Studies on the Cyclisation of 4-[2′-Cyclohexenyl]-3-hydroxy[1]benzopyran-2-one

The bicyclic coumarin derivative-1, 3 propano-2-bromo-1,2-dihydro-3H-pyrano [2, 3-c] [1]benzo-pyran-5-one (8) was synthesised by a sequence of reaction viz. acetylation of 4-[2′-cyclohexenyl] -3-hydroxy [1] benzopyran-2-one (4), addition of bromine to cyclohexenyl double bond and treating the resulting acetyldi-bromo derivative (7) with 4% alcoholic KOH. Benzofuro [2, 3-c] [1] -benzopyran-6-one (10) was synthesised from 4 via oxymercuration with mercuric acetate in methanol followed by dehydrogenative damercuration with Pd-C in refluxing diphenyl ether.     

POM‐Catalyzed In Situ Ligand Synthesis for the Construction of Metal Complexes and Their Use in the Formation of Coordination Polymers

Six organic–inorganic hybrid materials were synthesized by the in situ oxidation of neocuproine by using MoO₃/Na₂MoO₄ as the catalyst in the presence of Cu(NO₃)₂. The crystal structures of Mo8‐Cu4‐PHEN and Mo8‐Cu2‐5(2PIC) are composed of [Mo₈O₂₆]^4? polyoxometalate (POM) units, whereas the crystal structure of Mo6‐Cu‐COPHEN is composed of a [Mo₆O₁₉]^2? POM unit; both POM units could be considered as the active form of the catalyst. Reaction of the hybrid materials with 1,3,5‐benzenetricarboxylic acid (BTC) resulted in the formation of two different coordination polymers (CPs) under different reaction conditions. These CPs, depending on their structural attributes, exhibit distinct differences in the adsorption of H₂, CO₂, and water. The use of 2‐methylpyridine instead of neocuproine does not give any oxidation products under the same reaction conditions due to the incorrect positioning of the methyl group with respect to the Cu^II center.     

Layer-by-layer electrostatic assembly with a control over orientation of molecules: anisotropy of electrical conductivity and dielectric properties

While forming layer-by-layer (LbL) electrostatic assembly of a magnetic organic molecule, namely, nickel phthalocyanine (NiPc), we apply a magnetic field. The field orients the magnetic moment of the molecules on a monolayer along the direction of magnetic field. Such an orientation of the molecules is then electrostatically immobilized with a monolayer of a polycation. By repeating the dipping cycle, we form LbL films with planar NiPc molecules facing a particular direction. With NiPc's moment perpendicular to the molecular plane, two types of LbL films were formed: (a) NiPc's molecular plane parallel to the substrate (moment is perpendicular) and (b) molecules perpendicular to the substrate and facing one particular direction, the direction of magnetic field. Such films, with the molecules lying either (a) parallel or (b) perpendicular to the substrate, provide unique systems to study anisotropy of optical, dielectric, and electrical characteristics in these planar organic molecules. The latter film responds to the polarization of incident beam in electronic absorption spectroscopy. Here we show methods to obtain an orientation of molecules in LbL films and study anisotropy of dielectric constant and conductivity of the molecules in ultrathin films.     

A multistate switchable [3]rotacatenane

Rotacatenanes are exotic molecular compounds that can be visualized as a unique combination of a [2]catenane and a [2]rotaxane, thereby combining both the circumrotation of the ring component (rotary motion) and the shuttling of the dumbbell component (translational motion) in one structure. Herein, we describe a strategy for the synthesis of a new switchable [3]rotacatenane and the investigation of its switching properties, which rely on the formation of tetrathiafulvalene (TTF) radical π-dimer interactions-namely, the mixed-valence state (TTF(2) )(+.) and the radical-cation dimer state (TTF(+.) )(2) -under ambient conditions. A template-directed approach, based on donor-acceptor interactions, has been developed, resulting in an improved yield of the key precursor [2]catenane, prior to rotacatenation. The nature of the binding between the [2]catenane and selected π-electron-rich templates has been elucidated by using X-ray crystallography and UV/Vis spectroscopy as well as isothermal titration microcalorimetry. The multistate switching mechanism of the [3]rotacatenane has been demonstrated by cyclic voltammetry and EPR spectroscopy. Most notably, the radical-cation dimer state (TTF(+.) )(2) has been shown to enter into an equilibrium by forming the co-conformation in which the two 1,5-dioxynaphthalene (DNP) units co-occupy the cavity of tetracationic cyclophane, thus enforcing the separation of TTF radical-cation dimer (TTF(+.) )(2) . The population ratio of this equilibrium state was found to be 1:1. We believe that this research demonstrates the power of constructing complex molecular machines using template-directed protocols, enabling us to make the transition from simple molecular switches to their multistate variants for enhancing information storage in molecular electronic devices.     

Defect detection and localization in orthotropic wood slabs by inversion of dynamic surface displacements

The nondestructive evaluation inversion and generalized force-mapping techniques developed and demonstrated for isotropic thin plates by Bucaro et al. [(2004). "Detection and localization of inclusions in plates using inversion of point actuated surface displacements," J. Acoust. Soc. Am. 115, 201-206] are extended to the case of orthotropic plates. The extended techniques are applied to a finite-element generated numerical database for point excited wooden slabs with and without an internal defect at 5 and 10 kHz. Operation of the original isotropic algorithms on the wood surface displacements is shown to fail in recovering the uniform elastic parameters or in detecting and locating the defect. The new algorithms based on the wave equation for a thin, orthotropic plate successfully convert the surface displacements on the uniform wooden slab to elastic parameter maps which serve to detect and localize the defect in the flawed plate. The results, particularly at the higher frequency, indicate that the onset of failure in the thin plate approximation impacts both the inversion and the generalized force-mapping accuracy. However, in this case use of the inversion algorithm to obtain modified wave equation coefficients followed by operation of the force-mapping algorithm with these new parameters inserted is shown to successfully mitigate this effect.     

A perturbed angular correlation spectrometer for material science studies

A four-detector perturbed angular correlation (PAC) spectrometer has been developed with ultra-fast BaF₂ detectors to acquire four coincidence spectra simultaneously, two at 180° and two at 90°. This spectrometer has double efficiency compared to that of a three-detector set-up. Higher efficiency is desirable for PAC studies in solid state physics where large number of coincidences are required to obtain the PAC spectra with good statistics and is particularly useful when the half-lives of the parent probe nuclei used for PAC measurements are ∼2–3 days or less as in ¹¹¹In (2.8 d), ⁹⁹Mo (2.7 d) and ¹⁴⁰La (1.7 d). The performance of the spectrometer has been tested for the HfO₂ monoclinic crystal in the temperature range from 77 to 873 K and for the HfF₄·3H₂O crystal at room temperature. The polycrystalline HfO₂ has been synthesized from Hf metal by heating in air. The hydrated hafnium fluoride has been crystallized by dissolving Hf metal in 40% HF and drying slowly at room temperature.      

Synthesis of multi-wall carbon nanotubes by simple pyrolysis

A new pyrolysis technique has been developed for the synthesis of multi-walled carbon nanotubes (MWCNTs). In this simple method diethyl ether and nickelocene is pyrolysized in a reaction quartz tube without using carrier gas. The samples are prepared at pyrolysis temperatures of 650 and 950 ^°C and the effect of temperature on the tube morphology investigated. Purification has been done following the standard oxidation and acid bath treatment. The as-synthesized and purified nanotubes have been characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and micro-Raman spectroscopy. The technique has great advantages such as low cost and easy operation for the production of CNTs.     

Effect of Martensite Volume Fraction on Strain Partitioning Behavior of Dual Phase Steel

Monotonic deformation behavior of ferrite-martensite dual phase steels with martensite volume of 13-43% have been analyzed in the current investigation using micromechanics based finite element simulation on representative volume elements. The effects of martensite volume fraction on the strain partitioning behavior between soft ferrite matrix and hard martensite islands in dual phase steels during tensile deformation have been investigated. As a consequence of strain incompatibility between hard martensite and soft ferrite phases, inhomogeneous deformation and finally deformation localization occur during tensile deformation. Restricted local deformation in ferrite phase caused by the adjacent martensite islands triggers the local stress triaxiality development. As the martensite volume fraction increases, the local deformation restrictions in ferrite phase also increases and which results in higher stress triaxiality development. Similarly the strain partitioning behavior between ferrite matrix and martensite island is also influenced by the volume fraction of martensite. The strain partitioning coefficient increases with increasing martensite volume fraction.     

Branch-and-bound solves random binary IPs in poly(n)-time

Mathematical Programming - Branch-and-bound is the workhorse of all state-of-the-art mixed integer linear programming (MILP) solvers. These implementations of branch-and-bound typically use...     

Hyperpolarized 13C NMR Spectroscopy of Urine Samples at Natural Abundance by Quantitative Dissolution Dynamic Nuclear Polarization

Hyperpolarized nuclear magnetic resonance (NMR) offers an ensemble of methods that remarkably address the sensitivity issues of conventional NMR. Dissolution Dynamic Nuclear Polarization (d-DNP) provides a unique and general way to detect ¹³C NMR signals with a sensitivity enhanced by several orders of magnitude. The expanding application scope of d-DNP now encompasses the analysis of complex mixtures at natural ¹³C abundance. However, the application of d-DNP in this area has been limited to metabolite extracts. Here, we report the first d-DNP-enhanced ¹³C NMR analysis of a biofluid -urine- at natural abundance, offering unprecedented resolution and sensitivity for this challenging type of sample. We also show that accurate quantitative information on multiple targeted metabolites can be retrieved through a standard addition procedure.