Assignment of the C-13 NMR spectrum by correlation to dipolar coupled proton-pairs and estimation of order parameters of a thiophene based liquid crystal

Materials with widely varying molecular topologies and exhibiting liquid crystalline properties have attracted considerable attention in recent years. C-13 NMR spectroscopy is a convenient method for studying such novel systems. In this approach the assignment of the spectrum is the first step which is a non-trivial problem. Towards this end, we propose here a method that enables the carbon skeleton of the different sub-units of the molecule to be traced unambiguously. The proposed method uses a heteronuclear correlation experiment to detect pairs of nearby carbons with attached protons in the liquid crystalline core through correlation of the carbon chemical shifts to the double-quantum coherences of protons generated through the dipolar coupling between them. Supplemented by experiments that identify non-protonated carbons, the method leads to a complete assignment of the spectrum. We initially apply this method for assigning the C-13 spectrum of the liquid crystal 4-n-pentyl-4'-cyanobiphenyl oriented in the magnetic field. We then utilize the method to assign the aromatic carbon signals of a thiophene based liquid crystal thereby enabling the local order-parameters of the molecule to be estimated and the mutual orientation of the different sub-units to be obtained.

Stress Engineering using Si3N4 for stiction free release of SOI beams

We report on the effect of thin silicon nitride (Si3N4) induced tensile stress on the structural release of 200nm thick SOI beam, in the surface micro-machining process. A thin (20nm / 100nm) LPCVD grown Si3N4 is shown to significantly enhance the yield of released beam in wet release technique. This is especially prominent with increase in beam length, where the beams have higher tendency for stiction. We attribute this yield enhancement to the nitride induced tensile stress, as verified by buckling tendency and resonance frequency data obtained from optical profilometry and laser doppler vibrometry.

High Proton Mobility, Solvent Induced Single Crystal to Single Crystal Structural Transformation, and Related Studies on a Family of Compounds Formed from Mn-3 Oxo-Clusters

The reaction between 4,4'-sulfonyldibenzoic acid (H(2)SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, Mn-4(C14H8O6S)(4)(DMA)(2)]center dot 3DMA, I, and Mn-3(C14H8O6S)(3)(DMA)(2)(MeOH)]center dot DMA, IIa. Both structures have Mn-3 trimer oxo cluster units. While the Mn-3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn-3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn-3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of similar to 0.87 x 10(-3) Omega(-1) cm(-1) at 34 degrees C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5) and H3O](2)Mn-7(mu 3-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8) under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn-3 trimer clusters forming CoMn2(C14H8O6S)(3)(DMA)(2)(EtOH)]center dot DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

Non-uniform beams and stiff strings isospectral to axially loaded uniform beams and piano strings

In this paper, we derive analytical expressions for mass and stiffness functions of transversely vibrating clamped-clamped non-uniform beams under no axial loads, which are isospectral to a given uniform axially loaded beam. Examples of such axially loaded beams are beam columns (compressive axial load) and piano strings (tensile axial load). The Barcilon-Gottlieb transformation is invoked to transform the non-uniform beam equation into the axially loaded uniform beam equation. The coupled ODEs involved in this transformation are solved for two specific cases (pq (z) = k (0) and q = q (0)), and analytical solutions for mass and stiffness are obtained. Examples of beams having a rectangular cross section are shown as a practical application of the analysis. Some non-uniform beams are found whose frequencies are known exactly since uniform axially loaded beams with clamped ends have closed-form solutions. In addition, we show that the tension required in a stiff piano string with hinged ends can be adjusted by changing the mass and stiffness functions of a stiff string, retaining its natural frequencies.

Effects of hydrogen bonding on amide-proton chemical shift anisotropy in a proline-containing model peptide

Longitudinal relaxation due to cross-correlation between dipolar ((HN-1H alpha)-H-1) and amide-proton chemical shift anisotropy (H-1(N) CSA) has been measured in a model tripeptide Piv-(L)Pro-(L)Pro-(L)Phe-OMe. The peptide bond across diproline segment is known to undergo cis/trans isomerization and only in the cis form does the lone Phe amide-proton become involved in intramolecular hydrogen bonding. The strength of the cross correlated relaxation interference is found to be significantly different between cis and trans forms, and this difference is shown as an influence of intramolecular hydrogen bonding on the amide-proton CSA. (C) 2015 Elsevier B.V. All rights reserved.

Graphene oxide-Fe3O4 nanoparticle composite with high transverse proton relaxivity value for magnetic resonance imaging

The potential of graphene oxide-Fe3O4 nanoparticle (GO-Fe3O4) composite as an image contrast enhancing material in magnetic resonance imaging has been investigated. Proton relaxivity values were obtained in three different homogeneous dispersions of GO-Fe3O4 composites synthesized by precipitating Fe3O4 nanoparticles in three different reaction mixtures containing 0.01 g, 0.1 g, and 0.2 g of graphene oxide. A noticeable difference in proton relaxivity values was observed between the three cases. A comprehensive structural and magnetic characterization revealed discrete differences in the extent of reduction of the graphene oxide and spacing between the graphene oxide sheets in the three composites. The GO-Fe3O4 composite framework that contained graphene oxide with least extent of reduction of the carboxyl groups and largest spacing between the graphene oxide sheets provided the optimum structure for yielding a very high transverse proton relaxivity value. It was found that the GO-Fe3O4 composites possessed good biocompatibility with normal cell lines, whereas they exhibited considerable toxicity towards breast cancer cells. (C) 2015 AIP Publishing LLC.

CROSS-SECTIONAL ANALYSIS OF PRE-TWISTED THICK BEAMS USING VARIATIONAL ASYMPTOTIC METHOD

An asymptotically-exact methodology is presented for obtaining the cross-sectional stiffness matrix of a pre-twisted moderately-thick beam having rectangular cross sections and made of transversely isotropic materials. The anisotropic beam is modeled from 3-D elasticity, without any further assumptions. The beam is allowed to have large displacements and rotations, but small strain is assumed. The strain energy of the beam is computed making use of the constitutive law and the kinematical relations derived with the inclusion of geometrical nonlinearities and initial twist. Large displacements and rotations are allowed, but small strain is assumed. The Variational Asymptotic Method is used to minimize the energy functional, thereby reducing the cross section to a point on the reference line with appropriate properties, yielding a 1-D constitutive law. In this method as applied herein, the 2-D cross-sectional analysis is performed asymptotically by taking advantage of a material small parameter and two geometric small parameters. 3-D strain components are derived using kinematics and arranged as orders of the small parameters. Warping functions are obtained by the minimization of strain energy subject to certain set of constraints that renders the 1-D strain measures well-defined. Closed-form expressions are derived for the 3-D non-linear warping and stress fields. The model is capable of predicting interlaminar and transverse shear stresses accurately up to first order.

Analysis of Transverse Shear Strains in Pre-Twisted Thick Beams using Variational Asymptotic Method

The cross-sectional stiffness matrix is derived for a pre-twisted, moderately thick beam made of transversely isotropic materials and having rectangular cross sections. An asymptotically-exact methodology is used to model the anisotropic beam from 3-D elasticity, without any further assumptions. The beam is allowed to have large displacements and rotations, but small strain is assumed. The strain energy is computed making use of the beam constitutive law and kinematical relations derived with the inclusion of geometrical nonlinearities and an initial twist. The energy functional is minimized making use of the Variational Asymptotic Method (VAM), thereby reducing the cross section to a point on the beam reference line with appropriate properties, forming a 1-D constitutive law. VAM is a mathematical technique employed in the current problem to rigorously split the 3-D analysis of beams into two: a 2-D analysis over the beam cross-sectional domain, which provides a compact semi-analytical form of the properties of the cross sections, and a nonlinear 1-D analysis of the beam reference curve. In this method, as applied herein, the cross-sectional analysis is performed asymptotically by taking advantage of a material small parameter and two geometric small parameters. 3-D strain components are derived using kinematics and arranged in orders of the small parameters. Closed-form expressions are derived for the 3-D non-linear warping and stress fields. Warping functions are obtained by the minimization of strain energy subject to certain set of constraints that render the 1-D strain measures well-defined. The zeroth-order 3-D warping field thus yielded is then used to integrate the 3-D strain energy density over the cross section, resulting in the 1-D strain energy density, which in turn helps identify the corresponding cross-sectional stiffness matrix. The model is capable of predicting interlaminar and transverse shear stresses accurately up to first order.

Exploring isospectral cantilever beams using electromagnetism inspired optimization technique

Isospectral beams have identical free vibration frequency spectrum for a specific boundary condition. The problem of finding non-uniform beams which are isospectral to a given uniform beam, with fixed-free boundary condition, leads to a multimodal optimization problem. The first Q natural frequencies of the given uniform Euler-Bernoulli beam are determined using analytical solution. The first Q natural frequencies of a non-uniform beam are obtained with the help of finite element modeling. In order to obtain the non-uniform beams isospectral to a given uniform beam, an error function is designed, which calculates the difference between the spectra of the given uniform beam and the non-uniform beam. In our study, this error function is minimized using electromagnetism inspired optimization technique, a population based iterative algorithm inspired by the attraction-repulsion physics of electromagnetism. Numerical results show the existence of the isospectral non-uniform beams for a given uniform beam, which occur as local minima. Non-uniform beams isospectral to a damaged beam, are also explored using the proposed methodology to illustrate the fact that accurate structural damage identification is difficult by just frequency measurements. (C) 2012 Elsevier B.V. All rights reserved.

Experimental Analysis of Water Vapor Diffusion Through Porous Membranes in a Proton Exchange Membrane Fuel Cell

We report the diffusion characteristics of water vapor through two different porous media, viz., membrane electrode assembly (MEA) and gas diffusion layer (GDL) in a nonoperational fuel cell. Tunable diode laser absorption spectroscopy (TDLAS) was employed for measuring water vapor concentration in the test channel. Effects of the membrane pore size and the inlet humidity on the water vapor transport are quantified through mass flux and diffusion coefficient. Water vapor transport rate is found to be higher for GDL than for MEA. The flexibility and wide range of application of TDLAS in a fuel cell setup is demonstrated through experiments with a stagnant flow field on the dry side.

Efficient coupled polynomial interpolation scheme for out-of-plane free vibration analysis of curved beams

The performance of two curved beam finite element models based on coupled polynomial displacement fields is investigated for out-of-plane vibration of arches. These two-noded beam models employ curvilinear strain definitions and have three degrees of freedom per node namely, out-of-plane translation (v), out-of-plane bending rotation (theta(z)) and torsion rotation (theta(s)). The coupled polynomial interpolation fields are derived independently for Timoshenko and Euler-Bernoulli beam elements using the force-moment equilibrium equations. Numerical performance of these elements for constrained and unconstrained arches is compared with the conventional curved beam models which are based on independent polynomial fields. The formulation is shown to be free from any spurious constraints in the limit of `flexureless torsion' and `torsionless flexure' and hence devoid of flexure and torsion locking. The resulting stiffness and consistent mass matrices generated from the coupled displacement models show excellent convergence of natural frequencies in locking regimes. The accuracy of the shear flexibility added to the elements is also demonstrated. The coupled polynomial models are shown to perform consistently over a wide range of flexure-to-shear (EI/GA) and flexure-to-torsion (EI/GJ) stiffness ratios and are inherently devoid of flexure, torsion and shear locking phenomena. (C) 2015 Elsevier B.V. All rights reserved.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

Benchmark analytical solutions from beams with shared eigenpair

Structures with governing equations having identical inertial terms but somewhat differing stiffness terms can be termed flexurally analogous. An example of such a structure includes an axially loaded non-uniform beam and an unloaded uniform beam, for which an exact solution exists. We find that there exist shared eigenpairs (frequency and mode shapes) for a particular mode between such structures. Non-uniform beams with uniform axial loads, gravity loaded beams and rotating beams are considered and shared eigenpairs with uniform beams are found. In general, the derived flexural stiffness functions (FSF's) for the non-uniform beams required for the existence of shared eigenpair have internal singularities, but some of the singularities can be removed by an appropriate selection of integration constants using the theory of limits. The derived functions yield an insight into the relationship between the axial load and flexural stiffness of axially loaded beam structures. The derived functions can serve as benchmark solutions for numerical methods. (C) 2016 Elsevier Ltd. All rights reserved.

Nonrotating Beams Isospectral to Tapered Rotating Beams

In this paper, we seek to find nonrotating beams that are isospectral to a given tapered rotating beam. Isospectral structures have identical natural frequencies. We assume the mass and stiffness distributions of the tapered rotating beam to be polynomial functions of span. Such polynomial variations of mass and stiffness are typical of helicopter and wind turbine blades. We use the Barcilon-Gottlieb transformation to convert the fourth-order governing equations of the rotating and the nonrotating beams, from the (x, Y) frame of reference to a hypothetical (z, U) frame of reference. If the coefficients of both the equations in the (z, U) frame match with each other, then the nonrotating beam is isospectral to the given rotating beam. The conditions on matching the coefficients lead to a pair of coupled differential equations. Wesolve these coupled differential equations numerically using the fourth-order Runge-Kutta scheme. We also verify that the frequencies (given in the literature) of standard tapered rotating beams are the frequencies (obtained using the finite-element analysis) of the isospectral nonrotating beams. Finally, we present an example of beams having a rectangular cross-section to show the application of our analysis. Since experimental determination of rotating beam frequencies is a difficult task, experiments can be easily conducted on these isospectral nonrotating beams to calculate the frequencies of the rotating beam.