Parametric Studies on Saltwater Intrusion into Coastal Aquifers for Anticipate Sea Level Rise

Saltwater intrusion into coastal aquifers is a global issue, exacerbated by increasing demands for freshwater in coastal regions. This study investigates into the parametric analysis on saltwater intrusion in a conceptual, coastal, unconfined aquifer considering wide range of freshwater draft and anticipated sea level rise. The saltwater intrusion under various circumstances is simulated through parametric studies using MODFLOW, MT3DMS and SEAWAT. The MODFLOW is used to simulate the groundwater flow system under changing hydro-dynamics in coastal aquifer. To simulate solute transport MT3DMS and SEAWAT is used. The saltwater intrusion process has direct bearing on hydraulic conductivity and inversely related to porosity. It may also be noted that increase in recharge rate considered in the study does not have much influence on saltwater intrusion. Effect of freshwater draft at locations beyond half of the width of the aquifer considered has marginal effect and hence can be considered as safe zone for freshwater withdrawals. Due to the climate change effect, the anticipated rise in sea level of 0.88 m over a century is considered in the investigation. This causes increase in salinity intrusion by about 25%. The combined effect of sea level rise and freshwater draft (C) 2015 The Authors. Published by Elsevier B.V.

Disappearance of electron-hole asymmetry in nanoparticles of Nd1-xCaxMnO3(x=0.6, 0.4): magnetization and electron paramagnetic resonance evidence

We study and compare magnetic and electron paramagnetic resonance behaviors of bulk and nanoparticles of Nd1-xCaxMnO3 in hole doped (x = 0.4; NCMOH) and electron doped (x = 0.6; NCMOE) samples. NCMOH in bulk form shows a complex temperature dependence of magnetization M(T), with a charge ordering transition at similar to 250 K, an antiferromagnetic (AFM) transition at similar to 150 K, and a transition to a canted AFM phase/mixed phase at similar to 80 K. Bulk NCMOE behaves quite differently with just a charge ordering transition at similar to 280 K, thus providing a striking example of the so called electron-hole asymmetry. While our magnetization data on bulk samples are consistent with the earlier reports, the new results on the nanoparticles bring out drastic effects of size reduction. They show that M(T) behaviors of the two nanosamples are essentially similar in addition to the absence of the charge order in them thus providing strong evidence for vanishing of the electron-hole asymmetry in nanomanganites. This conclusion is further corroborated by electron paramagnetic resonance studies which show that the large difference in the ``g'' values and their temperature dependences found for the two bulk samples disappears as they approach a common behavior in the corresponding nanosamples. (C) 2015 AIP Publishing LLC.

Comparative study of magnetic ordering in bulk and nanoparticles of Sm0.65Ca0.35MnO3: Magnetization and electron magnetic resonance measurements

To explore the effect of size reduction to nanoscale on the hole doped Sm0.65Ca0.35MnO3 compound, dc magnetic measurements and electron magnetic resonance (EMR) were done on bulk and nanoparticle samples in the temperature range 10 <= T <= 300 K. Magnetization measurement showed that the bulk sample undergoes a charge ordering transition at 240K and shows a mixed magnetic phase at low temperature. However, the nanosample underwent a ferromagnetic transition at 75 K, and the charge ordered state was destabilized on size reduction down to nanoscale. The low-temperature ferromagnetic component is found to be enhanced in nanoparticles as compared to their bulk counterpart. Interestingly around room temperature, bulk particles show higher magnetization where as at low temperature nanoparticles show higher magnetization. Ferromagnetism in the bulk is due to super exchange where as ferromagnetism in nanoparticles is due to uncompensated spins of the surface layer. Temperature variation of EMR parameters correlates well with the results of magnetic measurements. The magnetic behaviour of the nanoparticles is understood in terms of the core shell scenario. (C) 2015 AIP Publishing LLC.

Electron Magnetic Resonance Studies of Nanosized Nd0.65Ca0.35 Mn1-xCrxO3 (x=0, 0.06, 0.1) Manganite

We report a systematic investigation of the temperature dependence of electron magnetic resonance (EMR) line width, intensity and resonance field for similar to 25 nm Nd0.65Ca0.35MnO3 (NCMO1), Nd0.65Ca0.35Mn0.94Cr0.06O3 (NCMO2) and Nd0.65Ca0.35Mn0.9Cr0.1O3 (NCMO3) nanoparticles prepared by sol-gel method. The EMR line widths for the three nano-samples differ significantly from one another below a temperature T (min) where the line width has a minimum. T (min) was found to be 130, 100 and 120 K for NCMO1, NCMO2 and NCMO3, respectively. Well above T (min) the line width values for the three samples are close to one another. The sharp upturn of EMR line width below T (min) is attributed to the formation of short range, ferromagnetically ordered clusters. Temperature dependence of EMR intensity shows a residual CO transition in NCMO1 and NCMO2 and a complete disappearance of it in NCMO3. The intensity undergoes significant increase below 120, 80 and 100 K for NCMO1, NCMO2 and NCMO3, respectively, indicating the onset of ferromagnetic transitions. The occurrence of ferromagnetic transition is further confirmed by magnetization hysteresis measurements. The decrease in T (C) in NCMO2 and NCMO3 compared to NCMO1 nanoparticles is understood to be due to the destruction of the double-exchange interaction by chromium doping. The resonance field decreases below the ferromagnetic onset temperatures for all the samples as expected. The combined effects of the reduction in size and of chromium doping in Mn site are discussed.

Simultaneous acquisition of three NMR spectra in a single experiment for rapid resonance assignments in metabolomics

NMR-based approach to metabolomics typically involves the collection of two-dimensional (2D) heteronuclear correlation spectra for identification and assignment of metabolites. In case of spectral overlap, a 3D spectrum becomes necessary, which is hampered by slow data acquisition for achieving sufficient resolution. We describe here a method to simultaneously acquire three spectra (one 3D and two 2D) in a single data set, which is based on a combination of different fast data acquisition techniques such as G-matrix Fourier transform (GFT) NMR spectroscopy, parallel data acquisition and non-uniform sampling. The following spectra are acquired simultaneously: (1) C-13 multiplicity edited GFT (3,2)D HSQC-TOCSY, (2) 2D H-1- H-1] TOCSY and (3) 2D C-13- H-1] HETCOR. The spectra are obtained at high resolution and provide high-dimensional spectral information for resolving ambiguities. While the GFT spectrum has been shown previously to provide good resolution, the editing of spin systems based on their CH multiplicities further resolves the ambiguities for resonance assignments. The experiment is demonstrated on a mixture of 21 metabolites commonly observed in metabolomics. The spectra were acquired at natural abundance of C-13. This is the first application of a combination of three fast NMR methods for small molecules and opens up new avenues for high-throughput approaches for NMR-based metabolomics.

A modified auxiliary excitation signal for achieving unidirectional ion ejection in quadrupole ion trap mass spectrometers operating in the resonance ejection mode

This paper proposes a technique to cause unidirectional ion ejection in a quadrupole ion trap mass spectrometer operated in the resonance ejection mode. In this technique a modified auxiliary dipolar excitation signal is applied to the endcap electrodes. This modified signal is a linear combination of two signals. The first signal is the nominal dipolar excitation signal which is applied across the endcap electrodes and the second signal is the second harmonic of the first signal, the amplitude of the second harmonic being larger than that of the fundamental. We have investigated the effect of the following parameters on achieving unidirectional ion ejection: primary signal amplitude, ratio of amplitude of second harmonic to that of primary signal amplitude, different operating points, different scan rates, different mass to charge ratios and different damping constants. In all these simulations unidirectional ejection of destabilized ions has been successfully achieved. (C) 2015 Elsevier B.V. All rights reserved.

Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

Mono layer to Interdigitated Partial Bilayer Smectic C Transition in Thiophene-Based Spacer Mesogens: X-ray Diffraction and C-13 Nuclear Magnetic Resonance Studies

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state C-13 NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

Synthesis of 3-dimensional porous graphene nanosheets using electron cyclotron resonance plasma enhanced chemical vapour deposition

Microwave plasma driven chemical vapour deposition was used to synthesize graphene nanosheets from a mixture of acetylene and hydrogen gas molecules. In this plasma, acetylene decomposes to carbon atoms that form nanostructures in the outlet plasma stream and get deposited on the substrate. The GNS consists of a few layers of graphene aligned vertically to the substrate. Graphene layers have been confirmed by high-resolution transmission electron microscopy, and Raman spectral studies were conducted to observe the defective nature of the sample. The growth of nanosheets in a vertical direction is assumed to be due to the effect of electric field and from the difference in the deposition rate in the axial and parallel directions. These vertical graphene sheets are attractive for various applications in energy storage and sensors.

MnFe2O4-Fe3O4 core-shell nanoparticles as a potential contrast agent for magnetic resonance imaging

In recent years, magnetic core-shell nanoparticles have received widespread attention due to their unique properties that can be used for various applications. We introduce here a magnetic core-shell nanoparticle system for potential application as a contrast agent in magnetic resonance imaging (MRI). MnFe2O4-Fe3O4 core-shell nanoparticles were synthesized by the wet-chemical synthesis method. Detailed structural and compositional charaterization confirmed the formation of a core-shell microstructure for the nanoparticles. Magnetic charaterization revealed the superparamagnetic nature of the as-synthesized core-shell nanoparticles. Average size and saturation magnetization values obtained for the as-synthesized core-shell nanoparticle were 12.5 nm and 69.34 emu g(-1) respectively. The transverse relaxivity value of the water protons obtained in the presence of the core-shell nanoparticles was 184.1 mM(-1) s(-1). To investigate the effect of the core-shell geometry towards enhancing the relaxivity value, transverse relaxivity values were also obtained in the presence of separately synthesized single phase Fe3O4 and MnFe2O4 nanoparticles. Average size and saturation magnetization values for the as-synthesized Fe3O4 nanoparticles were 12 nm and 65.8 emu g(-1) respectively. Average size and saturation magnetization values for the MnFe2O4 nanoparticles were 9 nm and 61.5 emu g(-1) respectively. The transverse relaxivity value obtained in the presence of single phase Fe3O4 and MnFe2O4 nanoparticles was 96.6 and 83.2 mM(-1) s(-1) respectively. All the nanoparticles (core-shell and single phase) were coated with chitosan by a surfactant exchange reaction before determining the relaxivity values. For similar nanoparticle sizes and saturation magnetization values, the highest value of the transverse relaxivity in the case of core-shell nanoparticles clearly illustrated that the difference in the magnetic nature of the core and shell phases in the core-shell nanoparticles creates greater magnetic inhomogeneity in the surrounding medium yielding a high value for proton relaxivity. The MnFe2O4-Fe3O4 core-shell nanoparticles exhibited extremely low toxicity towards the MCF-7 cell line. Taken together, this opens up new avenues for the use of core-shell nanoparticles in MRI.

A Study of Pressure-Dependent Squeeze Film Stiffness as a Resonance Modulator Using Static and Dynamic Measurements

We report on the resonant frequency modulation of inertial microelectromechanical systems (MEMS) structures due to squeeze film stiffness over a range of working pressures. Squeeze film effects have been studied extensively, but mostly in the context of damping and Q-factor determination of dynamic MEMS structures, typically suspended over a fixed substrate with a very thin air gap. Here, we show with experimental measurements and analytical calculations how the pressure-dependent air springs (squeeze film stiffness) change the resonant frequency of an inertial MEMS structure by as much as five times. For capturing the isolated effect of the squeeze film stiffness, we first determine the static stiffness of our structure with atomic force microscope probing and then study the effect of the air spring by measuring the dynamic response of the structure, thus finding the resonant frequencies while varying the air pressure from 1 to 905 mbar. We also verify our results by analytical and Finite Element Method calculations. Our findings show that the pressure-dependent squeeze film stiffness can affect a rather huge range of frequency modulation (>400%) and, therefore, can be used as a design parameter for exploiting this effect in MEMS devices. 2014-0310]

Neutron diffraction, Mossbauer effect and Electron Paramagnetic Resonance studies on multiferroic Pb(Fe2/3W1/3)O-3

Multiferroic Pb(Fe2/3W1/3)O-3 ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mossbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mossbauer spectra confirms the trivalent state of iron (Fe3+). The Mossbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe3+ ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe2/3W1/3)O-3 ceramic at 300 K. Considering neutron diffraction, Mossbauer and EPR results together, it may be stated here that Pb(Fe2/3W1/3)O-3 exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

Prior image based temporally constrained reconstruction algorithm for magnetic resonance guided high intensity focused ultrasound

Purpose: A prior image based temporally constrained reconstruction ( PITCR) algorithm was developed for obtaining accurate temperature maps having better volume coverage, and spatial, and temporal resolution than other algorithms for highly undersampled data in magnetic resonance (MR) thermometry. Methods: The proposed PITCR approach is an algorithm that gives weight to the prior image and performs accurate reconstruction in a dynamic imaging environment. The PITCR method is compared with the temporally constrained reconstruction (TCR) algorithm using pork muscle data. Results: The PITCR method provides superior performance compared to the TCR approach with highly undersampled data. The proposed approach is computationally expensive compared to the TCR approach, but this could be overcome by the advantage of reconstructing with fewer measurements. In the case of reconstruction of temperature maps from 16% of fully sampled data, the PITCR approach was 1.57x slower compared to the TCR approach, while the root mean square error using PITCR is 0.784 compared to 2.815 with the TCR scheme. Conclusions: The PITCR approach is able to perform more accurate reconstructions of temperature maps compared to the TCR approach with highly undersampled data in MR guided high intensity focused ultrasound. (C) 2015 American Association of Physicists in Medicine.

A dendrimer facilitates resonance energy transfer between hydrophobic aromatic guest molecules in water

A water soluble third generation poly(alkyl aryl ether) dendrimer was examined for its ability to solubilize hydrophobic polyaromatic molecules in water and facilitate non-radiative resonance energy transfer between them. One to two orders of magnitude higher aqueous solubilities of pyrene (PY), perylene (PE), acridine yellow (AY) and acridine orange (AO) were observed in presence of a defined concentration of the dendrimer. A reduction in the quantum yield of the donor PY* emission and a partial decrease in lifetime of the donor excited state revealed the occurrence of energy transfer from dendrimer solubilized excited PY to ground state PE molecules, both present within a dendrimer. The energy transfer efficiency was estimated to be similar to 61%. A cascade resonance energy transfer in a three component system, PY*-to-PE-to-AY and PY*-to-PE-to-AO, was demonstrated through incorporation of AY or AO in the two component PY-PE system. In the three-component system, excitation of PY resulted in emission from AY or AO via a cascade energy transfer process. Careful choice of dye molecules with good spectral overlap and the employment of dendrimer as the medium enabled us to expand absorption-emission wavelengths, from similar to 330 nm to similar to 600 nm in aqueous solution. (C) 2015 Elsevier B.V. All rights reserved.

Two-Phase Metallic Thermal Interface Materials Processed Through Liquid Phase Sintering Followed by Accumulative Roll Bonding

Thermal interface materials (TIMs) form a mechanical and thermal link between a heat source and a heat sink. Thus, they should have high thermal conductivity and high compliance to efficiently transfer heat and accommodate any differential strain between the heat source and the sink, respectively. This paper reports on the processing and the characterization of potential metallic TIM composite solders comprising of Cu, a high conductivity phase, uniformly embedded in In matrix, a highly compliant phase. We propose the fabrication of such a material by a two-step fabrication technique comprising of liquid phase sintering (LPS) followed by accumulative roll bonding (ARB). To demonstrate the efficacy of the employed two-step processing technique, an In-40 vol. % Cu composite solder was produced first using LPS with short sintering periods (30 or 60 s at 160 degrees C) followed by ARB up to five passes, each pass imposing a strain of 50%. Mechanical response and electrical and thermal conductivities of the fabricated samples were evaluated. It was observed that processing through ARB homogenizes the distribution of Cu in an In matrix, disintegrates the agglomerates of Cu powders, and also significantly increases thermal and electrical conductivities, almost attaining theoretically predicted values, without significantly increasing the flow stress. Furthermore, the processing technique also allows the insertion of desired foreign species, such as reduced graphene oxide, in In-Cu for further enhancing a target property, such as electrical conductivity.