Partial rotation of the isopropyl group in the solid state: single-crystal-to-single-crystal phase transformation in a carvacrol derivative

A hitherto unseen rotation of the isopropyl group in the solid state, predicted to be forbidden based on theoretical investigations, is reported. This C-C rotation observed during the temperature dependent single-crystal-to-single-crystal transformation is attributed to the concomitant changes in molecular structure and intermolecular packing.

Mononuclear five-coordinate cobalt(II) complexes with N-4-coordinate pyrazole based ligand and pseudohalogens: synthesis, structures, DNA and protein binding study

A series of mononuclear five-coordinate cobalt(II) complexes, Co(dbdmp)(X)]Y, where dbdmp=N,N-diethyl-N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1, 2-diamine, X=N-3(-)/NCO-/NCS- and Y=PF6-/BF4-/ClO4-, have been synthesized and characterized by microanalyses and spectroscopic techniques. Crystal structures of Co(N-3)(dbdmp)]PF6 (1), Co(N-3)(dbdmp)]ClO4 (3), Co(NCO)(dbdmp)]PF6 (4), Co(NCO)(dbdmp)]ClO4 (6), and Co(NCS)(dbdmp)]ClO4 (9) have been solved by single-crystal X-ray diffraction studies and showed that all the complexes have distorted trigonal bipyramidal geometry; PF6- counter anion containing complexes Co(N-3)(dbdmp)]PF6 and Co(NCO)(dbdmp)]PF6 have chiral space groups. The binding ability of synthesized complexes with CT-DNA and bovine serum albumin (BSA) has been studied by spectroscopic methods and viscosity measurements. The experimental results of absorption titration of cobalt(II) complexes with CT-DNA indicate that the complexes have ability to form adducts and they can stabilize the DNA helix. The cobalt(II) complexes exhibit good binding propensity to BSA protein.

High performance sol-gel spin-coated titanium dioxide dielectric based MOS structures

High-kappa TiO2 thin films have been fabricated using cost effective sol-gel and spin-coating technique on p-Si (100) wafer. Plasma activation process was used for better adhesion between TiO2 films and Si. The influence of annealing temperature on the structure-electrical properties of titania films were investigated in detail. Both XRD and Raman studies indicate that the anatase phase crystallizes at 400 degrees C, retaining its structural integrity up to 1000 degrees C. The thickness of the deposited films did not vary significantly with the annealing temperature, although the refractive index and the RMS roughness enhanced considerably, accompanied by a decrease in porosity. For electrical measurements, the films were integrated in metal-oxide-semiconductor (MOS) structure. The electrical measurements evoke a temperature dependent dielectric constant with low leakage current density. The Capacitance-voltage (C-V) characteristics of the films annealed at 400 degrees C exhibited a high value of dielectric constant (similar to 34). Further, frequency dependent C-V measurements showed a huge dispersion in accumulation capacitance due to the presence of TiO2/Si interface states and dielectric polarization, was found to follow power law dependence on frequency (with exponent `s'=0.85). A low leakage current density of 3.6 x 10(-7) A/cm(2) at 1 V was observed for the films annealed at 600 degrees C. The results of structure-electrical properties suggest that the deposition of titania by wet chemical method is more attractive and cost-effective for production of high-kappa materials compared to other advanced deposition techniques such as sputtering, MBE, MOCVD and AID. The results also suggest that the high value of dielectric constant kappa obtained at low processing temperature expands its scope as a potential dielectric layer in MOS device technology. (C) 2015 Elsevier Ltd. All rights reserved.

In-plane effective shear modulus of generalized circular honeycomb structures and bundled tubes in a diamond array structure

Use of circular hexagonal honeycomb structures and tube assemblies in energy absorption systems has attracted a large number of literature on their characterization under crushing and impact loads. Notwithstanding these, effective shear moduli (G*) required for complete transverse elastic characterization and in analyses of hierarchical structures have received scant attention. In an attempt to fill this void, the present study undertakes to evaluate G* of a generalized circular honeycomb structures and tube assemblies in a diamond array structure (DAS) with no restriction on their thickness. These structures present a potential to realize a spectrum of moduli with minimal modifications, a point of relevance for manufactures and designers. To evaluate G* in this paper, models based on technical theories - thin ring theory and curved beam theory - and rigorous theory of elasticity are investigated and corroborated with FEA employing contact elements. Technical theories which give a good match for thin HCS offer compact expressions for moduli which can be harvested to study sensitivity of moduli on topology. On the other hand, elasticity model offers a very good match over a large range of thickness along with exact analysis of stresses by employing computationally efficient expressions. (C) 2015 Elsevier Ltd. All rights reserved.

Estimation of nonlinearities from pseudodynamic and dynamic responses of bridge structures using the Delay Vector Variance method

Analysis of the variability in the responses of large structural systems and quantification of their linearity or nonlinearity as a potential non-invasive means of structural system assessment from output-only condition remains a challenging problem. In this study, the Delay Vector Variance (DVV) method is used for full scale testing of both pseudo-dynamic and dynamic responses of two bridges, in order to study the degree of nonlinearity of their measured response signals. The DVV detects the presence of determinism and nonlinearity in a time series and is based upon the examination of local predictability of a signal. The pseudo-dynamic data is obtained from a concrete bridge during repair while the dynamic data is obtained from a steel railway bridge traversed by a train. We show that DVV is promising as a marker in establishing the degree to which a change in the signal nonlinearity reflects the change in the real behaviour of a structure. It is also useful in establishing the sensitivity of instruments or sensors deployed to monitor such changes. (C) 2015 Elsevier B.V. All rights reserved.

Structural characterization of a mitochondrial 3-ketoacyl-CoA (T1)-like thiolase from Mycobacterium smegmatis

Thiolases catalyze the degradation and synthesis of 3-ketoacyl-CoA molecules. Here, the crystal structures of a T1-like thiolase (MSM-13 thiolase) from Mycobacterium smegmatis in apo and liganded forms are described. Systematic comparisons of six crystallographically independent unliganded MSM-13 thiolase tetramers (dimers of tight dimers) from three different crystal forms revealed that the two tight dimers are connected to a rigid tetramerization domain via flexible hinge regions, generating an asymmetric tetramer. In the liganded structure, CoA is bound to those subunits that are rotated towards the tip of the tetramerization loop of the opposing dimer, suggesting that this loop is important for substrate binding. The hinge regions responsible for this rotation occur near Val123 and Arg149. The L alpha 1-covering loop-L alpha 2 region, together with the N beta 2-N alpha 2 loop of the adjacent subunit, defines a specificity pocket that is larger and more polar than those of other tetrameric thiolases, suggesting that MSM-13 thiolase has a distinct substrate specificity. Consistent with this finding, only residual activity was detected with acetoacetyl-CoA as the substrate in the degradative direction. No activity was observed with acetyl-CoA in the synthetic direction. Structural comparisons with other well characterized thiolases suggest that MSM-13 thiolase is probably a degradative thiolase that is specific for 3-ketoacyl-CoA molecules with polar, bulky acyl chains.

Global response sensitivity analysis of uncertain structures

The problem of characterizing global sensitivity indices of structural response when system uncertainties are represented using probabilistic and (or) non-probabilistic modeling frameworks (which include intervals, convex functions, and fuzzy variables) is considered. These indices are characterized in terms of distance measures between a fiducial model in which uncertainties in all the pertinent variables are taken into account and a family of hypothetical models in which uncertainty in one or more selected variables are suppressed. The distance measures considered include various probability distance measures (Hellinger,l(2), and the Kantorovich metrics, and the Kullback-Leibler divergence) and Hausdorff distance measure as applied to intervals and fuzzy variables. Illustrations include studies on an uncertainly parametered building frame carrying uncertain loads. (C) 2015 Elsevier Ltd. All rights reserved.

DLTS analysis of amphoteric interface defects in high-TiO2 MOS structures prepared by sol-gel spin-coating

High-kappa TiO2 thin films have been fabricated from a facile, combined sol-gel spin - coating technique on p and n type silicon substrate. XRD and Raman studies headed the existence of anatase phase of TiO2 with a small grain size of 18 nm. The refractive index `n' quantified from ellipsometry is 2.41. AFM studies suggest a high quality, pore free films with a fairly small surface roughness of 6 angstrom. The presence of Ti in its tetravalent state is confirmed by XPS analysis. The defect parameters observed at the interface of Si/TiO2 were studied by capacitance - voltage (C - V) and deep level transient spectroscopy (DLTS). The flat - band voltage (V-FB) and the density of slow interface states estimated are -0.9, -0.44 V and 5.24x10(10), 1.03x10(11) cm(-2); for the NMOS and PMOS capacitors, respectively. The activation energies, interface state densities and capture cross -sections measured by DLTS are E-V + 0.30, E-C - 0.21 eV; 8.73x10(11), 6.41x10(11) eV(-1) cm(-2) and 5.8x10(-23), 8.11x10(-23) cm(2) for the NMOS and PMOS structures, respectively. A low value of interface state density in both P-and N-MOS structures makes it a suitable alternate dielectric layer for CMOS applications. And also very low value of capture cross section for both the carriers due to the amphoteric nature of defect indicates that the traps are not aggressive recombination centers and possibly can not contribute to the device operation to a large extent. (C) 2015 Author(s).

Uncertainty Quantification in Ultrasonic Wave Based Detection of Delamination in Composite Structures

In this paper we consider the problem of guided wave scattering from delamination in laminated composite and further the problem of estimating delamination size and layer-wise location from the guided wave measurement. Damage location and region/size can be estimated from time of flight and wave packet spread, whereas depth information can be obtained from wavenumber modulation in the carrier packet. The key challenge is that these information are highly sensitive to various uncertainties. Variation in reflected and transmitted wave amplitude in a bar due to boundary/interface uncertainty is studied to illustrate such effect. Effect of uncertainty in material parameters on the time of flight are estimated for longitudinal wave propagation. To evaluate the effect of uncertainty in delamination detection, we employ a time domain spectral finite element (tSFEM) scheme where wave propagation is modeled using higher-order interpolation with shape function have spectral convergence properties. A laminated composite beam with layer-wise placement of delamination is considered in the simulation. Scattering due to the presence of delamination is analyzed. For a single delamination, two identical waveforms are created at the two fronts of the delamination, whereas waves in the two sub-laminates create two independent waveforms with different wavelengths. Scattering due to multiple delaminations in composite beam is studied.

Air microjet system for non-contact force application and the actuation of micro-structures

We demonstrate a non-contact technique to apply calibrated and localized forces in the micro-Newton to milli-Newton range using an air microjet. An electromagnetically actuated diaphragm controlled by a signal generator is used to generate the air microjet. With a nozzle diameter of 150 mu m, the microjet diameter was maintained to a maximum of 1 mm at a distance of 5 mm from the nozzle. The force generated by the microjet was measured using a commercial force sensor to determine the velocity profile of the jet. Axial flow velocities of up to 25 m s(-1) were obtained at distances as long as 6 mm. The microjet exerted a force up to 1 mu N on a poly dimethyl siloxane (PDMS) micropillar (50 mu m in diameter, 157 mu m in height) and 415 mu N on a PDMS membrane (3 mm in diameter, 28 mu m thick). We also demonstrate that from a distance of 6 mm our microjet can exert a peak pressure of 187 Pa with a total force of about 84 mu N on a flat surface with 8 V operating voltage. Out of the cleanroom fabrication and robust design make this system cost effective and durable.

Efficient and practical synthesis of modular chiral beta-organochalcogeno amines, ArYCH2CH(R)NH2, and single crystal structures of (S) - MsOCH2CH(Bz)NH3+ center dot Cl- and (R)-MsOCH2CH(Ph)NH3+ center dot Cl-

Modular chiral I3-organochalcogeno amines, ArYCH2CH(R)NH2 (4a-4g) where R = Me, Bz, Ph; and ArY = PhS, BzSe and 4-MeOC6H4Te respectively have been synthesized and characterized. Compounds 4a-4g were synthesized (Method II) from chiral aminoalkyl 13-methanesulfonate hydrochlorides, MsOCH2CH(R)NH3+ center dot Cl- (2a-2c) through nucleophilic displacement of MsO- with organochalcogenolate (ArY-). In another attempt (Method I) chiral beta-organotelluro amines (4a-4c) were prepared by deprotection of chiral N-boc I3-organotelluro amides, 4-MeOC6H4TeCH2CH(R)NH-Boc (3a-3c), which in turn, 13,-,1 were made from chiral N-boc 13-methanesulfonate amides (la-lc) and ArTeNa. 1H, and FTIR spectra of all the compounds (3a-3c and 4a-4g) were characteristic. The composition of 3a-3c was determined by elemental analysis. The a]TD values of 3b-3c and 4a-4g were determined. The single crystal structures of (S)-2b and (R)-2c were determined by X-Ray diffraction studies. Both (S)-2b and (R)2c were crystallized in orthorhombic system and the Flack parameter x was found 0.08(12) and 0.00(2) respectively. The crystal of (S)-2b contain two asymmetric units with gauche (A) and staggered (B) conformations. There are NH Cl-, NH-O and CH-O intra and intermolecular secondary interactions in (S)-2b and (R)-2c resulting in supramolecular structures. (C) 2015 Elsevier By. All rights reserved.

Optimal input cross-power spectra in shake table testing of asymmetric structures

The study considers earthquake shake table testing of bending-torsion coupled structures under multi-component stationary random earthquake excitations. An experimental procedure to arrive at the optimal excitation cross-power spectral density (psd) functions which maximize/minimize the steady state variance of a chosen response variable is proposed. These optimal functions are shown to be derivable in terms of a set of system frequency response functions which could be measured experimentally without necessitating an idealized mathematical model to be postulated for the structure under study. The relationship between these optimized cross-psd functions to the most favourable/least favourable angle of incidence of seismic waves on the structure is noted. The optimal functions are also shown to be system dependent, mathematically the sharpest, and correspond to neither fully correlated motions nor independent motions. The proposed experimental procedure is demonstrated through shake table studies on two laboratory scale building frame models.

Response Dynamics of Recirculation Structures in Coaxial Nonpremixed Swirl-Stabilized Flames Subjected to Acoustic Forcing

This paper reports the time-mean and phase-locked response of nonreacting as well as reacting flow field in a coaxial swirling jet/flame (nonpremixed). Two distinct swirl intensities plus two different central pipe flow rates at each swirl setting are investigated. The maximum response is observed at the 105 Hz mode in the range of excitation frequencies (0-315 Hz). The flow/flame exhibited minimal response beyond 300 Hz. It is seen that the aspect ratio change of inner recirculation zone (IRZ) under nonreacting conditions (at responsive modes) manifests as a corresponding increase in the time-mean flame aspect ratio. This is corroborated by similar to 25% decrease in the IRZ transverse width in both flame and cold flow states. In addition, 105 Hz excited states are found to shed high energy regions (eddies) asymmetrically when compared to dormant 315 Hz pulsing frequency. The kinetic energy (KE) of the flow field is subsequently reduced due to acoustic excitation and a corresponding increase (similar to O (1)) in fluctuation intensity is witnessed. The lower swirl intensity case is found to be more responsive than the high swirl case as in the former flow state the resistance offered by IRZ to incoming acoustic perturbations is lower due to inherently low inertia. Next, the phase-locked analysis of flow and flame structure is employed to further investigate the phase dependence of flow/flame response. It is found that the asymmetric shifting of IRZ mainly results at 270 deg acoustic forcing. The 90 deg phase angle forcing is observed to convect the IRZ farther downstream in both swirl cases as compared to other phase angles. The present work aims primarily at providing a fluid dynamic view point to the observed nonpremixed flame response without considering the confinement effects.

Magnetic structures and magnetic phase transitions in the Mn-doped orthoferrite TbFeO3 studied by neutron powder diffraction

The magnetic structures and the magnetic phase transitions in the Mn-doped orthoferrite TbFeO3 studied using neutron powder diffraction are reported. Magnetic phase transitions are identified at T-N(Fe/Mn) approximate to 295K where a paramagnetic-to-antiferromagnetic transition occurs in the Fe/Mn sublattice, T-SR(Fe/Mn) approximate to 26K where a spin-reorientation transition occurs in the Fe/Mn sublattice and T-N(R) approximate to 2K where Tb-ordering starts to manifest. At 295 K, the magnetic structure of the Fe/Mn sublattice in TbFe0.5Mn0.5O3 belongs to the irreducible representation Gamma(4) (G(x)A(y)F(z) or Pb'n'm). A mixed-domain structure of (Gamma(1) + Gamma(4)) is found at 250K which remains stable down to the spin re-orientation transition at T-SR(Fe/Mn) approximate to 26K. Below 26K and above 250 K, the majority phase (>80%) is that of Gamma(4). Below 10K the high-temperature phase Gamma(4) remains stable till 2K. At 2 K, Tb develops a magnetic moment value of 0.6(2) mu(B)/f.u. and orders long-range in F-z compatible with the Gamma(4) representation. Our study confirms the magnetic phase transitions reported already in a single crystal of TbFe0.5Mn0.5O3 and, in addition, reveals the presence of mixed magnetic domains. The ratio of these magnetic domains as a function of temperature is estimated from Rietveld refinement of neutron diffraction data. Indications of short-range magnetic correlations are present in the low-Q region of the neutron diffraction patterns at T < T-SR(Fe/Mn). These results should motivate further experimental work devoted to measure electric polarization and magnetocapacitance of TbFe0.5Mn0.5O3. (C) 2016 AIP Publishing LLC.