     

Laboratory singing sand avalanches

Some desert sand dunes have the peculiar ability to emit a loud sound up to 110 dB, with a well-defined frequency: this phenomenon, known since early travelers (Darwin, Marco Polo, etc.), has been called the song of dunes. But only in late 19th century scientific observations were made, showing three important characteristics of singing dunes: first, not all dunes sing, but all the singing dunes are composed of dry and well-sorted sand; second, this sound occurs spontaneously during avalanches on a slip face; third this is not the only way to produce sound with this sand.More recent field observations have shown that during avalanches, the sound frequency does not depend on the dune size or shape, but on the grain diameter only, and scales as the square root of g/d - with g the gravity and d the diameter of the grains - explaining why all the singing dunes in the same vicinity sing at the same frequency.We have been able to reproduce these singing avalanches in laboratory on a hard plate, which made possible to study them more accurately than on the field. Signals of accelerometers at the flowing surface of the avalanche are compared to signals of microphones placed above, and it evidences a very strong vibration of the flowing layer at the same frequency as on the field, responsible for the emission of sound.Moreover, other characteristics of the booming dunes are reproduced and analyzed, such as a threshold under which no sound is produced, or beats in the sound that appears when the flow is too large. Finally, the size of the coherence zones emitting sound has been measured and discussed.     

Statistical Physics Approach to Liquid Crystals: Dynamics of Mobile Potts Model Leading to Smectic Phase,Phase Transition by Wang–Landau Method

We study the nature of the smectic–isotropic phase transition using a mobile 6-state Potts model. Each Potts state represents a molecular orientation. We show that with the choice of an appropriate microscopic Hamiltonian describing the interaction between individual molecules modeled by a mobile 6-state Potts spins, we observe the smectic phase dynamically formed when we cool the molecules from the isotropic phase to low temperatures (T). In order to elucidate the order of the transition and the low-T properties, we use the high-performance Wang–Landau flat energy-histogram technique. We show that the smectic phase goes to the liquid (isotropic) phase by melting/evaporating layer by layer starting from the film surface with increasing T. At a higher T, the whole remaining layers become orientationally disordered. The melting of each layer is characterized by a peak of the specific heat. Such a succession of partial transitions cannot be seen by the Metropolis algorithm. The successive layer meltings/evaporations at low T are found to have a first-order character by examining the energy histogram. These results are in agreement with experiments performed on some smectic liquid crystals.