Intestinal Permeability of β-Lapachone and Its Cyclodextrin Complexes and Physical Mixtures.

PubMed

Mangas-Sanjuan, Victor; Gutiérrez-Nieto, Jorge; Echezarreta-López, Magdalena; González-Álvarez, Isabel; González-Álvarez, Marta; Casabó, Vicente-Germán; Bermejo, Marival; Landin, Mariana

2016-12-01

β-Lapachone (βLAP) is a promising, poorly soluble, antitumoral drug. βLAP combination with cyclodextrins (CDs) improves its solubility and dissolution but there is not enough information about the impact of cyclodextrins on βLAP intestinal permeability. The objectives of this work were to characterize βLAP intestinal permeability and to elucidate cyclodextrins effect on the dissolution properties and on the intestinal permeability. The final goal was to evaluate CDs influence on the oral absorption of βLAP. Binary systems (physical mixtures and inclusion complexes) including βLAP and CDs (β-cyclodextrin: βCD, random-methyl-β-cyclodextrin: RMβCD and sulfobutylether-β-cyclodextrin: SBEβCD) have been prepared and analysed by differential scanning calorimetry. βLAP (and its combinations with CDs) absorption rate coefficients and effective permeability values have been determined in vitro in MDCK or MDCK-Mdr1 monolayers and in situ in rat by a closed loop perfusion technique. DSC results confirmed the formation of the inclusion complexes. βLAP-CDs inclusion complexes improve drug solubility and dissolution rate in comparison with physical mixtures. βLAP presented a high permeability value which can provide complete oral absorption. Its oral absorption is limited by its low solubility and dissolution rate. Cyclodextrin (both as physical mixtures and inclusion complexes) showed a positive effect on the intestinal permeability of βLAP. Complexation with CDs does not reduce βLAP intestinal permeability in spite of the potential negative effect of the reduction in free fraction of the drug. The use of RMβCD or SBEβCD inclusion complexes could benefit βLAP oral absorption by enhancing its solubility, dissolution rate and permeability.

A Comparative Study of Simulated and Measured Main Landing Gear Noise for Large Civil Transports

NASA Technical Reports Server (NTRS)

Konig, Benedikt; Fares, Ehab; Ravetta, Patricio; Khorrami, Mehdi R.

2017-01-01

Computational results for the NASA 26%-scale model of a six-wheel main landing gear with and without a toboggan-shaped noise reduction fairing are presented. The model is a high-fidelity representation of a Boeing 777-200 aircraft main landing gear. A lattice Boltzmann method was used to simulate the unsteady flow around the model in isolation. The computations were conducted in free-air at a Mach number of 0.17, matching a recent acoustic test of the same gear model in the Virginia Tech Stability Wind Tunnel in its anechoic configuration. Results obtained on a set of grids with successively finer spatial resolution demonstrate the challenge in resolving/capturing the flow field for the smaller components of the gear and their associated interactions, and the resulting effects on the high-frequency segment of the farfield noise spectrum. Farfield noise spectra were computed based on an FWH integral approach, with simulated pressures on the model solid surfaces or flow-field data extracted on a set of permeable surfaces enclosing the model as input. Comparison of these spectra with microphone array measurements obtained in the tunnel indicated that, for the present complex gear model, the permeable surfaces provide a more accurate representation of farfield noise, suggesting that volumetric effects are not negligible. The present study also demonstrates that good agreement between simulated and measured farfield noise can be achieved if consistent post-processing is applied to both physical and synthetic pressure records at array microphone locations.

A new high selective and sensitive turn-on fluorescent and ratiometric absorption chemosensor for Cu2+ based on benzimidazole in aqueous solution and its application in live cell.

PubMed

Bing, Qijing; Wang, Lin; Li, Donglin; Wang, Guang

2018-09-05

A new benzimidazole base turn-on fluorescent and ratiometric absorption chemosensor (L) bearing bidentate ligand for detection of Cu 2+ was designed and synthesized. Fluorescence and UV-vis spectra studies demonstrated that L can detect Cu 2+ ions in aqueous solution using fluorescence enhancement and ratiometric absorption sensing over a wide pH range. Both fluorescent and ratiometric absorption sensing of L for Cu 2+ possessed high selectivity and sensitivity over other competitive metal ions and had low detection limit. Job's plot, mass spectra and DFT calculation indicated the sensing mechanism is the complex formation between L and Cu 2+ with 1:2 stoichiometry. Fluorescence images of HepG2 in the absence and presence of Cu 2+ displayed L had cell permeability and detection ability for Cu 2+ in live cells. Copyright © 2018 Elsevier B.V. All rights reserved.

Absorption Characterization of Mn-Zr-Substituted La-Sr Hexaferrite Using Open-Circuit and Short-Circuit Approaches in 8.2-18 GHz Frequency Range

NASA Astrophysics Data System (ADS)

Narang, Sukhleen Bindra; Kaur, Pawandeep; Bahel, Shalini; Pubby, Kunal

2018-01-01

The present study reports on the microwave absorption characterization of Mn2+-Zr4+ substituted lanthanum strontium ferrites, Sr0.85La0.15(MnZr) x Fe12-2 x O19, where x = 0.0, 0.25, 0.50, 0.75 and 1.0 in the X- and Ku-band. The synthesized ferrites are characterized with regard to their electromagnetic properties such as complex permittivity ( {ɛ^' - jɛ^'' ) and complex permeability ( {μ^' - jμ^'' ) using vector network analysis in the 8.2-18 GHz frequency range. Real and imaginary parts of permittivity decrease with the increase in Mn-Zr concentration due to a reduction in electron hopping conduction and eddy current losses, respectively. Microwave permeability spectra are also affected by the doping. The amplitude of magnetic loss peak increases with the increase in doping except for the x = 1.0 composition. Two commonly used approaches, open-circuit and short-circuit, have been employed for the absorption analysis. The difference in the results of these two techniques is justified on the basis of the reflection mechanism. The presented experimental findings underline the potential of the synthesized compositions with Mn-Zr concentrations x = 0.25, 0.5 and 0.75 in the suppression of electromagnetic reflections and radar signatures.

Influence of Si concentration on the magnetization dynamics in as-sputtered FeCoSiN thin films at high frequencies

NASA Astrophysics Data System (ADS)

Xu, Feng; Chen, Xin; Ma, Yungui; Phuoc, N. N.; Zhang, Xiaoyu; Ong, C. K.

2008-10-01

In this work, the high-frequency magnetic permeability spectra of as-sputtered FeCoSiN films with various Si concentrations were investigated. The soft magnetic properties with an induced in-plane uniaxial anisotropy can only be obtained within some composition ranges because of the formation of different granular microstructures. The permeability spectra measured without any external fields (He) were well fitted based on the phenomenological Landau-Lifshitz-Gilbert equation. Results show that with the increase in Si concentration, the saturated magnetization 4πMs, the resonance frequency fr, the permeability μ, and the qualify factor Q values decrease, while the damping coefficient α and resonant frequency linewidth Δf increase. The increase in Gilbert damping coefficient α or G is ascribed to the increase in mosaicity or magnetic ripples with higher volume proportion of Si-rich matrix. The investigations on Δf-He relations indicate the extrinsic damping contribution from the two-magnon scattering in FeCoSiN, which is suggested to be due to the change in the granular microstructures compared with FeCoN.

Role of crystal orientation on electrical tuning of dynamic permeability in strain-mediated multiferroic structures

NASA Astrophysics Data System (ADS)

Phuoc, Nguyen N.; Ong, C. K.

2017-06-01

Multiferroic structures of FeCo/NiFe/[Pb(Mg1/3Nb2/3)O3]0.68-[PbTiO3]0.32 (PMN-PT) with three different crystal orientations of PMN-PT(0 1 1), PMN-PT(0 0 1) and PMN-PT(1 1 1) were fabricated by a sputtering deposition system. Their dynamic magnetic properties were characterized under various applied electrical fields. The sample with PMN-PT(0 1 1) orientation shows a large tuning of the permeability spectra while the ones with PMN-PT(0 0 1) and PMN-PT(1 1 1) orientations exhibit a moderate and little change in the permeability spectra, respectively. The result can be explained via the magnetoelectric effect by considering the role of the piezoelectric coefficients being highly dependent on the crystal orientation along which the PMN-PT is poled. This explanation is consistent with the static magnetic characteristics of the samples before and after poling.

Microwave and millimeter wave dielectric permittivity and magnetic permeability of epsilon-gallium-iron-oxide nano-powders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, Liu, E-mail: liu.chao@tufts.edu; Afsar, Mohammed N.; Ohkoshi, Shin-ichi

2015-05-07

In millimeter wave frequency range, hexagonal ferrites with high uniaxial anisotropic magnetic fields are used as absorbers. These ferrites include M-type barium ferrite (BaFe{sub 12}O{sub 19}) and strontium ferrite (SrFe{sub 12}O{sub 19}), which have natural ferromagnetic resonant frequency range from 40 GHz to 60 GHz. However, the higher frequency range lacks suitable materials that support the higher frequency ferromagnetic resonance. A series of gallium-substituted ε-iron oxides (ε-Ga{sub x}Fe{sub 2−x}O{sub 3}) are synthesized, which have ferromagnetic resonant frequencies appearing over the frequency range of 30 GHz to 150 GHz. The ε-Ga{sub x}Fe{sub 2−x}O{sub 3} is synthesized by the sol-gel method. The particlemore » sizes are observed to be smaller than 100 nm. In this paper, in-waveguide transmission and reflection method and the free space magneto-optical approach have been employed to study these newly developed ε-Ga{sub x}Fe{sub 2−x}O{sub 3} particles in millimeter waves. These techniques enable to obtain precise transmission spectra to determine the dielectric and magnetic properties of both isotropic and anisotropic ferrites in the microwave and millimeter wave frequency range from single set of direct measurements. The complex dielectric permittivity and magnetic permeability spectra of ε-Ga{sub x}Fe{sub 2−x}O{sub 3} are shown in this paper. Strong ferromagnetic resonances at different frequencies determined by the x parameter are found.« less

Mitochondrial oxygen consumption in permeabilized fibers and its link to colour changes in bovine M. semimembranosus muscle.

PubMed

Phung, V T; Khatri, M; Liland, K H; Slinde, E; Sørheim, O; Almøy, T; Saarem, K; Egelandsdal, B

2013-01-01

Animal and muscle characteristics were recorded for 41 cattle. The oxygen consumption rate (OCR) of M. semimembranosus was measured between 3.0-6.4h post mortem (PM3-6) and after 3 weeks in a vacuum pack at 4°C. Colour change measurements were performed following the 3 weeks using reflectance spectra (400-1,100 nm) and the colour coordinates L, a and b, with the samples being packaged in oxygen permeable film and stored at 4°C for 167 h. Significant individual animal differences in OCR at PM3-6 were found for mitochondrial complexes I and II. OCR of complex I declined with increased temperature and time PM, while residual oxygen-consuming side-reactions (ROX) did not. OCR of stored muscles was dominated by complex II respiration. A three-way regression between samples, colour variables collected upon air exposure and OCR of 3 weeks old fibres revealed a positive relationship between OCR and complex II activity and also between OCR and OCR(ROX). The presence of complex I and β-oxidation activities increased metmyoglobin formation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Microstructural dependence of Barkhausen noise and magnetic relaxation in the weld HAZ of an RPV steel

NASA Astrophysics Data System (ADS)

Park, Duck-Gun; Kim, Cheol Gi; Hong, Jun-Hwa

2000-06-01

Magnetic Barkhausen noise and permeability spectra have been measured to characterize different microstructure regions such as coarse-grain region, fine-grain region, intercritical structure (composed of tempered martensite and bainite) within the heat-affected zone (HAZ) of SA508-3 steel weldments using simulated HAZ microstructure sample. The intercritical region and coarse-grained region can be distinguished from the BNE and relaxation frequency. The BNE was decreased in the martensite regions and increased in the bainite regions by the post-weld heat treatment (PWHT). The change of relaxation frequency also showed similar trends, but the rate of change was less than that of BNE. The behavior of BNE and permeability spectra on the corresponding microstructure can be explained in terms of carbide morphology and residual stress related with domain wall motion.

Terahertz and infrared spectroscopic evidence of phonon-paramagnon coupling in hexagonal piezomagnetic YMnO3

NASA Astrophysics Data System (ADS)

Kadlec, C.; Goian, V.; Rushchanskii, K. Z.; Kužel, P.; Ležaić, M.; Kohn, K.; Pisarev, R. V.; Kamba, S.

2011-11-01

Terahertz and far-infrared electric and magnetic responses of hexagonal piezomagnetic YMnO3 single crystals are investigated. Antiferromagnetic resonance is observed in the spectra of magnetic permeability μa [H(ω) oriented within the hexagonal plane] below the Néel temperature TN. This excitation softens from 41 to 32 cm-1 upon heating and finally disappears above TN. An additional weak and heavily-damped excitation is seen in the spectra of complex dielectric permittivity ɛc within the same frequency range. This excitation contributes to the dielectric spectra in both antiferromagnetic and paramagnetic phases. Its oscillator strength significantly increases upon heating toward room temperature, thus providing evidence of piezomagnetic or higher-order couplings to polar phonons. Other heavily-damped dielectric excitations are detected near 100 cm-1 in the paramagnetic phase in both ɛc and ɛa spectra, and they exhibit similar temperature behavior. These excitations appearing in the frequency range of magnon branches well below polar phonons could remind electromagnons, however their temperature dependence is quite different. We have used density functional theory for calculating phonon dispersion branches in the whole Brillouin zone. A detailed analysis of these results and of previously published magnon dispersion branches brought us to the conclusion that the observed absorption bands stem from phonon-phonon and phonon-paramagnon differential absorption processes. The latter is enabled by strong short-range in-plane spin correlations in the paramagnetic phase.

Effect of temperature on the permeability of gas adsorbed coal under triaxial stress conditions

NASA Astrophysics Data System (ADS)

Li, Xiangchen; Yan, Xiaopeng; Kang, Yili

2018-04-01

The combined effects of gas sorption, stress and temperature play a significant role in the changing behavior of gas permeability in coal seams. The effect of temperature on nitrogen and methane permeability of naturally fractured coal is investigated. Coal permeability, P-wave velocity and axial strain were simultaneously measured under two effective stresses and six different temperatures. The results showed that the behavior of nitrogen and methane permeability presented nonmonotonic changes with increasing temperature. The variation in the P-wave velocity and axial strain showed a good correspondence with coal permeability. A higher effective stress limited the bigger deformation and caused the small change in permeability. Methane adsorption and desorption significantly influence the mechanical properties of coal and play an important role in the variations in coal permeability. The result of coal permeability during a complete stress-strain process showed that the variation in permeability is determined by the evolution of the internal structure. The increase in the temperature of the gas saturated coal causes the complex interaction between matrix swelling, matrix shrinkage and micro-fracture generation, which leads to the complex changes in coal structure and permeability. These results are helpful to understand the gas transport mechanism for exploiting coal methane by heat injection.

Characterization of excess pore pressures at the toe of the Nankai accretionary complex, Ocean Drilling Program sites 1173, 1174, and 808: Results of one-dimensional modeling

NASA Astrophysics Data System (ADS)

Gamage, K.; Screaton, E.

2006-04-01

Elevated fluid pore pressures play a critical role in the development of accretionary complexes, including the development of the décollement zone. In this study, we used measured permeabilities of core samples from Ocean Drilling Program (ODP) Leg 190 to develop a permeability-porosity relationship for hemipelagic sediments at the toe of the Nankai accretionary complex. This permeability-porosity relationship was used in a one-dimensional loading and fluid flow model to simulate excess pore pressures and porosities. Simulated excess pore pressure ratios (as a fraction of lithostatic pressure-hydrostatic pressure) using the best fit permeability-porosity relationship were lower than predicted from previous studies. We then tested sensitivity of excess pore pressure ratios in the underthrust sediments to bulk permeability, lateral stress in the prism, and a hypothetical low-permeability barrier at the décollement. Our results demonstrated significant increase in pore pressures below the décollement with lower bulk permeability, such as obtained by using the lower boundary of permeability-porosity data, or when a low-permeability barrier is added at the décollement. In contrast, pore pressures in the underthrust sediments demonstrated less sensitivity to added lateral stresses in the prism, although the profile of the excess pore pressure ratio is affected. Both simulations with lateral stress and a low-permeability barrier at the décollement resulted in sharp increases in porosity at the décollement, similar to that observed in measured porosities. Furthermore, in both scenarios, maximum excess pore pressure ratios were found at the décollement, suggesting that either of these factors would contribute to stable sliding along the décollement.

Combined effect of demagnetizing field and induced magnetic anisotropy on the magnetic properties of manganese-zinc ferrite composites

NASA Astrophysics Data System (ADS)

Babayan, V.; Kazantseva, N. E.; Moučka, R.; Sapurina, I.; Spivak, Yu. M.; Moshnikov, V. A.

2012-01-01

This work is devoted to the analysis of factors responsible for the high-frequency shift of the complex permeability (μ*) dispersion region in polymer composites of manganese-zinc (MnZn) ferrite, as well as to the increase in their thermomagnetic stability. The magnetic spectra of the ferrite and its composites with polyurethane (MnZn-PU) and polyaniline (MnZn-PANI) are measured in the frequency range from 1 MHz to 3 GHz in a longitudinal magnetization field of up to 700 Ое and in the temperature interval from -20 °С to +150 °С. The approximation of the magnetic spectra by a model, which takes into account the role of domain wall motion and magnetization rotation, allows one to determine the specific contribution of resonance processes associated with domain wall motion and the natural ferromagnetic resonance to the μ*. It is established that, at high frequencies, the μ* of the MnZn ferrite is determined solely by magnetization rotation, which occurs in the region of natural ferromagnetic resonance when the ferrite is in the “single domain” state. In the polymer composites of the MnZn ferrite, the high-frequency permeability is also determined mainly by the magnetization rotation; however, up to high values of magnetizing fields, there is a contribution of domain wall motion, thus the “single domain” state in ferrite is not reached. The frequency and temperature dependence of μ* in polymer composites are governed by demagnetizing field and the induced magnetic anisotropy. The contribution of the induced magnetic anisotropy is crucial for MnZn-PANI. It is attributed to the elastic stresses that arise due to the domain wall pinning by a polyaniline film adsorbed on the surface of the ferrite during in-situ polymerization.

Regional-dependent intestinal permeability and BCS classification: elucidation of pH-related complexity in rats using pseudoephedrine.

PubMed

Fairstein, Moran; Swissa, Rotem; Dahan, Arik

2013-04-01

Based on its lower Log P value relative to metoprolol, a marker for the low/high-permeability (P(eff)) class boundary, pseudoephedrine was provisionally classified as BCS low-permeability compound. On the other hand, following oral administration, pseudoephedrine fraction dose absorbed (F(abs)) and systemic bioavailability approaches 100%. This represents a challenge to the generally recognized P(eff)-F(abs) correlation. The purpose of this study was to elucidate the underlying mechanisms behind the confusion in pseudoephedrine's BCS classification. Pseudoephedrine's BCS solubility class was determined, and its physicochemical properties and intestinal permeability were thoroughly investigated, both in vitro and in vivo in rats, considering the complexity of the whole of the small intestine. Pseudoephedrine was found to be unequivocally a high-solubility compound. All of the permeability studies revealed similar phenomenon; at any given intestinal segment/pH, the permeability of metoprolol was higher than that of pseudoephedrine, however, as the intestinal region becomes progressively distal, and the pH gradually increases, pseudoephedrine's permeability rises above that of metoprolol in the former segment. This unique permeability pattern likely explains pseudoephedrine's complete absorption. In conclusion, pseudoephedrine is a BCS Class I compound; no discrepancy between P(eff) and F(abs) is involved in its absorption. Rather, it reflects the complexity behind P(eff) when considering the whole of the intestine. We propose to allow high-permeability classification to drugs with P(eff) that matches/exceeds the low/high class benchmark anywhere throughout the intestinal tract and not restricted necessarily to the jejunum.

The complexity of intestinal permeability: Assigning the correct BCS classification through careful data interpretation.

PubMed

Zur, Moran; Hanson, Allison S; Dahan, Arik

2014-09-30

While the solubility parameter is fairly straightforward when assigning BCS classification, the intestinal permeability (Peff) is more complex than generally recognized. In this paper we emphasize this complexity through the analysis of codeine, a commonly used antitussive/analgesic drug. Codeine was previously classified as a low-permeability compound, based on its lower LogP compared to metoprolol, a marker for the low-high permeability class boundary. In contrast, high fraction of dose absorbed (Fabs) was reported for codeine, which challenges the generally recognized Peff-Fabs correlation. The purpose of this study was to clarify this ambiguity through elucidation of codeine's BCS solubility/permeability class membership. Codeine's BCS solubility class was determined, and its intestinal permeability throughout the small intestine was investigated, both in vitro and in vivo in rats. Codeine was found to be unequivocally a high-solubility compound. All in vitro studies indicated that codeine's permeability is higher than metoprolol's. In vivo studies in rats showed similar permeability for both drugs throughout the entire small-intestine. In conclusion, codeine was found to be a BCS Class I compound. No Peff-Fabs discrepancy is involved in its absorption; rather, it reflects the risk of assigning BCS classification based on merely limited physicochemical characteristics. A thorough investigation using multiple experimental methods is prudent before assigning a BCS classification, to avoid misjudgment in various settings, e.g., drug discovery, formulation design, drug development and regulation. Copyright © 2013 Elsevier B.V. All rights reserved.

High microwave attenuation performance of planar carbonyl iron particles with orientation of shape anisotropy field

NASA Astrophysics Data System (ADS)

Guo, Cheng; Yang, Zhihong; Shen, Shile; Liang, Juan; Xu, Guoyue

2018-05-01

Planar anisotropy carbonyl iron (PACI) particles were prepared from commercial spherical carbonyl iron particles through a high performance ball-milling technique. The paraffin composites with orientation of shape anisotropy field for these PACI particles were obtained by applying an external magnetic field during the fabrication process. The frequency-dependent complex permeability values of these prepared paraffin composites have been investigated in the frequency range of 1-18 GHz. The results demonstrate that the orientation of shape anisotropy field for these PACI particles can effectively increase the complex permeability and decrease the complex permittivity values. Benefit from the enhancement in the complex permeability and reduction in the complex permittivity, the better impedance matching condition can be obtained and thus the good microwave absorption performance can be achieved for the samples with enough magnetic field orientation time.

Improving permeability and oral absorption of mangiferin by phospholipid complexation.

PubMed

Ma, Hequn; Chen, Hongming; Sun, Le; Tong, Lijin; Zhang, Tianhong

2014-03-01

Mangiferin is an active ingredient of medicinal plant with poor hydrophilicity and lipophilicity. Many reports focused on improving aqueous solubility, but oral bioavailability of mangiferin was still limited. In this study, we intended to increase not only solubility, but also membrane permeability of mangiferin by a phospholipid complexation technique. The new complex's physicochemical properties were characterized in terms of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), infrared absorption spectroscopy (IR), aqueous solubility, oil-water partition coefficient and in vitro dissolution. The intestinal absorption of the complex was studied by the rat in situ intestinal perfusion model. After oral administration of mangiferin-phospholipid complex and crude mangiferin in rats, the concentrations of mangiferin were determined by a validated RP-HPLC method. Results showed that the solubility of the complex in water and in n-octanol was enhanced and the oil-water partition coefficient was improved by 6.2 times and the intestinal permeability in rats was enhanced significantly. Peak plasma concentration and AUC of mangiferin from the complex (Cmax: 377.66 μg/L, AUC: 1039.94 μg/L*h) were higher than crude mangiferin (Cmax: 180 μg/L, AUC: 2355.63 μg/L*h). In view of improved solubility and enhanced permeability, phospholipid complexation technique can increase bioavailability of mangiferin by 2.3 times in comparison to the crude mangiferin. Copyright © 2013 Elsevier B.V. All rights reserved.

Thickness dependence of the magnetic anisotropy and dynamic magnetic response of ferromagnetic NiFe films

NASA Astrophysics Data System (ADS)

Silva, E. F.; Corrêa, M. A.; Della Pace, R. D.; Plá Cid, C. C.; Kern, P. R.; Carara, M.; Chesman, C.; Alves Santos, O.; Rodríguez-Suárez, R. L.; Azevedo, A.; Rezende, S. M.; Bohn, F.

2017-05-01

We investigate the thickness dependence of the magnetic anisotropy and dynamic magnetic response of ferromagnetic NiFe films. We go beyond quasi-static measurements and focus on the dynamic magnetic response by considering three complementary techniques: the ferromagnetic resonance, magnetoimpedance and magnetic permeability measurements. We verify remarkable modifications in the magnetic anisotropy, i.e. the well-known behavior of in-plane uniaxial magnetic anisotropy systems gives place to a complex magnetic behavior as the thickness increases, and splits the films in two groups according to the magnetic properties. We identify magnetoimpedance and magnetic permeability curves with multiple resonance peaks, as well as the evolution of the ferromagnetic resonance absorption spectra, as fingerprints of strong changes of the magnetic properties associated to the vanishing of the in-plane magnetic anisotropy and to the emergence of non-homogeneous magnetization configuration, local anisotropies and out-of-plane anisotropy contribution arisen as a consequence of the non-uniformities of the stress stored in the film as the thickness is increased and/or to the columnar growth of the film. We interpret the experimental results in terms of the structural and morphological properties, quasi-static magnetic behavior, magnetic domain structure and different mechanisms governing the magnetization dynamics at distinct frequency ranges.

Broadband complex permeability characterization of magnetic thin films using shorted microstrip transmission-line perturbation

NASA Astrophysics Data System (ADS)

Liu, Yan; Chen, Linfeng; Tan, C. Y.; Liu, H. J.; Ong, C. K.

2005-06-01

A brief review of the methods used for broadband complex permeability measurement of magnetic thin films up to microwave frequencies is given. In particular, the working principles of the transmission-line perturbation methods for the characterization of magnetic thin films are discussed, with emphasis on short-circuited planar transmission-line perturbation methods. The algorithms for calculating the complex permeability of magnetic thin films for short-circuited planar transmission-line perturbation methods are analyzed. A shorted microstrip line is designed and fabricated as a prototype measurement fixture. The structure of the microstrip fixture and the corresponding measurement procedure are discussed in detail. A piece of 340 nm thick FeTaN thin film deposited on Si substrate using sputtering method is characterized using the microstrip fixture. An improved technique for obtaining permeability by using a saturation magnetization field is demonstrated here, and the results fit well with the Landau-Lifchitz-Gilbert theory. Approaches to extending this method to other aspects in the investigation of magnetic thin film are also discussed.

New Methods of Esterification of Nanodiamonds in Fighting Breast Cancer-A Density Functional Theory Approach.

PubMed

Landeros-Martinez, Linda-Lucila; Glossman-Mitnik, Daniel; Orrantia-Borunda, Erasmo; Flores-Holguín, Norma

2017-10-19

The use of nanodiamonds as anticancer drug delivery vehicles has received much attention in recent years. In this theoretical paper, we propose using different esterification methods for nanodiamonds. The monomers proposed are 2-hydroxypropanal, polyethylene glycol, and polyglicolic acid. Specifically, the hydrogen bonds, infrared (IR) spectra, molecular polar surface area, and reactivity parameters are analyzed. The monomers proposed for use in esterification follow Lipinski's rule of five, meaning permeability is good, they have good permeation, and their bioactivity is high. The results show that the complex formed between tamoxifen and nanodiamond esterified with polyglicolic acid presents the greatest number of hydrogen bonds and a good amount of molecular polar surface area. Calculations concerning the esterified nanodiamond and reactivity parameters were performed using Density Functional Theory with the M06 functional and the basis set 6-31G (d); for the esterified nanodiamond-Tamoxifen complexes, the semi-empirical method PM6 was used. The solvent effect has been taken into account by using implicit modelling and the conductor-like polarizable continuum model.

Importin-β modulates the permeability of the nuclear pore complex in a Ran-dependent manner

PubMed Central

Lowe, Alan R; Tang, Jeffrey H; Yassif, Jaime; Graf, Michael; Huang, William YC; Groves, Jay T; Weis, Karsten; Liphardt, Jan T

2015-01-01

Soluble karyopherins of the importin-β (impβ) family use RanGTP to transport cargos directionally through the nuclear pore complex (NPC). Whether impβ or RanGTP regulate the permeability of the NPC itself has been unknown. In this study, we identify a stable pool of impβ at the NPC. A subpopulation of this pool is rapidly turned-over by RanGTP, likely at Nup153. Impβ, but not transportin-1 (TRN1), alters the pore's permeability in a Ran-dependent manner, suggesting that impβ is a functional component of the NPC. Upon reduction of Nup153 levels, inert cargos more readily equilibrate across the NPC yet active transport is impaired. When purified impβ or TRN1 are mixed with Nup153 in vitro, higher-order, multivalent complexes form. RanGTP dissolves the impβ•Nup153 complexes but not those of TRN1•Nup153. We propose that impβ and Nup153 interact at the NPC's nuclear face to form a Ran-regulated mesh that modulates NPC permeability. DOI: http://dx.doi.org/10.7554/eLife.04052.001 PMID:25748139

New insights into the hydrostratigraphy of the High Plains aquifer from three-dimensional visualizations based on well records

USGS Publications Warehouse

Macfarlane, P.A.

2009-01-01

Regional aquifers in thick sequences of continentally derived heterolithic deposits, such as the High Plains of the North American Great Plains, are difficult to characterize hydrostratigraphically because of their framework complexity and the lack of high-quality subsurface information from drill cores and geophysical logs. However, using a database of carefully evaluated drillers' and sample logs and commercially available visualization software, it is possible to qualitatively characterize these complex frameworks based on the concept of relative permeability. Relative permeability is the permeable fraction of a deposit expressed as a percentage of its total thickness. In this methodology, uncemented coarse and fine sediments are arbitrarily set at relative permeabilities of 100% and 0%, respectively, with allowances made for log entries containing descriptions of mixed lithologies, heterolithic strata, and cementation. To better understand the arrangement of high- and low-permeability domains within the High Plains aquifer, a pilot study was undertaken in southwest Kansas to create three-dimensional visualizations of relative permeability using a database of >3000 logs. Aggregate relative permeability ranges up to 99% with a mean of 51%. Laterally traceable, thick domains of >80% relative permeability embedded within a lower relative permeability matrix strongly suggest that preferred pathways for lateral and vertical water transmission exist within the aquifer. Similarly, domains with relative permeabilities of <45% are traceable laterally over appreciable distances in the sub-surface and probably act as leaky confining layers. This study shows that the aquifer does not consist solely of local, randomly distributed, hydrostratigraphic units, as suggested by previous studies. ?? 2009 Geological Society of America.

Temperature dependence dynamical permeability characterization of magnetic thin film using near-field microwave microscopy

NASA Astrophysics Data System (ADS)

Hung, Le Thanh; Phuoc, Nguyen N.; Wang, Xuan-Cong; Ong, C. K.

2011-08-01

A temperature dependence characterization system of microwave permeability of magnetic thin film up to 5 GHz in the temperature range from room temperature up to 423 K is designed and fabricated as a prototype measurement fixture. It is based on the near field microwave microscopy technique (NFMM). The scaling coefficient of the fixture can be determined by (i) calibrating the NFMM with a standard sample whose permeability is known; (ii) by calibrating the NFMM with an established dynamic permeability measurement technique such as shorted microstrip transmission line perturbation method; (iii) adjusting the real part of the complex permeability at low frequency to fit the value of initial permeability. The algorithms for calculating the complex permeability of magnetic thin films are analyzed. A 100 nm thick FeTaN thin film deposited on Si substrate by sputtering method is characterized using the fixture. The room temperature permeability results of the FeTaN film agree well with results obtained from the established short-circuited microstrip perturbation method. Temperature dependence permeability results fit well with the Landau-Lifshitz-Gilbert equation. The temperature dependence of the static magnetic anisotropy H_K^{sta}, the dynamic magnetic anisotropy H_K^{dyn}, the rotational anisotropy Hrot, together with the effective damping coefficient αeff, ferromagnetic resonance fFMR, and frequency linewidth Δf of the thin film are investigated. These temperature dependent magnetic properties of the magnetic thin film are important to the high frequency applications of magnetic devices at high temperatures.

TNF-α Signals Through PKCζ/NF-κB to Alter the Tight Junction Complex and Increase Retinal Endothelial Cell Permeability

PubMed Central

Aveleira, Célia A.; Lin, Cheng-Mao; Abcouwer, Steven F.; Ambrósio, António F.; Antonetti, David A.

2010-01-01

OBJECTIVE Tumor necrosis factor-α (TNF-α) and interleukin-1 beta (IL-1β) are elevated in the vitreous of diabetic patients and in retinas of diabetic rats associated with increased retinal vascular permeability. However, the molecular mechanisms underlying retinal vascular permeability induced by these cytokines are poorly understood. In this study, the effects of IL-1β and TNF-α on retinal endothelial cell permeability were compared and the molecular mechanisms by which TNF-α increases cell permeability were elucidated. RESEARCH DESIGN AND METHODS Cytokine-induced retinal vascular permeability was measured in bovine retinal endothelial cells (BRECs) and rat retinas. Western blotting, quantitative real-time PCR, and immunocytochemistry were performed to determine tight junction protein expression and localization. RESULTS IL-1β and TNF-α increased BREC permeability, and TNF-α was more potent. TNF-α decreased the protein and mRNA content of the tight junction proteins ZO-1 and claudin-5 and altered the cellular localization of these tight junction proteins. Dexamethasone prevented TNF-α–induced cell permeability through glucocorticoid receptor transactivation and nuclear factor-kappaB (NF-κB) transrepression. Preventing NF-κB activation with an inhibitor κB kinase (IKK) chemical inhibitor or adenoviral overexpression of inhibitor κB alpha (IκBα) reduced TNF-α–stimulated permeability. Finally, inhibiting protein kinase C zeta (PKCζ) using both a peptide and a novel chemical inhibitor reduced NF-κB activation and completely prevented the alterations in the tight junction complex and cell permeability induced by TNF-α in cell culture and rat retinas. CONCLUSIONS These results suggest that PKCζ may provide a specific therapeutic target for the prevention of vascular permeability in retinal diseases characterized by elevated TNF-α, including diabetic retinopathy. PMID:20693346

Improvement of high-frequency characteristics of Z-type hexaferrite by dysprosium doping

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mu Chunhong; Liu Yingli; Song Yuanqiang

2011-06-15

Z-type hexaferrite has great potential applications as anti-EMI material for magnetic devices in the GHz region. In this work, Dy-doped Z-type hexaferrites with nominal stoichiometry of Ba{sub 3}Co{sub 2}Dy{sub x}Fe{sub 24-x}O{sub 41} (x 0.0, 0.05, 0.5, 1.0) were prepared by an improved solid-state reaction method. The effects of rare earth oxide (Dy{sub 2}O{sub 3}) addition on the phase composition, microstructure and electromagnetic properties of the ceramics were investigated. Structure and micromorphology characterizations indicate that certain content of Dy doping will cause the emergence of the second phase Dy{sub 3}Fe{sub 5}O{sub 12} at the grain boundaries of the majority phase Z-typemore » hexaferrite, due to which the straightforward result is the grain refinement during the successive sintering process. Permeability spectra measurements show that the initial permeability reaches its maximum of 17 at 300 MHz with x = 0.5, while the cutoff frequency keeps above 800 MHz. The apparent specific anisotropy field H{sub K} of Dy-doped Z-type hexaferrites decreases with x increasing. The relationships among phase composition, grain size, permeability spectra, and anisotropy are theoretically investigated, and according to the analysis, Dy doping effects on its magnetic properties can be well explained and understood.« less

Permeability measurement and control for epoxy composites

NASA Astrophysics Data System (ADS)

Chang, Tsun-Hsu; Tsai, Cheng-Hung; Wong, Wei-Syuan; Chen, Yen-Ren; Chao, Hsien-Wen

2017-08-01

The coupling of the electric and magnetic fields leads to a strong interplay in materials' permittivity and permeability. Here, we proposed a specially designed cavity, called the mu cavity. The mu cavity, consisting of a mushroom structure inside a cylindrical resonator, is exclusively sensitive to permeability, but not to permittivity. It decouples materials' electromagnetic properties and allows an accurate measurement of the permeability. With the help of an epsilon cavity, these two cavities jointly determine the complex permeability and permittivity of the materials at microwave frequencies. Homemade epoxy-based composite materials were prepared and tested. Measurement and manipulation of the permeability and permittivity of the epoxy composites will be shown. The results will be compared with the effective medium theories.

A Systematic Procedure to Describe Shale Gas Permeability Evolution during the Production Process

NASA Astrophysics Data System (ADS)

Jia, B.; Tsau, J. S.; Barati, R.

2017-12-01

Gas flow behavior in shales is complex due to the multi-physics nature of the process. Pore size reduces as the in-situ stress increases during the production process, which will reduce intrinsic permeability of the porous media. Slip flow/pore diffusion enhances gas apparent permeability, especially under low reservoir pressures. Adsorption not only increases original gas in place but also influences gas flow behavior because of the adsorption layer. Surface diffusion between free gas and adsorption phase enhances gas permeability. Pore size reduction and the adsorption layer both have complex impacts on gas apparent permeability and non-Darcy flow might be a major component in nanopores. Previously published literature is generally incomplete in terms of coupling of all these four physics with fluid flow during gas production. This work proposes a methodology to simultaneously take them into account to describe a permeability evolution process. Our results show that to fully describe shale gas permeability evolution during gas production, three sets of experimental data are needed initially: 1) intrinsic permeability under different in-situ stress, 2) adsorption isotherm under reservoir conditions and 3) surface diffusivity measurement by the pulse-decay method. Geomechanical effects, slip flow/pore diffusion, adsorption layer and surface diffusion all play roles affecting gas permeability. Neglecting any of them might lead to misleading results. The increasing in-situ stress during shale gas production is unfavorable to shale gas flow process. Slip flow/pore diffusion is important for gas permeability under low pressures in the tight porous media. They might overwhelm the geomechanical effect and enhance gas permeability at low pressures. Adsorption layer reduces the gas permeability by reducing the effective pore size, but the effect is limited. Surface diffusion increases gas permeability more under lower pressures. The total gas apparent permeability might keep increasing during the gas production process when the surface diffusivity is larger than a critical value. We believe that our workflow proposed in this study will help describe shale gas permeability evolution considering all the underlying physics altogether.

Permeability structure of a highly heterogeneous transgressive-marine complex: Tocito Sandstone, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lambert, M.L.; Cole, R.D.

1996-01-01

The Tocito Sandstone Member of the Mancos Shale is an Upper Cretaceous shallow-marine sandstone and mudrock complex deposited along the western margin of the Western Interior seaway. The Tocito is a major hydrocarbon producer in the San Juan Basin (approximately 117 million barrels of oil and 79 billion cubic feet of gas). Because of reservoir heterogeneity, ultimate Tocito oil recovery factors are low, generally between 10 and 20 percent. To enhance understanding of permeability heterogeneity in the Tocito, we have undertaken a detailed surface and subsurface investigation. A total of 2,697 permeability measurements have been made using minipermeameters. Permeability variationmore » within the Tocito is controlled by two principal factors: lithofacies and burial/diagenetic history. Coarser grained and better sorted lithofacies have the highest permeability. The permeability values from outcrop and shallow subsurface cores are dramatically higher than those from deep subsurface cores. This is due to dissolution of grains and calcite cement, and decompaction that preferentially affected the outcrop and shallow subsurface. Correlation lengths for permeability values along horizontal transacts are typically less than 3 m, whereas those for vertical transacts are usually less than 0.6 m. These data suggest that small grid block sizes should be used during reservoir simulations if the investigator wishes to accurately capture the reservoir heterogeneity.« less

Permeability structure of a highly heterogeneous transgressive-marine complex: Tocito Sandstone, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lambert, M.L.; Cole, R.D.

1996-12-31

The Tocito Sandstone Member of the Mancos Shale is an Upper Cretaceous shallow-marine sandstone and mudrock complex deposited along the western margin of the Western Interior seaway. The Tocito is a major hydrocarbon producer in the San Juan Basin (approximately 117 million barrels of oil and 79 billion cubic feet of gas). Because of reservoir heterogeneity, ultimate Tocito oil recovery factors are low, generally between 10 and 20 percent. To enhance understanding of permeability heterogeneity in the Tocito, we have undertaken a detailed surface and subsurface investigation. A total of 2,697 permeability measurements have been made using minipermeameters. Permeability variationmore » within the Tocito is controlled by two principal factors: lithofacies and burial/diagenetic history. Coarser grained and better sorted lithofacies have the highest permeability. The permeability values from outcrop and shallow subsurface cores are dramatically higher than those from deep subsurface cores. This is due to dissolution of grains and calcite cement, and decompaction that preferentially affected the outcrop and shallow subsurface. Correlation lengths for permeability values along horizontal transacts are typically less than 3 m, whereas those for vertical transacts are usually less than 0.6 m. These data suggest that small grid block sizes should be used during reservoir simulations if the investigator wishes to accurately capture the reservoir heterogeneity.« less

Intraepithelial gammadelta+ lymphocytes maintain the integrity of intestinal epithelial tight junctions in response to infection.

PubMed

Dalton, Jane E; Cruickshank, Sheena M; Egan, Charlotte E; Mears, Rainy; Newton, Darren J; Andrew, Elizabeth M; Lawrence, Beth; Howell, Gareth; Else, Kathryn J; Gubbels, Marc-Jan; Striepen, Boris; Smith, Judith E; White, Stanley J; Carding, Simon R

2006-09-01

Intestinal epithelial integrity and permeability is dependent on intercellular tight junction (TJ) complexes. How TJ integrity is regulated remains unclear, although phosphorylation and dephosphorylation of the integral membrane protein occludin is an important determinant of TJ formation and epithelial permeability. We have investigated the role intestinal intraepithelial lymphocytes (iIELs) play in regulating epithelial permeability in response to infection. Recombinant strains of Toxoplasma gondii were used to assess intestinal epithelial barrier function and TJ integrity in mice with intact or depleted populations of iIELs. Alterations in epithelial permeability were correlated with TJ structure and the state of phosphorylation of occludin. iIEL in vivo reconstitution experiments were used to identify the iIELs required to maintain epithelial permeability and TJ integrity. In the absence of gammadelta+ iIELs, intestinal epithelial barrier function and the ability to restrict epithelial transmigration of Toxoplasma and the unrelated intracellular bacterial pathogen Salmonella typhimurium was severely compromised. Leaky epithelium in gammadelta+ iIEL-deficient mice was associated with the absence of phosphorylation of serine residues of occludin and lack of claudin 3 and zona occludens-1 proteins in TJ complexes. These deficiencies were attributable to the absence of a single subset of gammadelta T-cell receptor (TCR-Vgamma7+) iIELs that, after reconstituting gammadelta iIEL-deficient mice, restored epithelial barrier function and TJ complexes, resulting in increased resistance to infection. These findings identify a novel role for gammadelta+ iIELs in maintaining TJ integrity and epithelial barrier function that have implications for understanding the pathogenesis of intestinal inflammatory diseases associated with disruption of TJ complexes.

Investigation into the Emerging Role of the Basic Amino Acid L-Lysine in Enhancing Solubility and Permeability of BCS Class II and BCS Class IV Drugs.

PubMed

Abdelkader, Hamdy; Fathalla, Zeinab

2018-06-18

The search for a simple and scalable approach that can improve the two key biopharmaceutical processes (solubility and permeability) for BCS Class II and BCS Class IV has still been unmet need. In this study, L-lysine was investigated as a potential excipient to tackle problems with solubility and permeability. Bendazac (Class II); quercetin and rutin (Class IV) were employed. Drugs-lysine complexes in 1:1 M ratios were prepared by co-precipitation and co-grinding; characterized for solubility, partition coefficient, DSC, FTIR, SEM, dissolution rate and permeability. Chemical stability of quercetin-lysine and rutin-lysine was studied by assessing antioxidant capacity using Trolox and CUPRAC assays. Drugs-lysine salt/complexes were confirmed. Solubility enhancement factors ranged from 68- to 433-fold increases and dissolution rates were also significantly enhanced by up to 6-times, compared with drugs alone. With the exception of rutin-lysine, P app for bendazac-lysine and quercetin-lysine enhanced by 2.3- to 4-fold. P app for quercetin (Class IV) benefited more than bendazac (Class II) when complexed with lysine. This study warrants the use of L-lysine as a promising excipient for enhanced solubility and permeability of Class II and Class IV, providing that the solubility of the drug is ensured at 'the door step' of absorption sites.

Solubility behavior and biopharmaceutical classification of novel high-solubility ciprofloxacin and norfloxacin pharmaceutical derivatives.

PubMed

Breda, Susana A; Jimenez-Kairuz, Alvaro F; Manzo, Ruben H; Olivera, María E

2009-04-17

The hydrochlorides of the 1:3 aluminum:norfloxacin and aluminum:ciprofloxacin complexes were characterized according to the Biopharmaceutics Classification System (BCS) premises in comparison with their parent compounds. The pH-solubility profiles of the complexes were experimentally determined at 25 and 37 degrees C in the range of pH 1-8 and compared to that of uncomplexed norfloxacin and ciprofloxacin. Both complexes are clearly more soluble than the antibiotics themselves, even at the lowest solubility pHs. The increase in solubility was ascribed to the species controlling solubility, which were analyzed in the solid phases at equilibrium at selected pHs. Additionally, permeability was set as low, based on data reported in the scientific literature regarding oral bioavailability, intestinal and cell cultures permeabilities and also considering the influence of stoichiometric amounts of aluminum. The complexes fulfill the BCS criterion to be classified as class 3 compounds (high solubility/low permeability). Instead, the active pharmaceutical ingredients (APIs) currently used in solid dosage forms, norfloxacin and ciprofloxacin hydrochloride, proved to be BCS class 4 (low solubility/low permeability). The solubility improvement turns the complexes as potential biowaiver candidates from the scientific point of view and may be a good way for developing more dose-efficient formulations. An immediate release tablet showing very rapid dissolution was obtained. Its dissolution profile was compared to that of the commercial ciprofloxacin hydrochloride tablets allowing to dissolution of the complete dose at a critical pH such as 6.8.

The transition from brittle faulting to cataclastic flow: Permeability evolution

NASA Astrophysics Data System (ADS)

Zhu, Wenlu; Wong, Teng-Fong

1997-02-01

Triaxial compression experiments were conducted to investigate influences of stress and failure mode on axial permeability of five sandstones with porosities ranging from 15% to 35%. In the cataclastic flow regime, permeability and porosity changes closely track one another. A drastic decrease in permeability was triggered by the onset of shear-enhanced compaction caused by grain crushing and pore collapse. The compactive yield stress C* maps out a boundary in stress space separating two different types of permeability evolution. Before C* is attained, permeability and porosity both decrease with increasing effective mean stress, but they are independent of deviatoric stresses. However, with loading beyond C*, both permeability and porosity changes are strongly dependent on the deviatoric and effective mean stresses. In the brittle faulting regime, permeability and porosity changes are more complex. Before the onset of shear-induced dilation C', both permeability and porosity decrease with increasing effective mean stress. Beyond C', permeability may actually decrease in a dilating rock prior to brittle failure. After the peak stress has been attained, the development of a relatively impermeable shear band causes an accelerated decrease of permeability. Permeability evolution in porous sandstones is compared with that in low-porosity crystalline rocks. A conceptual model for the coupling of deformation and fluid transport is proposed in the form of a deformation-permeability map.

Octonacci photonic crystals with negative refraction index materials

NASA Astrophysics Data System (ADS)

Brandão, E. R.; Vasconcelos, M. S.; Anselmo, D. H. A. L.

2016-12-01

We investigate the optical transmission spectra for s-polarized (TE) and p-polarized (TM) waves in one-dimensional photonic quasicrystals on a quasiperiodic multilayer structure made up by alternate layers of SiO2 and metamaterials, organized by following the Octonacci sequence. Maxwell's equations and the transfer-matrix technique are used to derive the transmission spectra for the propagation of normally and obliquely incident optical fields. We assume Drude-Lorentz-type dispersive response for the dielectric permittivity and magnetic permeability of the metamaterials. For normally incident waves, we observe that the spectra does not have self-similar behavior or mirror symmetry and it also features the absence of optical band gap. Also for normally incident waves, we show regions of full transmittance when the incident angle θC = 0° in a particular frequency range.

Quantifying tight-gas sandstone permeability via critical path analysis

USDA-ARS?s Scientific Manuscript database

Rock permeability has been actively investigated over the past several decades by the geosciences community. However, its accurate estimation still presents significant technical challenges, especially in spatially complex rocks. In this letter, we apply critical path analysis (CPA) to estimate perm...

Permeability from complex conductivity: an evaluation of polarization magnitude versus relaxation time based geophysical length scales

NASA Astrophysics Data System (ADS)

Slater, L. D.; Robinson, J.; Weller, A.; Keating, K.; Robinson, T.; Parker, B. L.

2017-12-01

Geophysical length scales determined from complex conductivity (CC) measurements can be used to estimate permeability k when the electrical formation factor F describing the ratio between tortuosity and porosity is known. Two geophysical length scales have been proposed: [1] the imaginary conductivity σ" normalized by the specific polarizability cp; [2] the time constant τ multiplied by a diffusion coefficient D+. The parameters cp and D+ account for the control of fluid chemistry and/or varying minerology on the geophysical length scale. We evaluated the predictive capability of two recently presented CC permeability models: [1] an empirical formulation based on σ"; [2] a mechanistic formulation based on τ;. The performance of the CC models was evaluated against measured permeability; this performance was also compared against that of well-established k estimation equations that use geometric length scales to represent the pore scale properties controlling fluid flow. Both CC models predict permeability within one order of magnitude for a database of 58 sandstone samples, with the exception of those samples characterized by high pore volume normalized surface area Spor and more complex mineralogy including significant dolomite. Variations in cp and D+ likely contribute to the poor performance of the models for these high Spor samples. The ultimate value of such geophysical models for permeability prediction lies in their application to field scale geophysical datasets. Two observations favor the implementation of the σ" based model over the τ based model for field-scale estimation: [1] the limited range of variation in cp relative to D+; [2] σ" is readily measured using field geophysical instrumentation (at a single frequency) whereas τ requires broadband spectral measurements that are extremely challenging and time consuming to accurately measure in the field. However, the need for a reliable estimate of F remains a major obstacle to the field-scale implementation of either of the CC permeability models for k estimation.

A broadband permeability measurement of FeTaN lamination stack by the shorted microstrip line method

NASA Astrophysics Data System (ADS)

Chen, Xin; Ma, Yungui; Xu, Feng; Wang, Peng; Ong, C. K.

2009-01-01

In this paper, the microwave characteristics of a FeTaN lamination stack are studied with a shorted microstrip line method. The FeTaN lamination stack was fabricated by gluing 54 layers of FeTaN units with epoxy together. The FeTaN units were deposited on both sides of an 8 μm polyethylene terephthate (Mylar) film as the substrate by rf magnetron sputtering. On each side of the Mylar substrate, three 100-nm FeTaN layers are laminated with two 8 nm Al2O3 layers. The complex permeability of FeTaN lamination stack is calculated by the scattering parameters using the shorted load transmission line model based on the quasi-transverse-electromagnetic approximation. A full wave analysis combined with an optimization process is employed to determine the accurate effective permeability values. The optimized complex permeability data can be used for the microwave filter design.

Method for enhancing cell penetration of Gd3+-based MRI contrast agents by conjugation with hydrophobic fluorescent dyes.

PubMed

Yamane, Takehiro; Hanaoka, Kenjiro; Muramatsu, Yasuaki; Tamura, Keita; Adachi, Yusuke; Miyashita, Yasushi; Hirata, Yasunobu; Nagano, Tetsuo

2011-11-16

Gadolinium ion (Gd(3+)) complexes are commonly used as magnetic resonance imaging (MRI) contrast agents to enhance signals in T(1)-weighted MR images. Recently, several methods to achieve cell-permeation of Gd(3+) complexes have been reported, but more general and efficient methodology is needed. In this report, we describe a novel method to achieve cell permeation of Gd(3+) complexes by using hydrophobic fluorescent dyes as a cell-permeability-enhancing unit. We synthesized Gd(3+) complexes conjugated with boron dipyrromethene (BDP-Gd) and Cy7 dye (Cy7-Gd), and showed that these conjugates can be introduced efficiently into cells. To examine the relationship between cell permeability and dye structure, we further synthesized a series of Cy7-Gd derivatives. On the basis of MR imaging, flow cytometry, and ICP-MS analysis of cells loaded with Cy7-Gd derivatives, highly hydrophobic and nonanionic dyes were effective for enhancing cell permeation of Gd(3+) complexes. Furthermore, the behavior of these Cy7-Gd derivatives was examined in mice. Thus, conjugation of hydrophobic fluorescent dyes appears to be an effective approach to improve the cell permeability of Gd(3+) complexes, and should be applicable for further development of Gd(3+)-based MRI contrast agents.

Permeability evolution of shale during spontaneous imbibition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, N.; Karpyn, Z. T.; Liu, S.

Shales have small pore and throat sizes ranging from nano to micron scales, low porosity and limited permeability. The poor permeability and complex pore connectivity of shales pose technical challenges to (a) understanding flow and transport mechanisms in such systems and, (b) in predicting permeability changes under dynamic saturation conditions. This paper presents quantitative experimental evidence of the migration of water through a generic shale core plug using micro CT imaging. In addition, in-situ measurements of gas permeability were performed during counter-current spontaneous imbibition of water in nano-darcy permeability Marcellus and Haynesville core plugs. It was seen that water blocksmore » severely reduced the effective permeability of the core plugs, leading to losses of up to 99.5% of the initial permeability in experiments lasting 30 days. There was also evidence of clay swelling which further hindered gas flow. When results from this study were compared with similar counter-current gas permeability experiments reported in the literature, the initial (base) permeability of the rock was found to be a key factor in determining the time evolution of effective gas permeability during spontaneous imbibition. With time, a recovery of effective permeability was seen in the higher permeability rocks, while becoming progressively detrimental and irreversible in tighter rocks. Finally, these results suggest that matrix permeability of ultra-tight rocks is susceptible to water damage following hydraulic fracturing stimulation and, while shut-in/soaking time helps clearing-up fractures from resident fluid, its effect on the adjacent matrix permeability could be detrimental.« less

Permeability evolution of shale during spontaneous imbibition

DOE PAGES

Chakraborty, N.; Karpyn, Z. T.; Liu, S.; ...

2017-01-05

Shales have small pore and throat sizes ranging from nano to micron scales, low porosity and limited permeability. The poor permeability and complex pore connectivity of shales pose technical challenges to (a) understanding flow and transport mechanisms in such systems and, (b) in predicting permeability changes under dynamic saturation conditions. This paper presents quantitative experimental evidence of the migration of water through a generic shale core plug using micro CT imaging. In addition, in-situ measurements of gas permeability were performed during counter-current spontaneous imbibition of water in nano-darcy permeability Marcellus and Haynesville core plugs. It was seen that water blocksmore » severely reduced the effective permeability of the core plugs, leading to losses of up to 99.5% of the initial permeability in experiments lasting 30 days. There was also evidence of clay swelling which further hindered gas flow. When results from this study were compared with similar counter-current gas permeability experiments reported in the literature, the initial (base) permeability of the rock was found to be a key factor in determining the time evolution of effective gas permeability during spontaneous imbibition. With time, a recovery of effective permeability was seen in the higher permeability rocks, while becoming progressively detrimental and irreversible in tighter rocks. Finally, these results suggest that matrix permeability of ultra-tight rocks is susceptible to water damage following hydraulic fracturing stimulation and, while shut-in/soaking time helps clearing-up fractures from resident fluid, its effect on the adjacent matrix permeability could be detrimental.« less

Scattering of Microwaves by Steady-State Plasma Slabs, Columns, and Layers at Atmospheric Pressure

DTIC Science & Technology

1998-03-01

permeability unity is- (Fig 0) SÖ$ftS?S5 Pressure Plasmas Y=J7(er) . 2071 (1) where y is the complex propagation coefficient, w is the wave...a phase dependence expjtot-Yxl to a i„ ., permeability nnTty,^ J ’°SSy med’Um °f reIat<- ■j^r)^ • (1) where y is the complex propagation...preservation is an. issue. Some examples are food (solid or liquid) sterilization, pharmaceutical applications, and environmental applications ( soil

Microwave techniques for measuring complex permittivity and permeability of materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guillon, P.

1995-08-01

Different materials are of fundamental importance to the aerospace, microwave, electronics and communications industries, and include for example microwave absorbing materials, antennas lenses and radomes, substrates for MMIC and microwave components and antennaes. Basic measurements for the complex permittivity and permeability of those homogeneous solid materials in the microwave spectral region are described including hardware, instrumentation and analysis. Elevated temperature measurements as well as measurements intercomparisons, with a discussion of the strengths and weaknesses of each techniques are also presented.

The Andes Virus Nucleocapsid Protein Directs Basal Endothelial Cell Permeability by Activating RhoA

PubMed Central

Gorbunova, Elena E.; Simons, Matthew J.; Gavrilovskaya, Irina N.

2016-01-01

ABSTRACT Andes virus (ANDV) predominantly infects microvascular endothelial cells (MECs) and nonlytically causes an acute pulmonary edema termed hantavirus pulmonary syndrome (HPS). In HPS patients, virtually every pulmonary MEC is infected, MECs are enlarged, and infection results in vascular leakage and highly lethal pulmonary edema. We observed that MECs infected with the ANDV hantavirus or expressing the ANDV nucleocapsid (N) protein showed increased size and permeability by activating the Rheb and RhoA GTPases. Expression of ANDV N in MECs increased cell size by preventing tuberous sclerosis complex (TSC) repression of Rheb-mTOR-pS6K. N selectively bound the TSC2 N terminus (1 to 1403) within a complex containing TSC2/TSC1/TBC1D7, and endogenous TSC2 reciprocally coprecipitated N protein from ANDV-infected MECs. TSCs normally restrict RhoA-induced MEC permeability, and we found that ANDV infection or N protein expression constitutively activated RhoA. This suggests that the ANDV N protein alone is sufficient to activate signaling pathways that control MEC size and permeability. Further, RhoA small interfering RNA, dominant-negative RhoA(N19), and the RhoA/Rho kinase inhibitors fasudil and Y27632 dramatically reduced the permeability of ANDV-infected MECs by 80 to 90%. Fasudil also reduced the bradykinin-directed permeability of ANDV and Hantaan virus-infected MECs to control levels. These findings demonstrate that ANDV activation of RhoA causes MEC permeability and reveal a potential edemagenic mechanism for ANDV to constitutively inhibit the basal barrier integrity of infected MECs. The central importance of RhoA activation in MEC permeability further suggests therapeutically targeting RhoA, TSCs, and Rac1 as potential means of resolving capillary leakage during hantavirus infections. PMID:27795403

Artificial Lipid Membrane Permeability Method for Predicting Intestinal Drug Transport: Probing the Determining Step in the Oral Absorption of Sulfadiazine; Influence of the Formation of Binary and Ternary Complexes with Cyclodextrins.

PubMed

Delrivo, Alicia; Aloisio, Carolina; Longhi, Marcela R; Granero, Gladys

2018-04-01

We propose an in vitro permeability assay by using a modified lipid membrane to predict the in vivo intestinal passive permeability of drugs. Two conditions were tested, one with a gradient pH (pH 5.5 donor/pH 7.4 receptor) and the other with an iso-pH 7.4. The predictability of the method was established by correlating the obtained apparent intestinal permeability coefficients (P app ) and the oral dose fraction absorbed in humans (f a ) of 16 drugs with different absorption properties. The P app values correlated well with the absorption rates under the two conditions, and the method showed high predictability and good reproducibility. On the other hand, with this method, we successfully predicted the transport characteristics of oral sulfadiazine (SDZ). Also, the tradeoff between the increase in the solubility of SDZ by its complex formation with cyclodextrins and/or aminoacids and its oral permeability was assessed. Results suggest that SDZ is transported through the gastrointestinal epithelium by passive diffusion in a pH-dependent manner. These results support the classification of SDZ as a high/low borderline permeability compound and are in agreement with the Biopharmaceutics Classification Systems (BCS). This conclusion is consistent with the in vivo pharmacokinetic properties of SDZ.

How to include frequency dependent complex permeability Into SPICE models to improve EMI filters design?

NASA Astrophysics Data System (ADS)

Sixdenier, Fabien; Yade, Ousseynou; Martin, Christian; Bréard, Arnaud; Vollaire, Christian

2018-05-01

Electromagnetic interference (EMI) filters design is a rather difficult task where engineers have to choose adequate magnetic materials, design the magnetic circuit and choose the size and number of turns. The final design must achieve the attenuation requirements (constraints) and has to be as compact as possible (goal). Alternating current (AC) analysis is a powerful tool to predict global impedance or attenuation of any filter. However, AC analysis are generally performed without taking into account the frequency-dependent complex permeability behaviour of soft magnetic materials. That's why, we developed two frequency-dependent complex permeability models able to be included into SPICE models. After an identification process, the performances of each model are compared to measurements made on a realistic EMI filter prototype in common mode (CM) and differential mode (DM) to see the benefit of the approach. Simulation results are in good agreement with the measured ones especially in the middle frequency range.

Optimization on microwave absorbing properties of carbon nanotubes and magnetic oxide composite materials

NASA Astrophysics Data System (ADS)

Mingdong, Chen; Huangzhong, Yu; Xiaohua, Jie; Yigang, Lu

2018-03-01

Based on the physical principle of interaction between electromagnetic field and the electromagnetic medium, the relationship between microwave absorbing coefficient (MAC) and the electromagnetic parameters of materials was established. With the composite materials of nickel ferrite (NiFe2O4), carbon nanotubes (CNTs) and paraffin as an example, optimization on absorbing properties of CNTs/magnetic oxide composite materials was studied at the frequency range of 2-18 GHz, and a conclusion is drawn that the MAC is the biggest at the same frequency, when the CNTs is 10 wt% in the composite materials. Through study on the relationship between complex permeability and MAC, another interesting conclusion is drawn that MAC is obviously affected by the real part of complex permeability, and increasing real part of complex permeability is beneficial for improving absorbing properties. The conclusion of this paper can provide a useful reference for the optimization research on the microwave absorbing properties of CNTs/ferrite composite materials.

Substituent and Solvent Effects on the Absorption Spectra of Cation-π Complexes of Benzene and Borazine: A Theoretical Study.

PubMed

Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

2014-05-29

Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σ p and σ m ). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes.

Light-Induced Conversion of Chemical Permeability to Enhance Electron and Molecular Transfer in Nanoscale Assemblies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balgley, Renata; de Ruiter, Graham; Evmenenko, Guennadi

In this paper, we demonstrate how photochemically enhancing the permeability of metal–organic assemblies results in a significant enhancement of the electrochemical activity of metal complexes located within the assembly. The molecular assemblies consist of different layers of redox-active metal complexes ([M(mbpy-py)3][PF6]2; M = Ru or Os) that are separated by redox-inactive spacers consisting of 1,4-bis[2-(4-pyridyl)ethenyl]benzene (BPEB) and PdCl2 of variable thicknesses (0–13.4 nm). UV-irradiation (λ = 254 nm) of our assemblies induces a photochemical reaction in the redox-inactive spacer increasing the permeability of the assembly. The observed increase was evident by trapping organic (nBu4NBF4) and inorganic (NiCl2) salts inside themore » assemblies, and by evaluating the electrochemical response of quinones absorbed inside the molecular assemblies before and after UV irradiation. The increase in permeability is reflected by higher currents and a change in the directionality of electron transfer, i.e., from mono- to bidirectional, between the redox-active metal complexes and the electrode surface. The supramolecular structure of the assemblies dominates the overall electron transfer properties and overrules possible electron transfer mediated by the extensive π-conjugation of its individual organic components.« less

Multiferroic properties of microwave sintered PbFe12-xO19-δ

NASA Astrophysics Data System (ADS)

Prathap, S.; Madhuri, W.

2017-05-01

The effect of iron deficiency on the structural, electrical, ferroelectric and magnetic properties of nano PbFe12-xO19-δ (where x=0.0, 0.25, 0.50, 0.75, 1.0) hexaferrites prepared by sol-gel auto combustion and processed by microwaves are investigated. X-ray analysis confirms single phase magneto-plumbite phase formation. The surface morphology is studied from Field Emission Scanning Electron Microscope. Further, optical properties are investigated using Fourier Transform Infrared spectra and UV-visible spectra. AC electrical conductivity is estimated as a function of temperature and frequency in the range of room temperature (RT) to 500 °C and 100 Hz to 5MHz. AC electrical conduction analysis shows that conduction is mainly due to small polaron hopping mechanism. The variation of polarization with applied electric field exhibits hysteresis loop confirming the ferroelectric nature. The initial permeability studies with varying temperature reveals that the Curie transition temperature for the present series is around 400 °C. Variation of initial permeability with frequency ranging from 100 to 5 MHz shows a constant value (except for x=0.0) opening avenues for high frequency applications.

An analytical model for inductively coupled implantable biomedical devices with ferrite rods.

PubMed

Theilmann, P T; Asbeck, P M

2009-02-01

Using approximations applicable to near field coupled implants simplified expressions for the complex mutual inductance of coaxial aligned coils with and without a cylindrical ferrite rod are derived. Experimental results for ferrite rods of various sizes and permeabilities are presented to verify the accuracy of this expression. An equivalent circuit model for the inductive link between an implant and power coil is then presented and used to investigate how ferrite size, permeability and loss affect the power available to the implant device. Enhancements in coupling provided by high frequency, low permeability nickel zinc rods are compared with low frequency high permeability manganese zinc rods.

Quantitative Interpretation of Multifrequency Multimode EPR Spectra of Metal Containing Proteins, Enzymes, and Biomimetic Complexes.

PubMed

Petasis, Doros T; Hendrich, Michael P

2015-01-01

Electron paramagnetic resonance (EPR) spectroscopy has long been a primary method for characterization of paramagnetic centers in materials and biological complexes. Transition metals in biological complexes have valence d-orbitals that largely define the chemistry of the metal centers. EPR spectra are distinctive for metal type, oxidation state, protein environment, substrates, and inhibitors. The study of many metal centers in proteins, enzymes, and biomimetic complexes has led to the development of a systematic methodology for quantitative interpretation of EPR spectra from a wide array of metal containing complexes. The methodology is now contained in the computer program SpinCount. SpinCount allows simulation of EPR spectra from any sample containing multiple species composed of one or two metals in any spin state. The simulations are quantitative, thus allowing determination of all species concentrations in a sample directly from spectra. This chapter will focus on applications to transition metals in biological systems using EPR spectra from multiple microwave frequencies and modes. © 2015 Elsevier Inc. All rights reserved.

Low-frequency ESR studies on permeable and impermeable deuterated nitroxyl radicals in corn oil solution.

PubMed

David Jebaraj, D; Utsumi, Hideo; Milton Franklin Benial, A

2018-04-01

Low-frequency electron spin resonance studies were performed for 2 mM concentration of deuterated permeable and impermeable nitroxyl spin probes, 3-methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl and 3-carboxy-2,2,5,5,-tetramethyl-1-pyrrolidinyloxy in pure water and various concentrations of corn oil solution. The electron spin resonance parameters such as the line width, hyperfine coupling constant, g factor, rotational correlation time, permeability, and partition parameter were estimated. The broadening of line width was observed for nitroxyl radicals in corn oil mixture. The rotational correlation time increases with increasing concentration of corn oil, which indicates the less mobile nature of spin probe in corn oil mixture. The membrane permeability and partition parameter values were estimated as a function of corn oil concentration, which reveals that the nitroxyl radicals permeate equally into the aqueous phase and oil phase at the corn oil concentration of 50%. The electron spin resonance spectra demonstrate the permeable and impermeable nature of nitroxyl spin probes. From these results, the corn oil concentration was optimized as 50% for phantom studies. In this work, the corn oil and pure water mixture phantom models with various viscosities correspond to plasma membrane, and whole blood membrane with different hematocrit levels was studied for monitoring the biological characteristics and their interactions with permeable nitroxyl spin probe. These results will be useful for the development of electron spin resonance and Overhauser-enhanced magnetic resonance imaging modalities in biomedical applications. Copyright © 2017 John Wiley & Sons, Ltd.

Turbulence spectra in the noise source regions of the flow around complex surfaces

NASA Technical Reports Server (NTRS)

Olsen, W. A.; Boldman, D. R.

1983-01-01

The complex turbulent flow around three complex surfaces was measured in detail with a hot wire. The measured data include extensive spatial surveys of the mean velocity and turbulence intensity and measurements of the turbulence spectra and scale length at many locations. The publication of the turbulence data is completed by reporting a summary of the turbulence spectra that were measured within the noise source locations of the flow. The results suggest some useful simplifications in modeling the very complex turbulent flow around complex surfaces for aeroacoustic predictive models. The turbulence spectra also show that noise data from scale models of moderate size can be accurately scaled up to full size.

An evaluation of factors influencing pore pressure in accretionary complexes: Implications for taper angle and wedge mechanics

USGS Publications Warehouse

Saffer, D.M.; Bekins, B.A.

2006-01-01

At many subduction zones, accretionary complexes form as sediment is off-scraped from the subducting plate. Mechanical models that treat accretionary complexes as critically tapered wedges of sediment demonstrate that pore pressure controls their taper angle by modifying basal and internal shear strength. Here, we combine a numerical model of groundwater flow with critical taper theory to quantify the effects of sediment and de??collement permeability, sediment thickness, sediment partitioning between accretion and underthrusting, and plate convergence rate on steady state pore pressure. Our results show that pore pressure in accretionary wedges can be viewed as a dynamically maintained response to factors which drive pore pressure (source terms) and those that limit flow (permeability and drainage path length). We find that sediment permeability and incoming sediment thickness are the most important factors, whereas fault permeability and the partitioning of sediment have a small effect. For our base case model scenario, as sediment permeability is increased, pore pressure decreases from near-lithostatic to hydrostatic values and allows stable taper angles to increase from ??? 2.5?? to 8??-12.5??. With increased sediment thickness in our models (from 100 to 8000 m), increased pore pressure drives a decrease in stable taper angle from 8.4??-12.5?? to 15?? to <4??) with increased sediment thickness (from <1 to 7 km). One key implication is that hydrologic properties may strongly influence the strength of the crust in a wide range of geologic settings. Copyright 2006 by the American Geophysical Union.

The role of phospholipid as a solubility- and permeability-enhancing excipient for the improved delivery of the bioactive phytoconstituents of Bacopa monnieri.

PubMed

Saoji, Suprit D; Dave, Vivek S; Dhore, Pradip W; Bobde, Yamini S; Mack, Connor; Gupta, Deepak; Raut, Nishikant A

2017-10-15

In an attempt to improve the solubility and permeability of Standardized Bacopa Extract (SBE), a complexation approach based on phospholipid was employed. A solvent evaporation method was used to prepare the SBE-phospholipid complex (Bacopa Naturosome, BN). The formulation and process variables were optimized using a central-composite design. The formation of BN was confirmed by photomicroscopy, Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), and Powder X-ray Diffraction (PXRD). The saturation solubility, the in-vitro dissolution, and the ex-vivo permeability studies were used for the functional evaluation of the prepared complex. BN exhibited a significantly higher aqueous solubility compared to the pure SBE (20-fold), or the physical mixture of SBE and the phospholipid (13-fold). Similarly, the in-vitro dissolution revealed a significantly higher efficiency of the prepared complex (BN) in releasing the SBE (>97%) in comparison to the pure SCE (~42%), or the physical mixture (~47%). The ex-vivo permeation studies showed that the prepared BN significantly improved the permeation of SBE (>90%), compared to the pure SBE (~21%), or the physical mixture (~24%). Drug-phospholipid complexation may thus be a promising strategy for solubility enhancement of bioactive phytoconstituents. Copyright © 2016 Elsevier B.V. All rights reserved.

Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density Functional Theory

DTIC Science & Technology

2013-08-20

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--13-9479 Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using ...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density...structure associated with Fe, Mn, and Mg water complexes using time-dependent density functional theory (TD-DFT). Calculation of excited state resonance

The Ghost in the Machine: Fracking in the Earth's Complex Brittle Crust

NASA Astrophysics Data System (ADS)

Malin, P. E.

2015-12-01

This paper discusses in the impact of complex rock properties on practical applications like fracking and its associated seismic emissions. A variety of borehole measurements show that the complex physical properties of the upper crust cannot be characterized by averages on any scale. Instead they appear to follow 3 empirical rule: a power law distribution in physical scales, a lognormal distribution in populations, and a direct relation between changes in porosity and log(permeability). These rules can be directly related to the presence of fluid rich and seismically active fractures - from mineral grains to fault segments. (These are the "ghosts" referred to in the title.) In other physical systems, such behaviors arise on the boundaries of phase changes, and are studied as "critical state physics". In analogy to the 4 phases of water, crustal rocks progress upward from a un-fractured, ductile lower crust to nearly cohesionless surface alluvium. The crust in between is in an unstable transition. It is in this layer methods such as hydrofracking operate - be they in Oil and Gas, geothermal, or mining. As a result, nothing is predictable in these systems. Crustal models have conventionally been constructed assuming that in situ permeability and related properties are normally distributed. This approach is consistent with the use of short scale-length cores and logs to estimate properties. However, reservoir-scale flow data show that they are better fit to lognormal distributions. Such "long tail" distributions are observed for well productivity, ore vein grades, and induced seismic signals. Outcrop and well-log data show that many rock properties also show a power-law-type variation in scale lengths. In terms of Fourier power spectra, if peaks per km is k, then their power is proportional to 1/k. The source of this variation is related to pore-space connectivity, beginning with grain-fractures. We then show that a passive seismic method, Tomographic Fracture ImagingTM (TFI), can observe the distribution of this connectivity. Combined with TFI data, our fracture-connectivity model reveals the most significant crustal features and account for their range of passive and stimulated behaviors.

Machine learning framework for analysis of transport through complex networks in porous, granular media: A focus on permeability

NASA Astrophysics Data System (ADS)

van der Linden, Joost H.; Narsilio, Guillermo A.; Tordesillas, Antoinette

2016-08-01

We present a data-driven framework to study the relationship between fluid flow at the macroscale and the internal pore structure, across the micro- and mesoscales, in porous, granular media. Sphere packings with varying particle size distribution and confining pressure are generated using the discrete element method. For each sample, a finite element analysis of the fluid flow is performed to compute the permeability. We construct a pore network and a particle contact network to quantify the connectivity of the pores and particles across the mesoscopic spatial scales. Machine learning techniques for feature selection are employed to identify sets of microstructural properties and multiscale complex network features that optimally characterize permeability. We find a linear correlation (in log-log scale) between permeability and the average closeness centrality of the weighted pore network. With the pore network links weighted by the local conductance, the average closeness centrality represents a multiscale measure of efficiency of flow through the pore network in terms of the mean geodesic distance (or shortest path) between all pore bodies in the pore network. Specifically, this study objectively quantifies a hypothesized link between high permeability and efficient shortest paths that thread through relatively large pore bodies connected to each other by high conductance pore throats, embodying connectivity and pore structure.

Cardiotoxicity of acetogenins from Persea americana occurs through the mitochondrial permeability transition pore and caspase-dependent apoptosis pathways.

PubMed

Silva-Platas, Christian; García, Noemí; Fernández-Sada, Evaristo; Dávila, Daniel; Hernández-Brenes, Carmen; Rodríguez, Dariana; García-Rivas, Gerardo

2012-08-01

Acetogenins are cell-membrane permeable, naturally occurring secondary metabolites of plants such as Annonaceae, Lauraceae and other related phylogenic families. They belong to the chemical derivatives of polyketides, which are synthesized from fatty acid precursors. Although acetogenins have displayed diverse biological activities, the anti-proliferative effect on human cancer cells has been widely reported. Acetogenins are inhibitors of complex I in the electron transport chain therefore they interrupt ATP synthesis in mitochondria. We tested a new acetogenins-enriched extract from the seed of Persea americana in order to investigate if any toxicity was induced on cardiac tissue and determine the involved mechanism. In isolated perfused heart we found that contractility was completely inhibited at an accumulative dose of 77 μg/ml. In isolated cardiomyocytes, the acetogenins-enriched extract induced apoptosis through the activation of the intrinsic pathway at 43 μg/ml. In isolated mitochondria, it inhibited complex I activity on NADH-linked respiration, as would be expected, but also induced permeability transition on succinate-linked respiration. Cyclosporine A, a known blocker of permeability transition, significantly prevented the permeability transition triggered by the acetogenins-enriched extract. In addition, our acetogenins-enriched extract inhibited ADP/ATP exchange, suggesting that an important element in phosphate or adenylate transport was affected. In this manner we suggest that acetogenins-enriched extract from Persea americana could directly modulate permeability transition, an entity not yet associated with the acetogenins' direct effects, resulting in cardiotoxicity.

Investigation of structural, morphological and electromagnetic properties of Mg0.25Mn0.25Zn0.5-xSrxFe2O4 ferrites

NASA Astrophysics Data System (ADS)

Rahaman, Md. D.; Nusrat, Tania; Maleque, Rumana; Hossain, A. K. M. Akther

2018-04-01

Polycrystalline Mg0.25Mn0.25Zn0.5-xSrxFe2O4 (0 ≤ x ≤ 0.20) ferrites were synthesized using the solid state reaction sintering at 1373 K and 1473 K for 4 h. The XRD patterns revealed the formation of single phase cubic spinel with Sr2FeO4 and SrFe12O19 as impurity phases. The decrement in the lattice parameter for Sr2+ substituted samples is attributed to the difference in ionic radii of cations. The crystallite size decreases with increase in Sr2+ content. Low frequency dielectric dispersion is attributed due to the Maxwell-Wagner interfacial polarization. The appearance of the peak in dielectric loss spectrum for x = 0.15 and 0.20 at 1373 K and x = 0.20 at 1473 K suggests the presence of relaxing dipoles. The loss peak shifts towards lower frequency side with Sr2+ content at 1373 K which is due to the strengthening of dipole-dipole interactions. The complex impedance spectra clearly revealed that the both grain and grain boundary effects on the electrical properties. A complex electric modulus spectrum indicates that a non-Debye type of conductivity relaxation exists. The saturation magnetization and remanence gradually decreases with Sr2+ substitution which may be due to the existence of non-magnetic phase in the space between the magnetic particles and the substitution of Zn2+ cation in Mg0.25Mn0.25Zn0.5Fe2O4 ferrite lattice by Sr2+ content. The permeability decreases significantly while the cut-off frequency increases with the Sr2+ content at 1373 K and decreases at 1473 K, obeying the Snoek's law. The decrease in permeability with Sr2+ content is attributed due to the decrease in magnetization because non-magnetic ions weaken the inter-site exchange interaction.

High-Frequency Response and Voltage Noise in Magnetic Nanocomposites

NASA Astrophysics Data System (ADS)

Buznikov, N. A.; Iakubov, I. T.; Rakhmanov, A. L.; Kugel, K. I.; Sboychakov, A. O.

We study the noise spectra and high-frequency permeability of inhomogeneous magnetic materials consisting of single-domain magnetic nanoparticles embedded into an insulating matrix. Possible mechanisms of 1/f voltage noise in phase-separated manganites is analyzed. The material is modelled by a system of small ferromagnetic metallic droplets (magnetic polarons or ferrons) in insulating antiferromagnetic or paramagnetic matrix. The electron transport is related to tunnelling of charge carriers between droplets. One of the sources of the 1/f noise in such a system stems from fluctuations of the number of droplets with extra electron. In the case of strong magnetic anisotropy, the 1/f noise can arise also due to the fluctuations of the magnetic moments of ferrons. The high frequency magnetic permeability of nanocomposite film with magnetic particles in insulating non-magnetic matrix is studied in detail. The case of strong magnetic dipole interaction and strong magnetic anisotropy of ferromagnetic granules is considered. The composite is modelled by a cubic regular array of ferromagnetic particles. The high-frequency permeability tensor components are found as a functions of frequency, temperature, ferromagnetic phase content, and magnetic anisotropy. The results demonstrate that magnetic dipole interaction leads to a shift of the resonance frequencies towards higher values, and nanocomposite film could have rather high value of magnetic permeability in the microwave range.

High-Frequency Response and Voltage Noise in Magnetic Nanocomposites

NASA Astrophysics Data System (ADS)

Buznikov, N. A.; Iakubov, I. T.; Rakhmanov, A. L.; Kugel, K. I.; Sboychakov, A. O.

2010-12-01

We study the noise spectra and high-frequency permeability of inhomogeneous magnetic materials consisting of single-domain magnetic nanoparticles embedded into an insulating matrix. Possible mechanisms of 1/f voltage noise in phase-separated manganites is analyzed. The material is modelled by a system of small ferromagnetic metallic droplets (magnetic polarons or ferrons) in insulating antiferromagnetic or paramagnetic matrix. The electron transport is related to tunnelling of charge carriers between droplets. One of the sources of the 1/f noise in such a system stems from fluctuations of the number of droplets with extra electron. In the case of strong magnetic anisotropy, the 1/f noise can arise also due to the fluctuations of the magnetic moments of ferrons. The high frequency magnetic permeability of nanocomposite film with magnetic particles in insulating non-magnetic matrix is studied in detail. The case of strong magnetic dipole interaction and strong magnetic anisotropy of ferromagnetic granules is considered. The composite is modelled by a cubic regular array of ferromagnetic particles. The high-frequency permeability tensor components are found as a functions of frequency, temperature, ferromagnetic phase content, and magnetic anisotropy. The results demonstrate that magnetic dipole interaction leads to a shift of the resonance frequencies towards higher values, and nanocomposite film could have rather high value of magnetic permeability in the microwave range.

Effect of lactobacilli on paracellular permeability in the gut.

PubMed

Ahrne, Siv; Hagslatt, Marie-Louise Johansson

2011-01-01

Paracellular permeability is determined by the complex structures of junctions that are located between the epithelial cells. Already in 1996, it was shown that the human probiotic strain Lactobacillus plantarum 299v and the rat-originating strain Lactobacillus reuteri R2LC could reduce this permeability in a methotrexate-induced colitis model in the rat. Subsequently, many animal models and cell culture systems have shown indications that lactobacilli are able to counteract increased paracellular permeability evoked by cytokines, chemicals, infections, or stress. There have been few human studies focusing on the effect of lactobacilli on intestinal paracellular permeability but recently it has been shown that they could influence the tight junctions. More precisely, short-term administration of L. plantarum WCSF1 to healthy volunteers increased the relocation of occludin and ZO-1 into the tight junction area between duodenal epithelial cells.

Observation of Electronic Excitation Transfer Through Light Harvesting Complex II Using Two-Dimensional Electronic-Vibrational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewis, Nicholas H. C.; Gruenke, Natalie L.; Oliver, Thomas A. A.

Light-harvesting complex II (LHCII) serves a central role in light harvesting for oxygenic photosynthesis and is arguably the most important photosynthetic antenna complex. In this article, we present two-dimensional electronic–vibrational (2DEV) spectra of LHCII isolated from spinach, demonstrating the possibility of using this technique to track the transfer of electronic excitation energy between specific pigments within the complex. We assign the spectral bands via comparison with the 2DEV spectra of the isolated chromophores, chlorophyll a and b, and present evidence that excitation energy between the pigments of the complex are observed in these spectra. Lastly, we analyze the essential componentsmore » of the 2DEV spectra using singular value decomposition, which makes it possible to reveal the relaxation pathways within this complex.« less

Classification of cassava starch films by physicochemical properties and water vapor permeability quantification by FTIR and PLS.

PubMed

Henrique, C M; Teófilo, R F; Sabino, L; Ferreira, M M C; Cereda, M P

2007-05-01

Cassava starches are widely used in the production of biodegradable films, but their resistance to humidity migration is very low. In this work, commercial cassava starch films were studied and classified according to their physicochemical properties. A nondestructive method for water vapor permeability determination, which combines with infrared spectroscopy and multivariate calibration, is also presented. The following commercial cassava starches were studied: pregelatinized (amidomax 3550), carboxymethylated starch (CMA) of low and high viscosities, and esterified starches. To make the films, 2 different starch concentrations were evaluated, consisting of water suspensions with 3% and 5% starch. The filmogenic solutions were dried and characterized for their thickness, grammage, water vapor permeability, water activity, tensile strength (deformation force), water solubility, and puncture strength (deformation). The minimum thicknesses were 0.5 to 0.6 mm in pregelatinized starch films. The results were treated by means of the following chemometric methods: principal component analysis (PCA) and partial least squares (PLS) regression. PCA analysis on the physicochemical properties of the films showed that the differences in concentration of the dried material (3% and 5% starch) and also in the type of starch modification were mainly related to the following properties: permeability, solubility, and thickness. IR spectra collected in the region of 4000 to 600 cm(-1) were used to build a PLS model with good predictive power for water vapor permeability determination, with mean relative errors of 10.0% for cross-validation and 7.8% for the prediction set.

Photonic band gap spectra in Octonacci metamaterial quasicrystals

NASA Astrophysics Data System (ADS)

Brandão, E. R.; Vasconcelos, M. S.; Albuquerque, E. L.; Fulco, U. L.

2017-02-01

In this work we study theoretically the photonic band gap spectra for a one-dimensional quasicrystal made up of SiO2 (layer A) and a metamaterial (layer B) organized following the Octonacci sequence, where its nth-stage Sn is given by the inflation rule Sn =Sn - 1Sn - 2Sn - 1 for n ≥ 3 , with initial conditions S1 = A and S2 = B . The metamaterial is characterized by a frequency dependent electric permittivity ε(ω) and magnetic permeability μ(ω) . The polariton dispersion relation is obtained analytically by employing a theoretical calculation based on a transfer-matrix approach. A quantitative analysis of the spectra is then discussed, stressing the distribution of the allowed photonic band widths for high generations of the Octonacci structure, which depict a self-similar scaling property behavior, with a power law depending on the common in-plane wavevector kx .

In vitro biopharmaceutical evaluation of ciprofloxacin/metal cation complexes for pulmonary administration.

PubMed

Brillault, J; Tewes, F; Couet, W; Olivier, J C

2017-01-15

Pulmonary delivery of fluoroquinolones (FQs) is an interesting approach to treat lung infections as it may lead to high local concentrations while minimizing systemic exposure. However, FQs have a rapid diffusion through the lung epithelium giving the pulmonary route no advantage compared to the oral route. Interactions between FQs and metal cations form complexes which limit the diffusion through the epithelial barrier and would reduce the absorption of FQs and maintain high concentrations in the lung. The effects of this complexation depend on the FQ and the metal cations and optimum partners should be selected through in vitro experiments prior to aerosol drug formulation. In this study, CIP was chosen as a representative FQ and 5 cations (Ca 2+ , Mg 2+ , Zn 2+ , Al 3+ , Cu 2+ ) were selected to study the complexation and its effects on permeability, antimicrobial efficacy and cell toxicity. The results showed that the apparent association constants between CIP and cations ranked with the descending order: Cu 2+ >Al 3+ >Zn 2+ >Mg 2+ >Ca 2+ . When a target of 80% complexation was reached with the adequate concentrations of cations, the CIP permeability through the Calu-3 lung epithelial cells was decreased of 50%. Toxicity of the CIP on the Calu-3 cells, with an EC50 evaluated at 7μM, was not significantly affected by the presence of the cations. The minimum inhibitory concentration of CIP for Pseudomonas aeruginosa was not affected or slightly increased in the range of cation concentrations tested, except for Mg 2+ . In conclusion, permeability was the main parameter that was affected by the metal cation complexation while cell toxicity and antimicrobial activity were not or slightly modified. Cu 2+ , with the highest apparent constant of association and with no effect on cell toxicity and antimicrobial activity of the CIP, appeared as a promising cation for the development of a controlled-permeability formulation of CIP for lung treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Real-Time Tracking the Synthesis and Degradation of Albumin in Complex Biological Systems with a near-Infrared Fluorescent Probe.

PubMed

Jin, Qiang; Feng, Lei; Zhang, Shui-Jun; Wang, Dan-Dan; Wang, Fang-Jun; Zhang, Yi; Cui, Jing-Nan; Guo, Wen-Zhi; Ge, Guang-Bo; Yang, Ling

2017-09-19

In this study, a novel fluorescent detection system for biological sensing of human albumin (HA) was developed on the basis of the pseudoesterase activity and substrate preference of HA. The designed near-infrared (NIR) fluorescent probe (DDAP) could be effectively hydrolyzed by HA, accompanied by significant changes in both color and fluorescence spectrum. The sensing mechanism was fully investigated by fluorescence spectroscopy, NMR, and mass spectra. DDAP exhibited excellent selectivity and sensitivity toward HA over a variety of human plasma proteins, hydrolases, and abundant biomolecules found in human body. The probe has been successfully applied to measure native HA in diluted plasma samples and the secreted HA in the hepatocyte culture supernatant. DDAP has also been used for fluorescence imaging of HA reabsorption in living renal cells, and the results show that the probe exhibits good cell permeability, low cytotoxicity and high imaging resolution. Furthermore, DDAP has been successfully used for real-time tracking the uptaking and degradation of albumin in ex vivo mouse kidney models for the first time. All these results clearly demonstrated that DDAP-based assay held great promise for real-time sensing and tracking HA in complex biological systems, which would be very useful for basic researches and clinical diagnosis of HA-associated diseases.

The regulation of vascular endothelial growth factor-induced microvascular permeability requires Rac and reactive oxygen species.

PubMed

Monaghan-Benson, Elizabeth; Burridge, Keith

2009-09-18

Vascular permeability is a complex process involving the coordinated regulation of multiple signaling pathways in the endothelial cell. It has long been documented that vascular endothelial growth factor (VEGF) greatly enhances microvascular permeability; however, the molecular mechanisms controlling VEGF-induced permeability remain unknown. Treatment of microvascular endothelial cells with VEGF led to an increase in reactive oxygen species (ROS) production. ROS are required for VEGF-induced permeability as treatment with the free radical scavenger, N-acetylcysteine, inhibited this effect. Additionally, treatment with VEGF caused ROS-dependent tyrosine phosphorylation of both vascular-endothelial (VE)-cadherin and beta-catenin. Rac1 was required for the VEGF-induced increase in permeability and adherens junction protein phosphorylation. Knockdown of Rac1 inhibited VEGF-induced ROS production consistent with Rac lying upstream of ROS in this pathway. Collectively, these data suggest that VEGF leads to a Rac-mediated generation of ROS, which, in turn, elevates the tyrosine phosphorylation of VE-cadherin and beta-catenin, ultimately regulating adherens junction integrity.

Spectroscopic and structural study of the newly synthesized heteroligand complex of copper with creatinine and urea.

PubMed

Gangopadhyay, Debraj; Singh, Sachin Kumar; Sharma, Poornima; Mishra, Hirdyesh; Unnikrishnan, V K; Singh, Bachcha; Singh, Ranjan K

2016-02-05

Study of copper complex of creatinine and urea is very important in life science and medicine. In this paper, spectroscopic and structural study of a newly synthesized heteroligand complex of copper with creatinine and urea has been discussed. Structural studies have been carried out using DFT calculations and spectroscopic analyses were carried out by FT-IR, Raman, UV-vis absorption and fluorescence techniques. The copper complex of creatinine and the heteroligand complex were found to have much increased water solubility as compared to pure creatinine. The analysis of FT-IR and Raman spectra helps to understand the coordination properties of the two ligands and to determine the probable structure of the heteroligand complex. The LIBS spectra of the heteroligand complex reveal that the complex is free from other metal impurities. UV-visible absorption spectra and the fluorescence emission spectra of the aqueous solution of Cu-Crn-urea heteroligand complex at different solute concentrations have been analyzed and the complex is found to be rigid and stable in its monomeric form at very low concentrations. Copyright © 2015 Elsevier B.V. All rights reserved.

Glutamine Supplementation Attenuates Ethanol-Induced Disruption of Apical Junctional Complexes in Colonic Epithelium and Ameliorates Gut Barrier Dysfunction and Fatty Liver in Mice

PubMed Central

Chaudhry, Kamaljit K.; Shukla, Pradeep K.; Mir, Hina; Manda, Bhargavi; Gangwar, Ruchika; Yadav, Nikki; McMullen, Megan; Nagy, Laura E.; Rao, RadhaKrishna

2015-01-01

Previous in vitro studies showed that glutamine (Gln) prevents acetaldehyde-induced disruption of tight junctions and adherens junctions in Caco-2 cell monolayers and human colonic mucosa. In the present study, we evaluated the effect of Gln supplementation on ethanol-induced gut barrier dysfunction and liver injury in mice in vivo. Ethanol feeding caused a significant increase in inulin permeability in distal colon. Elevated permeability was associated with a redistribution of tight junction and adherens junction proteins and depletion of detergent-insoluble fractions of these proteins, suggesting that ethanol disrupts apical junctional complexes in colonic epithelium and increases paracellular permeability. Ethanol-induced increase in colonic mucosal permeability and disruption of junctional complexes were most severe in mice fed Gln-free diet. Gln supplementation attenuated ethanol-induced mucosal permeability and disruption of tight junctions and adherens junctions in a dose-dependent manner, indicating the potential role of glutamine in nutritional intervention to alcoholic tissue injury. Gln supplementation dose-dependently elevated reduced-protein thiols in colon without affecting the level of oxidized-protein thiols. Ethanol feeding depleted reduced protein thiols and elevated oxidized protein thiols. Ethanol-induced protein thiol oxidation was most severe in mice fed Gln-free diet and absent in mice fed Gln-supplemented diet, suggesting that antioxidant effect is one of the likely mechanisms involved in Gln-mediated amelioration of ethanol-induced gut barrier dysfunction. Ethanol feeding elevated plasma transaminase and liver triglyceride, which was accompanied by histopathologic lesions in the liver; ethanol-induced liver damage was attenuated by Gln supplementation. These results indicate that Gln supplementation ameliorates alcohol-induced gut and liver injury. PMID:26365579

Determination of permeability coefficients of ophthalmic drugs through different layers of porcine, rabbit and bovine eyes.

PubMed

Loch, Christian; Zakelj, Simon; Kristl, Albin; Nagel, Stefan; Guthoff, Rudolf; Weitschies, Werner; Seidlitz, Anne

2012-08-30

To treat ophthalmic diseases like glaucoma or inflammatory disorders topically applied ophthalmic formulations such as eye drops are usually used. In addition, novel ophthalmic implants releasing drug substances locally into different parts of the eye are available today. In the work presented here, the permeability coefficients of selected drugs (ciprofloxacin hydrochloride, lidocaine hydrochloride, timolol maleate) for ophthalmic tissues were determined using side-by-side diffusion chambers (so-called Ussing chambers). Sclera, conjunctiva, cornea, choroidea-retina-complex and a complex of conjunctiva-sclera-choroidea-retina were excised from fresh porcine, rabbit and bovine eyes. In the porcine eye tissues the highest P(app) values were obtained for conjunctiva with the exception of lidocaine. Therefore, it can be estimated that a certain amount of drug diffuses or is transported through conjunctiva after application. The P(app) values for sclera were also higher than those for cornea and even more, the surface area of sclera which is available for drug absorption is much larger than that of cornea when applying an implant. The obtained permeability coefficients for sclera and conjunctiva indicate that the administration of periocular implants can be an alternative to topically applied formulations. The complexes of the tissues were a significantly (p<0.01) stronger barrier to the investigated substances than the separated tissues. Distinct differences in permeability coefficients between the investigated animal tissues were observed. Overall the highest P(app) values for all mounted tissues were obtained with the rabbit, followed by porcine and bovine eyes. Because of these distinct interspecies differences one must be very careful when selecting the proper animal model for the permeability experiments. Copyright © 2012 Elsevier B.V. All rights reserved.

[Effect of damage integrity rat brain synaptic membranes on the functional activity GABA(A)-receptor/Cl(-)-ionophore complex in the CNC].

PubMed

Rebrov, I G; Kalinina, M V

2013-01-01

Functional activity of the CGABA(A)-receptor/Cl(-) ionophore complex was investigated the muscimol-stimulated entry of the radioactive isotope 36Cl(-) in synaptoneurosomes in changing the structure and permeability of neuronal membranes. Integrity of the membranes was damaged by removal of Ca(+2) and Mg(+2) from the incubation medium and by the method of freezing-thawing synaptoneurosomes. In both cases, an increase in basal 36Cl(-) entry into synaptoneurosomes, indicating increased nonspecific permeability of neuronal membranes, and decreased activity the CABA(A)-receptor/Cl(-) ionophore complex. The conclusion about the relationship of processes damage neuronal membranes and reducing the inhibitory processes in the epileptic focus.

Effective High-Frequency Permeability of Compacted Metal Powders

NASA Astrophysics Data System (ADS)

Volkovskaya, I. I.; Semenov, V. E.; Rybakov, K. I.

2018-03-01

We propose a model for determination of the effective complex permeability of compacted metal-powder media. It is based on the equality of the magnetic moment in a given volume of the media with the desired effective permeability to the total magnetic moment of metal particles in the external high-frequency magnetic field, which arises due to excitation of electric eddy currents in the particles. Calculations within the framework of the proposed model allow us to refine the values of the real and imaginary components of the permeability of metal powder compacts in the microwave band. The conditions of applicability of the proposed model are formulated, and their fulfillment is verified for metal powder compacts in the microwave and millimeter wavelength bands.

Permeability of C2C12 myotube membranes is influenced by stretch velocity.

PubMed

Burkholder, Thomas J

2003-05-30

Mechanical signals are critical to the growth and maintenance of skeletal muscle, but the mechanism by which these signals are transduced by the cell remains unknown. This work examined the hypothesis that stretch conditions influence membrane permeability consistent with a role for membrane permeability in mechanotransduction. C2C12 myotubes were grown in conditions that encourage uniform alignment and subjected to uniform mechanical deformation in the presence of fluorescein labeled dextran to evaluate membrane permeability as a function of stretch amplitude and velocity. Within a physiologically relevant range of conditions, a complex interaction between the two aspects of stretch was observed, with velocity contributing most strongly at large stretch amplitudes. This suggests that membrane viscosity could contribute to mechanotransduction.

Effect of Lactobacilli on Paracellular Permeability in the Gut

PubMed Central

Ahrne, Siv; Hagslatt, Marie-Louise Johansson

2011-01-01

Paracellular permeability is determined by the complex structures of junctions that are located between the epithelial cells. Already in 1996, it was shown that the human probiotic strain Lactobacillus plantarum 299v and the rat-originating strain Lactobacillus reuteri R2LC could reduce this permeability in a methotrexate-induced colitis model in the rat. Subsequently, many animal models and cell culture systems have shown indications that lactobacilli are able to counteract increased paracellular permeability evoked by cytokines, chemicals, infections, or stress. There have been few human studies focusing on the effect of lactobacilli on intestinal paracellular permeability but recently it has been shown that they could influence the tight junctions. More precisely, short-term administration of L. plantarum WCSF1 to healthy volunteers increased the relocation of occludin and ZO-1 into the tight junction area between duodenal epithelial cells. PMID:22254077

Percolation behaviour in the magnetic permeability and electrical conductivity in conducting magnetic - Insulating non magnetic binary composites

NASA Astrophysics Data System (ADS)

McLachlan, David S.; Doyle, Terence B.; Sauti, Godfrey

2018-07-01

Experimental results of the complex magnetic permeability (μ) and the electrical conductivity (σ) of a granular paramagnetic Gadolinium Gallium Garnet (GGG: 0.3-26 vol%) and Teflon (PTFE) system are presented and discussed in relation to previously published (conductivity) and unpublished (permeability) studies on granular Fe3O4 - talc and Ni - talc wax systems. In these systems plots of the real conductivity (σm‧) against the volume fraction (φ) lie on characteristic sigmoid curves that when fitted to the Two Exponent Phenomenological Percolation Equation (TEPPE) confirm the existence of "percolation microstructures" with critical volume fractions (φc). The plots of the real and imaginary permeability (μm‧) and (μm″) satisfactorily fit to the TEPPE using the φc obtained in each case from the "conductivity" measurements. In all three cases the conductivity results gave the exponent t > 2, and the permeability results gave t < 1.

Retrieval of complex χ(2) parts for quantitative analysis of sum-frequency generation intensity spectra

PubMed Central

Hofmann, Matthias J.; Koelsch, Patrick

2015-01-01

Vibrational sum-frequency generation (SFG) spectroscopy has become an established technique for in situ surface analysis. While spectral recording procedures and hardware have been optimized, unique data analysis routines have yet to be established. The SFG intensity is related to probing geometries and properties of the system under investigation such as the absolute square of the second-order susceptibility χ(2)2. A conventional SFG intensity measurement does not grant access to the complex parts of χ(2) unless further assumptions have been made. It is therefore difficult, sometimes impossible, to establish a unique fitting solution for SFG intensity spectra. Recently, interferometric phase-sensitive SFG or heterodyne detection methods have been introduced to measure real and imaginary parts of χ(2) experimentally. Here, we demonstrate that iterative phase-matching between complex spectra retrieved from maximum entropy method analysis and fitting of intensity SFG spectra (iMEMfit) leads to a unique solution for the complex parts of χ(2) and enables quantitative analysis of SFG intensity spectra. A comparison between complex parts retrieved by iMEMfit applied to intensity spectra and phase sensitive experimental data shows excellent agreement between the two methods. PMID:26450297

Carbohydrate-Based Host-Guest Complexation of Hydrophobic Antibiotics for the Enhancement of Antibacterial Activity.

PubMed

Jeong, Daham; Joo, Sang-Woo; Shinde, Vijay Vilas; Cho, Eunae; Jung, Seunho

2017-08-08

Host-guest complexation with various hydrophobic drugs has been used to enhance the solubility, permeability, and stability of guest drugs. Physical changes in hydrophobic drugs by complexation have been related to corresponding increases in the bioavailability of these drugs. Carbohydrates, including various derivatives of cyclodextrins, cyclosophoraoses, and some linear oligosaccharides, are generally used as host complexation agents in drug delivery systems. Many antibiotics with low bioavailability have some limitations to their clinical use due to their intrinsically poor aqueous solubility. Bioavailability enhancement is therefore an important step to achieve the desired concentration of antibiotics in the treatment of bacterial infections. Antibiotics encapsulated in a complexation-based drug delivery system will display improved antibacterial activity making it possible to reduce dosages and overcome the serious global problem of antibiotic resistance. Here, we review the present research trends in carbohydrate-based host-guest complexation of various hydrophobic antibiotics as an efficient delivery system to improve solubility, permeability, stability, and controlled release.

Predicting chemically-induced skin reactions. Part II: QSAR models of skin permeability and the relationships between skin permeability and skin sensitization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alves, Vinicius M.; Laboratory for Molecular Modeling, Division of Chemical Biology and Medicinal Chemistry, Eshelman School of Pharmacy, University of North Carolina, Chapel Hill, NC 27599; Muratov, Eugene

Skin permeability is widely considered to be mechanistically implicated in chemically-induced skin sensitization. Although many chemicals have been identified as skin sensitizers, there have been very few reports analyzing the relationships between molecular structure and skin permeability of sensitizers and non-sensitizers. The goals of this study were to: (i) compile, curate, and integrate the largest publicly available dataset of chemicals studied for their skin permeability; (ii) develop and rigorously validate QSAR models to predict skin permeability; and (iii) explore the complex relationships between skin sensitization and skin permeability. Based on the largest publicly available dataset compiled in this study, wemore » found no overall correlation between skin permeability and skin sensitization. In addition, cross-species correlation coefficient between human and rodent permeability data was found to be as low as R{sup 2} = 0.44. Human skin permeability models based on the random forest method have been developed and validated using OECD-compliant QSAR modeling workflow. Their external accuracy was high (Q{sup 2}{sub ext} = 0.73 for 63% of external compounds inside the applicability domain). The extended analysis using both experimentally-measured and QSAR-imputed data still confirmed the absence of any overall concordance between skin permeability and skin sensitization. This observation suggests that chemical modifications that affect skin permeability should not be presumed a priori to modulate the sensitization potential of chemicals. The models reported herein as well as those developed in the companion paper on skin sensitization suggest that it may be possible to rationally design compounds with the desired high skin permeability but low sensitization potential. - Highlights: • It was compiled the largest publicly-available skin permeability dataset. • Predictive QSAR models were developed for skin permeability. • No concordance between skin sensitization and skin permeability has been found. • Structural rules for optimizing sensitization and penetration were established.« less

Determinants for membrane association and permeabilization of the coxsackievirus 2B protein and the identification of the Golgi complex as the target organelle.

PubMed

de Jong, Arjan S; Wessels, Els; Dijkman, Henri B P M; Galama, Jochem M D; Melchers, Willem J G; Willems, Peter H G M; van Kuppeveld, Frank J M

2003-01-10

The 2B protein of enterovirus is responsible for the alterations in the permeability of secretory membranes and the plasma membrane in infected cells. The structural requirements for the membrane association and the subcellular localization of this essential virus protein, however, have not been defined. Here, we provide evidence that the 2B protein is an integral membrane protein in vivo that is predominantly localized at the Golgi complex upon individual expression. Addition of organelle-specific targeting signals to the 2B protein revealed that the Golgi localization is an absolute prerequisite for the ability of the protein to modify plasma membrane permeability. Expression of deletion mutants and heterologous proteins containing specific domains of the 2B protein demonstrated that each of the two hydrophobic regions could mediate membrane binding individually. However, the presence of both hydrophobic regions was required for the correct membrane association, efficient Golgi targeting, and the membrane-permeabilizing activity of the 2B protein, suggesting that the two hydrophobic regions are cooperatively involved in the formation of a membrane-integral complex. The formation of membrane-integral pores by the 2B protein in the Golgi complex and the possible mechanism by which a Golgi-localized virus protein modifies plasma membrane permeability are discussed.

Predicting chemically-induced skin reactions. Part II: QSAR models of skin permeability and the relationships between skin permeability and skin sensitization

PubMed Central

Alves, Vinicius M.; Muratov, Eugene; Fourches, Denis; Strickland, Judy; Kleinstreuer, Nicole; Andrade, Carolina H.; Tropsha, Alexander

2015-01-01

Skin permeability is widely considered to be mechanistically implicated in chemically-induced skin sensitization. Although many chemicals have been identified as skin sensitizers, there have been very few reports analyzing the relationships between molecular structure and skin permeability of sensitizers and non-sensitizers. The goals of this study were to: (i) compile, curate, and integrate the largest publicly available dataset of chemicals studied for their skin permeability; (ii) develop and rigorously validate QSAR models to predict skin permeability; and (iii) explore the complex relationships between skin sensitization and skin permeability. Based on the largest publicly available dataset compiled in this study, we found no overall correlation between skin permeability and skin sensitization. In addition, cross-species correlation coefficient between human and rodent permeability data was found to be as low as R2=0.44. Human skin permeability models based on the random forest method have been developed and validated using OECD-compliant QSAR modeling workflow. Their external accuracy was high (Q2ext = 0.73 for 63% of external compounds inside the applicability domain). The extended analysis using both experimentally-measured and QSAR-imputed data still confirmed the absence of any overall concordance between skin permeability and skin sensitization. This observation suggests that chemical modifications that affect skin permeability should not be presumed a priori to modulate the sensitization potential of chemicals. The models reported herein as well as those developed in the companion paper on skin sensitization suggest that it may be possible to rationally design compounds with the desired high skin permeability but low sensitization potential. PMID:25560673

Resonance Raman and surface-enhanced resonance Raman spectra of LH2 antenna complex from Rhodobacter sphaeroides and Ectothiorhodospira sp. excited in the Qx and Qy transitions.

PubMed

Chumanov, G; Picorel, R; Ortiz de Zarate, I; Cotton, T M; Seibert, M

2000-05-01

Well-resolved vibrational spectra of LH2 complex isolated from two photosynthetic bacteria, Rhodobacter sphaeroides and Ectothiorhodospira sp., were obtained using surface-enhanced resonance Raman scattering (SERRS) exciting into the Qx and the Qy transitions of bacteriochlorophyll a. High-quality SERRS spectra in the Qy region were accessible because the strong fluorescence background was quenched near the roughened Ag surface. A comparison of the spectra obtained with 590 nm and 752 nm excitation in the mid- and low-frequency regions revealed spectral differences between the two LH2 complexes as well as between the LH2 complexes and isolated bacteriochlorophyll a. Because peripheral modes of pigments contribute mainly to the low-frequency spectral region, frequencies and intensities of many vibrational bands in this region are affected by interactions with the protein. The results demonstrate that the microenvironment surrounding the pigments within the two LH2 complexes is somewhat different, despite the fact that the complexes exhibit similar electronic absorption spectra. These differences are most probably due to specific pigment-pigment and pigment-protein interactions within the LH2 complexes, and the approach might be useful for addressing subtle static and dynamic structural variances between pigment-protein complexes from different sources or in complexes altered chemically or genetically.

Iron-tannin-framework complex modified PES ultrafiltration membranes with enhanced filtration performance and fouling resistance.

PubMed

Fang, Xiaofeng; Li, Jiansheng; Li, Xin; Pan, Shunlong; Sun, Xiuyun; Shen, Jinyou; Han, Weiqing; Wang, Lianjun; Van der Bruggen, Bart

2017-11-01

In this work, an iron-tannin-framework (ITF) complex was introduced to a poly (ether sulfone) (PES) casting solution as a hydrophilic additive to fabricate ITF/PES ultrafiltration (UF) membranes via non-solvent-induced phase separation (NIPS). The structure and performance of the PES membranes with ITF concentrations ranging from 0 to 0.9wt.% were systematically investigated by scanning electron microscopy, water contact angle, permeability, protein rejection and fouling resistance measurements. The results indicate that the pore structure and surface properties of PES UF membranes can be regulated by incorporating the ITF complex. Compared with classical PES membranes, ITF/PES membranes were found to have an increased hydrophilicity and porosity and reduced surface pore size. Importantly, a simultaneous enhancement of permeability and separation performance was observed for the blend membranes, which indicates that the introduction of the ITF complex can break through the trade-off between permeability and selectivity of UF membranes.When the ITF content was 0.3wt.%, the permeability reached a maximum of 319.4(L/m 2 h) at 0.1MPa, which is 1.6 times higher than that of the classical PES membrane. Furthermore, the BSA rejection increased from 25.9% for the PES membrane to 95.9% for the enhanced membrane. In addition, the same membrane showed an improved fouling resistance (higher flux recovery and lower adhesion force) and stable hydrophilicity (unchanged after incubation in deionized water for 30days). The simple, green and cost-effective preparation process and the outstanding filtration performance highlight the potential of ITF/PES membranes for practical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

IQGAP1 Interacts with Components of the Slit Diaphragm Complex in Podocytes and Is Involved in Podocyte Migration and Permeability In Vitro

PubMed Central

Rigothier, Claire; Auguste, Patrick; Welsh, Gavin I.; Lepreux, Sébastien; Deminière, Colette; Mathieson, Peter W.; Saleem, Moin A.; Ripoche, Jean; Combe, Christian

2012-01-01

IQGAP1 is a scaffold protein that interacts with proteins of the cytoskeleton and the intercellular adhesion complex. In podocytes, IQGAP1 is associated with nephrin in the glomerular slit diaphragm (SD) complex, but its role remains ill-defined. In this work, we investigated the interaction of IQGAP1 with the cytoskeleton and SD proteins in podocytes in culture, and its role in podocyte migration and permeability. Expression, localization, and interactions between IQGAP1 and SD or cytoskeletal proteins were determined in cultured human podocytes by Western blot (WB), immunocytolocalization (IC), immunoprecipitation (IP), and In situ Proximity Ligation assay (IsPL). Involvement of IQGAP1 in migration and permeability was also assessed. IQGAP1 expression in normal kidney biopsies was studied by immunohistochemistry. IQGAP1 expression by podocytes increased during their in vitro differentiation. IC, IP, and IsPL experiments showed colocalizations and/or interactions between IQGAP1 and SD proteins (nephrin, MAGI-1, CD2AP, NCK 1/2, podocin), podocalyxin, and cytoskeletal proteins (α-actinin-4). IQGAP1 silencing decreased podocyte migration and increased the permeability of a podocyte layer. Immunohistochemistry on normal human kidney confirmed IQGAP1 expression in podocytes and distal tubular epithelial cells and also showed an expression in glomerular parietal epithelial cells. In summary, our results suggest that IQGAP1, through its interaction with components of SD and cytoskeletal proteins, is involved in podocyte barrier properties. PMID:22662192

Analysis and application of classification methods of complex carbonate reservoirs

NASA Astrophysics Data System (ADS)

Li, Xiongyan; Qin, Ruibao; Ping, Haitao; Wei, Dan; Liu, Xiaomei

2018-06-01

There are abundant carbonate reservoirs from the Cenozoic to Mesozoic era in the Middle East. Due to variation in sedimentary environment and diagenetic process of carbonate reservoirs, several porosity types coexist in carbonate reservoirs. As a result, because of the complex lithologies and pore types as well as the impact of microfractures, the pore structure is very complicated. Therefore, it is difficult to accurately calculate the reservoir parameters. In order to accurately evaluate carbonate reservoirs, based on the pore structure evaluation of carbonate reservoirs, the classification methods of carbonate reservoirs are analyzed based on capillary pressure curves and flow units. Based on the capillary pressure curves, although the carbonate reservoirs can be classified, the relationship between porosity and permeability after classification is not ideal. On the basis of the flow units, the high-precision functional relationship between porosity and permeability after classification can be established. Therefore, the carbonate reservoirs can be quantitatively evaluated based on the classification of flow units. In the dolomite reservoirs, the average absolute error of calculated permeability decreases from 15.13 to 7.44 mD. Similarly, the average absolute error of calculated permeability of limestone reservoirs is reduced from 20.33 to 7.37 mD. Only by accurately characterizing pore structures and classifying reservoir types, reservoir parameters could be calculated accurately. Therefore, characterizing pore structures and classifying reservoir types are very important to accurate evaluation of complex carbonate reservoirs in the Middle East.

Optical properties of antiferromagnetic/ion-crystal superlattices

NASA Astrophysics Data System (ADS)

Ta, Jin-Xing; Song, Yu-Ling; Wang, Xuan-Zhang

2012-01-01

Transmission, refraction and absorption properties of an antiferromagnetic/ion-crystal superlattice are investigated. The transmission spectra based on FeF2/TlBr superlattices reveal that there exist two intriguing guided modes in a wide stop band. Additionally, FeF2/TlBr superlattices possess either the negative refraction or the quasi left-handedness, or even simultaneously hold them at certain frequencies of two guided modes, which require both negative magnetic permeability of antiferromagnetic layers and negative permittivity of ion-crystal layers. Frequency regimes of the guided modes will be dependent on the magnitude of the external magnetic field. Therefore, handedness and refraction properties of the system can be manipulated by modifying the external magnetic field. Absorption spectra exhibit that absorption corresponding to guided modes is noticeable.

Fracture-permeability behavior of shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carey, J. William; Lei, Zhou; Rougier, Esteban

The fracture-permeability behavior of Utica shale, an important play for shale gas and oil, was investigated using a triaxial coreflood device and X-ray tomography in combination with finite-discrete element modeling (FDEM). Fractures generated in both compression and in a direct-shear configuration allowed permeability to be measured across the faces of cylindrical core. Shale with bedding planes perpendicular to direct-shear loading developed complex fracture networks and peak permeability of 30 mD that fell to 5 mD under hydrostatic conditions. Shale with bedding planes parallel to shear loading developed simple fractures with peak permeability as high as 900 mD. In addition tomore » the large anisotropy in fracture permeability, the amount of deformation required to initiate fractures was greater for perpendicular layering (about 1% versus 0.4%), and in both cases activation of existing fractures are more likely sources of permeability in shale gas plays or damaged caprock in CO₂ sequestration because of the significant deformation required to form new fracture networks. FDEM numerical simulations were able to replicate the main features of the fracturing processes while showing the importance of fluid penetration into fractures as well as layering in determining fracture patterns.« less

Fracture-permeability behavior of shale

DOE PAGES

Carey, J. William; Lei, Zhou; Rougier, Esteban; ...

2015-05-08

The fracture-permeability behavior of Utica shale, an important play for shale gas and oil, was investigated using a triaxial coreflood device and X-ray tomography in combination with finite-discrete element modeling (FDEM). Fractures generated in both compression and in a direct-shear configuration allowed permeability to be measured across the faces of cylindrical core. Shale with bedding planes perpendicular to direct-shear loading developed complex fracture networks and peak permeability of 30 mD that fell to 5 mD under hydrostatic conditions. Shale with bedding planes parallel to shear loading developed simple fractures with peak permeability as high as 900 mD. In addition tomore » the large anisotropy in fracture permeability, the amount of deformation required to initiate fractures was greater for perpendicular layering (about 1% versus 0.4%), and in both cases activation of existing fractures are more likely sources of permeability in shale gas plays or damaged caprock in CO₂ sequestration because of the significant deformation required to form new fracture networks. FDEM numerical simulations were able to replicate the main features of the fracturing processes while showing the importance of fluid penetration into fractures as well as layering in determining fracture patterns.« less

The CO 2 with dimethylamine reaction: ab initio predicted vibrational spectra

NASA Astrophysics Data System (ADS)

Jamróz, M. H.; Dobrowolski, J. Cz.; Borowiak, M. A.

1999-05-01

The IR spectra of CO 2, dimethylamine (DMA), (DMA) 2 dimers, DMA⋯CO 2 (2 : 1) complex, dimethylcarbamic acid (DMCA), DMCA⋯DMA (1 : 1) complex, DMCA -, and DMA(H) + were calculated at the B3PW91/6-31G** level. Potential energy distribution (PED) was calculated for predicted spectra to form basis for elucidation of experimental IR data. The stabilisation energy of the studied complexes was corrected by counterpoise method.

There and back again: The life and death of magma permeability in volcanic conduits

NASA Astrophysics Data System (ADS)

Wadsworth, F. B.; Vasseur, J.; Llewellin, E. W.; Lavallée, Y.; Kendrick, J. E.; Dobson, K. J.; Heap, M. J.; Kushnir, A. R.; Dingwell, D. B.

2017-12-01

Permeability of magma to gas is one of the key controls on the propoensity for explosive volcanism on the terrestrial planets. The magma filling upper-crustal volcanic conduits must become permeable in order for gas overpressure in pore spaces to dissipate. Once permeable, magma may densify and the pore network may re-seal itself. Permeability may be developed in one or more of 3 end-member pore-space geometries: (1) bubble-dominated, (2) crack-dominated, or (3) particle dominated. We take each geometry in turn and explore how we can scale the evolution of permeability with porosity. To do this we use 3 different data types. First, we compile the large body of published measurements of natural, synthetic and analogue volcanic rocks covering a range of pore space complexity. Second, we compile and conduct in situ measurements of permeability evolution for densifying granular systems or crack-formation in deforming magmas. Third, we conduct stochastic simulations in which we systematically build random heterogeneous porous media from overlapping spheres and use lattice-Boltzmann simulations of fluid flow to find the permeability. These data permit us to isolate individual controls on the permeability in each geometry in turn. Permeability can be readily formed by bubble coalescence, fracturing or fragmentation, and by forced gas percolation. Similarly, permeability can be reduced by bubble shrinking and pinch off, fracture healing, and volcanic welding. We broadly consider the kinetics of these processes and provide useful tools for predicting the longevity of different permeable network types. We summarize these findings by considering the potential of silicic volcanoes to outgas prior to significant overpressure buildup, possibly controlling the liklihood of large explosive behaviour.

Two-photon excitation spectroscopy of carotenoid-containing and carotenoid-depleted LH2 complexes from purple bacteria.

PubMed

Stepanenko, Ilya; Kompanetz, Viktor; Makhneva, Zoya; Chekalin, Sergey; Moskalenko, Andrei; Razjivin, Andrei

2009-08-27

We applied two-photon fluorescence excitation spectroscopy to LH2 complex from purple bacteria Allochromatium minutissimum and Rhodobacter sphaeroides . Bacteriochlorophyll fluorescence was measured under two-photon excitation of the samples within the 1200-1500 nm region. Spectra were obtained for both carotenoid-containing and -depleted complexes of each bacterium to allow their direct comparison. The depletion of carotenoids did not alter the two-photon excitation spectra of either bacteria. The spectra featured a wide excitation band around 1350 nm (2x675 nm, 14,800 cm(-1)) which strongly resembled two-photon fluorescence excitation spectra of similar complexes published by other authors. We consider obtained experimental data to be evidence of direct two-photon excitation of bacteriochlorophyll excitonic states in this spectral region.

Spectral characterization, thermal and biological activity studies of Schiff base complexes derived from 4,4‧-Methylenedianiline, ethanol amine and benzil

NASA Astrophysics Data System (ADS)

Emam, Sanaa Moustafa

2017-04-01

Some new metal(II) complexes of asymmetric Schiff base ligand were prepared by template technique. The shaped complexes are in binuclear structures and were explained through elemental analysis, molar conductivity, various spectroscopic methods (IR, U.V-Vis, XRD, ESR), thermal (TG) and magnetic moment measurements. The IR spectra were done demonstrating that the Schiff base ligand acts as neutral tetradentate moiety in all metal complexes. The electronic absorption spectra represented octahedral geometry for all complexes, while, the ESR spectra for Cu(II) complex showed axially symmetric g-tensor parameter with g׀׀ > g⊥ > 2.0023 indicating to 2B1g ground state with (dx2-y2)1 configuration. The nature of the solid residue created from TG estimations was affirmed utilizing IR and XRD spectra. The biological activity of the prepared complexes was studied against Land Snails. Additionally, the in vitro antitumor activity of the synthesized complexes with Hepatocellular Carcinoma cell (Hep-G2) was examined. It was observed that Zn(II) complex (5), exhibits a high inhibition of growth of the cell line with IC50 of 7.09 μg/mL.

A laboratory study to estimate pore geometric parameters of sandstones using complex conductivity and nuclear magnetic resonance for permeability prediction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osterman, Gordon; Keating, Kristina; Binley, Andrew

Here, we estimate parameters from the Katz and Thompson permeability model using laboratory complex electrical conductivity (CC) and nuclear magnetic resonance (NMR) data to build permeability models parameterized with geophysical measurements. We use the Katz and Thompson model based on the characteristic hydraulic length scale, determined from mercury injection capillary pressure estimates of pore throat size, and the intrinsic formation factor, determined from multisalinity conductivity measurements, for this purpose. Two new permeability models are tested, one based on CC data and another that incorporates CC and NMR data. From measurements made on forty-five sandstone cores collected from fifteen different formations,more » we evaluate how well the CC relaxation time and the NMR transverse relaxation times compare to the characteristic hydraulic length scale and how well the formation factor estimated from CC parameters compares to the intrinsic formation factor. We find: (1) the NMR transverse relaxation time models the characteristic hydraulic length scale more accurately than the CC relaxation time (R 2 of 0.69 and 0.33 and normalized root mean square errors (NRMSE) of 0.16 and 0.21, respectively); (2) the CC estimated formation factor is well correlated with the intrinsic formation factor (NRMSE50.23). We demonstrate that that permeability estimates from the joint-NMR-CC model (NRMSE50.13) compare favorably to estimates from the Katz and Thompson model (NRMSE50.074). Lastly, this model advances the capability of the Katz and Thompson model by employing parameters measureable in the field giving it the potential to more accurately estimate permeability using geophysical measurements than are currently possible.« less

A laboratory study to estimate pore geometric parameters of sandstones using complex conductivity and nuclear magnetic resonance for permeability prediction

DOE PAGES

Osterman, Gordon; Keating, Kristina; Binley, Andrew; ...

2016-03-18

Here, we estimate parameters from the Katz and Thompson permeability model using laboratory complex electrical conductivity (CC) and nuclear magnetic resonance (NMR) data to build permeability models parameterized with geophysical measurements. We use the Katz and Thompson model based on the characteristic hydraulic length scale, determined from mercury injection capillary pressure estimates of pore throat size, and the intrinsic formation factor, determined from multisalinity conductivity measurements, for this purpose. Two new permeability models are tested, one based on CC data and another that incorporates CC and NMR data. From measurements made on forty-five sandstone cores collected from fifteen different formations,more » we evaluate how well the CC relaxation time and the NMR transverse relaxation times compare to the characteristic hydraulic length scale and how well the formation factor estimated from CC parameters compares to the intrinsic formation factor. We find: (1) the NMR transverse relaxation time models the characteristic hydraulic length scale more accurately than the CC relaxation time (R 2 of 0.69 and 0.33 and normalized root mean square errors (NRMSE) of 0.16 and 0.21, respectively); (2) the CC estimated formation factor is well correlated with the intrinsic formation factor (NRMSE50.23). We demonstrate that that permeability estimates from the joint-NMR-CC model (NRMSE50.13) compare favorably to estimates from the Katz and Thompson model (NRMSE50.074). Lastly, this model advances the capability of the Katz and Thompson model by employing parameters measureable in the field giving it the potential to more accurately estimate permeability using geophysical measurements than are currently possible.« less

Vibrational spectra, powder X-ray diffractions and physical properties of cyanide complexes with 1-ethylimidazole

NASA Astrophysics Data System (ADS)

Kürkçüoğlu, Güneş Süheyla; Kiraz, Fulya Çetinkaya; Sayın, Elvan

2015-10-01

The heteronuclear tetracyanonickelate(II) complexes of the type [M(etim)Ni(CN)4]n (hereafter, abbreviated as M-Ni-etim, M = Mn(II), Fe(II) or Co(II); etim = 1-ethylimidazole, C5H8N2) were prepared in powder form and characterized by FT-IR and Raman spectroscopy, powder X-ray diffraction (PXRD), thermal (TG; DTG and DTA), and elemental analysis techniques. The structures of these complexes were elucidated using vibrational spectra and powder X-ray diffraction patterns with the peak assignment to provide a better understanding of the structures. It is shown that the spectra are consistent with a proposed crystal structure for these compounds derived from powder X-ray diffraction measurements. Vibrational spectra of the complexes were presented and discussed with respect to the internal modes of both the etim and the cyanide ligands. The C, H and N analyses were carried out for all the complexes. Thermal behaviors of these complexes were followed using TG, DTG and DTA curves in the temperature range 30-700 °C in the static air atmosphere. The FT-IR, Raman spectra, thermal and powder X-ray analyses revealed no significant differences between the single crystal and powder forms. Additionally, electrical and magnetic properties of the complexes were investigated. The FT-IR and Raman spectroscopy, PXRD, thermal and elemental analyses results propose that these complexes are similar in structure to the Hofmann-type complexes.

Single-Molecule Spectroscopy Unmasks the Lowest Exciton State of the B850 Assembly in LH2 from Rps. acidophila

PubMed Central

Kunz, Ralf; Timpmann, Kõu; Southall, June; Cogdell, Richard J.; Freiberg, Arvi; Köhler, Jürgen

2014-01-01

We have recorded fluorescence-excitation and emission spectra from single LH2 complexes from Rhodopseudomonas (Rps.) acidophila. Both types of spectra show strong temporal spectral fluctuations that can be visualized as spectral diffusion plots. Comparison of the excitation and emission spectra reveals that for most of the complexes the lowest exciton transition is not observable in the excitation spectra due to the cutoff of the detection filter characteristics. However, from the spectral diffusion plots we have the full spectral and temporal information at hand and can select those complexes for which the excitation spectra are complete. Correlating the red most spectral feature of the excitation spectrum with the blue most spectral feature of the emission spectrum allows an unambiguous assignment of the lowest exciton state. Hence, application of fluorescence-excitation and emission spectroscopy on the same individual LH2 complex allows us to decipher spectral subtleties that are usually hidden in traditional ensemble spectroscopy. PMID:24806933

Intracellular Ca2+ release mediates cationic but not anionic poly(amidoamine) (PAMAM) dendrimer-induced tight junction modulation.

PubMed

Avaritt, Brittany R; Swaan, Peter W

2014-09-01

Poly(amidoamine) (PAMAM) dendrimers show great promise for utilization as oral drug delivery vehicles. These polymers are capable of traversing epithelial barriers, and have been shown to translocate by both transcellular and paracellular routes. While many proof-of-concept studies have shown that PAMAM dendrimers improve intestinal transport, little information exists on the mechanisms of paracellular transport, specifically dendrimer-induced tight junction modulation. Using anionic G3.5 and cationic G4 PAMAM dendrimers with known absorption enhancers, we investigated tight junction modulation in Caco-2 monolayers by visualization and mannitol permeability and compared dendrimer-mediated tight junction modulation to that of established permeation enhancers. [(14)C]-Mannitol permeability in the presence and absence of phospholipase C-dependent signaling pathway inhibitors was also examined and indicated that this pathway may mediate dendrimer-induced changes in permeability. Differences between G3.5 and G4 in tight junction protein staining and permeability with inhibitors were evident, suggesting divergent mechanisms were responsible for tight junction modulation. These dissimilarities are further intimated by the intracellular calcium release caused by G4 but not G3.5. Based on our results, it is apparent that the underlying mechanisms of dendrimer permeability are complex, and the complexities are likely a result of the density and sign of the surface charges of PAMAM dendrimers. The results of this study will have implications on the future use of PAMAM dendrimers for oral drug delivery.

Single crystal X- and Q-band EPR spectroscopy of a binuclear Mn(2)(III,IV) complex relevant to the oxygen-evolving complex of photosystem II.

PubMed

Yano, Junko; Sauer, Kenneth; Girerd, Jean-Jacques; Yachandra, Vittal K

2004-06-23

The anisotropic g and hyperfine tensors of the Mn di-micro-oxo complex, [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN, were derived by single-crystal EPR measurements at X- and Q-band frequencies. This is the first simulation of EPR parameters from single-crystal EPR spectra for multinuclear Mn complexes, which are of importance in several metalloenzymes; one of them is the oxygen-evolving complex in photosystem II (PS II). Single-crystal [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN EPR spectra showed distinct resolved (55)Mn hyperfine lines in all crystal orientations, unlike single-crystal EPR spectra of other Mn(2)(III,IV) di-micro-oxo bridged complexes. We measured the EPR spectra in the crystal ab- and bc-planes, and from these spectra we obtained the EPR spectra of the complex along the unique a-, b-, and c-axes of the crystal. The crystal orientation was determined by X-ray diffraction and single-crystal EXAFS (Extended X-ray Absorption Fine Structure) measurements. In this complex, the three crystallographic axes, a, b, and c, are parallel or nearly parallel to the principal molecular axes of Mn(2)(III,IV)O(2)(phen)(4) as shown in the crystallographic data by Stebler et al. (Inorg. Chem. 1986, 25, 4743). This direct relation together with the resolved hyperfine lines significantly simplified the simulation of single-crystal spectra in the three principal directions due to the reduction of free parameters and, thus, allowed us to define the magnetic g and A tensors of the molecule with a high degree of reliability. These parameters were subsequently used to generate the solution EPR spectra at both X- and Q-bands with excellent agreement. The anisotropic g and hyperfine tensors determined by the simulation of the X- and Q-band single-crystal and solution EPR spectra are as follows: g(x) = 1.9887, g(y) = 1.9957, g(z) = 1.9775, and hyperfine coupling constants are A(III)(x) = |171| G, A(III)(y) = |176| G, A(III)(z) = |129| G, A(IV)(x) = |77| G, A(IV)(y) = |74| G, A(IV)(z) = |80| G.

Monitoring CO2 penetration and storage in the brine-saturated low permeable sandstone by the geophysical exploration technologies

NASA Astrophysics Data System (ADS)

Honda, H.; Mitani, Y.; Kitamura, K.; Ikemi, H.; Imasato, M.

2017-12-01

Carbon dioxide (CO2) capture and storage (CCS) plays a vital role in reducing greenhouse gas emissions. In the northern part of Kyushu region of Japan, complex geological structure (Coalfield) is existed near the CO2 emission source and has 1.06 Gt of CO2 storage capacity. The geological survey shows that these layers are formed by low permeable sandstone. It is necessary to monitor the CO2 behavior and clear the mechanisms of CO2 penetration and storage in the low permeable sandstone. In this study, measurements of complex electrical impedance (Z) and elastic wave velocity (P-wave velocity: Vp) were conducted during the supercritical CO2 injection experiment into the brine-saturated low permeable sandstone. The experiment conditions were as follows; Confining pressure: 20 MPa, Initial pore pressure: 10 MPa, 40 °, CO2 injection rate: 0.01 to 0.5 mL/min. Z was measured in the center of the specimen and Vp were measured at three different heights of the specimen at constant intervals. In addition, we measured the longitudinal and lateral strain at the center of the specimen, the pore pressure and CO2 injection volume (CO2 saturation). During the CO2 injection, the change of Z and Vp were confirmed. In the drainage terms, Vp decreased drastically once CO2 reached the measurement cross section.Vp showed the little change even if the flow rate increased (CO2 saturation increased). On the other hand, before the CO2 front reached, Z decreased with CO2-dissolved brine. After that, Z showed continuously increased as the CO2 saturation increased. From the multi-parameter (Hydraulic and Rock-physics parameters), we revealed the detail CO2 behavior in the specimen. In the brine-saturated low permeable sandstone, the slow penetration of CO2 was observed. However, once CO2 has passed, the penetration of CO2 became easy in even for brine-remainded low permeable sandstone. We conclude low permeable sandstone has not only structural storage capacity but also residual tapping (Capillary trapping) capacity. There is a positive possibility to conduct CCS in the low-quality reservoir (low permeable sandstone).

Theoretical and experimental evaluation of effective stress-induced sorption capacity change and its influence on coal permeability

NASA Astrophysics Data System (ADS)

Li, Chengwu; Dong, Lihui; Xu, Xiaomeng; Hu, Po; Tian, Jianwei; Zhang, Yihuai; Yang, Leilei

2017-06-01

The gas sorption effect is an important factor affecting the gas permeability of a coal seam, which has been proved in many previous experimental measurements and analytical permeability studies. However, the sorption capacity of coal is usually not static due to the complexity of external stress variation and internal gas media features. The stress-induced sorption capacity variation and its effect on the coal permeability change have not been fully identified yet. Thus, in this paper we present a preliminary evaluation of the stress-induced sorption capacity change by introducing the adsorption capacity modified term, and an experiment is carried out to verify the influence of the altered effective stress on coal permeability. Langmuir-like adsorption deformation constant parameters were combined into the modified coal permeability model and were given values to fully estimate the influence on permeability caused by the modification term. We found that different change modes of effective stress would yield different change effects on the permeability, that is, with the same effective stress change amount, the altered external stress-induced change had less influence than the altered-pore pressure-induced change; however, both modes demonstrated that the model taking sorption capacity change into consideration is more consistent with the experimental data. The effect of sorption capacity change on coal permeability variation was also found to be tightly connected with the physical and mechanical properties of the coal itself. It is proved that considering stress-induced sorption ability change has a critical role in characterizing the permeability variation of coal.

Gradual changes in permeability of inner mitochondrial membrane precede the mitochondrial permeability transition.

PubMed

Balakirev, M Y; Zimmer, G

1998-08-01

Some compounds are known to induce solute-nonselective permeability of the inner mitochondrial membrane (IMM) in Ca2+-loaded mitochondria. Existing data suggest that this process, following the opening of a mitochondrial permeability transition pore, is preceded by different solute-selective permeable states of IMM. At pH 7, for instance, the K0.5 for Ca2+-induced pore opening is 16 microM, a value 80-fold above a therapeutically relevant shift of intracellular Ca2+ during ischemia in vivo. The present work shows that in the absence of Ca2+, phenylarsine oxide and tetraalkyl thiuram disulfides (TDs) are able to induce a complex sequence of IMM permeability changes. At first, these agents activated an electrogenic K+ influx into the mitochondria. This K+-specific pathway had K0.5 = 35 mM for K+ and was inhibited by bromsulfalein with Ki = 2.5 microM. The inhibitors of mitochondrial KATP channel, ATP and glibenclamide, did not inhibit K+ transport via this pathway. Moreover, 50 microM glibenclamide induced by itself K+ influx into the mitochondria. After the increase in K+ permeability of IMM, mitochondria become increasingly permeable to protons. Mechanisms of H+ leak and nonselective permeability increase could also be different depending on the type of mitochondrial permeability transition (MPT) inducer. Thus, permeabilization of mitochondria induced by phenylarsine oxide was fully prevented by ADP and/or cyclosporin A, whereas TD-induced membrane alterations were insensitive toward these inhibitors. It is suggested that MPT in vivo leading to irreversible apoptosis is irrelevant in reversible ischemia/reperfusion injury. Copyright 1998 Academic Press.

Mucoadhesion vs mucus permeability of thiolated chitosan polymers and their resulting nanoparticles using a quartz crystal microbalance with dissipation (QCM-D).

PubMed

Oh, Sejin; Borrós, Salvador

2016-11-01

The aim of this present study was to evaluate the combination properties between mucoadhesion/mucus permeability of thiolated chitosans (TC) and their resulting nanoparticles using a quartz crystal microbalance with dissipation (QCM-D). The QCM-D experiments were conducted at pH 4 or 6.8 to assess the interaction between thiolated polymers, with low (TCL), medium (TCM) and high (TCH) contents of free thiol groups, and native porcine gastric mucin (NPGM). TCL was chosen for further carriers as it showed higher permeability into the NPGM layer compared to TCM and TCH. In this study, we describe a formulation of a novel carrier comprised by positively charged TCL, negatively charged DNA and degradable oligopeptide-modified poly(β-amino ester)s (PBAEs), which were employed in order to approach for tuning particle size and surface charge of complexes. TCL/PBAE complexes with or without DNA were characterized using dynamic light scattering. Mechanism of adsorption or permeation of the TCL/PBAE/DNA complexes into the NPGM barrier was investigated with QCM-D, which is a highly sensitive technique for studying nanomechanical (viscoelastic) changes of the substrates. This work might provide that the QCM-D technique would be a promising method to monitor the dynamic behaviour between complexes and NPGM. Copyright © 2016 Elsevier B.V. All rights reserved.

An improved method for permeability estimation of the bioclastic limestone reservoir based on NMR data

NASA Astrophysics Data System (ADS)

Ge, Xinmin; Fan, Yiren; Liu, Jianyu; Zhang, Li; Han, Yujiao; Xing, Donghui

2017-10-01

Permeability is an important parameter in formation evaluation since it controls the fluid transportation of porous rocks. However, it is challengeable to compute the permeability of bioclastic limestone reservoirs by conventional methods linking petrophysical and geophysical data, due to the complex pore distributions. A new method is presented to estimate the permeability based on laboratory and downhole nuclear magnetic resonance (NMR) measurements. We divide the pore space into four intervals by the inflection points between the pore radius and the transversal relaxation time. Relationships between permeability and percentages of different pore intervals are investigated to investigate influential factors on the fluid transportation. Furthermore, an empirical model, which takes into account of the pore size distributions, is presented to compute the permeability. 212 core samples in our case show that the accuracy of permeability calculation is improved from 0.542 (SDR model), 0.507 (TIM model), 0.455 (conventional porosity-permeability regressions) to 0.803. To enhance the precision of downhole application of the new model, we developed a fluid correction algorithm to construct the water spectrum of in-situ NMR data, aiming to eliminate the influence of oil on the magnetization. The result reveals that permeability is positively correlated with percentages of mega-pores and macro-pores, but negatively correlated with the percentage of micro-pores. Poor correlation is observed between permeability and the percentage of meso-pores. NMR magnetizations and T2 spectrums after the fluid correction agree well with laboratory results for samples saturated with water. Field application indicates that the improved method provides better performance than conventional models such as Schlumberger-Doll Research equation, Timur-Coates equation, and porosity-permeability regressions.

Exfoliated BN shell-based high-frequency magnetic core-shell materials.

PubMed

Zhang, Wei; Patel, Ketan; Ren, Shenqiang

2017-09-14

The miniaturization of electric machines demands high frequency magnetic materials with large magnetic-flux density and low energy loss to achieve a decreased dimension of high rotational speed motors. Herein, we report a solution-processed high frequency magnetic composite (containing a nanometal FeCo core and a boron nitride (BN) shell) that simultaneously exhibits high electrical resistivity and magnetic permeability. The frequency dependent complex initial permeability and the mechanical robustness of nanocomposites are intensely dependent on the content of BN insulating phase. The results shown here suggest that insulating magnetic nanocomposites have potential for application in next-generation high-frequency electric machines with large electrical resistivity and permeability.

Combining a Deconvolution and a Universal Library Search Algorithm for the Nontarget Analysis of Data-Independent Acquisition Mode Liquid Chromatography-High-Resolution Mass Spectrometry Results.

PubMed

Samanipour, Saer; Reid, Malcolm J; Bæk, Kine; Thomas, Kevin V

2018-04-17

Nontarget analysis is considered one of the most comprehensive tools for the identification of unknown compounds in a complex sample analyzed via liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS). Due to the complexity of the data generated via LC-HRMS, the data-dependent acquisition mode, which produces the MS 2 spectra of a limited number of the precursor ions, has been one of the most common approaches used during nontarget screening. However, data-independent acquisition mode produces highly complex spectra that require proper deconvolution and library search algorithms. We have developed a deconvolution algorithm and a universal library search algorithm (ULSA) for the analysis of complex spectra generated via data-independent acquisition. These algorithms were validated and tested using both semisynthetic and real environmental data. A total of 6000 randomly selected spectra from MassBank were introduced across the total ion chromatograms of 15 sludge extracts at three levels of background complexity for the validation of the algorithms via semisynthetic data. The deconvolution algorithm successfully extracted more than 60% of the added ions in the analytical signal for 95% of processed spectra (i.e., 3 complexity levels multiplied by 6000 spectra). The ULSA ranked the correct spectra among the top three for more than 95% of cases. We further tested the algorithms with 5 wastewater effluent extracts for 59 artificial unknown analytes (i.e., their presence or absence was confirmed via target analysis). These algorithms did not produce any cases of false identifications while correctly identifying ∼70% of the total inquiries. The implications, capabilities, and the limitations of both algorithms are further discussed.

[Investigation of permeability of intranasal formulations using Side-Bi-Side horizontal diffusion cell].

PubMed

Horváth Tamás; Ambrus, Rita; Szabóné, Révész Piroska

2015-01-01

Nowadays the nasal route has received a great attention as a reliable administration for the systemic administration. In the Department of Pharmaceutical Technology, University of Szeged, the main research work is the design and development of innovative nasal formulations, which can open new possibilities for some well-known agents and may also help some drug-candidates delivery problems. The aim of this work was to present some reliable models for investigation of permeability, such as Spectra/Por Dialisys Membran, ZelluTrans/Roth Mini Dialyzer, μFLUX diffusion Cell, Navicyte Vertical and Horizontal Diffusion Chamber System and In-line Cell. In addition, the horizontal membrane diffusion model (Side-Bi-Side) was used to investigate in vitro and ex vivo studies of permeability of meloxicam in comparison with the vertical diffusion cell (Franz). The present study investigated the meloxicam in different dosage forms (powder, spray, gel). It was found that the Side-Bi-Side cell is suitable to test the nasal formulations, but the uniform distribution of the active substance cannot be ensured in donor place by increasing the viscosity of the compositions, therefore the Franz cell is recommended for investigation of nasal gel. Previous measurement cannot be found related to this topic.

Dicoumarol complexes of Cu(II) based on 1,10-phenanthroline: Synthesis, X-ray diffraction studies, thermal behavior and biological evaluation

NASA Astrophysics Data System (ADS)

Dholariya, Hitesh R.; Patel, Ketan S.; Patel, Jiten C.; Patel, Kanuprasad D.

2013-05-01

A series of Cu(II) complexes containing dicoumarol derivatives and 1, 10-phenanthroline have been synthesized. Structural and spectroscopic properties of ligands were studied on the basis of mass spectra, NMR (1H and 13C) spectra, FT-IR spectrophotometry and elemental analysis, while physico-chemical, spectroscopic and thermal properties of mixed ligand complexes have been studied on the basis of infrared spectra, mass spectra, electronic spectra, powder X-ray diffraction, elemental analysis and thermogravimetric analysis. X-ray diffraction study suggested the suitable octahedral geometry for hexa-coordinated state. The kinetic parameters such as order of reaction (n), energy of activation (Ea), entropy (S*), pre-exponential factor (A), enthalpy (H*) and Gibbs free energy (G*) have been calculated using Freeman-Carroll method. Ferric-reducing antioxidant power (FRAP) of all complexes were measured. All the compounds were screened for their antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, Streptococcus pyogenes and Bacillus subtilis, while antifungal activity against Candida albicans and Aspergillus niger have been carried out. Also compounds against Mycobacterium tuberculosis shows clear enhancement in the anti-tubercular activity upon copper complexation.

Roles of URLs in Probing Controls on Induced Seismicity and Permeability Evolution

NASA Astrophysics Data System (ADS)

Elsworth, D.

2014-12-01

The generation and extension of new fractures and the development of controlled slip and opening are an implicit component in both forming and in enhancing flow pathways to unlock hydrocarbons and geothermal energy in otherwise very low permeability formations. The opposite is true for containment structures and caprocks. The complex stress state coupled with pre-existing fracture networks means that new flow pathways may develop in complex ways including varied modes of dilatation and slip, deformation that may be seismic or aseismic and permeability that may net increase of decrease. Where this deformation relies on either the reactivation, extension or development of fractures, this evolution is intrinsically scale dependent requiring that an improved understanding of this dynamic response must interrogate its evolution at representative scales - scales of decimeters to a few meters. We explore the controls on instability through frictional slip and instability including changes related to environmental conditions and physical properties. The former relate to changes in effective stress driven by fluid pressures, thermal and chemical stresses and the latter to changes in strength and stability conditioned on initial or evolving mineralogy. We identify important contemporary questions that are intrinsically scale dependent and may be effectively probed by field experimentation linking deformation and permeability.

Development and validation of a low-frequency modeling code for high-moment transmitter rod antennas

NASA Astrophysics Data System (ADS)

Jordan, Jared Williams; Sternberg, Ben K.; Dvorak, Steven L.

2009-12-01

The goal of this research is to develop and validate a low-frequency modeling code for high-moment transmitter rod antennas to aid in the design of future low-frequency TX antennas with high magnetic moments. To accomplish this goal, a quasi-static modeling algorithm was developed to simulate finite-length, permeable-core, rod antennas. This quasi-static analysis is applicable for low frequencies where eddy currents are negligible, and it can handle solid or hollow cores with winding insulation thickness between the antenna's windings and its core. The theory was programmed in Matlab, and the modeling code has the ability to predict the TX antenna's gain, maximum magnetic moment, saturation current, series inductance, and core series loss resistance, provided the user enters the corresponding complex permeability for the desired core magnetic flux density. In order to utilize the linear modeling code to model the effects of nonlinear core materials, it is necessary to use the correct complex permeability for a specific core magnetic flux density. In order to test the modeling code, we demonstrated that it can accurately predict changes in the electrical parameters associated with variations in the rod length and the core thickness for antennas made out of low carbon steel wire. These tests demonstrate that the modeling code was successful in predicting the changes in the rod antenna characteristics under high-current nonlinear conditions due to changes in the physical dimensions of the rod provided that the flux density in the core was held constant in order to keep the complex permeability from changing.

Transformable ferroelectric control of dynamic magnetic permeability

NASA Astrophysics Data System (ADS)

Jiang, Changjun; Jia, Chenglong; Wang, Fenglong; Zhou, Cai; Xue, Desheng

2018-02-01

Magnetic permeability, which measures the response of a material to an applied magnetic field, is crucial to the performance of magnetic devices and related technologies. Its dynamic value is usually a complex number with real and imaginary parts that describe, respectively, how much magnetic power can be stored and lost in the material. Control of permeability is therefore closely related to energy redistribution within a magnetic system or energy exchange between magnetic and other degrees of freedom via certain spin-dependent interactions. To avoid a high power consumption, direct manipulation of the permeability with an electric field through magnetoelectric coupling leads to high efficiency and simple operation, but remains a big challenge in both the fundamental physics and material science. Here we report unambiguous evidence of ferroelectric control of dynamic magnetic permeability in a Co /Pb (Mg1/3Nb2/3) 0.7Ti0.3O3 (Co/PMN-PT) heterostructure, in which the ferroelectric PMN-PT acts as an energy source for the ferromagnetic Co film via an interfacial linear magnetoelectric interaction. The electric field tuning of the magnitude and line shape of the permeability offers a highly localized means of controlling magnetization with ultralow power consumption. Additionally, the emergence of negative permeability promises a new way of realizing functional nanoscale metamaterials with adjustable refraction index.

Comparative study on antifungal activities of chitosan nanoparticles and chitosan silver nano composites against Fusarium oxysporum species complex.

PubMed

Dananjaya, S H S; Erandani, W K C U; Kim, Cheol-Hee; Nikapitiya, Chamilani; Lee, Jehee; De Zoysa, Mahanama

2017-12-01

Though the metal nanoparticles (NPs) have been shown favorable results against fungal diseases, erratic environmental toxicity of NPs have raised serious concerns against their applications. Hence, it is vital to modify antifungal compounds into safe substitutes over synthetic chemicals. In this study, antifungal effects of chitosan nanoparticles (CNPs) and chitosan silver nanocomposites (CAgNCs) were compared against Fusarium oxysporum species complex. CNPs and CAgNCs were synthesized, characterized and compared based on the transmission electron microscope, X-ray diffraction, UV-vis absorbance spectra, particle size distribution, zeta potential and thermal stability analysis. Ultra-structural analysis on mycelium membrane of treated F. oxysporum showed that CNPs and CAgNCs could induce a pronounced membrane damage and disruption of the mycelium surface, increase the membrane permeability, and even cell disintegration. CAgNCs showed a significantly higher radial growth inhibition than CNPs in all the tested concentrations. Both CNPs and CAgNCs were not only effective in reducing the fungal growth, but also caused morphological and ultrastructural changes in the pathogen, thereby suggesting its usage as an antifungal dispersion system to control F. oxysporum. Additionally, CNPs and CAgNCs therapy reduced the F. oxysporum infection in zebrafish. Data demonstrates biologically active CNPs and CAgNCs are promising antifungal agents against F. oxysporum. Copyright © 2017 Elsevier B.V. All rights reserved.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment.

PubMed

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M

2018-01-05

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag 2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514nm and the SERS spectra at 785 and 514nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag 2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag 2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 10 4 , was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes. Copyright © 2017 Elsevier B.V. All rights reserved.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment

NASA Astrophysics Data System (ADS)

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M.

2018-01-01

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514 nm and the SERS spectra at 785 and 514 nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785 nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514 nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 104, was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes.

Exciplex electroluminescence and photoluminescence spectra of the new organic materials based on zinc complexes of sulphanylamino-substituted ligands.

PubMed

Kaplunov, Mikhail G; Krasnikova, Svetlana S; Nikitenko, Sergey L; Sermakasheva, Natalia L; Yakushchenko, Igor K

2012-04-03

We have investigated the electroluminescence spectra of the electroluminescent devices based on the new zinc complexes of amino-substituted benzothiazoles and quinolines containing the C-N-M-N chains in their chelate cycles. The spectra exhibit strong exciplex bands in the green to yellow region 540 to 590 nm due to interaction of the excited states of zinc complexes and triaryl molecules of the hole-transporting layer. For some devices, the intrinsic luminescence band of 460 nm in the blue region is also observed along with the exciplex band giving rise to an almost white color of the device emission. The exciplex band can be eliminated if the material of the hole-transporting layer is not a triarylamine derivative. We have also found the exciplex emission in the photoluminescence spectra of the films containing blends of zinc complex and triphenylamine material.

Exciplex electroluminescence and photoluminescence spectra of the new organic materials based on zinc complexes of sulphanylamino-substituted ligands

PubMed Central

2012-01-01

We have investigated the electroluminescence spectra of the electroluminescent devices based on the new zinc complexes of amino-substituted benzothiazoles and quinolines containing the C-N-M-N chains in their chelate cycles. The spectra exhibit strong exciplex bands in the green to yellow region 540 to 590 nm due to interaction of the excited states of zinc complexes and triaryl molecules of the hole-transporting layer. For some devices, the intrinsic luminescence band of 460 nm in the blue region is also observed along with the exciplex band giving rise to an almost white color of the device emission. The exciplex band can be eliminated if the material of the hole-transporting layer is not a triarylamine derivative. We have also found the exciplex emission in the photoluminescence spectra of the films containing blends of zinc complex and triphenylamine material. PMID:22471942

Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

NASA Astrophysics Data System (ADS)

Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

2009-06-01

Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

Electron Spin Resonance Studies of Carbonic Anhydrase: Transition Metal Ions and Spin-Labeled Sulfonamides*

PubMed Central

Taylor, June S.; Mushak, Paul; Coleman, Joseph E.

1970-01-01

Electron spin resonance (esr) spectra of Cu(II) and Co(II) carbonic anhydrase, and a spin-labeled sulfonamide complex of the Zn(II) enzyme, are reported. The coordination geometry of Cu(II) bound in the enzyme appears to have approximately axial symmetry. Esr spectra of enzyme complexes with metal-binding anions also show axial symmetry and greater covalency, in the order ethoxzolamide < SH- < N3- ≤ CN-. Well-resolved superhyperfine structure in the spectrum of the cyanide complex suggests the presence of two, and probably three, equivalent nitrogen ligands from the protein. Esr spectra of the Co(II) enzyme and its complexes show two types of Co(II) environment, one typical of the native enzyme and the 1:1 CN- complex, and one typical of a 2:1 CN- complex. Co(II) in the 2:1 complex appears to be low-spin and probably has a coordination number of 5. Binding of a spin-labeled sulfonamide to the active center immobilizes the free radical. The similarity of the esr spectra of spin-labeled Zn(II) and Co(II) carbonic anhydrases suggests that the conformation at the active center is similar in the two metal derivatives. PMID:4320976

Spectral Studies of Iron Coordination in Hemeprotein Complexes

PubMed Central

Brill, Arthur S.; Sandberg, Howard E.

1968-01-01

In order to evaluate the feasibility of observing the spectral behavior of protein groups in the coordination sphere of the iron in hemeproteins, criteria are developed to determine whether or not the application of difference absorption spectroscopy to the study of complex formation will be successful. Absolute absorption spectra, 300-1100 mμ, from bacterial catalase complexes are displayed, and the infrared bands correlated with magnetic susceptibility values of similar complexes of other hemeproteins. Dissociation constants for the formation of cyanide and azide complexes of metmyoglobin, methemoglobin, bacterial catalase, and horseradish peroxidase are given. Difference spectra, 210-280 mμ, are displayed for cyanide and azide complexes of these hemeproteins. A band at 235-241 mμ is found in the difference spectra of all low-spin vs. high-spin complexes. The factors which favor the assignment of this band to a transition involving a histidine residue are presented. PMID:5699802

Single-molecule spectroscopy unmasks the lowest exciton state of the B850 assembly in LH2 from Rps. acidophila.

PubMed

Kunz, Ralf; Timpmann, Kõu; Southall, June; Cogdell, Richard J; Freiberg, Arvi; Köhler, Jürgen

2014-05-06

We have recorded fluorescence-excitation and emission spectra from single LH2 complexes from Rhodopseudomonas (Rps.) acidophila. Both types of spectra show strong temporal spectral fluctuations that can be visualized as spectral diffusion plots. Comparison of the excitation and emission spectra reveals that for most of the complexes the lowest exciton transition is not observable in the excitation spectra due to the cutoff of the detection filter characteristics. However, from the spectral diffusion plots we have the full spectral and temporal information at hand and can select those complexes for which the excitation spectra are complete. Correlating the red most spectral feature of the excitation spectrum with the blue most spectral feature of the emission spectrum allows an unambiguous assignment of the lowest exciton state. Hence, application of fluorescence-excitation and emission spectroscopy on the same individual LH2 complex allows us to decipher spectral subtleties that are usually hidden in traditional ensemble spectroscopy. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Single- and two-phase flow in microfluidic porous media analogs based on Voronoi tessellation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Mengjie; Xiao, Feng; Johnson-Paben, Rebecca

2012-01-01

The objective of this study was to create a microfluidic model of complex porous media for studying single and multiphase flows. Most experimental porous media models consist of periodic geometries that lend themselves to comparison with well-developed theoretical predictions. However, most real porous media such as geological formations and biological tissues contain a degree of randomness and complexity that is not adequately represented in periodic geometries. To design an experimental tool to study these complex geometries, we created microfluidic models of random homogeneous and heterogeneous networks based on Voronoi tessellations. These networks consisted of approximately 600 grains separated by amore » highly connected network of channels with an overall porosity of 0.11 0.20. We found that introducing heterogeneities in the form of large cavities within the network changed the permeability in a way that cannot be predicted by the classical porosity-permeability relationship known as the Kozeny equation. The values of permeability found in experiments were in excellent agreement with those calculated from three-dimensional lattice Boltzmann simulations. In two-phase flow experiments of oil displacement with water we found that the surface energy of channel walls determined the pattern of water invasion, while the network topology determined the residual oil saturation. These results suggest that complex network topologies lead to fluid flow behavior that is difficult to predict based solely on porosity. The microfluidic models developed in this study using a novel geometry generation algorithm based on Voronoi tessellation are a new experimental tool for studying fluid and solute transport problems within complex porous media.« less

Oral Delivery of Lipophilic Drugs: The Tradeoff between Solubility Increase and Permeability Decrease When Using Cyclodextrin-Based Formulations

PubMed Central

Beig, Avital; Agbaria, Riad; Dahan, Arik

2013-01-01

The purpose of this study was to investigate the impact of oral cyclodextrin-based formulation on both the apparent solubility and intestinal permeability of lipophilic drugs. The apparent solubility of the lipophilic drug dexamethasone was measured in the presence of various HPβCD levels. The drug’s permeability was measured in the absence vs. presence of HPβCD in the rat intestinal perfusion model, and across Caco-2 cell monolayers. The role of the unstirred water layer (UWL) in dexamethasone’s absorption was studied, and a simplified mass-transport analysis was developed to describe the solubility-permeability interplay. The PAMPA permeability of dexamethasone was measured in the presence of various HPβCD levels, and the correlation with the theoretical predictions was evaluated. While the solubility of dexamethasone was greatly enhanced by the presence of HPβCD (K1∶1 = 2311 M−1), all experimental models showed that the drug’s permeability was significantly reduced following the cyclodextrin complexation. The UWL was found to have no impact on the absorption of dexamethasone. A mass transport analysis was employed to describe the solubility-permeability interplay. The model enabled excellent quantitative prediction of dexamethasone’s permeability as a function of the HPβCD level. This work demonstrates that when using cyclodextrins in solubility-enabling formulations, a tradeoff exists between solubility increase and permeability decrease that must not be overlooked. This tradeoff was found to be independent of the unstirred water layer. The transport model presented here can aid in striking the appropriate solubility-permeability balance in order to achieve optimal overall absorption. PMID:23874557

Fractal Theory for Permeability Prediction, Venezuelan and USA Wells

NASA Astrophysics Data System (ADS)

Aldana, Milagrosa; Altamiranda, Dignorah; Cabrera, Ana

2014-05-01

Inferring petrophysical parameters such as permeability, porosity, water saturation, capillary pressure, etc, from the analysis of well logs or other available core data has always been of critical importance in the oil industry. Permeability in particular, which is considered to be a complex parameter, has been inferred using both empirical and theoretical techniques. The main goal of this work is to predict permeability values on different wells using Fractal Theory, based on a method proposed by Pape et al. (1999). This approach uses the relationship between permeability and the geometric form of the pore space of the rock. This method is based on the modified equation of Kozeny-Carman and a fractal pattern, which allows determining permeability as a function of the cementation exponent, porosity and the fractal dimension. Data from wells located in Venezuela and the United States of America are analyzed. Employing data of porosity and permeability obtained from core samples, and applying the Fractal Theory method, we calculated the prediction equations for each well. At the beginning, this was achieved by training with 50% of the data available for each well. Afterwards, these equations were tested inferring over 100% of the data to analyze possible trends in their distribution. This procedure gave excellent results in all the wells in spite of their geographic distance, generating permeability models with the potential to accurately predict permeability logs in the remaining parts of the well for which there are no core samples, using even porority logs. Additionally, empirical models were used to determine permeability and the results were compared with those obtained by applying the fractal method. The results indicated that, although there are empirical equations that give a proper adjustment, the prediction results obtained using fractal theory give a better fit to the core reference data.

Digital Rock Physics Aplications: Visualisation Complex Pore and Porosity-Permeability Estimations of the Porous Sandstone Reservoir

NASA Astrophysics Data System (ADS)

Handoyo; Fatkhan; Del, Fourier

2018-03-01

Reservoir rock containing oil and gas generally has high porosity and permeability. High porosity is expected to accommodate hydrocarbon fluid in large quantities and high permeability is associated with the rock’s ability to let hydrocarbon fluid flow optimally. Porosity and permeability measurement of a rock sample is usually performed in the laboratory. We estimate the porosity and permeability of sandstones digitally by using digital images from μCT-Scan. Advantages of the method are non-destructive and can be applied for small rock pieces also easily to construct the model. The porosity values are calculated by comparing the digital image of the pore volume to the total volume of the sandstones; while the permeability values are calculated using the Lattice Boltzmann calculations utilizing the nature of the law of conservation of mass and conservation of momentum of a particle. To determine variations of the porosity and permeability, the main sandstone samples with a dimension of 300 × 300 × 300 pixels are made into eight sub-cubes with a size of 150 × 150 × 150 pixels. Results of digital image modeling fluid flow velocity are visualized as normal velocity (streamline). Variations in value sandstone porosity vary between 0.30 to 0.38 and permeability variations in the range of 4000 mD to 6200 mD. The results of calculations show that the sandstone sample in this research is highly porous and permeable. The method combined with rock physics can be powerful tools for determining rock properties from small rock fragments.

Influence of cold isostatic pressing on the magnetic properties of Ni-Zn-Cu ferrite

NASA Astrophysics Data System (ADS)

Le, Trong Trung; Valdez-Nava, Zarel; Lebey, Thierry; Mazaleyrat, Frédéric

2018-04-01

In power electronics, there is the need to develop solutions to increase the power density of converters. Interleaved multicellular transformers allow interleaving many switching cells and, as a result, a possible increase in the power density. This converter is often composed of a magnetic core having the function of an intercell transformer (ICT) and, depending on the complexity of the designed architecture, its shape could be extremely complex. The switching frequencies (1-10 MHz) for the new wide band gap semiconductors (SiC, GaN) allow to interleave switching cell at higher frequencies than silicon-based semiconductors (<1 MHz). Intercell transformers must follow this increase in frequency times-fold the number of switching cells. Current applications for ICT transformers use Mn-Zn based materials, but their limit in frequency drive raises the need of higher frequency magnetic materials, such Ni-Zn ferrites. These materials can operate in medium and high power converters up to 10 MHz. We propose to use Ni0,30Zn0,57Cu0,15Fe2O4 ferrite and to compress it by cold isostatic pressing (CIP) into a a green ceramic block and to machine it to obtain the desired ICT of complex shape prior sintering. We compare the magnetic permeability spectra and hysteresis loops the CIP and uniaxially pressed ferrites. The effect of temperature and sintering time as well as high-pressure on properties will be presented in detail. The magnetic properties of the sintered cores are strongly dependent on the microstructure obtained.

Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

DTIC Science & Technology

2016-06-03

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited-State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited-state

An intelligent detecting system for permeability prediction of MBR.

PubMed

Han, Honggui; Zhang, Shuo; Qiao, Junfei; Wang, Xiaoshuang

2018-01-01

The membrane bioreactor (MBR) has been widely used to purify wastewater in wastewater treatment plants. However, a critical difficulty of the MBR is membrane fouling. To reduce membrane fouling, in this work, an intelligent detecting system is developed to evaluate the performance of MBR by predicting the membrane permeability. This intelligent detecting system consists of two main parts. First, a soft computing method, based on the partial least squares method and the recurrent fuzzy neural network, is designed to find the nonlinear relations between the membrane permeability and the other variables. Second, a complete new platform connecting the sensors and the software is built, in order to enable the intelligent detecting system to handle complex algorithms. Finally, the simulation and experimental results demonstrate the reliability and effectiveness of the proposed intelligent detecting system, underlying the potential of this system for the online membrane permeability for detecting membrane fouling of MBR.

Phase-sensitive terahertz spectroscopy with backward-wave oscillators in reflection mode.

PubMed

Pronin, A V; Goncharov, Yu G; Fischer, T; Wosnitza, J

2009-12-01

In this article we describe a method which allows accurate measurements of the complex reflection coefficient r = absolute value(r) x exp(i phi(R)) of a solid at frequencies of 1-50 cm(-1) (30 GHz-1.5 THz). Backward-wave oscillators are used as sources for monochromatic coherent radiation tunable in frequency. The amplitude of the complex reflection (the reflectivity) is measured in a standard way, while the phase shift, introduced by the reflection from the sample surface, is measured using a Michelson interferometer. This method is particular useful for nontransparent samples, where phase-sensitive transmission measurements are not possible. The method requires no Kramers-Kronig transformation in order to extract the sample's electrodynamic properties (such as the complex dielectric function or complex conductivity). Another area of application of this method is the study of magnetic materials with complex dynamic permeabilities different from unity at the measurement frequencies (for example, colossal-magnetoresistance materials and metamaterials). Measuring both the phase-sensitive transmission and the phase-sensitive reflection allows for a straightforward model-independent determination of the dielectric permittivity and magnetic permeability of such materials.

Phase-sensitive terahertz spectroscopy with backward-wave oscillators in reflection mode

NASA Astrophysics Data System (ADS)

Pronin, A. V.; Goncharov, Yu. G.; Fischer, T.; Wosnitza, J.

2009-12-01

In this article we describe a method which allows accurate measurements of the complex reflection coefficient r̂=|r̂|ṡexp(iφR) of a solid at frequencies of 1-50 cm-1 (30 GHz-1.5 THz). Backward-wave oscillators are used as sources for monochromatic coherent radiation tunable in frequency. The amplitude of the complex reflection (the reflectivity) is measured in a standard way, while the phase shift, introduced by the reflection from the sample surface, is measured using a Michelson interferometer. This method is particular useful for nontransparent samples, where phase-sensitive transmission measurements are not possible. The method requires no Kramers-Kronig transformation in order to extract the sample's electrodynamic properties (such as the complex dielectric function or complex conductivity). Another area of application of this method is the study of magnetic materials with complex dynamic permeabilities different from unity at the measurement frequencies (for example, colossal-magnetoresistance materials and metamaterials). Measuring both the phase-sensitive transmission and the phase-sensitive reflection allows for a straightforward model-independent determination of the dielectric permittivity and magnetic permeability of such materials.

Spectroscopic investigation on the energy transfer process in photosynthetic apparatus of cyanobacteria

NASA Astrophysics Data System (ADS)

Li, Ye; Wang, Bei; Ai, Xi-Cheng; Zhang, Xing-Kang; Zhao, Jing-Quan; Jiang, Li-Jin

2004-06-01

In this work, we employ cyanobacteria, Spirulina platensis, and separate their photosynthetic apparatus, phycobilisome (PBS), thylakoid membrane and phycobilisome-thylakoid membrane complex. The steady state absorption spectra, fluorescence spectra and corresponding deconvoluted spectra and picosecond time-resolved spectra are used to investigate the energy transfer process in phycobilisome-thylakoid membrane complex. The results on steady state spectra show chlorophylls of the photosystem II are able to transfer excitation energy to phycobilisome with Chl a molecules selectively excited. The decomposition of the steady state spectra further suggest the uphill energy transfer originate from chlorophylls of photosystem II to cores of phycobilisome, while rods and cores of phycobilisome cannot receive energy from the chlorophylls of photosystem I. The time constant for the back energy transfer process is 18 ps.

Mathematical modelling of the transport of hydroxypropyl-β-cyclodextrin inclusion complexes of ranitidine hydrochloride and furosemide loaded chitosan nanoparticles across a Caco-2 cell monolayer.

PubMed

Sadighi, Armin; Ostad, S N; Rezayat, S M; Foroutan, M; Faramarzi, M A; Dorkoosh, F A

2012-01-17

Chitosan nanoparticles (CS-NPs) have been used to enhance the permeability of furosemide and ranitidine hydrochloride (ranitidine HCl) which were selected as candidates for two different biopharmaceutical drug classes having low permeability across Caco-2 cell monolayers. Drugs loaded CS-NPs were prepared by ionic gelation of CS and pentasodium tripolyphosphate (TPP) which added to the drugs inclusion complexes with hydroxypropyl-β-cyclodextrin (HP-βCD). The stability constants for furosemide/HP-βCD and ranitidine HCl/HP-βCD were calculated as 335 M(-1) and 410 M(-1), whereas the association efficiencies (AE%) of the drugs/HP-βCD inclusion complexes with CS-NPs were determined to be 23.0 and 19.5%, respectively. Zetasizer and scanning electron microscopy (SEM) were used to characterise drugs/HP-βCD-NPs size and morphology. Transport of both nano and non-nano formulations of drugs/HP-βCD complexes across a Caco-2 cell monolayer was assessed and fitted to mathematical models. Furosemide/HP-βCD-NPs demonstrated transport kinetics best suited for the Higuchi model, whereas other drug formulations demonstrated power law transportation behaviour. Permeability experiments revealed that furosemide/HP-βCD and ranitidine HCl/HP-βCD nano formulations greatly induce the opening of tight junctions and enhance drug transition through Caco-2 monolayers. Copyright © 2011 Elsevier B.V. All rights reserved.

Proposed Reference Spectral Irradiance Standards to Improve Photovoltaic Concentrating System Design and Performance Evaluation: Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Myers, D. R.; Emery, K. E.; Gueymard, C.

2002-05-01

This conference paper describes the American Society for Testing and Materials (ASTM), the International Electrotechnical Commission (IEC), and the International Standards Organization (ISO) standard solar terrestrial spectra (ASTM G-159, IEC-904-3, ISO 9845-1) provide standard spectra for photovoltaic performance applications. Modern terrestrial spectral radiation models and knowledge of atmospheric physics are applied to develop suggested revisions to update the reference spectra. We use a moderately complex radiative transfer model (SMARTS2) to produce the revised spectra. SMARTS2 has been validated against the complex MODTRAN radiative transfer code and spectral measurements. The model is proposed as an adjunct standard to reproduce the referencemore » spectra. The proposed spectra represent typical clear sky spectral conditions associated with sites representing reasonable photovoltaic energy production and weathering and durability climates. The proposed spectra are under consideration by ASTM.« less

FT-Raman and FT-IR spectra of some heterobimetallic complexes with phenylcyclopentadienyl ligands

NASA Astrophysics Data System (ADS)

Nie, Chong-Shi; Guo, Jianhua; Qian, Changtao; Tan, Ying

1996-11-01

The FT-Raman and selected IR spectra of 14 heterobimetallic complexes of (CO) 3CrC 6H 5-C 5H 4M(CO) n(NO) mX (M = transition metal, X = other ligands) are reported. FT-Raman exhibits distinct strong characteristic bands of coordinated C 6H 5-C 5H 4 ligand ring deformation near 1540, 1490 and 1280 cm -1 and the coordinated phenyl ring deformation mode near 1000 cm -1, which are negligible in IR spectra. It is also easy to find the M-CO stretching and M-C-O bending as well as phenyl-M stretching bands in the FT-Raman spectra. The v(CO) IR absorptions in THF solution were reasonably assigned according to the local symmetry of the complexes.

Better Spectrometers, Beautiful Spectra and Confusion for All

NASA Technical Reports Server (NTRS)

Pearson, J. C.; Brauer, C. S.; Drouin, B. J.; Yu, S.

2009-01-01

The confluence of enormous improvements in submillimeter receivers and the development of powerful large scale observatories is about to force astrophysics and the sciences that support it to develop novel approaches for interpretation of data. The historical method of observing one or two lines and carefully analyzing them in the context of a simple model is now only applicable for distant objects where only a few lines are strong enough to be observable. Modern observatories collect many GHz of high signal-to-noise spectra in a single observation and in many cases, at sufficiently high spatial resolution to start resolving chemically distinct regions. The observatories planned for the near future and the inevitable upgrades of existing facilities will make large spectral data sets the rule rather than the exception in many areas of molecular astrophysics. The methodology and organization required to fully extract the available information and interpret these beautiful spectra represents a challenge to submillimeter astrophysics similar in magnitude to the last few decades of effort in improving receivers. The quality and abundance of spectra effectively prevents line-by-line analysis from being a time efficient proposition, however, global analysis of complex spectra is a science in its infancy. Spectroscopy at several other wavelengths have developed a number of techniques to analyze complex spectra, which can provide a great deal of guidance to the molecular astrophysics community on how to attack the complex spectrum problem. Ultimately, the challenge is one of organization, similar to building observatories, requiring teams of specialists combining their knowledge of dynamical, structural, chemical and radiative models with detailed knowledge in molecular physics and gas and grain surface chemistry to extract and exploit the enormous information content of complex spectra. This paper presents a spectroscopists view of the necessary elements in a tool for complex spectral analysis.

Spectroscopic studies on some fluorescent mixed-ligand titanium(IV) complexes.

PubMed

Baranwal, Balram Prasad; Singh, Alok Kumar; Varma, Anand

2011-12-15

A novel route to synthesize some titanium(IV) complexes containing acetylacetone, straight chain carboxylic acid and hydroxycarboxylic acid ligands has been investigated. Complexes with the general formula [Ti(acac)Cl(2-n)(OOCR*)(n)(OOCC(15)H(31))] (where Hacac=acetylacetone, R*COOH=hydroxycarboxylic acids and n=1 or 2) have been isolated and characterized. Molecular weight determinations indicated mononuclear nature of the complexes. LMCT bands were observed in the electronic spectra. Infrared spectra suggested bidentate nature of the ligands. Fluorescent behaviour of the complexes was noticed on the basis of fluorescence spectra. Powder XRD indicated them to be semi-crystalline having the crystallite size in 136-185 nm range. Transmission electron microscopy (TEM) indicated spherical particles of ~ 200 nm diameter. On the basis of physico-chemical studies, it is suggested that titanium is having coordination number 7 or 8 in these complexes. Copyright © 2011 Elsevier B.V. All rights reserved.

A fully-coupled discontinuous Galerkin spectral element method for two-phase flow in petroleum reservoirs

NASA Astrophysics Data System (ADS)

Taneja, Ankur; Higdon, Jonathan

2018-01-01

A high-order spectral element discontinuous Galerkin method is presented for simulating immiscible two-phase flow in petroleum reservoirs. The governing equations involve a coupled system of strongly nonlinear partial differential equations for the pressure and fluid saturation in the reservoir. A fully implicit method is used with a high-order accurate time integration using an implicit Rosenbrock method. Numerical tests give the first demonstration of high order hp spatial convergence results for multiphase flow in petroleum reservoirs with industry standard relative permeability models. High order convergence is shown formally for spectral elements with up to 8th order polynomials for both homogeneous and heterogeneous permeability fields. Numerical results are presented for multiphase fluid flow in heterogeneous reservoirs with complex geometric or geologic features using up to 11th order polynomials. Robust, stable simulations are presented for heterogeneous geologic features, including globally heterogeneous permeability fields, anisotropic permeability tensors, broad regions of low-permeability, high-permeability channels, thin shale barriers and thin high-permeability fractures. A major result of this paper is the demonstration that the resolution of the high order spectral element method may be exploited to achieve accurate results utilizing a simple cartesian mesh for non-conforming geological features. Eliminating the need to mesh to the boundaries of geological features greatly simplifies the workflow for petroleum engineers testing multiple scenarios in the face of uncertainty in the subsurface geology.

Large-scale model of flow in heterogeneous and hierarchical porous media

NASA Astrophysics Data System (ADS)

Chabanon, Morgan; Valdés-Parada, Francisco J.; Ochoa-Tapia, J. Alberto; Goyeau, Benoît

2017-11-01

Heterogeneous porous structures are very often encountered in natural environments, bioremediation processes among many others. Reliable models for momentum transport are crucial whenever mass transport or convective heat occurs in these systems. In this work, we derive a large-scale average model for incompressible single-phase flow in heterogeneous and hierarchical soil porous media composed of two distinct porous regions embedding a solid impermeable structure. The model, based on the local mechanical equilibrium assumption between the porous regions, results in a unique momentum transport equation where the global effective permeability naturally depends on the permeabilities at the intermediate mesoscopic scales and therefore includes the complex hierarchical structure of the soil. The associated closure problem is numerically solved for various configurations and properties of the heterogeneous medium. The results clearly show that the effective permeability increases with the volume fraction of the most permeable porous region. It is also shown that the effective permeability is sensitive to the dimensionality spatial arrangement of the porous regions and in particular depends on the contact between the impermeable solid and the two porous regions.

Characterizing flow in oil reservoir rock using SPH: absolute permeability

NASA Astrophysics Data System (ADS)

Holmes, David W.; Williams, John R.; Tilke, Peter; Leonardi, Christopher R.

2016-04-01

In this paper, a three-dimensional smooth particle hydrodynamics (SPH) simulator for modeling grain scale fluid flow in porous rock is presented. The versatility of the SPH method has driven its use in increasingly complex areas of flow analysis, including flows related to permeable rock for both groundwater and petroleum reservoir research. While previous approaches to such problems using SPH have involved the use of idealized pore geometries (cylinder/sphere packs etc), in this paper we detail the characterization of flow in models with geometries taken from 3D X-ray microtomographic imaging of actual porous rock; specifically 25.12 % porosity dolomite. This particular rock type has been well characterized experimentally and described in the literature, thus providing a practical `real world' means of verification of SPH that will be key to its acceptance by industry as a viable alternative to traditional reservoir modeling tools. The true advantages of SPH are realized when adding the complexity of multiple fluid phases, however, the accuracy of SPH for single phase flow is, as yet, under developed in the literature and will be the primary focus of this paper. Flow in reservoir rock will typically occur in the range of low Reynolds numbers, making the enforcement of no-slip boundary conditions an important factor in simulation. To this end, we detail the development of a new, robust, and numerically efficient method for implementing no-slip boundary conditions in SPH that can handle the degree of complexity of boundary surfaces, characteristic of an actual permeable rock sample. A study of the effect of particle density is carried out and simulation results for absolute permeability are presented and compared to those from experimentation showing good agreement and validating the method for such applications.

The absorption spectra of the complexes of uranium (VI) with some β-diketones

USGS Publications Warehouse

Feinstein, H.I.

1956-01-01

The absorption spectra of the complexes of uranium (VI) with four β-dike tones were determined under various conditions of pH, concentration of uranium, and alcohol concentration. Under optimum conditions, the maximum molar absorptivity (31,200) is obtained using 2-furoyltrifluoroacetone. This compares with about 4,000 and 19,000 for the thiocyanate and dibenzoylmethane complexes, respectively.

Localized Versus Distributed Deformation as a Control on the Evolution of Permeability in Anhydrite Rocks

NASA Astrophysics Data System (ADS)

Collettini, C.; de Paola, N.; Faulkner, D.

2007-12-01

We have taken an experimental approach to understand and quantify the deformation processes and fluid flow within anhydrite-bearing fault damage zones during the seismic cycle. Triaxial loading tests have been performed on borehole samples of anhydrites at room temperature, 100 MPa confining pressure (Pc), and range of pore fluid pressures (Pf). Permeability and porosity development was continuously measured throughout the deformation experiments. The tests were conducted on samples with different grain sizes (10 microns to 1 mm) that were cored in different directions relative to the macroscopic foliation. Static permeability measurements have been carried out to determine the permeability anisotropy and sensitivity of the permeability on the effective pressure (Pc - Pf). Our results show that the brittle-ductile transition occurs for effective pressures (Pe) between 20 to 40 MPa and is almost independent of fabric orientation and grain size. Brittle failure is localized along discrete fractures and is always associated with a sudden stress drop. Conversely, ductile failure occurs by distributed deformation along cataclastic bands. In this case no stress drop is observed. Static permeability measurements show increasing values of permeability for decreasing values of Pe, (k = 10E-20 - 10E-22 m2). During single cycle loading tests, the evolution of the permeability is controlled by the failure mode: permeability begins to increase significantly at 40% and 80% of the max load for samples displaying brittle and ductile behaviour, respectively. The permeability values, immediately prior to failure, are about three orders of magnitude higher than the initial values. Multiple cycling tests, within the ductile field, show that permeability starts increasing at only 40% and 30% of the max load during the second and third loading cycle, respectively. Our results show that the history of deformation and the mode of deformation can control the evolution of the permeability, and that they are more significant than other factors such as fabric and grain size. In natural environments, fluid pressure fluctuations, such as might be experienced during the seismic cycle, can promote a switch from localized (brittle behaviour) to more distributed (ductile behaviour) deformation, leading to complex permeability patterns.

Coupled Fracture and Flow in Shale in Hydraulic Fracturing

NASA Astrophysics Data System (ADS)

Carey, J. W.; Mori, H.; Viswanathan, H.

2014-12-01

Production of hydrocarbon from shale requires creation and maintenance of fracture permeability in an otherwise impermeable shale matrix. In this study, we use a combination of triaxial coreflood experiments and x-ray tomography characterization to investigate the fracture-permeability behavior of Utica shale at in situ reservoir conditions (25-50 oC and 35-120 bars). Initially impermeable shale core was placed between flat anvils (compression) or between split anvils (pure shear) and loaded until failure in the triaxial device. Permeability was monitored continuously during this process. Significant deformation (>1%) was required to generate a transmissive fracture system. Permeability generally peaked at the point of a distinct failure event and then dropped by a factor of 2-6 when the system returned to hydrostatic failure. Permeability was very small in compression experiments (< 1 mD), possibly because of limited fracture connectivity through the anvils. In pure share experiments, shale with bedding planes perpendicular to shear loading developed complex fracture networks with narrow apertures and peak permeability of 30 mD. Shale with bedding planes parallel to shear loading developed simple fractures with large apertures and a peak permeability as high as 1 D. Fracture systems held at static conditions for periods of several hours showed little change in effective permeability at hydrostatic conditions as high as 140 bars. However, permeability of fractured systems was a function of hydrostatic pressure, declining in a pseudo-linear, exponential fashion as pressure increased. We also observed that permeability decreased with increasing fluid flow rate indicating that flow did not follow Darcy's Law, possibly due to non-laminar flow conditions, and conformed to Forscheimer's law. The coupled deformation and flow behavior of Utica shale, particularly the large deformation required to initiate flow, indicates the probable importance of activation of existing fractures in hydraulic fracturing and that these fractures can have adequate permeability for the production of hydrocarbon.

Connexin Channel Permeability to Cytoplasmic Molecules

PubMed Central

Harris, Andrew L.

2007-01-01

Connexin channels are known to be permeable to a variety of cytoplasmic molecules. The first observation of second messenger junctional permeability, made ∼30 years ago, sparked broad interest in gap junction channels as mediators of intercellular molecular signaling. Since then, much has been learned about the diversity of connexin channels with regard to isoform diversity, tissue and developmental distribution, modes of channel regulation, assembly and expression, biochemical modification and permeability, all of which appear to be dynamically regulated. This information has expanded the potential roles of connexin channels in development, physiology and disease, and made their elucidation much more complex - 30 years ago such an orchestra of junctional dynamics was unanticipated. Only recently, however, have investigators been able to directly address, in this more complex framework, the key issue: What specific biological molecules, second messengers and others, are able to permeate the various types of connexin channels, and how well? An important related issue, given the ever-growing list of connexin-related pathologies, is how these permeabilities are altered by disease-causing connexin mutations. Together, many studies show that a variety of cytoplasmic molecules can permeate the different types of connexin channels. A few studies reveal differences in permeation by different molecules through a particular type of connexin channel, and differences in permeation by a particular molecule through different types of connexin channels. This article describes and evaluates the various methods used to obtain these data, presents an annotated compilation of the results, and discusses the findings in the context of what can be inferred about mechanism of selectivity and potential relevance to signaling. The data strongly suggest that highly specific interactions take place between connexin pores and specific biological molecular permeants, and that those interactions determine which cytoplasmic molecules can permeate and how well. At this time, the nature of those interactions is unclear. One hopes that with more detailed permeability and structural information, the specific molecular mechanisms of the selectivity can be elucidated. PMID:17470375

2D and 3D graphical representation of the propagation of electromagnetic waves at the interface with a material with general effective complex permittivity and permeability

NASA Astrophysics Data System (ADS)

Diaz, A.; Ramos, J. G.; Friedman, J. S.

2017-09-01

We developed a web-based instructional and research tool that demonstrates the behavior of electromagnetic waves as they propagate through a homogenous medium and through an interface where the second medium can be characterized by an effective complex permittivity and permeability. Either p- or s-polarization wave components can be chosen and the graphical interface includes 2D wave and 3D component representations. The program enables the study of continuity of electromagnetic components, critical angle, Brewster angle, absorption and amplification, behavior of light in sub-unity and negative-index materials, Poynting vector and phase velocity behavior, and positive and negative Goos- Hänchen shifts.

Control of the permeability of fractures in geothermal rocks

NASA Astrophysics Data System (ADS)

Faoro, Igor

This thesis comprises three journal articles that will be submitted for publication (Journal of Geophysical Research-Solid Earth). Their respective titles are: "Undrained through Drained Evolution of Permeability in Dual Permeability Media" by Igor Faoro, Derek Elsworth and Chris Marone, "Evolution of Stiffness and Permeability in Fractures Subject to Thermally-and Mechanically-Activated Dissolution" by Igor Faoro, Derek Elsworth Chris Marone; "Linking permeability and mechanical damage for basalt from Mt. Etna volcano (Italy)" by Igor Faoro, Sergio Vinciguerra, Chris Marone and Derek Elsworth. Undrained through Drained Evolution of Permeability in Dual Permeability Media: temporary permeability changes of fractured aquifers subject to earthquakes have been observed and recorded worldwide, but their comprehension still remains a complex issue. In this study we report on flow-through fracture experiments on cracked westerly cores that reproduce, at laboratory scale, those (steps like) permeability changes that have been recorded when earthquakes occur. In particular our experiments show that under specific test boundary conditions, rapid increments of pore pressure induce transient variations of flow rate of the fracture whose peak magnitudes decrease as the variations of the effective stresses increase. We identify that the observed hydraulic behavior of the fracture is due to two principal mechanisms of origin; respectively mechanical (shortening of core) and poro-elastic (radial diffusion of the pore fluid into the matrix of the sample) whose interaction cause respectively an instantaneous opening and then a progressive closure of the fracture. Evolution of Stiffness and Permeability in Fractures Subject to Thermally-and Mechanically-Activated Dissolution: we report the results of radial flow-through experiments conducted on heated samples of Westerly granite. These experiments are performed to examine the influence of thermally and mechanically activated dissolution on the mechanical (stiffness) and transport (stress-permeability) characteristics of fractures. The sample is thermally stressed to 80 °C and measurements of the constrained axial stress acting on the sample and of the flow rate of the fracture are recorded with time. Net efflux of dissolved mineral mass is also measured periodically to provide a record of rates of net mass removal. During the experiment the fracture permeability shows high sensitivity to the changing conditions of stress and temperature but no significant permanent variation of permeability have been recorded once the thermal cycle ends. Linking permeability and mechanical damage for basalt from Mt. Etna volcano (Italy): volcanic edifices, such as Mt. Etna volcano (Italy), are affected from repeated episodes of pressurization due to magma emplacement from deep reservoirs to shallow depths. This mechanism pressurizes the large aquifers within the edifice and increases the level of crack damage within the rocks of the edifice over extended periods of times. In order to improve our understanding of the complex coupling between circulating fluids and the development of crack damage we performed flow-through tests using cylindrical cores of Etna Basalt (Etna, Italy) cyclically loaded either by constant increments of the principal stress: sigma1 (deviatoric condition), or by increments of the effective confining pressure: sigma1 = sigma 2 = sigma3 (isostatic conditions). Under hydrostatic stresses, the permeability values of the intact sample decrease linearly with the increments of pressure and range between 5.2*10-17 m2 and 1.5*10-17m2. At deviatoric stresses (up to 60 MPa) the permeability from the initial value of 5*10-17 m2 slightly decays to the minimum value of 2*10 -17 m2 observed when the axial deviatoric stresses range between 40 MPa and 60 MPa. For higher deviatoric stresses, increases to 10-16 m2 are then observed up to the peak stress at 92 MPa. After failure the permeability persisted steady at the value of 8*10-16 m2 for the whole duration of the test, independently from the applied stress. We interpreted the decrease observed as due to the progressive closure of the voids space, as the axial load is incremented.

[Synthesis and study on the interaction of rare earth complexes of N', N-bis(2-pyridinecarboxamide)-1, 2-ethane with DNA].

PubMed

Lu, Xiao-Hong; Lin, Qiu-Yue; Hu, Rui-Ding; Liu, Wei-Dong; Feng, Jie

2007-06-01

Four rare earth complexes of N', N-bis(2-pyridinecarboxamide)-1, 2-ethane were synthesized and characterized by elemental analysis, conductivity measurement, thermal studies, IR and electronic spectra. The composition of the four complexes is [Ln(H2L)(NO3)2](NO3) x 3H2O (Ln=Sm, Eu, Gd, Tb). Results of spectral measurements indicate that the oxygen of carbonyl and the nitrogen of pyridyl coordinate with Ln(III) respectively, and the NO3- shows bidentate coordination. So the four complexes are 1 : 1 chelated complexes. The interaction between [Sm(H2L) (NO3)2](NO3) x 3H2O and DNA was studied by employing UV-Visible (UV-Vis) spectra, fluorescence spectra and SERS spectra. Experimental results show that with the incremental addition of DNA, the bands at 265 nm show hypochromism accompanied by a small red shift and the binding constant Kb Obtained is 1.24 x 10(5). Meanwhile fluorescence spectra show that the addition of [Sm(H2L) (NO3)2] (NO3) x 3H2O to DNA pretreated with EB causes an appreciable reduction in fluorescence intensity, indicating that the complex competes with ethidium bromide in binding to DNA, and free ethidium bromide increases. The addition of DNA causes the SERS signals of the complex to weaken and the band at 1 282 cm(-1) to disappear, which suggests that the planar pyridine molecule of the ligand may partly be inserted into the double-stranded helix plane in DNA, making pi electronic density of aromatic rings in complex change. The above phenomena indicate that [Sm(H2L) (NO3)] (NO3) x 3H2O interacts intensively with DNA.

Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alperovich, Igor; Smolentsev, Grigory; Moonshiram, Dooshaye

2015-09-17

L{sub 2,3}-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[Ru{sub 2}{sup III}O(H{sub 2}O){sub 2}(bpy){sub 4}]{sup 4+} water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex show considerably different splitting of the Ru L{sub 2,3} absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L{sub 2,3}-edges XASmore » spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L{sub 2,3}-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals.« less

A novel matrix dispersion based on phospholipid complex for improving oral bioavailability of baicalein: preparation, in vitro and in vivo evaluations.

PubMed

Zhou, Yang; Dong, Wujun; Ye, Jun; Hao, Huazhen; Zhou, Junzhuo; Wang, Renyun; Liu, Yuling

2017-11-01

Phospholipid complex is one of the most successful approaches for enhancing oral bioavailability of poorly absorbed plant constituents. But the sticky property of phospholipids results in an unsatisfactory dissolution of drugs. In this study, a matrix dispersion of baicalein based on phospholipid complex (BaPC-MD) was first prepared by a discontinuous solvent evaporation method, in which polyvinylpyrrolidone-K30 (PVP-K30) was employed for improving the dispersibility of baicalein phospholipid complex (BaPC) and increasing dissolution of baicalein. The combination ratio of baicalein and phospholipids in BaPC-MD was 99.39% and baicalein was still in a complete complex state with phospholipid in BaPC-MD. Differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier Transform Infrared (FTIR) analyzes demonstrated that baicalein was fully transformed to an amorphous state in BaPC-MD and phospholipid complex formed. The water-solubility and n-octanol solubility of baicalein in BaPC-MD significantly increased compared with those of pure baicalein. Compared with baicalein and BaPC, the cumulative dissolution of BaPC-MD at 120 min increased 2.77- and 1.23-fold, respectively. In vitro permeability study in Caco-2 cells indicated that the permeability of BaPC-MD was remarkably higher than those of baicalein and BaPC. Pharmacokinetic study showed that the average C max of BaPC-MD was significantly increased compared to baicalein and BaPC. AUC 0-14 h of BaPC-MD was 5.01- and 1.91-fold of baicalein and BaPC, respectively. The novel BaPC-MD significantly enhanced the oral bioavailability of baicalein by improving the dissolution and permeability of baicalein without destroying the complexation state of baicalein and phospholipids. The current drug delivery system provided an optimal strategy to significantly enhance oral bioavailability for poorly water-soluble drugs.

Clay and Shale Permeability at Lab to Regional Scale

NASA Astrophysics Data System (ADS)

Neuzil, C.

2017-12-01

Because clays, shales, and other clay-rich media tend to be only poorly permeable, and are laterally extensive and voluminous, they play key roles in problems as diverse as groundwater supply, waste confinement, exploitation of conventional and unconventional oil and gas, and deformation and failure in the crust. Clay and shale permeability is a crucial but often highly uncertain analysis parameter; direct measurements are challenging, error-prone, and - perhaps most importantly - provide information only at quite small scales. Fortunately, there has been a dramatic increase in clay and shale permeability data from sources that include scientific ocean drilling, nuclear waste repository research, groundwater resource studies, liquid waste and CO2 sequestration, and oil and gas research. The effect of lithology as well as porosity on matrix permeability can now be examined and permeability - scale relations are becoming discernable. A significant number of large-scale permeability estimates have been obtained by inverse methods that essentially treat large-scale flow systems as natural experiments. They suggest surprisingly little scale-dependence in clay and shale permeabilities in subsiding basins and accretionary complexes. Stable continental settings present a different picture; as depths increase beyond 1 km, scale dependence mostly disappears even over the largest areas. At depths less than 1 km, secondary permeability is not always present over areas of 1 - 10 km2, but always evident for areas in excess of about 103 km2. Transmissive fractures have been observed in very low porosity (< 0.03) shales in these settings, but the cause of scale dependence in other cases is unclear; it may reflect time-dependent, or "dynamic" conditions, including irreversible and ongoing changes imposed on subsurface flow systems by human activities.

Dopamine enhances duodenal epithelial permeability via the dopamine D5 receptor in rodent.

PubMed

Feng, X-Y; Zhang, D-N; Wang, Y-A; Fan, R-F; Hong, F; Zhang, Y; Li, Y; Zhu, J-X

2017-05-01

The intestinal barrier is made up of epithelial cells and intercellular junctional complexes to regulate epithelial ion transport and permeability. Dopamine (DA) is able to promote duodenal epithelial ion transport through D1-like receptors, which includes subtypes of D 1 (D 1 R) and D 5 (D 5 R), but whether D1-like receptors influence the duodenal permeability is unclear. FITC-dextran permeability, short-circuit current (I SC ), Western blot, immunohistochemistry and ELISA were used in human D 5 R transgenic mice and hyperendogenous enteric DA (HEnD) rats in this study. Dopamine induced a downward deflection in I SC and an increase in FITC-dextran permeability of control rat duodenum, which were inhibited by the D1-like receptor antagonist, SCH-23390. However, DA decreased duodenal transepithelial resistance (TER), an effect also reversed by SCH-23390. A strong immunofluorescence signal for D 5 R, but not D 1 R, was observed in the duodenum of control rat. In human D 5 R knock-in transgenic mice, duodenal mucosa displayed an increased basal I SC with high FITC-dextran permeability and decreased TER with a lowered expression of tight junction proteins, suggesting attenuated duodenal barrier function in these transgenic mice. D 5 R knock-down transgenic mice manifested a decreased basal I SC with lowered FITC-dextran permeability. Moreover, an increased FITC-dextran permeability combined with decreased TER and tight junction protein expression in duodenal mucosa were also observed in HEnD rats. This study demonstrates, for the first time, that DA enhances duodenal permeability of control rat via D 5 R, which provides new experimental and theoretical evidence for the influence of DA on duodenal epithelial barrier function. © 2016 Scandinavian Physiological Society. Published by John Wiley & Sons Ltd.

Impact of Three-Phase Relative Permeability and Hysteresis Models on Forecasts of Storage Associated With CO2-EOR

NASA Astrophysics Data System (ADS)

Jia, Wei; McPherson, Brian; Pan, Feng; Dai, Zhenxue; Moodie, Nathan; Xiao, Ting

2018-02-01

Geological CO2 sequestration in conjunction with enhanced oil recovery (CO2-EOR) includes complex multiphase flow processes compared to CO2 storage in deep saline aquifers. Two of the most important factors affecting multiphase flow in CO2-EOR are three-phase relative permeability and associated hysteresis, both of which are difficult to measure and are usually represented by numerical interpolation models. The purpose of this study is to improve understanding of (1) the relative impacts of different three-phase relative permeability models and hysteresis models on CO2 trapping mechanisms, and (2) uncertainty associated with these two factors. Four different three-phase relative permeability models and three hysteresis models were applied to simulations of an active CO2-EOR site, the SACROC unit located in western Texas. To eliminate possible bias of deterministic parameters, we utilized a sequential Gaussian simulation technique to generate 50 realizations to describe heterogeneity of porosity and permeability, based on data obtained from well logs and seismic survey. Simulation results of forecasted CO2 storage suggested that (1) the choice of three-phase relative permeability model and hysteresis model led to noticeable impacts on forecasted CO2 sequestration capacity; (2) impacts of three-phase relative permeability models and hysteresis models on CO2 trapping are small during the CO2-EOR injection period, and increase during the post-EOR CO2 injection period; (3) the specific choice of hysteresis model is more important relative to the choice of three-phase relative permeability model; and (4) using the recommended three-phase WAG (Water-Alternating-Gas) hysteresis model may increase the impact of three-phase relative permeability models and uncertainty due to heterogeneity.

Increased permeability to polyethylene glycol 4000 in rabbits with experimental colitis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seidman, E.G.; Hanson, D.G.; Walker, W.A.

1986-01-01

Little information is available regarding colonic permeability to macromolecules in health or disease states. In vivo permeability of rabbit colon to (/sup 14/C)polyethylene glycol 4000 (/sup 14/C-PEG) was examined in the presence of immune complex-mediated experimental colitis and compared with that of partially treated (control) and normal rabbits. Permeability was assessed by urinary /sup 14/C-PEG excretion after intrarectal administration of 0.1 mM solution of /sup 14/C-PEG (1 ml/kg, 7.5 X 10(6) cpm/ml). Experimental colitis greatly increased colonic permeability (p less than 0.001 in two-way analysis of variance) compared with control and normal groups (2.06% +/- 0.19%, 0.14% +/- 0.04%, andmore » 0.01% +/- 0.004%, respectively, of rectally administered counts). Gel diffusion chromatography showed that absorbed /sup 14/C-PEG was excreted into urine unchanged, demonstrating its applicability as an inert, nonmetabolizable macromolecular probe. Urinary clearance after mesenteric vein administration of /sup 14/C-PEG was similar in normal animals and animals with colitis, implicating colonic absorption as the source of the group differences. Postmortem histology confirmed the acute colitis lesions in the experimental group. These findings support the hypothesis that nonspecific colonic inflammation is associated with significant alterations of mucosal permeability.« less

Multiparameter Analysis of Gas Transport Phenomena in Shale Gas Reservoirs: Apparent Permeability Characterization.

PubMed

Shen, Yinghao; Pang, Yu; Shen, Ziqi; Tian, Yuanyuan; Ge, Hongkui

2018-02-08

The large amount of nanoscale pores in shale results in the inability to apply Darcy's law. Moreover, the gas adsorption of shale increases the complexity of pore size characterization and thus decreases the accuracy of flow regime estimation. In this study, an apparent permeability model, which describes the adsorptive gas flow behavior in shale by considering the effects of gas adsorption, stress dependence, and non-Darcy flow, is proposed. The pore size distribution, methane adsorption capacity, pore compressibility, and matrix permeability of the Barnett and Eagle Ford shales are measured in the laboratory to determine the critical parameters of gas transport phenomena. The slip coefficients, tortuosity, and surface diffusivity are predicted via the regression analysis of the permeability data. The results indicate that the apparent permeability model, which considers second-order gas slippage, Knudsen diffusion, and surface diffusion, could describe the gas flow behavior in the transition flow regime for nanoporous shale. Second-order gas slippage and surface diffusion play key roles in the gas flow in nanopores for Knudsen numbers ranging from 0.18 to 0.5. Therefore, the gas adsorption and non-Darcy flow effects, which involve gas slippage, Knudsen diffusion, and surface diffusion, are indispensable parameters of the permeability model for shale.

Individual Component Map of Rotatory Strength (ICM-RS) and Rotatory Strength Density (RSD) plots as analysis tools of circular dicroism spectra of complex systems.

PubMed

Chang, Le; Baseggio, Oscar; Sementa, Luca; Cheng, Daojian; Fronzoni, Giovanna; Toffoli, Daniele; Aprà, Edoardo; Stener, Mauro; Fortunelli, Alessandro

2018-06-13

We introduce Individual Component Maps of Rotatory Strength (ICM-RS) and Rotatory Strength Density (RSD) plots as analysis tools of chiro-optical linear response spectra deriving from time-dependent density functional theory (TDDFT) simulations. ICM-RS and RSD allow one to visualize the origin of chiro-optical response in momentum or real space, including signed contributions and therefore highlighting cancellation terms that are ubiquitous in chirality phenomena, and should be especially useful in analyzing the spectra of complex systems. As test cases, we use ICM-RS and RSD to analyze circular dichroism spectra of selected (Ag-Au)30(SR)18 monolayer-protected metal nanoclusters, showing the potential of the proposed tools to derive insight and understanding, and eventually rational design, in chiro-optical studies of complex systems.

Preservation of samples for dissolved mercury

USGS Publications Warehouse

Hamlin, S.N.

1989-01-01

Water samples for dissolved mercury requires special treatment because of the high chemical mobility and volatility of this element. Widespread use of mercury and its compounds has provided many avenues for contamination of water. Two laboratory tests were done to determine the relative permeabilities of glass and plastic sample bottles to mercury vapor. Plastic containers were confirmed to be quite permeable to airborne mercury, glass containers were virtually impermeable. Methods of preservation include the use of various combinations of acids, oxidants, and complexing agents. The combination of nitric acid and potassium dichromate successfully preserved mercury in a large variety of concentrations and dissolved forms. Because this acid-oxidant preservative acts as a sink for airborne mercury and plastic containers are permeable to mercury vapor, glass bottles are preferred for sample collection. To maintain a healthy work environment and minimize the potential for contamination of water samples, mercury and its compounds are isolated from the atmosphere while in storage. Concurrently, a program to monitor environmental levels of mercury vapor in areas of potential contamination is needed to define the extent of mercury contamination and to assess the effectiveness of mercury clean-up procedures.Water samples for dissolved mercury require special treatment because of the high chemical mobility and volatility of this element. Widespread use of mercury and its compounds has provided many avenues for contamination of water. Two laboratory tests were done to determine the relative permeabilities of glass and plastic sample bottles to mercury vapor. Plastic containers were confirmed to be quite permeable to airborne mercury, glass containers were virtually impermeable. Methods of preservation include the use of various combinations of acids, oxidants, and complexing agents. The combination of nitric acid and potassium dichromate successfully preserved mercury in a large variety of concentrations and dissolved forms.

Water permeability of spider dragline silk.

PubMed

Li, Xiang; Eles, Philip T; Michal, Carl A

2009-05-11

The water permeability of spider dragline silk was studied by measuring changes in amide deuteration of D(2)O-soaked silk with solid-state NMR. (13)C-D rotational-echo double-resonance (REDOR) NMR experiments showed that chemical exchange of amide hydrogen occurs in a large fraction of amino acids, including over 50% of alanine residues, which are known to exist predominantly in beta-sheet crystallites. This suggests that a substantial fraction of the crystalline regions are permeable to water, at least on the time scale of hours, implying that they are more dynamic, and therefore susceptible to chemical exchange with water, than previously thought. Wideline deuterium NMR spectra of dried D(2)O-soaked silk showed a combination of quadrupolar broadened and motionally averaged isotropic components whose intensities change on the time scale of hours. These results are interpreted in terms of chemical exchange between deuterium on the protein backbone, residual water within the silk, and water vapor in the ambient atmosphere. A simple compartmental model fits the results well and yields rate constants for the exchange processes. The model requires the inclusion of a compartment that does not undergo exchange. This compartment, likely related to the crystalline region, is interesting because it is accessible to water in wet silk, but impervious to any remaining free water when the silk is dried.

Percutaneous absorption of sunscreen agents from liquid paraffin: self-association of octyl salicylate and effects on skin flux.

PubMed

Jiang, R; Roberts, M S; Prankerd, R J; Benson, H A

1997-07-01

This study provides an investigation of the availability of octyl salicylate (OS), a common sunscreen agent, from liquid paraffin and the effect of OS on skin permeability. A model membrane system to isolate the vehicle effect from membrane permeability has been developed. Partitioning of OS between liquid paraffin and aqueous receptor phases was conducted. Partition coefficients increased with increase in OS concentration. A range of OS concentrations in liquid paraffin was diffused across human epidermis and synthetic membranes into 4% bovine serum albumin in phosphate-buffered saline and 50% ethanol. Absorption profiles of OS obtained from silicone and low-density polyethylene (LDPE) membranes were similar to each other but higher than for the high-density polyethylene [HDPE (3 times)] membrane and human epidermis (15 times). The steady state fluxes and apparent permeability coefficients (Kp') obtained from the diffusion studies showed the same trends with all membranes, except for the HDPE membrane which showed greater increase in flux and Kp' at concentrations above 30%. IR spectra showed that several bands of OS were shifted with concentrations, and the molecular models further suggested that the main contribution to the self-association is from non-1,4 van der Waals interactions.

The interaction of nifedipine with selected cyclodextrins and the subsequent solubility-permeability trade-off.

PubMed

Beig, Avital; Miller, Jonathan M; Dahan, Arik

2013-11-01

The purpose of this study was to investigate the interaction of 2-hydroxypropyl-β-cyclodextrin (HPβCD) and 2,6-dimethyl-β-cyclodextrin (DMβCD) with the lipophilic drug nifedipine and to investigate the subsequent solubility-permeability interplay. Solubility curves of nifedipine with HPβCD and DMβCD in MES buffer were evaluated using phase solubility methods. Then, the apparent permeability of nifedipine was investigated as a function of increasing HPβCD/DMβCD concentration in the hexadecane-based PAMPA model. The interaction with nifedipine was CD dependent; significantly higher stability constant was obtained for DMβCD in comparison with HPβCD. Moreover, nifedipine displays different type of interaction with these CDs; a 1:1 stoichiometric inclusion complex was apparent with HPβCD, while 1:2 stoichiometry was apparent for DMβCD. In all cases, decreased apparent intestinal permeability of nifedipine as a function of increasing CD level and nifedipine apparent solubility was obtained. A quasi-equilibrium mass transport analysis was developed to explain this solubility-permeability interplay; the model enabled excellent quantitative prediction of nifedipine's permeability as a function of CD concentrations. This work demonstrates that when using CDs in solubility-enabling formulations, a trade-off exists between solubility increase and permeability decrease that must not be overlooked. This trade-off was found to be independent of the type of CD-drug interaction. The transport model presented here can aid in striking the appropriate solubility-permeability balance in order to achieve optimal overall absorption. Copyright © 2013 Elsevier B.V. All rights reserved.

Ligand field photofragmentation spectroscopy of [Ag(L)N]2+ complexes in the gas phase: experiment and theory.

PubMed

Guan, Jingang; Puskar, Ljiljana; Esplugas, Ricardo O; Cox, Hazel; Stace, Anthony J

2007-08-14

Experiments have been undertaken to record photofragmentation spectra from a series of [Ag(L)N]2+ complexes in the gas phase. Spectra have been obtained for silver(II) complexed with the ligands (L): acetone, 2-pentanone, methyl-vinyl ketone, pyridine, and 4-methyl pyridine (4-picoline) with N in the range of 4-7. A second series of experiments using 1,1,1,3-fluoroacetone, acetonitrile, and CO2 as ligands failed to show any evidence of photofragmentation. Interpretation of the experimental data has come from time-dependent density functional theory (TDDFT), which very successfully accounts for trends in the spectra in terms of subtle differences in the properties of the ligands. Taking a sample of three ligands, acetone, pyridine, and acetonitrile, the calculations show all the spectral transitions to involve ligand-to-metal charge transfer, and that wavelength differences (or lack of spectra) arise from small changes in the energies of the molecular orbitals concerned. The calculations account for an absence in the spectra of any effects due to Jahn-Teller distortion, and they also reveal structural differences between complexes where the coordinating atom is either oxygen or nitrogen that have implications for the stability of silver(II) compounds. Where possible, comparisons have also been made with the physical properties of condensed phase silver(II) complexes.

Using artificial intelligence to predict permeability from petrographic data

NASA Astrophysics Data System (ADS)

Ali, Maqsood; Chawathé, Adwait

2000-10-01

Petrographic data collected during thin section analysis can be invaluable for understanding the factors that control permeability distribution. Reliable prediction of permeability is important for reservoir characterization. The petrographic elements (mineralogy, porosity types, cements and clays, and pore morphology) interact with each other uniquely to generate a specific permeability distribution. It is difficult to quantify accurately this interaction and its consequent effect on permeability, emphasizing the non-linear nature of the process. To capture these non-linear interactions, neural networks were used to predict permeability from petrographic data. The neural net was used as a multivariate correlative tool because of its ability to learn the non-linear relationships between multiple input and output variables. The study was conducted on the upper Queen formation called the Shattuck Member (Permian age). The Shattuck Member is composed of very fine-grained arkosic sandstone. The core samples were available from the Sulimar Queen and South Lucky Lake fields located in Chaves County, New Mexico. Nineteen petrographic elements were collected for each permeability value using a combined minipermeameter-petrographic technique. In order to reduce noise and overfitting the permeability model, these petrographic elements were screened, and their control (ranking) with respect to permeability was determined using fuzzy logic. Since the fuzzy logic algorithm provides unbiased ranking, it was used to reduce the dimensionality of the input variables. Based on the fuzzy logic ranking, only the most influential petrographic elements were selected as inputs for permeability prediction. The neural net was trained and tested using data from Well 1-16 in the Sulimar Queen field. Relying on the ranking obtained from the fuzzy logic analysis, the net was trained using the most influential three, five, and ten petrographic elements. A fast algorithm (the scaled conjugate gradient method) was used to optimize the network weight matrix. The net was then successfully used to predict the permeability in the nearby South Lucky Lake field, also in the Shattuck Member. This study underscored various important aspects of using neural networks as non-linear estimators. The neural network learnt the complex relationships between petrographic control and permeability. By predicting permeability in a remotely-located, yet geologically similar field, the generalizing capability of the neural network was also demonstrated. In old fields, where conventional petrographic analysis was routine, this technique may be used to supplement core permeability estimates.

Ultra-high resistive and anisotropic CoPd-CaF2 nanogranular soft magnetic films prepared by tandem-sputtering deposition

NASA Astrophysics Data System (ADS)

Naoe, Masayuki; Kobayashi, Nobukiyo; Ohnuma, Shigehiro; Iwasa, Tadayoshi; Arai, Ken-Ichi; Masumoto, Hiroshi

2015-10-01

Ultra-high resistive and anisotropic soft magnetic films for gigahertz applications are desirable to demonstrate the really practical films. Here we present a study of novel nanogranular films fabricated by tandem-sputtering deposition. Their electromagnetic properties and nanostructure have also been discussed. These films consisted of nanocrystallized CoPd alloy-granules and CaF2 matrix, and a specimen having a composition of (Co0.69Pd0.31)52-(Ca0.31F0.69)48 exhibited distinct in-plane uniaxial anisotropy after uniaxial field annealing with granule growth. Its complex permeability spectra have a ferromagnetic resonance frequency extending to the Super-High-Frequency band due to its higher anisotropy field, and its frequency response was quite well reproduced by a numerical calculation based on the Landau-Lifshitz-Gilbert equation. Furthermore, it was clarified that the CaF2-based nanogranular film exhibits a hundredfold higher electrical resistivity than conventional oxide or nitride-based films. Higher resistivity enables the film thickness to achieve a margin exceeding threefold against eddy current loss. The greater resistivity of nanogranular films is attributed to the wide energy bandgap and superior crystallinity of CaF2 matrix.

Robust computation of dipole electromagnetic fields in arbitrarily anisotropic, planar-stratified environments.

PubMed

Sainath, Kamalesh; Teixeira, Fernando L; Donderici, Burkay

2014-01-01

We develop a general-purpose formulation, based on two-dimensional spectral integrals, for computing electromagnetic fields produced by arbitrarily oriented dipoles in planar-stratified environments, where each layer may exhibit arbitrary and independent anisotropy in both its (complex) permittivity and permeability tensors. Among the salient features of our formulation are (i) computation of eigenmodes (characteristic plane waves) supported in arbitrarily anisotropic media in a numerically robust fashion, (ii) implementation of an hp-adaptive refinement for the numerical integration to evaluate the radiation and weakly evanescent spectra contributions, and (iii) development of an adaptive extension of an integral convergence acceleration technique to compute the strongly evanescent spectrum contribution. While other semianalytic techniques exist to solve this problem, none have full applicability to media exhibiting arbitrary double anisotropies in each layer, where one must account for the whole range of possible phenomena (e.g., mode coupling at interfaces and nonreciprocal mode propagation). Brute-force numerical methods can tackle this problem but only at a much higher computational cost. The present formulation provides an efficient and robust technique for field computation in arbitrary planar-stratified environments. We demonstrate the formulation for a number of problems related to geophysical exploration.

Rapid one-step whole blood C-reactive protein magnetic permeability immunoassay with monoclonal antibody conjugated nanoparticles as superparamagnetic labels and enhanced sedimentation.

PubMed

Ibraimi, Filiz; Kriz, Dario; Lu, Min; Hansson, Lars-Olof; Kriz, Kirstin

2006-02-01

A rapid (5.5 min) one-step whole blood C-reactive protein (CRP) magnetic permeability immunoassay utilizing monoclonal antibody conjugated dextran iron oxide nanoparticles (70 nm) as superparamagnetic labels and mixed fractions (1:1 ratio of 15-40 and 60 microm) of polyclonal anti-CRP conjugated silica microparticles for enhanced sedimentation is described. In this one-step assay procedure, a whole blood sample (4 microl) is applied to an assay glass vial, containing both antibody conjugates, and mixed for 30 s. The target analyte, CRP, forms a sandwich complex between the conjugated nanoparticles and microparticles, and, subsequently, the complex sediments under normal gravitation within 5 min to the bottom of the vial. The magnetic permeability increase of the sediment due to the presence of the complexed superparamagnetic nanoparticles is determined using an inductance-based transducer. Assayed patient whole blood samples were compared with the Abbott Diagnostics Architect reference method. A strong linear correlation was observed for the CRP concentration range 0-260 mg/l in whole blood (y=1.001x+0.42, R2=0.982, n=50). The CRP assay presented showed a limit of detection of 3 mg/l and a total imprecision (coefficient of variation) of 10.5%. On the basis of our observations, we propose a rapid, one-step, CRP assay for near-patient testing.

Infrared spectra of some acetone—magnesium adducts

NASA Astrophysics Data System (ADS)

Hisatsune, I. C.

Co-deposition of atomic magnesium with excess acetone at liquid-nitrogen temperature produces an unstable charge-transfer complex with a characteristic carbonyl infrared band at 1595 cm -1 and stable acetone adducts in which the metal atom bridges the carbonyl bond (π-complex) or coordinates to the oxygen atom (σ-complex). Infrared spectra of these complexes with (CH 3) 2CO and (CD 3) 2CO have been obtained. Corroborations for these adducts were obtained from infrared studies of acetone matrices with atomic copper and acetaldehyde matrices with atomic magnesium and with atomic copper. Infrared spectra of an acetone adduct and a dimethyl ether adduct of the Grignard reagent CH 3MgI have also been obtained. Hydrolysis of a σ-adduct gives acetone but isopropyl alcohol is obtained from hydrolysis of the π-adduct.

A Mathematical Motivation for Complex-Valued Convolutional Networks.

PubMed

Tygert, Mark; Bruna, Joan; Chintala, Soumith; LeCun, Yann; Piantino, Serkan; Szlam, Arthur

2016-05-01

A complex-valued convolutional network (convnet) implements the repeated application of the following composition of three operations, recursively applying the composition to an input vector of nonnegative real numbers: (1) convolution with complex-valued vectors, followed by (2) taking the absolute value of every entry of the resulting vectors, followed by (3) local averaging. For processing real-valued random vectors, complex-valued convnets can be viewed as data-driven multiscale windowed power spectra, data-driven multiscale windowed absolute spectra, data-driven multiwavelet absolute values, or (in their most general configuration) data-driven nonlinear multiwavelet packets. Indeed, complex-valued convnets can calculate multiscale windowed spectra when the convnet filters are windowed complex-valued exponentials. Standard real-valued convnets, using rectified linear units (ReLUs), sigmoidal (e.g., logistic or tanh) nonlinearities, or max pooling, for example, do not obviously exhibit the same exact correspondence with data-driven wavelets (whereas for complex-valued convnets, the correspondence is much more than just a vague analogy). Courtesy of the exact correspondence, the remarkably rich and rigorous body of mathematical analysis for wavelets applies directly to (complex-valued) convnets.

A smart membrane based on an antigen-responsive hydrogel.

PubMed

Zhang, Rongsheng; Bowyer, Adrian; Eisenthal, Robert; Hubble, John

2007-07-01

Hydrogel membranes have been fabricated that incorporate antibody/antigen moieties. The permeability of large solutes through these membranes is dependent on the presence of soluble antigen that can compete with the internal interactions between antibody and antigen leading to an increase in gel mesh size. Specifically, the membrane's structure is based on a dextran backbone grafted with a fluorescein isothiocyanate (FITC) antigen and a sheep anti-FITC IgG antibody. The backbone is covalently cross-linked by conjugated divinyl sulfone (DVS) groups. The gel structure is additionally stabilized by affinity crosslinks formed by biospecific interactions between the bound IgG and FITC. FTIR spectra of the gel are consistent with formation of covalent bonds between cysteine groups in the IgG and DVS groups in the dextran. Results obtained using isothermal titration calorimetry (ITC) confirmed the competitive interaction binding between IgG-FITC-dextran and free sodium fluorescein at pH 5.0. Scanning electron microscopy (SEM) of samples prepared using cryofixation and cryofracturing techniques showed that observed changes in permeability correlate with free fluorescein-dependent structural changes in the gel. Three-dimensional images obtained from confocal laser scanning microscopy show that these changes occur throughout the gel and indicate that SEM results are not artifacts of sample preparation. The permeability of these gels, as shown by blue-dextran (12 kDa) diffusion, increases in response to the presence of free fluorescein of the external medium, which causes competitive displacement of the affinity cross-links. Sequential addition and removal of sodium fluorescein showed that these permeability changes are reversible. (c) 2006 Wiley Periodicals, Inc.

Impact Of Three-Phase Relative Permeability and Hysteresis Models On Forecasts of Storage Associated with CO2-EOR

NASA Astrophysics Data System (ADS)

Jia, W.; Pan, F.; McPherson, B. J. O. L.

2015-12-01

Due to the presence of multiple phases in a given system, CO2 sequestration with enhanced oil recovery (CO2-EOR) includes complex multiphase flow processes compared to CO2 sequestration in deep saline aquifers (no hydrocarbons). Two of the most important factors are three-phase relative permeability and hysteresis effects, both of which are difficult to measure and are usually represented by numerical interpolation models. The purposes of this study included quantification of impacts of different three-phase relative permeability models and hysteresis models on CO2 sequestration simulation results, and associated quantitative estimation of uncertainty. Four three-phase relative permeability models and three hysteresis models were applied to a model of an active CO2-EOR site, the SACROC unit located in western Texas. To eliminate possible bias of deterministic parameters on the evaluation, a sequential Gaussian simulation technique was utilized to generate 50 realizations to describe heterogeneity of porosity and permeability, initially obtained from well logs and seismic survey data. Simulation results of forecasted pressure distributions and CO2 storage suggest that (1) the choice of three-phase relative permeability model and hysteresis model have noticeable impacts on CO2 sequestration simulation results; (2) influences of both factors are observed in all 50 realizations; and (3) the specific choice of hysteresis model appears to be somewhat more important relative to the choice of three-phase relative permeability model in terms of model uncertainty.

Resin Film Infusion (RFI) Process Modeling for Large Transport Aircraft Wing Structures

NASA Technical Reports Server (NTRS)

Knott, Tamara W.; Loos, Alfred C.

2000-01-01

Resin film infusion (RFI) is a cost-effective method for fabricating stiffened aircraft wing structures. The RFI process lends itself to the use of near net shape textile preforms manufactured through a variety of automated textile processes such as knitting and braiding. Often, these advanced fiber architecture preforms have through-the-thickness stitching for improved damage tolerance and delamination resistance. The challenge presently facing RFI is to refine the process to ensure complete infiltration and cure of a geometrically complex shape preform with the high fiber volume fraction needed for structural applications. An accurate measurement of preform permeability is critical for successful modeling of the RFI resin infiltration process. Small changes in the permeability can result in very different infiltration behavior and times. Therefore, it is important to accurately measure the permeabilities of the textile preforms used in the RFI process. The objective of this investigation was to develop test methods that can be used to measure the compaction behavior and permeabilities of high fiber volume fraction, advanced fiber architecture textile preforms. These preforms are often highly compacted due to through-the-thickness stitching used to improve damage tolerance. Test fixtures were designed and fabricated and used to measure both transverse and in-plane permeabilities. The fixtures were used to measure the permeabilities of multiaxial warp knit and triaxial braided preforms at fiber volume fractions from 55% to 65%. In addition, the effects of stitching characteristics, thickness, and batch variability on permeability and compaction behavior were investigated.

Cohesiveness tunes assembly and morphology of FG nucleoporin domain meshworks – Implications for nuclear pore permeability

PubMed Central

Eisele, Nico B.; Labokha, Aksana A.; Frey, Steffen; Görlich, Dirk; Richter, Ralf P.

2013-01-01

Nuclear pore complexes control the exchange of macromolecules between the cytoplasm and the nucleus. A selective permeability barrier that arises from a supramolecular assembly of intrinsically unfolded nucleoporin domains rich in phenylalanine-glycine dipeptides (FG domains) fills the nuclear pore. There is increasing evidence that selective transport requires cohesive FG domain interactions. To understand the functional roles of cohesive interactions, we studied monolayers of end-grafted FG domains as a bottom-up nanoscale model system of the permeability barrier. Based on detailed physicochemical analysis of the model films and comparison of the data with polymer theory, we propose that cohesiveness is tuned to promote rapid assembly of the permeability barrier and to generate a stable and compact pore-filling meshwork with a small mesh size. Our results highlight the functional importance of weak interactions, typically a few kBT per chain, and contribute important information to understand the mechanism of size-selective transport. PMID:24138862

Quantum chemical calculations and experimental investigations on 2-aminobenzoic acid-cyclodiphosph(V)azane derivative and its homo-binuclear Cu(II) complex

NASA Astrophysics Data System (ADS)

El-Gogary, Tarek M.; Alaghaz, Abdel-Nasser M. A.; Ammar, Reda A. A.

2012-03-01

A novel 2-aminobenzoic acid-cyclodiphosph(V)azane ligand H4L and its homo-binuclear Cu(II) complex of the type [Cu2L(H2O)2].2.5 H2O in which L is 1,3-di(-o-pyridyl)-2,4-(dioxo)-2',4'-bis-(2-iminobenzoic acid) cyclodiphosph(V)azane, were synthesized and characterized by different physical techniques. Infrared spectra of the complex indicate deprotonation and coordination of the imine NH and carboxyl COOH groups. It also confirms that nitrogen atom of the pyridine ring contribute to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square-planar geometry for the Cu(II) complex. The elemental analyses and thermogravimetric results have justified the [Cu2L(H2O)2]·2.5H2O composition of the complex. Quantum chemical calculations were utilized to explore the electronic structure and stability of the H4L as well as the binuclear Cu(II) complex. Computational studies have been carried out at the DFT-B3LYP/6-31G(d) level of theory on the structural and spectroscopic properties of H4L and its binuclear Cu(II) complex. Different tautomers and geometrical isomers of the ligand were optimized at the ab initio DFT level. Simulated IR frequencies were scaled and compared with that experimentally measured. TD-DFT method was used to compute the UV-VIS spectra which show good agreement with measured electronic spectra.

UV Spectra of Tris(2,2'-bipyridine)-M(II) Complex Ions in Vacuo (M = Mn, Fe, Co, Ni, Cu, Zn).

PubMed

Xu, Shuang; Smith, James E T; Weber, J Mathias

2016-11-21

We present electronic spectra in the π-π* region of a series of tris(bpy)-M(II) complex ions (bpy = 2,2'-bipyridine; M = Mn, Fe, Co, Ni, Cu, Zn) in vacuo for the first time. By applying photodissociation spectroscopy to cryogenically cooled and mass selected [M II (bpy) 3 ] 2+ ions, we obtain the intrinsic spectra of these ions at low temperature without perturbation by solvent interaction or crystal lattice shifts. This allows spectroscopic analysis of these complex ions in greater detail than possible in the condensed phase. We interpret our experimental data by comparison with time-dependent density functional theory.

Infrared spectroscopy of copper-resveratrol complexes: A joint experimental and theoretical study

NASA Astrophysics Data System (ADS)

Chiavarino, B.; Crestoni, M. E.; Fornarini, S.; Taioli, S.; Mancini, I.; Tosi, P.

2012-07-01

Infrared multiple-photon dissociation spectroscopy has been used to record vibrational spectra of charged copper-resveratrol complexes in the 3500-3700 cm-1 and 1100-1900 cm-1 regions. Minimum energy structures have been determined by density functional theory calculations using plane waves and pseudopotentials. In particular, the copper(I)-resveratrol complex presents a tetra-coordinated metal bound with two carbon atoms of the alkenyl moiety and two closest carbons of the adjoining resorcinol ring. For these geometries vibrational spectra have been calculated by using linear response theory. The good agreement between experimental and calculated IR spectra for the selected species confirms the overall reliability of the proposed geometries.

Unified pipe network method for simulation of water flow in fractured porous rock

NASA Astrophysics Data System (ADS)

Ren, Feng; Ma, Guowei; Wang, Yang; Li, Tuo; Zhu, Hehua

2017-04-01

Rock masses are often conceptualized as dual-permeability media containing fractures or fracture networks with high permeability and porous matrix that is less permeable. In order to overcome the difficulties in simulating fluid flow in a highly discontinuous dual-permeability medium, an effective unified pipe network method is developed, which discretizes the dual-permeability rock mass into a virtual pipe network system. It includes fracture pipe networks and matrix pipe networks. They are constructed separately based on equivalent flow models in a representative area or volume by taking the advantage of the orthogonality of the mesh partition. Numerical examples of fluid flow in 2-D and 3-D domain including porous media and fractured porous media are presented to demonstrate the accuracy, robustness, and effectiveness of the proposed unified pipe network method. Results show that the developed method has good performance even with highly distorted mesh. Water recharge into the fractured rock mass with complex fracture network is studied. It has been found in this case that the effect of aperture change on the water recharge rate is more significant in the early stage compared to the fracture density change.

Peptide Identification by Database Search of Mixture Tandem Mass Spectra*

PubMed Central

Wang, Jian; Bourne, Philip E.; Bandeira, Nuno

2011-01-01

In high-throughput proteomics the development of computational methods and novel experimental strategies often rely on each other. In certain areas, mass spectrometry methods for data acquisition are ahead of computational methods to interpret the resulting tandem mass spectra. Particularly, although there are numerous situations in which a mixture tandem mass spectrum can contain fragment ions from two or more peptides, nearly all database search tools still make the assumption that each tandem mass spectrum comes from one peptide. Common examples include mixture spectra from co-eluting peptides in complex samples, spectra generated from data-independent acquisition methods, and spectra from peptides with complex post-translational modifications. We propose a new database search tool (MixDB) that is able to identify mixture tandem mass spectra from more than one peptide. We show that peptides can be reliably identified with up to 95% accuracy from mixture spectra while considering only a 0.01% of all possible peptide pairs (four orders of magnitude speedup). Comparison with current database search methods indicates that our approach has better or comparable sensitivity and precision at identifying single-peptide spectra while simultaneously being able to identify 38% more peptides from mixture spectra at significantly higher precision. PMID:21862760

TOF-SIMS imaging of protein adsorption on dialysis membrane

NASA Astrophysics Data System (ADS)

Aoyagi, Satoka; Hayama, Msayo; Hasegawa, Urara; Sakai, Kiyotaka; Hoshi, Takahiro; Kudo, Masahiro

2004-06-01

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is capable of chemical imaging of proteins on insulated samples such as hollow-fiber dialysis membranes. Albumin loss and a lowering of diffusive permeability caused by protein adsorption on dialysis membranes should be reduced in order to enhance dialysis adequacy of the patients. Bovine serum albumin (BSA)-adsorbed hollow-fiber dialysis membranes were tested in the present study. TOF-SIMS images and spectra of both native membranes and BSA-adsorbed membranes were compared in order to identify secondary ions related to BSA and membranes. Peaks of secondary ions related to BSA and each membrane were selected by means of information theory, and they are characterized by principal component analysis (PCA). Chemical images of BSA adsorption on both native and treated membranes were obtained to find that BSA permeability and interaction between the membranes and BSA definitely depend on the properties of a membrane. TOF-SIMS imaging obtained with information theory is a powerful tool to estimate protein adsorption on the dialysis membranes.

Electromagnetic wave absorbing properties and hyperfine interactions of Fe—Cu—Nb—Si—B nanocomposites

NASA Astrophysics Data System (ADS)

Han, Man-Gui; Guo, Wei; Wu, Yan-Hui; Liu, Min; Magundappa, L. Hadimani

2014-08-01

The Fe—Cu—Nb—Si—B alloy nanocomposite containing two ferromagnetic phases (amorphous phase and nanophase phase) is obtained by properly annealing the as-prepared alloys. High resolution transmission electron microscopy (HR-TEM) images show the coexistence of these two phases. It is found that Fe—Si nanograins are surrounded by the retained amorphous ferromagnetic phase. Mössbauer spectroscopy measurements show that the nanophase is the D03-type Fe—Si phase, which is employed to find the atomic fractions of resonant 57Fe atoms in these two phases. The microwave permittivity and permeability spectra of Fe—Cu—Nb—Si—B nanocomposite are measured in the frequency range of 0.5 GHz-10 GHz. Large relative microwave permeability values are obtained. The results show that the absorber containing the nanocomposite flakes with a volume fraction of 28.59% exhibits good microwave absorption properties. The reflection loss of the absorber is less than -10 dB in a frequency band of 1.93 GHz-3.20 GHz.

Physicochemical and Mechanical Properties of Bambara Groundnut Starch Films Modified with Stearic Acid.

PubMed

Oyeyinka, Samson A; Singh, Suren; Amonsou, Eric O

2017-01-01

The physicochemical and mechanical properties of biofilm prepared from bambara starch modified with varying concentrations of stearic acid (0%, 2.5%, 3.5%, 5%, 7%, and 10%) were studied. By scanning electron microscopy, bambara starch films modified with stearic acid (≥3.5%) showed a progressively rough surface compared to those with 2.5% stearic acid and the control. Fourier transform infrared spectroscopy spectra revealed a peak shift of approximately 31 cm -1 , suggesting the promotion of hydrogen bond formation between hydroxyl groups of starch and stearic acid. The addition of 2.5% stearic acid to bambara starch film reduced water vapor permeability by approximately 17%. Bambara starch films modified with higher concentration of stearic acid were more opaque and showed significantly high melting temperatures. However, mechanical properties of starch films were generally negatively affected by stearic acid. Bambara starch film may be modified with 2.5% stearic acid for improved water vapor permeability and thermal stability with minimal effect on tensile strength. © 2016 Institute of Food Technologists®.

PHO-ERK1/2 interaction with mitochondria regulates the permeability transition pore in cardioprotective signaling.

PubMed

Hernández-Reséndiz, Sauri; Zazueta, Cecilia

2014-07-11

The molecular mechanism(s) by which extracellular signal-regulated kinase 1/2 (ERK1/2) and other kinases communicate with downstream targets have not been fully determined. Multiprotein signaling complexes undergoing spatiotemporal redistribution may enhance their interaction with effector proteins promoting cardioprotective response. Particularly, it has been proposed that some active kinases in association with caveolae may converge into mitochondria. Therefore, in this study we investigate if PHO-ERK1/2 interaction with mitochondria may provide a mechanistic link in the regulation of these organelles in cardioprotective signaling. Using a model of dilated cardiomyopathy followed by ischemia-reperfusion injury, we determined ERK1/2 signaling at the level of mitochondria and evaluated its effect on the permeability transition pore. The most important finding of the present study is that, under cardioprotective conditions, a subpopulation of activated ERK1/2 was directed to the mitochondrial membranes through vesicular trafficking, concurring with increased phosphorylation of mitochondrial proteins and inhibition of the mitochondrial permeability transition pore opening. In addition, our results suggest that vesicles enriched with caveolin-3 could form structures that may drive ERK1/2, GSK3β and Akt to mitochondria. Signaling complexes including PHO-ERK, PHO-Akt, PHO-eNOS and caveolin-3 contribute to cardioprotection by directly targeting the mitochondrial proteome and regulating the opening of the permeability transition pore in this model. Copyright © 2013 Elsevier Inc. All rights reserved.

The low/high BCS permeability class boundary: physicochemical comparison of metoprolol and labetalol.

PubMed

Zur, Moran; Gasparini, Marisa; Wolk, Omri; Amidon, Gordon L; Dahan, Arik

2014-05-05

Although recognized as overly conservative, metoprolol is currently the common low/high BCS permeability class boundary reference compound, while labetalol was suggested as a potential alternative. The purpose of this study was to identify the various characteristics that the optimal marker should exhibit, and to investigate the suitability of labetalol as the permeability class reference drug. Labetalol's BCS solubility class was determined, and its physicochemical properties and intestinal permeability were thoroughly investigated, both in vitro and in vivo in rats, considering the complexity of the whole of the small intestine. Labetalol was found to be unequivocally a high-solubility compound. In the pH range throughout the small intestine (6.5-7.5), labetalol exhibited pH-dependent permeability, with higher permeability at higher pH values. While in vitro octanol-buffer partitioning (Log D) values of labetalol were significantly higher than those of metoprolol, the opposite was evident in the in vitro PAMPA permeability assay. The results of the in vivo perfusion studies in rats lay between the two contradictory in vitro studies; metoprolol was shown to have moderately higher rat intestinal permeability than labetalol. Theoretical distribution of the ionic species of the drugs was in corroboration with the experimental in vitro and the in vivo data. We propose three characteristics that the optimal permeability class reference drug should exhibit: (1) fraction dose absorbed in the range of 90%; (2) the optimal marker drug should be absorbed largely via passive transcellular permeability, with no/negligible carrier-mediated active intestinal transport (influx or efflux); and (3) the optimal marker drug should preferably be nonionizable. The data presented in this paper demonstrate that neither metoprolol nor labetalol can be regarded as optimal low/high-permeability class boundary standard. While metoprolol is too conservative due to its complete absorption, labetalol has been shown to be a substrate for P-gp-mediated efflux transport, and both drugs exhibit significant segmental-dependent permeability along the gastrointestinal tract. Nevertheless, the use of metoprolol as the marker compound does not carry a risk of bioinequivalence: Peff value similar to or higher than metoprolol safely indicates high-permeability classification. On the other hand, a more careful data analysis is needed if labetalol is used as the reference compound.

Effect of cyclodextrin complexation on the aqueous solubility and solubility/dose ratio of praziquantel.

PubMed

Maragos, Stratos; Archontaki, Helen; Macheras, Panos; Valsami, Georgia

2009-01-01

Praziquantel (PZQ), the primary drug of choice in the treatment of schistosomiasis, is a highly lipophilic drug that possesses high permeability and low aqueous solubility and is, therefore, classified as a Class II drug according to the Biopharmaceutics Classification System (BCS). In this work, beta-cyclodextrin (beta-CD) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD) were used in order to determine whether increasing the aqueous solubility of a drug by complexation with CDs, a BCS-Class II compound like PZQ could behave as BCS-Class I (highly soluble/highly permeable) drug. Phase solubility and the kneading and lyophilization techniques were used for inclusion complex preparation; solubility was determined by UV spectroscopy. The ability of the water soluble polymer polyvinylpyrolidone (PVP) to increase the complexation and solubilization efficiency of beta-CD and HP-beta-CD for PZQ was examined. Results showed significant improvement of PZQ solubility in the presence of both cyclodextrins but no additional effect in the presence of PVP. The solubility/dose ratios values of PZQ-cyclodextrin complexes calculated considering the low (150 mg) and the high dose (600 mg) of PZQ, used in practice, indicate that PZQ complexation with CDs may result in drug dosage forms that would behave as a BCS-Class I depending on the administered dose.

Anion Photoelectron Spectroscopic Studies of NbCr(CO)_n- (n = 2,3) Heterobimetallic Carbonyl Complexes

NASA Astrophysics Data System (ADS)

Baudhuin, Melissa A.; Boopalachandran, Praveenkumar; Leopold, Doreen

2015-06-01

Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)2- and NbCr(CO)3- complexes prepared by addition of Cr(CO)6 vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities (± 0.007 eV) are measured to be 1.668 eV for NbCr(CO)2 and 1.162 eV for NbCr(CO)3, values which exceed the 0.793 eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl complexes and of NbCr and NbCr-, which have formal bond orders of 5.5 (2Δ) and 6 (1σ+), respectively. These comparisons help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond on the chromium-carbonyl interactions.

Synthesis and characterization of pure and Li⁺ activated Alq₃ complexes for green and blue organic light emitting diodes and display devices.

PubMed

Bhagat, S A; Borghate, S V; Kalyani, N Thejo; Dhoble, S J

2014-08-01

Pure and Li(+)-doped Alq3 complexes were synthesized by simple precipitation method at room temperature, maintaining the stoichiometric ratio. These complexes were characterized by X-ray diffraction, ultraviolet-visible absorption and Fourier transform infrared and photoluminescence (PL) spectra. X-ray diffraction analysis reveals the crystalline nature of the synthesized complexes, while Fourier transform infrared spectroscopy confirm the molecular structure, the completion of quinoline ring formation and presence of quinoline structure in the metal complex. Ultraviolet-visible and PL spectra revealed that Li(+) activated Alq3 complexes exhibit the highest intensity in comparison to pure Alq3 phosphor. Thus, Li(+) enhances PL emission intensity when doped into Alq3 phosphor. The excitation spectra lie in the range of 383-456 nm. All the synthesized complexes other than Liq give green emission, while Liq gives blue emission with enhanced intensity. Thus, he synthesized phosphors are the best suitable candidates for green- and blue-emitting organic light emitting diode, PL liquid-crystal display and solid-state lighting applications. Copyright © 2013 John Wiley & Sons, Ltd.

Synthesis, spectroscopic, thermal and structural properties of [M(3-aminopyridine)2Ni(μ-CN)2(CN)2]n (M(II) = Co and Cu) heteropolynuclear cyano-bridged complexes

NASA Astrophysics Data System (ADS)

Kartal, Zeki

2016-01-01

Two novel cyano-bridged heteropolynuclear complexes, [Co(3-aminopyridine)2Ni(μ-CN)2(CN)2]n and [Cu(3-aminopyridine)2Ni(μ-CN)2(CN)2]n have been synthesized and characterized by elemental, thermal, FT-IR and FT-Raman spectroscopies. The structures of complexes have been determined by X-ray powder diffraction. The FT-IR and FT-Raman spectra of complexes have been recorded in the region of 3500-400 cm-1 and 3500-100 cm-1, respectively. General information was acquired about structural properties of these complexes from FT-IR and FT-Raman spectra by considering changes at characteristic peaks of the cyano group and 3AP. The splitting of the ν(Ctbnd N) stretching bands in the FT-IR spectra for complexes indicates the presence of terminal and bridging cyanides. The thermal behaviors of these complexes have been also investigated in the range of 25-950 °C using TG and DTG methods. Magnetic susceptibility measurements were made at room temperature using Gouy-balance.

Modeling relative permeability of water in soil: Application of effective-medium approximation and percolation theory

NASA Astrophysics Data System (ADS)

Ghanbarian, Behzad; Sahimi, Muhammad; Daigle, Hugh

2016-07-01

Accurate prediction of the relative permeability to water under partially saturated condition has broad applications and has been studied intensively since the 1940s by petroleum, chemical, and civil engineers, as well as hydrologists and soil scientists. Many models have been developed for this purpose, ranging from those that represent the pore space as a bundle of capillary tubes, to those that utilize complex networks of interconnected pore bodies and pore throats with various cross-section shapes. In this paper, we propose an approach based on the effective-medium approximation (EMA) and percolation theory in order to predict the water relative permeability. The approach is general and applicable to any type of porous media. We use the method to compute the water relative permeability in porous media whose pore-size distribution follows a power law. The EMA is invoked to predict the relative permeability from the fully saturated pore space to some intermediate water saturation that represents a crossover from the EMA to what we refer to as the "critical region." In the critical region below the crossover water saturation Swx, but still above the critical water saturation Swc (the residual saturation or the percolation threshold of the water phase), the universal power law predicted by percolation theory is used to compute the relative permeability. To evaluate the accuracy of the approach, data for 21 sets of undisturbed laboratory samples were selected from the UNSODA database. For 14 cases, the predicted relative permeabilities are in good agreement with the data. For the remaining seven samples, however, the theory underestimates the relative permeabilities. Some plausible sources of the discrepancy are discussed.

Increased platelet factor 4 and aberrant permeability of follicular fluid in PCOS.

PubMed

Huang, Chu-Chun; Chou, Chia-Hung; Chen, Shee-Uan; Ho, Hong-Nerng; Yang, Yu-Shih; Chen, Mei-Jou

2018-05-17

Abnormal folliculogenesis is one of the cardinal presentations of polycystic ovarian syndrome (PCOS) and permeability of follicular wall has been proposed to be involved in the normal follicular growth. However, whether or not there is a change in intrafollicular permeability underlies PCOS is unknown. This was a tertiary center-based case-control study. From 2014 to 2015, thirteen patients with PCOS who underwent in vitro fertilization-embryo transfer (IVF-ET) were enrolled. Eleven normo-ovulatory patients who underwent IVF-ET due to male factor and/or tubal factor infertility were enrolled as the control group. The influence of ovarian follicular fluid (FF) on endothelial cell permeability was evaluated using a human umbilical vein endothelial cell monolayer permeability assay. The intrafollicular expression profiles of angiogenesis-related proteins were analyzed using a Human Angiogenesis Protein Array Kit. The FF from PCOS patients caused significantly poorer endothelial cell permeability comparing with the effect of FF from the control group (46% ± 12% vs. 58% ± 9%, P = 0.023). Among the 55 angiogenesis-related proteins tested, there was a significantly higher level of intrafollicular platelet factor 4 (PF4) and PF4/IL-8 complex in the PCOS group (p = 0.004). The anti-permeability effect of PF4 was related to the decrease in the intercellular gaps and antagonistic binding with IL-8. Our study provides the first evidence of the pathophysiologic contribution of the well-known angiostatic protein, PF4, on human reproductive biology. The increase of the intrafollicular PF4 and its anti-permeability effect might affect the formation of FF and folliculogenesis in PCOS. Copyright © 2018. Published by Elsevier B.V.

Distinctive EPR signals provide an understanding of the affinity of bis-(3-hydroxy-4-pyridinonato) copper(II) complexes for hydrophobic environments.

PubMed

Rangel, Maria; Leite, Andreia; Silva, André M N; Moniz, Tânia; Nunes, Ana; Amorim, M João; Queirós, Carla; Cunha-Silva, Luís; Gameiro, Paula; Burgess, John

2014-07-07

In this work we report the synthesis and characterization of a set of 3-hydroxy-4-pyridinone copper(ii) complexes with variable lipophilicity. EPR spectroscopy was used to characterize the structure of copper(ii) complexes in solution, and as a tool to gain insight into solvent interactions. EPR spectra of solutions of the [CuL2] complexes recorded in different solvents reveal the presence of two copper species whose ratio depends on the nature of the solvent. Investigation of EPR spectra in the pure solvents methanol, dimethylsulfoxide, dichloromethane and their 50% (v/v) mixtures with toluene allowed the characterization of two types of copper signals (gzz = 2.30 and gzz = 2.26) whose spin-Hamiltonian parameters are consistent with solvated and non-solvated square-planar copper(ii) complexes. Regarding the potential biological application of ligands and complexes and to get insight into the partition properties in water-membrane interfaces, EPR spectra were also obtained in water-saturated octanol, an aqueous solution buffered at pH = 7.4 and liposome suspensions, for three compounds representative of different hydro-lipophilic balances. Analysis of the EPR spectra obtained in liposomes allowed establishment of the location of the complexes in the water and lipid phases. In view of the results of this work we put forward the use of EPR spectroscopy to assess the affinity of copper(ii) complexes for a hydrophobic environment and also to obtain indirect information about the lipophilicity of the ligands and similar EPR silent complexes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bauer, Stephen J.; Flint, Gregory Mark

Accurate knowledge of thermophysical properties of concrete is considered extremely important for meaningful models to be developed of scenarios wherein the concrete is rapidly heated. Test of solid propellant burns on samples of concrete from Launch Complex 17 of the Cape Canaveral show spallation and fragmentation. In response to the need for accurate modeling scenarios of these observations, an experimental program to determine the permeability and thermal properties of the concrete was developed. Room temperature gas permeability measurements of Launch Complex 17 of the Cape Canaveral concrete dried at 50°C yield permeability estimates of 0.07mD (mean), and thermal properties (thermalmore » conductivity, diffusivity, and specific heat) were found to vary with temperatures from room temperature to 300°C. Thermal conductivity ranges from 1.7-1.9 W/mK at 50°C to 1.0-1.15 W/mK at 300°C, thermal diffusivity ranges from 0.75-0.96 mm 2/s at 50°C to 0.44-0.58 mm 2/s at 300°C, and specific heat ranges from 1.76-2.32 /m 3K to 2.00-2.50 /m 3K at 300°C.« less

Regulation of intestinal permeability: The role of proteases

PubMed Central

Van Spaendonk, Hanne; Ceuleers, Hannah; Witters, Leonie; Patteet, Eveline; Joossens, Jurgen; Augustyns, Koen; Lambeir, Anne-Marie; De Meester, Ingrid; De Man, Joris G; De Winter, Benedicte Y

2017-01-01

The gastrointestinal barrier is - with approximately 400 m2 - the human body’s largest surface separating the external environment from the internal milieu. This barrier serves a dual function: permitting the absorption of nutrients, water and electrolytes on the one hand, while limiting host contact with noxious luminal antigens on the other hand. To maintain this selective barrier, junction protein complexes seal the intercellular space between adjacent epithelial cells and regulate the paracellular transport. Increased intestinal permeability is associated with and suggested as a player in the pathophysiology of various gastrointestinal and extra-intestinal diseases such as inflammatory bowel disease, celiac disease and type 1 diabetes. The gastrointestinal tract is exposed to high levels of endogenous and exogenous proteases, both in the lumen and in the mucosa. There is increasing evidence to suggest that a dysregulation of the protease/antiprotease balance in the gut contributes to epithelial damage and increased permeability. Excessive proteolysis leads to direct cleavage of intercellular junction proteins, or to opening of the junction proteins via activation of protease activated receptors. In addition, proteases regulate the activity and availability of cytokines and growth factors, which are also known modulators of intestinal permeability. This review aims at outlining the mechanisms by which proteases alter the intestinal permeability. More knowledge on the role of proteases in mucosal homeostasis and gastrointestinal barrier function will definitely contribute to the identification of new therapeutic targets for permeability-related diseases. PMID:28405139

Brittle structures and their role in controlling porosity and permeability in a complex Precambrian crystalline-rock aquifer system in the Colorado Rocky Mountain front range

USGS Publications Warehouse

Caine, Jonathan S.; Tomusiak, S.R.A.

2003-01-01

Expansion of the Denver metropolitan area has resulted in substantial residential development in the foothills of the Rocky Mountain Front Range. This type of sub-urban growth, characteristic of much of the semiarid intermountain west, often relies on groundwater from individual domestic wells and is exemplified in the Turkey Creek watershed. The watershed is underlain by complexly deformed and fractured crystalline bedrock in which groundwater resources are poorly understood, and concerns regarding groundwater mining and degradation have arisen. As part of a pilot project to establish quantitative bounds on the groundwater resource, an outcrop-based geologic characterization and numerical modeling study of the brittle structures and their controls on the flow system was initiated. Existing data suggest that ground-water storage, flow, and contaminant transport are primarily controlled by a heterogeneous array of fracture networks. Inspections of well-permit data and field observations led to a conceptual model in which three dominant lithologic groups underlying sparse surface deposits form the aquifer system-metamorphic rocks, a complex array of granitic intrusive rocks, and major brittle fault zones. Pervasive but variable jointing of each lithologic group forms the "background" permeability structure and is an important component of the bulk storage capacity. This "background" is cut by brittle fault zones of varying structural styles and by pegmatite dikes, both with much higher fracture intensities relative to "background" that likely make them spatially complex conduits. Probabilistic, discrete-fracture-network and finite-element modeling was used to estimate porosity and permeability at the outcrop scale using fracture network data collected in the field. The models were conditioned to limited aquifer test and borehole geophysical data and give insight into the relative hydraulic properties between locations and geologic controls on storage and flow. Results from this study reveal a complex aquifer system in which the upper limits on estimated hydraulic properties suggest limited storage capacity and permeability as compared with many sedimentary-rock and surficial-deposit aquifers.

Bayesian deconvolution and quantification of metabolites in complex 1D NMR spectra using BATMAN.

PubMed

Hao, Jie; Liebeke, Manuel; Astle, William; De Iorio, Maria; Bundy, Jacob G; Ebbels, Timothy M D

2014-01-01

Data processing for 1D NMR spectra is a key bottleneck for metabolomic and other complex-mixture studies, particularly where quantitative data on individual metabolites are required. We present a protocol for automated metabolite deconvolution and quantification from complex NMR spectra by using the Bayesian automated metabolite analyzer for NMR (BATMAN) R package. BATMAN models resonances on the basis of a user-controllable set of templates, each of which specifies the chemical shifts, J-couplings and relative peak intensities for a single metabolite. Peaks are allowed to shift position slightly between spectra, and peak widths are allowed to vary by user-specified amounts. NMR signals not captured by the templates are modeled non-parametrically by using wavelets. The protocol covers setting up user template libraries, optimizing algorithmic input parameters, improving prior information on peak positions, quality control and evaluation of outputs. The outputs include relative concentration estimates for named metabolites together with associated Bayesian uncertainty estimates, as well as the fit of the remainder of the spectrum using wavelets. Graphical diagnostics allow the user to examine the quality of the fit for multiple spectra simultaneously. This approach offers a workflow to analyze large numbers of spectra and is expected to be useful in a wide range of metabolomics studies.

Phosphorescence/microwave double-resonance spectra of tryptophan perturbed by methylmercury(II).

PubMed Central

Davis, J M; Maki, A H

1982-01-01

Amplitude-modulated phosphorescence/microwave double-resonance (AM-PMDR) spectra are reported for complexes of methylmercury(II) cation, designated CH3Hg(II), with tryptophan and glyceraldehyde-3-phosphate dehydrogenase (GPDHase; from rabbit muscle). Wavelength shifts are observed in the AM-PMDR spectra of CH3Hg(II)-tryptophan, which are obtained by microwave pumping in distinct zero-field D + E magnetic resonance transitions, demonstrating that AM-PMDR can be used to display selectively the phosphorescence spectra of structurally distinct complexes with different zero-field splittings. The AM-PMDR spectra accurately represent the phosphorescence of CH3Hg(II)-tryptophan. Binding of CH3Hg(II) to a cysteine site of GDPHase perturbs the luminescence of one of the two optically resolved tryptophan. The AM-PMDR spectrum of the perturbed tryptophan is obtained by microwave pumping of the D + E magnetic resonance signal, which can be observed optically only in the presence of a heavy atom perturbation. The resulting spectrum is broadened and shifted to the blue relative to the corresponding tryptophan phosphorescence spectrum of the uncomplexed enzyme. Comparison of the AM-PMDR spectra of CH3Hg(II)-tryptophan and CH3Hg(II)-GPDHase suggests that there are differences in the mechanisms of heavy atom perturbation in these complexes. PMID:6956860

Complex conductivity of organic-rich shales

NASA Astrophysics Data System (ADS)

Woodruff, W. F.; Revil, A.; Torres-Verdin, C.

2013-12-01

We can accurately determine the intrinsic anisotropy and material properties in the laboratory, providing empirical evidence of transverse isotropy and the polarization of the organic and metallic fractions in saturated and unsaturated shales. We develop two distinct approaches to obtain the complex conductivity tensor from spectral induced polarization (SIP) measurements. Experimental results indicate clear anisotropy, and characterize the effects of thermal maturation, TOC, and pyrite, aiding in the calibration and interpretation of geophysical data. SIP is a non-intrusive measurement, sensitive to the surface conductance of mineral grains, frequency-dependent polarization of the electrical double layer, and bulk conductivity of the pore water. The in-phase and quadrature components depend upon parameters of principal importance in unconventional shale formation evaluation (e.g., the distribution of pore throat sizes, formation factor, permeability, salinity and cation exchange capacity (CEC), fluid saturation and wettability). In addition to the contribution of the electrical double layer of non-conducting minerals to surface conductivity, we have observed a clear relaxation associated with kerogen pyrolysis, pyrite distribution, and evidence that the CEC of the kerogen fraction may also contribute, depending on thermal maturation history. We utilize a recent model for anisotropic complex conductivity, and rigorous experimental protocols to quantify the role of kerogen and pyrolysis on surface and quadrature conductivity in mudrocks. The complex conductivity tensor σ* describes the directional dependence of electrical conduction in a porous medium, and accounts for both conduction and polarization. The complex-valued tensor components are given as σ*ij , where σ'ij represents in-phase and σ"ij denotes quadrature conductivities. The directional dependence of the complex conductivity tensor is relegated to the textural properties of the material. The components of the formation factor and connectivity (tortuosity) tensors Fij and Tij (affecting the bulk and surface conductivity, respectively) are correlated as Fij=TijΦ. Both conductivity and connectivity tensors share the same eigenvectors; the anisotropy ratio is equivalent in TI media. At high pore water salinity, surface and quadrature conductivity share the same bulk tortuosity; when surface conductivity dominates (low salinity), conductivity is controlled by the surface conductance, and the tortuosity of electrical current along mineral surfaces usually higher than that of the pore water. We developed two distinct SIP measurement protocols to obtain the tensor: (1) azimuthal sampling and inversion of phasor potentials through the full-field solution of the Laplace equation; (2) direct measurement of complex conductivity eigenvalues by polarized, single-component stimulus current. Experiments also include unsaturated and saturated measurements with three brines of known salinity and pH, at log-distributed frequencies ranging 1 mHz to 45 kHz. Both azimuthal spectra and eigenvalue spectra validate the theoretical model and illustrate the effectiveness of the protocols themselves. We obtain the textural tensors and invert key parameters including Archie exponents and CEC, and characterize the relaxation phenomena associated with kerogen content and maturity for multiphase fluid systems.

Synthesis and binding properties of arylethyne-linked porphyrin-zinc complexes for organic electronics applications.

PubMed

Reainthippayasakul, W; Paosawatyanyong, B; Bhanthumnavin, W

2013-05-01

Conjugated meso-alkynyl 5,15-dimesitylporphyrin metal complexes have been synthesized by Sonogashira coupling reaction in good yields. Alkynyl groups were chosen as a link at the meso positions in order to extend the pi-conjugated length of porphyrin rings. These synthesized porphyrin derivatives were characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. Moreover, UV-visible spectroscopy and fluorescence spectroscopy were also used to investigate their photophysical properties. It has been demonstrated that central metal ions as well as meso substituents on porphyrin rings affected the electronic absorption and emission spectra of the compounds. Spectroscopic results revealed that alkyne-linked porphyrin metal complexes showed higher pi-conjugation compared with porphyrin building blocks resulting in red shifts in both absorption and emission spectra. Coordination properties of synthesized porphyrins were preliminarily investigated by UV-visible absorption and fluorescence emission spectroscopic titration with pyridine as axial ligand. The formation of porphyrin-pyridine complexes resulted in significant red shifts in absorption spectra and decrease of fluorescence intensity in emission spectra. Moreover, the 1H NMR titration experiments suggested that central metal ions play an important role to coordinate with pyridine and the coordination of porphyrin zinc(II) complex with pyridine occur in a 1:1 ratio. From these spectroscopic results, alkyne-linked porphyrin metal complexes offer potential applications as materials for optical organic nanosensors.

Frequency-Dependence of Relative Permeability in Steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowler, N.

2006-03-06

A study to characterize metal plates by means of a model-based, broadband, four-point potential drop measurement technique has shown that the relative permeability of alloy 1018 low-carbon steel is complex and a function of frequency. A magnetic relaxation is observed at approximately 5 kHz. The relaxation can be described in terms of a parametric (Cole-Cole) model. Factors which influence the frequency, amplitude and breadth of the relaxation, such as applied current amplitude, sample geometry and disorder (e.g. percent carbon content and surface condition), are considered.

The algorithmic details of polynomials application in the problems of heat and mass transfer control on the hypersonic aircraft permeable surfaces

NASA Astrophysics Data System (ADS)

Bilchenko, G. G.; Bilchenko, N. G.

2018-03-01

The hypersonic aircraft permeable surfaces heat and mass transfer effective control mathematical modeling problems are considered. The analysis of the control (the blowing) constructive and gasdynamical restrictions is carried out for the porous and perforated surfaces. The functions classes allowing realize the controls taking into account the arising types of restrictions are suggested. Estimates of the computational complexity of the W. G. Horner scheme application in the case of using the C. Hermite interpolation polynomial are given.

On the role of low-permeability beds in the acquisition of F and SO4 concentrations in a multi-layer aquifer, South-West France.

PubMed

Malcuit, E; Atteia, O; Larroque, F; Franceschi, M; Pryet, A

2014-11-15

Fluoride (F(-)) commonly threatens groundwater quality. This is the case around the city of Bordeaux (France), where numerous wells tapping the thick and complex Eocene aquifer are contaminated by fluoride, which presents an issue for drinking water supply. The joint analysis of the spatial distribution of fluoride with other species like sulfate suggests that concentrations are mainly related to the occurrence of low-permeability layers containing evaporites or fluorite deposits. In order to identify the origin of the observed concentrations, a radial flow and transport model is implemented at the borehole scale. The hydraulic conductivity of the low-permeability layers and the vertical dispersivity of the aquifer were optimized to match the observed values of sulfate and fluoride concentrations. Interestingly, each of these parameters influences differently the simulated concentrations. This model has been successfully implemented to a neighboring well with the same parameter values, which tests the approach. The major conclusions drawn are: (i) the contamination in fluoride originates from the low-permeability layers, (ii) every low-permeability layer intercepted by the well releases fluoride (iii) Contamination not only originates from pore water of low-permeability layers, but may persist with long-term pumping due to mineral dissolution. As a consequence, fluoride contamination is likely to persist for a long time and the only solution to reduce fluoride concentration in abstracted water is to seal well screens facing low-permeability layers. Copyright © 2014 Elsevier B.V. All rights reserved.

Orientation hydrogen-bonding effect on vibronic spectra of isoquinoline in water solvent: Franck-Condon simulation and interpretation

NASA Astrophysics Data System (ADS)

Liu, Yu-Hui; Wang, Shi-Ming; Wang, Chen-Wen; Zhu, Chaoyuan; Han, Ke-Li; Lin, Sheng-Hsien

2016-10-01

The excited-state orientation hydrogen-bonding dynamics, and vibronic spectra of isoquinoline (IQ) and its cationic form IQc in water have been investigated at the time-dependent density functional theory quantum chemistry level plus Franck-Condon simulation and interpretation. The excited-state orientation hydrogen bond strengthening has been found in IQ:H2O complex due to the charge redistribution upon excitation; this is interpreted by simulated 1:1 mixed absorption spectra of free IQ and IQ:H2O complex having best agreement with experimental results. Conversely, the orientation hydrogen bond in IQc:H2O complex would be strongly weakening in the S1 state and this is interpreted by simulated absorption spectra of free IQc having best agreement with experimental results. By performing Franck-Condon simulation, it reveals that several important vibrational normal modes with frequencies about 1250 cm-1 involving the wagging motion of the hydrogen atoms are very sensitive to the formation of the orientation hydrogen bond for the IQ/IQc:H2O complex and this is confirmed by damped Franck-Condon simulation with free IQ/IQc in water. However, the emission spectra of the IQ and IQc in water have been found differently. Upon the excitation, the simulated fluorescence of IQ in water is dominated by the IQ:H2O complex; thus hydrogen bond between IQ and H2O is much easier to form in the S1 state. While the weakened hydrogen bond in IQc:H2O complex is probably cleaved upon the laser pulse because the simulated emission spectrum of the free IQc is in better agreement with the experimental results.

TD-M06-2X insights into the absorption and emission spectra of dichlorvos and its molecularly imprinted recognition by methacrylic acid.

PubMed

Cheng, Xueli

2016-11-01

The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in methanol, water, and chloroform in the molecularly imprinted recognition were investigated systematically. The M06-2X results revealed that: 1) the hydroxyl groups in polar solvents such as methanol and water may markedly influence the weak interactions, and then alter the adsorption and emission spectra; 2) the electronic excitation in absorption spectra of dichlorvos is dominated by the configuration HOMO → LUMO, but in the most stable dichlorvos-MAA it becomes the ππ* excitation of HOMO → LUMO + 1; 3) Mulliken charges reveal that dichlorvos almost dissociates to Cl - and a cation in its S 1 excitation state; 4) the phosphorescence spectra of dichlorvos-MAA are relatively weak. Graphical Abstract The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in the molecularly imprinted recognition of dichlorvos were investigated systematically in methanol, water, and chloroform as solvents.

Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene

NASA Technical Reports Server (NTRS)

Bera, Partha P.; Head-Gordon, Martin; Lee, Timothy J.

2013-01-01

The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal/mol for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal/mol in C4H4 +, but only 6 kcal/mol in C4H8 +. The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.

Solid phase excitation-emission fluorescence method for the classification of complex substances: Cortex Phellodendri and other traditional Chinese medicines as examples.

PubMed

Gu, Yao; Ni, Yongnian; Kokot, Serge

2012-09-13

A novel, simple and direct fluorescence method for analysis of complex substances and their potential substitutes has been researched and developed. Measurements involved excitation and emission (EEM) fluorescence spectra of powdered, complex, medicinal herbs, Cortex Phellodendri Chinensis (CPC) and the similar Cortex Phellodendri Amurensis (CPA); these substances were compared and discriminated from each other and the potentially adulterated samples (Caulis mahoniae (CM) and David poplar bark (DPB)). Different chemometrics methods were applied for resolution of the complex spectra, and the excitation spectra were found to be the most informative; only the rank-ordering PROMETHEE method was able to classify the samples with single ingredients (CPA, CPC, CM) or those with binary mixtures (CPA/CPC, CPA/CM, CPC/CM). Interestingly, it was essential to use the geometrical analysis for interactive aid (GAIA) display for a full understanding of the classification results. However, these two methods, like the other chemometrics models, were unable to classify composite spectral matrices consisting of data from samples of single ingredients and binary mixtures; this suggested that the excitation spectra of the different samples were very similar. However, the method is useful for classification of single-ingredient samples and, separately, their binary mixtures; it may also be applied for similar classification work with other complex substances.

Spectra, energy levels, and energy transition of lanthanide complexes with cinnamic acid and its derivatives

NASA Astrophysics Data System (ADS)

Zhou, Kaining; Feng, Zhongshan; Shen, Jun; Wu, Bing; Luo, Xiaobing; Jiang, Sha; Li, Li; Zhou, Xianju

2016-04-01

High resolution spectra and luminescent lifetimes of 6 europium(III)-cinnamic acid complex {[Eu2L6(DMF)(H2O)]·nDMF·H2O}m (L = cinnamic acid I, 4-methyl-cinnamic acid II, 4-chloro-cinnamic acid III, 4-methoxy-cinnamic acid IV, 4-hydroxy-cinnamic acid V, 4-nitro-cinnamic acid VI; DMF = N, N-dimethylformamide, C3H7NO) were recorded from 8 K to room temperature. The energy levels of Eu3 + in these 6 complexes are obtained from the spectra analysis. It is found that the energy levels of the central Eu3 + ions are influenced by the nephelauxetic effect, while the triplet state of ligand is lowered by the p-π conjugation effect of the para-substituted functional groups. The best energy matching between the ligand triplet state and the central ion excited state is found in complex I. While the other complexes show poorer matching because the gap of 5D0 and triplet state contracts.

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

DOE PAGES

Martin-Diaconescu, Vlad; Gennari, Marcello; Gerey, Bertrand; ...

2014-12-10

Calcium K-edge pre-edges coupled with TD-DFT theoretical calculation of spectra provide a powerful approach for the characterization of complex calcium centers in inorganic and bioinorganic chemistry. Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodologymore » to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.« less

Emplacement and dewatering of the world's largest exposed sand injectite complex

NASA Astrophysics Data System (ADS)

Sherry, Timothy J.; Rowe, Christie D.; Kirkpatrick, James D.; Brodsky, Emily E.

2012-08-01

Sandstone injectites form by up or down-section flow of a mobilized sand slurry through fractures in overlying rock. They act as reservoirs and high-permeability conduits through lower permeability rock in hydrocarbon systems. The Yellow Bank Creek Complex, Santa Cruz County, California is the largest known exposure of a sandstone injectite in the world. The complex contains granular textures that record processes of sand slurry flow, multiple pore fluids, and dewatering after emplacement. The injection was initially mobilized from a source containing both water and hydrocarbons. The water-sand slurry reached emplacement depth first, due to lower fluid viscosity. As the sand slurry emplaced, the transition from slurry flow to pore water percolation occurred. This transition resulted in preferred flow channels ˜6 mm wide in which sand grains were weakly aligned (laminae). The hydrocarbon-sand slurry intruded the dewatering sands and locally deformed the laminae. Compaction of the injectite deposit and pore fluid escape caused spaced compaction bands and dewatering pipes which created convolutions of the laminae. The hydrocarbon-rich sand slurry is preserved today as dolomite-cemented sand with oil inclusions. The laminae in this injectite are easily detected due to preferential iron oxide-cementation of the well-aligned sand laminae, and lack of cement in the alternating laminae. Subtle textures like these may develop during sand flow and be present but difficult to detect in other settings. They may explain permeability anisotropy in other sand deposits.

Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation.

PubMed

Luo, Jing; Farrell, James

2013-01-01

Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE.

Syntheses and characterization of Ru(III) with chelating containing ONNO donor quadridentate Schiff bases.

PubMed

Refat, Moamen S; El-Korashy, Sabry A; Kumar, Deo Nandan; Ahmed, Ahmed S

2008-09-01

Complexes of ruthenium(III) with N,N'-disalicylidene-l,2-phenylenediamine (H2dsp), N,N'-disalicylidene-3,4-diaminotoluene (H2dst), 4-nitro-N,N'-disalicylidene-1,2-phenylenediamine (H2ndsp) and N,N'-disalicylidene ethylenediamine (H2salen) have been prepared and characterized by elemental analysis, molar conductivity, spectral methods (mid-infrared, 1H NMR and UV-vis spectra) and simultaneous thermal analysis (TG and DTG) techniques. The molar conductance measurements proved that all these complexes are non-electrolytes. The electronic spectra measurements were used to infer the structures. The IR spectra of the ligands and their complexes are used to identify the type of bonding. The kinetic thermodynamic parameters such as: E*, DeltaH*, DeltaS* and DeltaG* are estimated from the DTG curves. The four ligands and their complexes have been studied for their possible biological antifungal activity.

Theoretical study of optical activity of 1:1 hydrogen bond complexes of water with S-warfarin

NASA Astrophysics Data System (ADS)

Dadsetani, Mehrdad; Abdolmaleki, Ahmad; Zabardasti, Abedin

2016-11-01

The molecular interaction between S-warfarin (SW) and a single water molecule was investigated using the B3LYP method at 6-311 ++G(d,p) basis set. The vibrational spectra of the optimized complexes have been investigated for stabilization checking. Quantum theories of atoms in molecules, natural bond orbitals, molecular electrostatic potentials and energy decomposition analysis methods have been applied to analyze the intermolecular interactions. The intermolecular charge transfer in the most stable complex is in the opposite direction from those in the other complexes. The optical spectra and the hyperpolarizabilities of SW-water hydrogen bond complexes have been computed.

Simple Emergent Power Spectra from Complex Inflationary Physics

NASA Astrophysics Data System (ADS)

Dias, Mafalda; Frazer, Jonathan; Marsh, M. C. David

2016-09-01

We construct ensembles of random scalar potentials for Nf-interacting scalar fields using nonequilibrium random matrix theory, and use these to study the generation of observables during small-field inflation. For Nf=O (few ), these heavily featured scalar potentials give rise to power spectra that are highly nonlinear, at odds with observations. For Nf≫1 , the superhorizon evolution of the perturbations is generically substantial, yet the power spectra simplify considerably and become more predictive, with most realizations being well approximated by a linear power spectrum. This provides proof of principle that complex inflationary physics can give rise to simple emergent power spectra. We explain how these results can be understood in terms of large Nf universality of random matrix theory.

Simple Emergent Power Spectra from Complex Inflationary Physics.

PubMed

Dias, Mafalda; Frazer, Jonathan; Marsh, M C David

2016-09-30

We construct ensembles of random scalar potentials for N_{f}-interacting scalar fields using nonequilibrium random matrix theory, and use these to study the generation of observables during small-field inflation. For N_{f}=O(few), these heavily featured scalar potentials give rise to power spectra that are highly nonlinear, at odds with observations. For N_{f}≫1, the superhorizon evolution of the perturbations is generically substantial, yet the power spectra simplify considerably and become more predictive, with most realizations being well approximated by a linear power spectrum. This provides proof of principle that complex inflationary physics can give rise to simple emergent power spectra. We explain how these results can be understood in terms of large N_{f} universality of random matrix theory.

Terahertz Time Domain Spectroscopy of Complex Organic Molecules in Astrophysically Relevant Ices

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Ioppolo, Sergio; Allodi, Marco A.; Kelley, Matthew J.; Blake, Geoffrey A.

2013-06-01

We have constructed a new system to study the spectra of astrophysically-relevant ice analogs using THz time-domain spectroscopy from 300 GHz - 7 THz. Here, we present our initial efforts to explore the spectra of pure ices of simple, abundant interstellar species as well as complex organic molecules (COMs) and COM-doped ice mixtures. We will present preliminary spectra of pure H_2O, CO_2, methanol (CH_3OH), and methyl formate (CH_3COOH) ices, as well as spectra of these molecules embedded in a variety of other relevant interstellar analogs. Our results are discussed in the context of astronomical observations and the possibility of probing ice compositions in the absence of a background radiation source.

Excitation Dynamics in Phycoerythrin 545: Modeling of Steady-State Spectra and Transient Absorption with Modified Redfield Theory

PubMed Central

Novoderezhkin, Vladimir I.; Doust, Alexander B.; Curutchet, Carles; Scholes, Gregory D.; van Grondelle, Rienk

2010-01-01

Abstract We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex. PMID:20643051

XAP, a program for deconvolution and analysis of complex X-ray spectra

USGS Publications Warehouse

Quick, James E.; Haleby, Abdul Malik

1989-01-01

The X-ray analysis program (XAP) is a spectral-deconvolution program written in BASIC and specifically designed to analyze complex spectra produced by energy-dispersive X-ray analytical systems (EDS). XAP compensates for spectrometer drift, utilizes digital filtering to remove background from spectra, and solves for element abundances by least-squares, multiple-regression analysis. Rather than base analyses on only a few channels, broad spectral regions of a sample are reconstructed from standard reference spectra. The effects of this approach are (1) elimination of tedious spectrometer adjustments, (2) removal of background independent of sample composition, and (3) automatic correction for peak overlaps. Although the program was written specifically to operate a KEVEX 7000 X-ray fluorescence analytical system, it could be adapted (with minor modifications) to analyze spectra produced by scanning electron microscopes, electron microprobes, and probes, and X-ray defractometer patterns obtained from whole-rock powders.

Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra.

PubMed

Roussis, Stilianos G; Proulx, Richard

2003-03-15

A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.

Resonance Raman study of a two-chromophore system. The 2:1 complex of hexamethylbenzene with tetracyanoethylene

NASA Astrophysics Data System (ADS)

Mark Britt, B.; McHale, Jeanne L.

1997-05-01

Raman excitation profiles are presented for the 2:1 electron donor-acceptor (EDA) complex of hexamethylbenzene (HMB) and tetracyanoethylene (TCNE) in cyclohexane. Though the absorption and Raman spectra of the 1:1 and 2:1 complexes are similar, distinct differences are found in the Raman excitation profiles (REPs) of vibrational modes common to both systems. REPs of the 2:1 complex show intensity cancellation that is taken as evidence for interference of two charge-transfer excited states. The implications of the observed spectra concerning excited state electron delocalization are considered.

The deconvolution of complex spectra by artificial immune system

NASA Astrophysics Data System (ADS)

Galiakhmetova, D. I.; Sibgatullin, M. E.; Galimullin, D. Z.; Kamalova, D. I.

2017-11-01

An application of the artificial immune system method for decomposition of complex spectra is presented. The results of decomposition of the model contour consisting of three components, Gaussian contours, are demonstrated. The method of artificial immune system is an optimization method, which is based on the behaviour of the immune system and refers to modern methods of search for the engine optimization.

Biguanides inhibit complex I, II and IV of rat liver mitochondria and modify their functional properties.

PubMed

Drahota, Z; Palenickova, E; Endlicher, R; Milerova, M; Brejchova, J; Vosahlikova, M; Svoboda, P; Kazdova, L; Kalous, M; Cervinkova, Z; Cahova, M

2014-01-01

In this study, we focused on an analysis of biguanides effects on mitochondrial enzyme activities, mitochondrial membrane potential and membrane permeability transition pore function. We used phenformin, which is more efficient than metformin, and evaluated its effect on rat liver mitochondria and isolated hepatocytes. In contrast to previously published data, we found that phenformin, after a 5 min pre-incubation, dose-dependently inhibits not only mitochondrial complex I but also complex II and IV activity in isolated mitochondria. The enzymes complexes inhibition is paralleled by the decreased respiratory control index and mitochondrial membrane potential. Direct measurements of mitochondrial swelling revealed that phenformin increases the resistance of the permeability transition pore to Ca(2+) ions. Our data might be in agreement with the hypothesis of Schäfer (1976) that binding of biguanides to membrane phospholipids alters membrane properties in a non-specific manner and, subsequently, different enzyme activities are modified via lipid phase. However, our measurements of anisotropy of fluorescence of hydrophobic membrane probe diphenylhexatriene have not shown a measurable effect of membrane fluidity with the 1 mM concentration of phenformin that strongly inhibited complex I activity. Our data therefore suggest that biguanides could be considered as agents with high efficacy but low specifity.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Analysis of the Alkali Metal Diatomic Spectra; Using molecular beams and ultracold molecules

NASA Astrophysics Data System (ADS)

Kim, Jin-Tae

2014-12-01

This ebook illustrates the complementarity of molecular beam (MB) spectra and ultracold molecule (UM) spectra in unraveling the complex electronic spectra of diatomic alkali metal molecules, using KRb as a prime example. Researchers interested in molecular spectroscopy, whether physicist, chemist, or engineer, may find this ebook helpful and may be able to apply similar ideas to their molecules of interest.

The ring-shaped thermal field of Stefanos crater, Nisyros Island: a conceptual model

NASA Astrophysics Data System (ADS)

Pantaleo, M.; Walter, T. R.

2014-04-01

Fumarole fields related to hydrothermal processes release the heat of the underground through permeable pathways. Thermal changes, therefore, are likely to depend also on the size and permeability variation of these pathways. There may be different explanations for the observed permeability changes, such as fault control, lithology, weathering/alteration, heterogeneous sediment accumulation/erosion and physical changes of the fluids (e.g., temperature and viscosity). A common difficulty, however, in surface temperature field studies at active volcanoes is that the parameters controlling the ascending routes of fluids are poorly constrained in general. Here we analyze the crater of Stefanos, Nisyros (Greece), and highlight complexities in the spatial pattern of the fumarole field related to permeability conditions. We combine high-resolution infrared mosaics and grain-size analysis of soils, aiming to elaborate parameters controlling the appearance of the fumarole field. We find a ring-shaped thermal field located within the explosion crater, which we interpret to reflect near-surface contrasts of the soil granulometry and volcanotectonic history at depth. We develop a conceptual model of how the ring-shaped thermal field formed at the Stefanos crater and similarly at other volcanic edifices, highlighting the importance of local permeability contrast that may increase or decrease the thermal fluid flux.

Morphologic and Aerodynamic Considerations Regarding the Plumed Seeds of Tragopogon pratensis and Their Implications for Seed Dispersal.

PubMed

Casseau, Vincent; De Croon, Guido; Izzo, Dario; Pandolfi, Camilla

2015-01-01

Tragopogon pratensis is a small herbaceous plant that uses wind as the dispersal vector for its seeds. The seeds are attached to parachutes that increase the aerodynamic drag force and increase the total distance travelled. Our hypothesis is that evolution has carefully tuned the air permeability of the seeds to operate in the most convenient fluid dynamic regime. To achieve final permeability, the primary and secondary fibres of the pappus have evolved with complex weaving; this maximises the drag force (i.e., the drag coefficient), and the pappus operates in an "optimal" state. We used computational fluid dynamics (CFD) simulations to compute the seed drag coefficient and compare it with data obtained from drop experiments. The permeability of the parachute was estimated from microscope images. Our simulations reveal three flow regimes in which the parachute can operate according to its permeability. These flow regimes impact the stability of the parachute and its drag coefficient. From the permeability measurements and drop experiments, we show how the seeds operate very close to the optimal case. The porosity of the textile appears to be an appropriate solution to achieve a lightweight structure that allows a low terminal velocity, a stable flight and a very efficient parachute for the velocity at which it operates.

Critical Dynamics of Gravito-Convective Mixing in Geological Carbon Sequestration

PubMed Central

Soltanian, Mohamad Reza; Amooie, Mohammad Amin; Dai, Zhenxue; Cole, David; Moortgat, Joachim

2016-01-01

When CO2 is injected in saline aquifers, dissolution causes a local increase in brine density that can cause Rayleigh-Taylor-type gravitational instabilities. Depending on the Rayleigh number, density-driven flow may mix dissolved CO2 throughout the aquifer at fast advective time-scales through convective mixing. Heterogeneity can impact density-driven flow to different degrees. Zones with low effective vertical permeability may suppress fingering and reduce vertical spreading, while potentially increasing transverse mixing. In more complex heterogeneity, arising from the spatial organization of sedimentary facies, finger propagation is reduced in low permeability facies, but may be enhanced through more permeable facies. The connectivity of facies is critical in determining the large-scale transport of CO2-rich brine. We perform high-resolution finite element simulations of advection-diffusion transport of CO2 with a focus on facies-based bimodal heterogeneity. Permeability fields are generated by a Markov Chain approach, which represent facies architecture by commonly observed characteristics such as volume fractions. CO2 dissolution and phase behavior are modeled with the cubic-plus-association equation-of-state. Our results show that the organization of high-permeability facies and their connectivity control the dynamics of gravitationally unstable flow. We discover new flow regimes in both homogeneous and heterogeneous media and present quantitative scaling relations for their temporal evolution. PMID:27808178

Effect of preparation conditions on properties and permeability of chitosan-sodium hexametaphosphate capsules.

PubMed

Angelova, N; Hunkeler, D

2001-01-01

Capsules were obtained by interpolymer complexation between chitosan (polycation) and sodium hexametaphosphate (SMP, oligoanion). The effect of the preparation conditions on the capsule characteristics was evaluated. Specifically, the influence of variables such as pH, ionic strength, reagent concentration, and additives on the capsule permeability properties was investigated using dextran as a model permeant. The capsule membrane permeability was found to increase by decreasing the chitosan/SMP ratio as well as adding mannitol to the oligoanion recipient bath. Increasing the ionic strength or the pH of the initial chitosan solution was also found to enhance the membrane permeability, moving the membrane exclusion limit to higher values. Generally, the capsules prepared tinder all tested conditions had a relatively low permeability which rarely exceeded a molecular cut-off of 40 kD based on dextran standards. Furthermore, the diffusion rate showed a strong temporal dependence, indicating that the capsules prepared under various conditions exhibit different apparent pore size densities on the surface. The results indicated that, in order to obtain the desired capsule mass-transfer properties, the preparation conditions should be carefully considered and adjusted. Adding a polyol as well as low salt amount (less than 0.15%) is preferable as a means of modulating the diffusion characteristics, without disturbing the capsule mechanical stability.

Morphologic and Aerodynamic Considerations Regarding the Plumed Seeds of Tragopogon pratensis and Their Implications for Seed Dispersal

PubMed Central

2015-01-01

Tragopogon pratensis is a small herbaceous plant that uses wind as the dispersal vector for its seeds. The seeds are attached to parachutes that increase the aerodynamic drag force and increase the total distance travelled. Our hypothesis is that evolution has carefully tuned the air permeability of the seeds to operate in the most convenient fluid dynamic regime. To achieve final permeability, the primary and secondary fibres of the pappus have evolved with complex weaving; this maximises the drag force (i.e., the drag coefficient), and the pappus operates in an “optimal” state. We used computational fluid dynamics (CFD) simulations to compute the seed drag coefficient and compare it with data obtained from drop experiments. The permeability of the parachute was estimated from microscope images. Our simulations reveal three flow regimes in which the parachute can operate according to its permeability. These flow regimes impact the stability of the parachute and its drag coefficient. From the permeability measurements and drop experiments, we show how the seeds operate very close to the optimal case. The porosity of the textile appears to be an appropriate solution to achieve a lightweight structure that allows a low terminal velocity, a stable flight and a very efficient parachute for the velocity at which it operates. PMID:25938765

Direct numerical simulation of supercritical gas flow in complex nanoporous media: Elucidating the relationship between permeability and pore space geometry

NASA Astrophysics Data System (ADS)

Landry, C. J.; Prodanovic, M.; Eichhubl, P.

2015-12-01

Mudrocks and shales are currently a significant source of natural gas and understanding the basic transport properties of these formations is critical to predicting long-term production, however, the nanoporous nature of mudrocks presents a unique challenge. Mudrock pores are predominantly in the range of 1-100 nm, and within this size range the flow of gas at reservoir conditions will fall within the slip-flow and early transition-flow regime (0.001 < Kn < 1.0). Therefore, flow-rates will significantly deviate from Navier-Stokes predictions. Currently, the study of slip-flows is mostly limited to simple tube and channel geometries, but the geometry of mudrock pores is often sponge-like (organic matter) and/or platy (clays). Here we present a local effective viscosity lattice Boltzmann model (LEV-LBM) constructed for flow simulation in the slip- and early-transition flow regimes, adapted here for complex geometries. At the macroscopic scale the LEV-LBM is parameterized with local effective viscosities at each node to capture the variance of the mean free path of gas molecules in a bounded system. The LEV-LBM is first validated in simple tube geometries, where excellent agreement with linearized Boltzmann solutions is found for Knudsen numbers up to 1.0. The LEV-LBM is then employed to quantify the length effect on the apparent permeability of tubes, which suggests pore network modeling of flow in the slip and early-transition regime will result in overestimation unless the length effect is considered. Furthermore, the LEV-LBM is used to evaluate the predictive value of commonly measured pore geometry characteristics such as porosity, pore size distribution, and specific solid surface area for the calculation of permeability. We show that bundle of tubes models grossly overestimate apparent permeability, as well as underestimate the increase in apparent permeability with decreasing pressure as a result of excluding topology and pore shape from calculations.

Bioinspired nanovalves with selective permeability and pH sensitivity

NASA Astrophysics Data System (ADS)

Zheng, Z.; Huang, X.; Schenderlein, M.; Moehwald, H.; Xu, G.-K.; Shchukin, D. G.

2015-01-01

Biological systems with controlled permeability and release functionality, which are among the successful examples of living beings to survive in evolution, have attracted intensive investigation and have been mimicked due to their broad spectrum of applications. We present in this work, for the first time, an example of nuclear pore complexes (NPCs)-inspired controlled release system that exhibits on-demand release of angstrom-sized molecules. We do so in a cost-effective way by stabilizing porous cobalt basic carbonates as nanovalves and realizing pH-sensitive release of entrapped subnano cargo. The proof-of-concept work also consists of the establishment of two mathematical models to explain the selective permeability of the nanovalves. Finally, gram-sized (or larger) quantities of the bio-inspired controlled release system can be synthesized through a scaling-up strategy, which opens up opportunities for controlled release of functional molecules in wider practical applications.Biological systems with controlled permeability and release functionality, which are among the successful examples of living beings to survive in evolution, have attracted intensive investigation and have been mimicked due to their broad spectrum of applications. We present in this work, for the first time, an example of nuclear pore complexes (NPCs)-inspired controlled release system that exhibits on-demand release of angstrom-sized molecules. We do so in a cost-effective way by stabilizing porous cobalt basic carbonates as nanovalves and realizing pH-sensitive release of entrapped subnano cargo. The proof-of-concept work also consists of the establishment of two mathematical models to explain the selective permeability of the nanovalves. Finally, gram-sized (or larger) quantities of the bio-inspired controlled release system can be synthesized through a scaling-up strategy, which opens up opportunities for controlled release of functional molecules in wider practical applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06378c

Interpretation of hydraulic tests performed at a carbonate rock site for CO2 storage

NASA Astrophysics Data System (ADS)

María Gómez Castro, Berta; Fernández López, Sheila; Carrera, Jesús; de Simone, Silvia; Martínez, Lurdes; Roetting, Tobias; Soler, Joaquim; Ortiz, Gema; de Dios, Carlos; Huber, Christophe

2014-05-01

Interpretation of hydraulic tests performed at a carbonate rock site for CO2 storage Berta Gómez, Sheila Fernández, Tobias Roetting, Lurdes Martínez, Silvia de Simone, Joaquim Soler, Jesus Carrera, Gema Ortiz, Christophe Huber, Carlos de Dios Proper design of CO2 geological storage facilities requires knowledge of the reservoir hydraulic parameters. Specifically, permeability controls the flux of CO2, the rate at which it dissolves, local and regional pressure buildup and the likelihood of induced seismicity. Permeability is obtained from hydraulic tests, which may yield local permeability, which controls injectivity, and large scale permeability, which controls pressure buildup at the large scale. If pressure response measurements are obtained at different elevations, hydraulic tests may also yield vertical permeability, which controls the rate at which CO2 dissolves. The objective of this work is to discuss the interpretation of hydraulic tests at deep reservoirs and the conditions under which these permeabilities can be obtained. To achieve this objective, we have built a radially symmetric model, including a skin and radial as well as vertical heterogeneity. We use this model to simulate hydraulic tests with increasing degrees of complexity about the medium response. We start by assuming Darcy flow, then add coupled mechanical effects (fractures opening) and, finally, we add thermal effects. We discuss how these affect the conventional interpretation of the tests and how to identify their presence. We apply these findings to the interpretation of hydraulic tests at Hontomin.

DFT calculations of the structures and vibrational spectra of the [Fe(bpy) 3] 2+ and [Ru(bpy) 3] 2+ complexes

NASA Astrophysics Data System (ADS)

Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

2008-09-01

Structures of the [M(bpy) 3] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1E MLCT excited state.

Effect of substituent of terpyridines on the in vitro antioxidant, antitubercular, biocidal and fluorescence studies of copper(II) complexes with clioquinol

NASA Astrophysics Data System (ADS)

Kharadi, G. J.

2014-01-01

An octahedral complexes of copper with clioquinol(CQ) and substituted terpyridine have been synthesized. The Cu(II) complexes have been characterized by elemental analyses, thermogravimetric analyses, magnetic moment measurements, FT-IR, electronic, 1H NMR and FAB mass spectra. Antimycobacterial screening of ligand and its copper compound against Mycobacterium tuberculosis shows clear enhancement in the antitubercular activity upon copper complexation. Ferric-reducing anti-oxidant power of all complexes were measured. The fluorescence spectra of complexes show red shift, which may be due to the chelation by the ligands to the metal ion. It enhances ligand ability to accept electrons and decreases the electron transition energy. The antimicrobial efficiency of the complexes were tested on five different microorganisms and showed good biological activity.

Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes

NASA Astrophysics Data System (ADS)

Sagdinc, Seda; Pir, Hacer

2009-07-01

The vibrational study in the solid state of flurbiprofen and its Cu(II) and Hg(II) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its complexes gave evidence that flurbiprofen binds metal (II) through the carboxylate oxygen. The fully optimized equilibrium structure of flurbiprofen and its metal complexes was obtained by density functional B3LYP method by using LanL2DZ and 6-31 G(d,p) basis sets. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of flurbiprofen were calculated by density functional B3LYP methods by using 6-31G(d,p) basis set. The scaled theoretical wavenumbers showed very good agreement with the experimental values. The electronic properties of the free molecule and its complexes were also performed at B3LYP/6-31G(d,p) level of theory. Detailed interpretations of the infrared and Raman spectra of flurbiprofen are reported. The UV-vis spectra of flurbiprofen and its metal complexes were also investigated in organic solvents.

Quantum-chemical, NMR, FT IR, and ESI MS studies of complexes of colchicine with Zn(II).

PubMed

Jankowski, Wojciech; Kurek, Joanna; Barczyński, Piotr; Hoffmann, Marcin

2017-04-01

Colchicine is a tropolone alkaloid from Colchicinum autumnale. It shows antifibrotic, antimitotic, and anti-inflammatory activities, and is used to treat gout and Mediterranean fever. In this work, complexes of colchicine with zinc(II) nitrate were synthesized and investigated using DFT, 1 H and 13 C NMR, FT IR, and ESI MS. The counterpoise-corrected and uncorrected interaction energies of these complexes were calculated. We also calculated their 1 H, 13 C NMR, and IR spectra and compared them with the corresponding experimentally obtained data. According to the ESI MS mass spectra, colchicine forms stable complexes with zinc(II) nitrate that have various stoichiometries: 2:1, 1:1:1, and 2:1:1 with respect to colchichine, Zn(II), and nitrate ion. All of the complexes were investigated using the quantum theory of atoms in molecules (QTAIM). The calculated and the measured spectra showed differences before and after the complexation process. Calculated electron densities and bond critical points indicated the presence of bonds between the ligands and the central cation in the investigated complexes that satisfied the quantum theory of atoms in molecules. Graphical Abstract DFT, NMR, FT IR, ESI MS, QTAIM and puckering studies of complexes of colchicine with Zn(II).

Proton transfer complexes based on some π-acceptors having acidic protons with 3-amino-6-[2-(2-thienyl)vinyl]-1,2,4-triazin-5(4 H)-one donor: Synthesis and spectroscopic characterizations

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

2011-05-01

Charge transfer complexes based on 3-amino-6-[2-(2-thienyl)vinyl]-1,2,4-triazin-5(4 H)-one (ArNH 2) organic basic donor and pi-acceptors having acidic protons such as picric acid (PiA), hydroquinone (Q(OH) 2) and 3,5-dinitrobenzene (DNB) have been synthesized and spectroscopically studied. The sbnd NH3+ ammonium ion was formed under the acid-base theory through proton transfer from an acidic to basic centers in all charge transfer complexes resulted. The values of formation constant ( KCT) and molar extinction coefficient ( ɛCT) which were estimated from the spectrophotometric studies have a dramatic effect for the charge transfer complexes with differentiation of pi-acceptors. For further studies the vibrational spectroscopy of the [( ArNH3+)(PiA -)] (1), [( ArNH3+)(Q (OH)2-)] (2) and [( ArNH3+)(DNB -)] (3) of (1:1) charge transfer complexes of (donor: acceptor) were characterized by elemental analysis, infrared spectra, Raman spectra, 1H and 13CNMR spectra. The experimental data of elemental analyses of the charge transfer complexes (1), (2) and (3) were in agreement with calculated data. The IR and Raman spectra of (1), (2) and (3) are indicated to the presence of bands around 3100 and 1600 cm -1 distinguish to sbnd NH3+. The thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) techniques were performed to give knowledge about thermal stability behavior of the synthesized charge transfer complexes. The morphological features of start materials and charge transfer complexes were investigated using scanning electron microscopy (SEM) and optical microscopy.

Development of Overpressures at Nankai Accretionary Prism, Ocean Drilling Program Sites 1173 and 1174

NASA Astrophysics Data System (ADS)

Gamage, K.; Screaton, E.

2003-12-01

In this study, we used a one-dimensional model of sedimentation, initial prism loading, and fluid flow to examine the development of overpressures at the toe of the Nankai accretionary complex. A permeability-porosity relationship was established for hemipelagic sediments from laboratory measured permeabilities as an input to the model. Vertical permeabilities were measured for 10 core samples from the Ocean Drilling Program (ODP) Leg 190, Sites 1173 and 1174, from the upper and lower Shikoku Basin facies. Both sites were drilled along the Muroto Transect through the dècollement zone or its equivalent. Site 1173 is located 11 km seaward of the deformation front and it represents the undeformed incoming sediments, where as Site 1174 represents sediments within the proto-thrust zone. Although turbidite-rich sediments dominate the Nankai accretionary prism, the dècollement and underthrust sediments are primarily composed of hemipelagic muds. Using the permeability-porosity relationship, our modeling results indicate excess pore pressures that are greater than 30% of lithostatic pressure at the toe of the prism at a convergence rate of 4cm/yr. These values are slightly lower than previously inferred excess pore pressures estimated from porosity data. Additional runs were conducted to simulate a 10-m thick low permeability barrier at the dècollement where vertical fluid flow is restricted. The low permeability barrier required a permeability less than 1 x 10-19 m2 to generate excess pore pressures greater than 50% of lithostatic pressure. Modeling was further extended to test the significance of variable prism loading rates due to uncertainties in the convergence rate and affects of lateral stress above the dècollement.

Reanalysis of in situ permeability measurements in the Barbados décollement

USGS Publications Warehouse

Bekins, B.A.; Matmon, D.; Screaton, E.J.; Brown, K.M.

2011-01-01

A cased and sealed borehole in the Northern Barbados accretionary complex was the site of the first attempts to measure permeability in situ along a plate boundary décollement. Three separate efforts at Hole 949C yielded permeability estimates for the décollement spanning four orders of magnitude. An analysis of problems encountered during installation of the casing and seals provides insights into how the borehole conditions may have led to the wide range of results. During the installation, sediments from the surrounding formation repeatedly intruded into the borehole and casing. Stress analysis shows that the weak sediments were deforming plastically and the radial and tangential stresses around the borehole were significantly lower than lithostatic. This perturbed stress state may explain why the test pressure records showed indications of hydrofracture at pressures below lithostatic, and permeabilities rose rapidly as the estimated effective stress dropped below 0.8 MPa. Even after the borehole was sealed, the plastic deformation of the formation and relatively large gap of the wire wrapped screen allowed sediment to flow into the casing. Force equilibrium calculations predict sediment would have filled the borehole to 10 cm above the top of the screen by the time slug tests were conducted 1.5 years after the borehole was sealed. Reanalysis of the slug test results with these conditions yields several orders of magnitude higher permeability estimates than the original analysis which assumed an open casing. Overall the results based on only the tests with no sign of hydrofracture yield a permeability range of 10−14–10−15 m2 and a rate of increase in permeability with decreasing effective stress consistent with laboratory tests on samples from the décollement zone.

Identification of small-scale low and high permeability layers using single well forced-gradient tracer tests: fluorescent dye imaging and modelling at the laboratory-scale.

PubMed

Barns, Gareth L; Thornton, Steven F; Wilson, Ryan D

2015-01-01

Heterogeneity in aquifer permeability, which creates paths of varying mass flux and spatially complex contaminant plumes, can complicate the interpretation of contaminant fate and transport in groundwater. Identifying the location of high mass flux paths is critical for the reliable estimation of solute transport parameters and design of groundwater remediation schemes. Dipole flow tracer tests (DFTTs) and push-pull tests (PPTs) are single well forced-gradient tests which have been used at field-scale to estimate aquifer hydraulic and transport properties. In this study, the potential for PPTs and DFTTs to resolve the location of layered high- and low-permeability layers in granular porous media was investigated with a pseudo 2-D bench-scale aquifer model. Finite element fate and transport modelling was also undertaken to identify appropriate set-ups for in situ tests to determine the type, magnitude, location and extent of such layered permeability contrasts at the field-scale. The characteristics of flow patterns created during experiments were evaluated using fluorescent dye imaging and compared with the breakthrough behaviour of an inorganic conservative tracer. The experimental results show that tracer breakthrough during PPTs is not sensitive to minor permeability contrasts for conditions where there is no hydraulic gradient. In contrast, DFTTs are sensitive to the type and location of permeability contrasts in the host media and could potentially be used to establish the presence and location of high or low mass flux paths. Numerical modelling shows that the tracer peak breakthrough time and concentration in a DFTT is sensitive to the magnitude of the permeability contrast (defined as the permeability of the layer over the permeability of the bulk media) between values of 0.01-20. DFTTs are shown to be more sensitive to deducing variations in the contrast, location and size of aquifer layered permeability contrasts when a shorter central packer is used. However, larger packer sizes are more likely to be practical for field-scale applications, with fewer tests required to characterise a given aquifer section. The sensitivity of DFTTs to identify layered permeability contrasts was not affected by test flow rate. Copyright © 2014 Elsevier B.V. All rights reserved.

Uv Spectroscopy on Gas Phase Cu(I)-BIPYRIDYL Complexes

NASA Astrophysics Data System (ADS)

Xu, Shuang; Christopher, Casey; Weber, J. Mathias

2015-06-01

Transition metal complexes with bipyridine ligands are of great interest in metal-organic chemistry, since they are prototypes for many applications in photochemistry and homogeneous catalysis. Under-coordinated bipyridyl complexes are elusive species in the condensed phase, and the ligand-induced changes in electronic structure are of fundamental interest. We present UV photodissociation spectra of mass-selected monocationic copper(I)-bipyridyl complexes [bpy-Cu-L]+ with different ligands (L = H2O, D2, N2, MeOH, Cl). Complexes were prepared via electrospray ionization of copper/bipyridine solutions followed by accumulation and buffer gas cooling in a cryogenic Paul trap. In addition, we show spectra of similar species based on copper oxide, [bpy-CuO-L]+.

Optical and photoconductivity spectra of novel Ag₂In₂SiS₆ and Ag₂In₂GeS₆ chalcogenide crystals.

PubMed

Chmiel, M; Piasecki, M; Myronchuk, G; Lakshminarayana, G; Reshak, Ali H; Parasyuk, O G; Kogut, Yu; Kityk, I V

2012-06-01

Complex spectral studies of near-band gap and photoconductive spectra for novel Ag(2)In(2)SiS(6) and Ag(2)In(2)GeS(6) single crystals are presented. The spectral dependences of photoconductivity clearly show an existence of spectral maxima within the 450 nm-540 nm and 780 nm-920 nm. The fundamental absorption edge is analyzed by Urbach rule. The origin of the spectral photoconductivity spectral maxima is discussed. Temperature dependences of the spectra were done. The obtained spectral features allow to propose the titled crystals as photosensors. An analysis of the absorption and photoconductivity spectra is given within a framework of oversimplified spectroscopic model of complex chalcogenide crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Direct effect of Taxol on free radical formation and mitochondrial permeability transition.

PubMed

Varbiro, G; Veres, B; Gallyas, F; Sumegi, B

2001-08-15

To elucidate the potential role of mitochondria in Taxol-induced cytotoxicity, we studied its direct mitochondrial effects. In Percoll-gradient purified liver mitochondria, Taxol induced large amplitude swelling in a concentration-dependent manner in the microM range. Opening of the permeability pore was also confirmed by the access of mitochondrial matrix enzymes for membrane impermeable substrates in Taxol-treated mitochondria. Taxol induced the dissipation of mitochondrial membrane potential (DeltaPsi) determined by Rhodamine123 release and induced the release of cytochrome c from the intermembrane space. All these effects were inhibited by 2.5 microM cyclosporine A. Taxol significantly increased the formation of reactive oxygen species (ROS) in both the aqueous and the lipid phase as determined by dihydrorhodamine123 and resorufin derivative. Cytochrome oxidase inhibitor CN(-), azide, and NO abrogated the Taxol-induced mitochondrial ROS formation while inhibitors of the other respiratory complexes and cyclosporine A had no effect. We confirmed that the Taxol-induced collapse of DeltaPsi and the induction of ROS production occurs in BRL-3A cells. In conclusion, Taxol-induced adenine nucleotide translocase-cyclophilin complex mediated permeability transition, and cytochrome oxidase mediated ROS production. Because both cytochrome c release and mitochondrial ROS production can induce suicide pathways, the direct mitochondrial effects of Taxol may contribute to its cytotoxicity.

Cyclometalated Iminophosphorane Gold(III) and Platinum(II) Complexes. A Highly Permeable Cationic Platinum(II) Compound with Promising Anticancer Properties

PubMed Central

2015-01-01

New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg2Cl62– or PF6– respectively, display almost identical IC50 values in the sub-micromolar range (25–335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspase-independent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration. PMID:26147404

Detection of carbon monoxide (CO) as a furnace byproduct using a rotating mask spectrometer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinclair, Michael B.; Flemming, Jeb Hunter; Blair, Raymond

2006-02-01

Sandia National Laboratories, in partnership with the Consumer Product Safety Commission (CPSC), has developed an optical-based sensor for the detection of CO in appliances such as residential furnaces. The device is correlation radiometer based on detection of the difference signal between the transmission spectrum of the sample multiplied by two alternating synthetic spectra (called Eigen spectra). These Eigen spectra are derived from a priori knowledge of the interferents present in the exhaust stream. They may be determined empirically for simple spectra, or using a singular value decomposition algorithm for more complex spectra. Data is presented on the details of themore » design of the instrument and Eigen spectra along with results from detection of CO in background N{sub 2}, and CO in N{sub 2} with large quantities of interferent CO{sub 2}. Results indicate that using the Eigen spectra technique, CO can be measured at levels well below acceptable limits in the presence of strongly interfering species. In addition, a conceptual design is presented for reducing the complexity and cost of the instrument to a level compatible with consumer products.« less

Particle size reduction to the nanometer range: a promising approach to improve buccal absorption of poorly water-soluble drugs

PubMed Central

Rao, Shasha; Song, Yunmei; Peddie, Frank; Evans, Allan M

2011-01-01

Poorly water-soluble drugs, such as phenylephrine, offer challenging problems for buccal drug delivery. In order to overcome these problems, particle size reduction (to the nanometer range) and cyclodextrin complexation were investigated for permeability enhancement. The apparent solubility in water and the buccal permeation of the original phenylephrine coarse powder, a phenylephrine–cyclodextrin complex and phenylephrine nanosuspensions were characterized. The particle size and particle surface properties of phenylephrine nanosuspensions were used to optimize the size reduction process. The optimized phenylephrine nanosuspension was then freeze dried and incorporated into a multi-layered buccal patch, consisting of a small tablet adhered to a mucoadhesive film, yielding a phenylephrine buccal product with good dosage accuracy and improved mucosal permeability. The design of the buccal patch allows for drug incorporation without the need to change the mucoadhesive component, and is potentially suited to a range of poorly water-soluble compounds. PMID:21753876

Particle size reduction to the nanometer range: a promising approach to improve buccal absorption of poorly water-soluble drugs.

PubMed

Rao, Shasha; Song, Yunmei; Peddie, Frank; Evans, Allan M

2011-01-01

Poorly water-soluble drugs, such as phenylephrine, offer challenging problems for buccal drug delivery. In order to overcome these problems, particle size reduction (to the nanometer range) and cyclodextrin complexation were investigated for permeability enhancement. The apparent solubility in water and the buccal permeation of the original phenylephrine coarse powder, a phenylephrine-cyclodextrin complex and phenylephrine nanosuspensions were characterized. The particle size and particle surface properties of phenylephrine nanosuspensions were used to optimize the size reduction process. The optimized phenylephrine nanosuspension was then freeze dried and incorporated into a multi-layered buccal patch, consisting of a small tablet adhered to a mucoadhesive film, yielding a phenylephrine buccal product with good dosage accuracy and improved mucosal permeability. The design of the buccal patch allows for drug incorporation without the need to change the mucoadhesive component, and is potentially suited to a range of poorly water-soluble compounds.

Microwave absorption properties of flake-shaped Co particles composites at elevated temperature (293-673 K) in X band

NASA Astrophysics Data System (ADS)

Wang, Guowu; Li, Xiling; Wang, Peng; Zhang, Junming; Wang, Dian; Qiao, Liang; Wang, Tao; Li, Fashen

2018-06-01

The complex permeability and permittivity of the easy-plane anisotropic Co/polyimide composite at high temperature (293-673 K) in X band were measured. The results show that both the complex permeability and permittivity increase with the increase of temperature in the measured temperature range. The calculated absorption properties display that the intensity of the reflection loss (RL) peak first increases and then decreases with the increase of temperature, and reaches the maximum (-52 dB) at 523 K. At each temperature, the composite can achieve the RL exceeding -10 dB in the whole X band. The composite can even work stably for more than 20 min with the excellent absorption performance under 673 K. In addition, the RL performance of the composite at high temperature is better than that at room temperature.

Strain-dependent permeability of volcanic rocks.

NASA Astrophysics Data System (ADS)

Farquharson, Jamie; Heap, Michael; Baud, Patrick

2016-04-01

We explore permeability evolution during deformation of volcanic materials using a suite of rocks with varying compositions and physical properties (such as porosity ϕ). 40 mm × 20 mm cylindrical samples were made from a range of extrusive rocks, including andesites from Colima, Mexico (ϕ˜0.08; 0.18; 0.21), Kumamoto, Japan (ϕ˜0.13), and Ruapehu, New Zealand (ϕ˜0.15), and basalt from Mt Etna, Italy (ϕ˜0.04). Gas permeability of each sample was measured before and after triaxial deformation using a steady-state benchtop permeameter. To study the strain-dependence of permeability in volcanic rocks, we deformed samples to 2, 3, 4, 6, and 12 % axial strain at a constant strain rate of 10-5 s-1. Further, the influence of failure mode - dilatant or compactant - on permeability was assessed by repeating experiments at different confining pressures. During triaxial deformation, porosity change of the samples was monitored by a servo-controlled pore fluid pump. Below an initial porosity of ˜0.18, and at low confining pressures (≤ 20 MPa), we observe a dilatant failure mode (shear fracture formation). With increasing axial strain, stress is accommodated by fault sliding and the generation of ash-sized gouge between the fracture planes. In higher-porosity samples, or at relatively higher confining pressures (≥ 60 MPa), we observe compactant deformation characterised by a monotonous decrease in porosity with increasing axial strain. The relative permeability k' is given by the change in permeability divided by the initial reference state. When behaviour is dilatant, k' tends to be positive: permeability increases with progressive deformation. However, results suggest that after a threshold amount of strain, k' can decrease. k' always is negative (permeability decreases during deformation) when compaction is the dominant behaviour. Our results show that - in the absence of a sealing or healing process - the efficiency of a fault to transmit fluids is correlated to the degree of strain to which is subjected. Volcanic processes such as dome extrusion, which involve progressive strain on complex fault systems, have been seen to cause fault sliding and the prolific generation of fault gouge. Our results indicate that the permeability of these faults will tend to remain constant or increase during continued extrusion, allowing magmatic gases to readily outgas through permeable fault architectures despite the generation and accumulation of gouge. On the other hand, deeper regions of the edifice that will typically be compacting due to the relatively higher confining pressures, will exhibit a continuous decrease in permeability. The interplay between permeability-increasing and permeability-decreasing processes within the edifice is likely to influence outgassing and eruptive cycles at active volcanoes.

A transmission line method for the measurement of microwave permittivity and permeability

NASA Astrophysics Data System (ADS)

Lederer, P. G.

1990-12-01

A method for determining complex permittivity and permeability at microwave frequencies from two port S parameter measurements of lossy solids in coaxial or waveguide transmission lines is described. The use of the TRL (Through Reflect Line) calibration scheme allows the measuring system to be calibrated right up to the specimen faces thereby eliminating most of the sample cell from the measurement and allowing suitable materials to be molded directly into the specimen cell in order to eliminate air gaps between specimen and transmission line walls. Some illustrative measurements for dielectric and magnetic materials are presented.

Theoretical Study on the Photoelectron Spectra of Ln(COT)2-: Lanthanide Dependence of the Metal-Ligand Interaction.

PubMed

Nakajo, Erika; Masuda, Tomohide; Yabushita, Satoshi

2016-12-08

We have performed a theoretical analysis of the recently reported photoelectron (PE) spectra of the series of sandwich complex anions Ln(COT) 2 - (Ln = La-Lu, COT = 1,3,5,7-cyclooctatetraene), focusing on the Ln dependence of the vertical detachment energies. For most Ln, the π molecular orbitals, largely localized on the COT ligands, have the energy order of e 1g < e 1u < e 2g < e 2u as in the actinide analogues, reflecting the substantial orbital interaction with the Ln 5d and 5p orbitals. Thus, it would be expected that the lanthanide contraction would increase the orbital interaction so that the overlaps between the COT π and Ln atomic orbitals tend to increase across the series. However, the PE spectra and theoretical calculations were not consistent with this expectation, and the details have been clarified in this study. Furthermore, the energy level splitting patterns of the anion and neutral complexes have been studied by multireference ab initio methods, and the X peak splittings observed in the PE spectra only for the middle-range Ln complexes were found to be due to the specific interaction between the Ln 4f and ligand π orbitals of the neutral complexes in e 2u symmetry. Because the magnitude of this 4f-ligand interaction depends critically on the final state 4f electron configuration and the spin state, a significant Ln dependence in the PE spectra is explained.

VizieR Online Data Catalog: IRS spectra with features of crystalline silicates (Chen+, 2016)

NASA Astrophysics Data System (ADS)

Chen, R.; Luo, A.; Liu, J.; Jiang, B.

2018-04-01

Spectra taken by the IRS (Houck et al. 2004ApJS..154...18H) on the Spitzer space telescope (Werner et al. 2004ApJS..154....1W) are now publicly available. These spectra are produced using the bksub.tbl products from SL and LL modules of final SSC pipeline, version 18.18. From the IRS data archive, we found a collection of 16986 low-resolution spectra. The spectra are merged by four slits: SL2 (5.21-7.56 μm), SL1 (7.57-14.28 μm), LL2 (14.29-20.66 μm), and LL1 (20.67-38.00 μm). As crystalline silicates have no features in the SL2 band, we choose the spectra that include all the other three bands: SL1, LL2, and LL1 so that the object has a continuous spectrum from about 7.5-38 μm. In this way, five of the seven infrared complexes of crystalline silicates are covered, i.e., the 10, 18, 23, 28, and 33 μm complexes. (5 data files).

Simulation of electron energy loss spectra of nanomaterials with linear-scaling density functional theory

DOE PAGES

Tait, E. W.; Ratcliff, L. E.; Payne, M. C.; ...

2016-04-20

Experimental techniques for electron energy loss spectroscopy (EELS) combine high energy resolution with high spatial resolution. They are therefore powerful tools for investigating the local electronic structure of complex systems such as nanostructures, interfaces and even individual defects. Interpretation of experimental electron energy loss spectra is often challenging and can require theoretical modelling of candidate structures, which themselves may be large and complex, beyond the capabilities of traditional cubic-scaling density functional theory. In this work, we present functionality to compute electron energy loss spectra within the onetep linear-scaling density functional theory code. We first demonstrate that simulated spectra agree withmore » those computed using conventional plane wave pseudopotential methods to a high degree of precision. The ability of onetep to tackle large problems is then exploited to investigate convergence of spectra with respect to supercell size. As a result, we apply the novel functionality to a study of the electron energy loss spectra of defects on the (1 0 1) surface of an anatase slab and determine concentrations of defects which might be experimentally detectable.« less

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.; Piana, M.J.

2002-01-01

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatitebased in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 ??M was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations ???4700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 A??. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios ???0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.

Spectra, energy levels, and energy transition of lanthanide complexes with cinnamic acid and its derivatives.

PubMed

Zhou, Kaining; Feng, Zhongshan; Shen, Jun; Wu, Bing; Luo, Xiaobing; Jiang, Sha; Li, Li; Zhou, Xianju

2016-04-05

High resolution spectra and luminescent lifetimes of 6 europium(III)-cinnamic acid complex {[Eu2L6(DMF)(H2O)]·nDMF·H2O}m (L=cinnamic acid I, 4-methyl-cinnamic acid II, 4-chloro-cinnamic acid III, 4-methoxy-cinnamic acid IV, 4-hydroxy-cinnamic acid V, 4-nitro-cinnamic acid VI; DMF=N, N-dimethylformamide, C3H7NO) were recorded from 8 K to room temperature. The energy levels of Eu(3+) in these 6 complexes are obtained from the spectra analysis. It is found that the energy levels of the central Eu(3+) ions are influenced by the nephelauxetic effect, while the triplet state of ligand is lowered by the p-π conjugation effect of the para-substituted functional groups. The best energy matching between the ligand triplet state and the central ion excited state is found in complex I. While the other complexes show poorer matching because the gap of (5)D0 and triplet state contracts. Copyright © 2016 Elsevier B.V. All rights reserved.

Elaboration, characterization and application of polysulfone and polyacrylic acid blends as ultrafiltration membranes for removal of some heavy metals from water.

PubMed

Mbareck, Chamekh; Nguyen, Quang Trong; Alaoui, Ouafa Tahiri; Barillier, Daniel

2009-11-15

Polysulfone (PSf)/polyacrylic acid ultrafiltration (PSf/PAA) membranes were prepared from a polymer blend in dimethylformamide by coagulation in water according to the wet phase inversion method. Immobilization of water-soluble PAA within the non-soluble PSf matrix was proven by the increase of ion exchange capacity and the intensity of the carboxyl groups' peak with the increase of PAA content as shown by Fourier transform infrared spectra. These results lead to consider that PSf and PAA form a semi-interpenetrating polymer networks. The obtained membranes showed a decrease of mean surface-pore sizes, the overall porosity and the hydraulic permeability with the increase in PAA content. Such results were imputed to the morphologic modifications of PSf film with the immobilization of increasing PAA amount. PSf/PAA membranes showed high lead, cadmium and chromium rejection which reaches 100% at pH superior to 5.7 and a low rejection at low pH. Moreover, the heavy metal rejection decreases with feed solution concentration and applied pressure increases. These behaviors were attributed to the role of carboxylic groups in ion exchange or complexation. As a matter of fact, the strong lead ion-PAA interactions were revealed by the scanning electron microscopy with energy dispersive X-rays (SEM-EDX).

Physical and mechanical properties of gelatin-CMC composite films under the influence of electrostatic interactions.

PubMed

Esteghlal, Sara; Niakousari, Mehrdad; Hosseini, Seyed Mohammad Hashem

2018-07-15

The objective of current study was to examine the electrostatic interactions between gelatin and carboxymethyl cellulose (CMC) as a function of pH and mixing ratio (MR) and to observe how the physical and mechanical properties of gelatin-CMC composite films are affected by these interactions. The interaction between biopolymers was studied using turbidometric analysis at different gelatin: CMC MRs and pH values. A reduction in pH and MR enhanced the electrostatic interactions; while, decreased the relative viscosity of mixed system. Physical and mechanical properties of resultant composite films were examined and compared with those of control gelatin films. Changes in the intensity of interactions between the two biopolymers resulted in films with different properties. Polymer complexation led to formation of resistant film networks of less solubility and swellability. Water vapor permeability (WVP) was not significantly (P≤0.05) influenced by incorporating CMC into continuous gelatin films. Composite films prepared at MR of 9:1 and pH opt (corresponding to the maximum amount of interaction) revealed different characteristics such as maximum amounts of WVP and swelling and minimum amounts of tensile strength and solubility. FTIR spectra of composite films confirmed that gelatin and CMC were not covalently bonded. Copyright © 2018 Elsevier B.V. All rights reserved.

Infrared spectra of hexamethylbenzene—tetracyanoethylene complexes at high pressures

NASA Astrophysics Data System (ADS)

Yamada, Haruka; Saheki, Masao

Infrared spectra of hexamethylbenzene(HMB)—tetracyanoethylene(TCNE), 1:1 and 2:1, complexes were measured under high pressures, 11˜4,000 bar. It was found that the CC stretching (A g) band of TCNE became much stronger at high pressures than at 1 bar and that the intensity increase of this band was especially large for both of the complexes. Based on these facts the strong appearance of the CC band at 1 bar, which is inconsistent with the symmetry consideration derived from X-ray analysis, can be discussed.

[Raman spectra of complexes of rare earth nitrate with histidine].

PubMed

Gao, S; Ji, M; Liu, J; Hou, Y; Chen, S

1999-12-01

Raman spectra of solid complexes RE(His)(NO3)3 x H2O (RE = La-Nd, Sm-Lu, Y; His = L-alpha-histidine ) have been investigated. The results indicate that RE3+ coordinates with one O atome of carboxyl group in the complex, while amino group and imidazole ring do not take part in coordination and NO3 is double coordination. The vibration peaks of carboxyl group delta(v)COO-(as-s) were plotted against the atomic number of the lanthanoids, which obeys Oddo-Harkins law.

High-Permeability Magnetic Polymer Additives for Lightweight Electromagnetic Shielding

DTIC Science & Technology

2015-08-01

organometallic complexes containing Fe2+ cations. [Cp] = cyclopentadiene; [Py] = pyrrole ; [Imid] = imidazole. ΔEmag values calculated with DFT using the...27 Table A-6 Energy difference between high- and low-spin magnetic states in transition metal ion- pyrrole (Py) complexes...2-],52 pyrrole (C4NH5),53 and other heterocyclic ligands.36,54 The cyclopentadienyl ligand, in particular, is ubiquitous in organometallic chemistry

Operation of passive membrane systems for drinking water treatment.

PubMed

Oka, P A; Khadem, N; Bérubé, P R

2017-05-15

The widespread adoption of submerged hollow fibre ultrafiltration (UF) for drinking water treatment is currently hindered by the complexity and cost of these membrane systems, especially in small/remote communities. Most of the complexity is associated with auxiliary fouling control measures, which include backwashing, air sparging and chemical cleaning. Recent studies have demonstrated that sustained operation without fouling control measures is possible, but little is known regarding the conditions under which extended operation can be sustained with minimal to no fouling control measures. The present study investigated the contribution of different auxiliary fouling control measures to the permeability that can be sustained, with the intent of minimizing the mechanical and operational complexity of submerged hollow fiber UF membrane systems while maximizing their throughput capacity. Sustained conditions could be achieved without backwashing, air sparging or chemical cleaning (i.e. passive operation), indicating that these fouling control measures can be eliminated, substantially simplifying the mechanical and operational complexity of submerged hollow fiber UF systems. The adoption of hydrostatic pressure (i.e. gravity) to provide the driving force for permeation further reduced the system complexity. Approximately 50% of the organic material in the raw water was removed during treatment. The sustained passive operation and effective removal of organic material was likely due to the microbial community that established itself on the membrane surface. The permeability that could be sustained was however only approximately 20% of that which can be maintained with fouling control measures. Retaining a small amount of air sparging (i.e. a few minutes daily) and incorporating a daily 1-h relaxation (i.e. permeate flux interruption) period prior to sparging more than doubled the permeability that could be sustained. Neither the approach used to interrupt the permeate flux nor that developed to draw air into the system for sparging using gravity add substantial mechanical or operational complexity to the system. The high throughput capacity that can be sustained by eliminating all but a couple of simple fouling control measures make passive membrane systems ideally suited to provide high quality water especially where access to financial resources, technical expertise and/or electrical power is limited. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photo-degradation of CT-DNA with a series of carbothioamide ruthenium (II) complexes - Synthesis and structural analysis

NASA Astrophysics Data System (ADS)

Muthuraj, V.; Umadevi, M.

2018-04-01

The present research article is related with the method of preparation, structure and spectroscopic properties of a series of carbothioamide ruthenium (II) complexes with N and S donor ligands namely, 2-((6-chloro-4-oxo-4H-chromen-3-yl)methylene) hydrazine carbothioamide (ClChrTs)/2-((6-methoxy-4-oxo-4H-chromen-3-yl)methylene)hydrazine carbothioamide (MeOChrTS). The synthesized complexes were characterized by several techniques using analytical methods as well as by spectral techniques such as FT-IR, 1HNMR, 13CNMR, ESI mass and thermogravimetry/differential thermal analysis (TG-DTA). The IR spectra shows that the ligand acts as a neutral bidentate with N and S donor atoms. The biological activity of the prepared compounds and metal complexes were tested against cell line of calf-thymus DNA via an intercalation mechanism (MCF-7). In addition, the interaction of Ru(II) complexes and its free ligands with CT-DNA were also investigated by titration with UV-Vis spectra, fluorescence spectra, and Circular dichroism studies. Results suggest that both of the two Ru(II) complexes can bind with calf-thymus DNA via an intercalation mechanism.

Identification of different coordination geometries by XAFS in copper(II) complexes with trimesic acid

NASA Astrophysics Data System (ADS)

Gaur, A.; Klysubun, W.; Soni, Balram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2016-10-01

X-ray absorption spectroscopy (XAS) is very useful in revealing the information about geometric and electronic structure of a transition-metal absorber and thus commonly used for determination of metal-ligand coordination. But XAFS analysis becomes difficult if differently coordinated metal centers are present in a system. In the present investigation, existence of distinct coordination geometries around metal centres have been studied by XAFS in a series of trimesic acid Cu(II) complexes. The complexes studied are: Cu3(tma)2(im)6 8H2O (1), Cu3(tma)2(mim)6 17H2O (2), Cu3(tma)2(tmen)3 8.5H2O (3), Cu3(tma) (pmd)3 6H2O (ClO4)3 (4) and Cu3(tma)2 3H2O (5). These complexes have not only Cu metal centres with different coordination but in complexes 1-3, there are multiple coordination geometries present around Cu centres. Using XANES spectra, different coordination geometries present in these complexes have been identified. The variation observed in the pre-edge features and edge features have been correlated with the distortion of the specific coordination environment around Cu centres in the complexes. XANES spectra have been calculated for the distinct metal centres present in the complexes by employing ab-initio calculations. These individual spectra have been used to resolve the spectral contribution of the Cu centres to the particular XANES features exhibited by the experimental spectra of the multinuclear complexes. Also, the variation in the 4p density of states have been calculated for the different Cu centres and then correlated with the features originated from corresponding coordination of Cu. Thus, these spectral features have been successfully utilized to detect the presence of the discrete metal centres in a system. The inferences about the coordination geometry have been supported by EXAFS analysis which has been used to determine the structural parameters for these complexes.

Technique for Performing Dielectric Property Measurements at Microwave Frequencies

NASA Technical Reports Server (NTRS)

Barmatz, Martin B. (Inventor); Jackson, Henry W. (Inventor)

2014-01-01

A method, system, apparatus, and computer readable medium has been provided with the ability to obtain a complex permittivity dielectric or a complex permeability micron of a sample in a cavity. One or more complex-valued resonance frequencies f(sub m) of the cavity, wherein each f(sub m) is a measurement, are obtained. Maxwell's equations are solved exactly for dielectric, and/or micron, using the f(sub m) as known quantities, thereby obtaining the dielectric and/or micron of the sample.

Advanced instrumental methods for analyzing organics in solid waste: The use of gas chromatography/matrix isolation infrared spectroscopy (GC/MIIR) and supercritical fluid chromatography (SFC) for waste characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raphaelian, L.A.; Boparai, A.S.; Schneider, J.F.

1987-01-01

Objectives of this research project were: (1) to enhance the capabilities of analyzing the complex mixtures found in coal wastes by using gas chromatography/matrix isolation infrared spectroscopy (GC/MIIR); (2) to separate, by supercritical fluid chromatography (SFC), the complex mixtures found in coal wastes into a few, less-complex mixtures so that analysis by gas chromatography (GC/MS) and GC/MIIR would be simplified. Preliminary results are presented for the mass spectra and infrared spectra of xylene isomers, gas chromatogram of 12 C/sub 2/-Napthalenes, averaged IR spectrum and a comparison of matrix isolation with light-pipe infrared spectra. A SFC chromatogram of polynuclear aromatic hydrocarbonsmore » is also presented. 2 refs., 5 figs.« less

The electronic spectra and the structures of the individual copper(II) chloride and bromide complexes in acetonitrile according to steady-state absorption spectroscopy and DFT/TD-DFT calculations

NASA Astrophysics Data System (ADS)

Olshin, Pavel K.; Myasnikova, Olesya S.; Kashina, Maria V.; Gorbunov, Artem O.; Bogachev, Nikita A.; Kompanets, Viktor O.; Chekalin, Sergey V.; Pulkin, Sergey A.; Kochemirovsky, Vladimir A.; Skripkin, Mikhail Yu.; Mereshchenko, Andrey S.

2018-03-01

The results of spectrophotometric study and quantum chemical calculations for copper(II) chloro- and bromocomplexes in acetonitrile are reported. Electronic spectra of the individual copper(II) halide complexes were obtained in a wide spectral range 200-2200 nm. Stability constants of the individual copper(II) halide complexes in acetonitrile were calculated: log β1 = 8.5, log β2 = 15.6, log β3 = 22.5, log β4 = 25.7 for [CuCln]2-n and log β1 = 17.0, log β2 = 24.6, log β3 = 28.1, log β4 = 30.4 for [CuBrn]2-n. Structures of the studied complexes were optimized and electronic spectra were simulated using DFT and TD-DFT methodologies, respectively. According to the calculations, the more is the number of halide ligands the less is coordination number of copper ion.

Signs of antimetastatic activity of palladium complexes of methylenediphosphonic acid in IR spectra

NASA Astrophysics Data System (ADS)

Tolstorozhev, G. B.; Skornyakov, I. V.; Pekhnio, V. I.; Kozachkova, A. N.; Sharykina, N. I.

2012-07-01

We have used Fourier transform IR spectroscopy methods to study normal mouse lung tissue and also after subcutaneous transplantation of a B-16 melanoma tumor in the tissue. We also studied tissues with B-16 melanoma after they were treated with coordination compounds based on palladium complexes of methylenediphosphonic acid. The IR spectra of the lung tissues with metastases in the region of the C = O stretching vibrations are different from the IR spectra of normal tissue. We identified spectroscopic signs of the presence of metastases in the lung. We show that when a cancerous tumor is treated with a preparation of palladium complexes of methylenediphosphonic acid, the spectroscopic signs of the presence of metastases in the lung are missing. After treatment with the optimal dose of this drug, the IR spectrum of the lung tissue in which multiple metastases were present before treatment corresponds to the spectrum of normal tissue. We have determined the efficacy of the antitumor activity of coordination compounds based on palladium complexes of methylenediphosphonic acid.

Isolation of Ion-Driven Conformations in Diphenylacetylene Molecular Switches Using Cryogenic Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Wolk, Arron B.; Garand, Etienne; Jones, Ian M.; Kamrath, Michael Z.; Hamilton, Rew; Johnson, Mark A.

2012-06-01

We report the infrared predissociation spectra of a family of ionic diphenylacetylene molecular switch complexes. The electrosprayed complexes were trapped and cooled in a cryogenic (10K) quadrupole ion trap and tagged with molecular deuterium. The infrared spectra of the vibrationally cold species reveal sharp transitions over a wide energy range (800 - 3800 cm-1), facilitating comparison to harmonic spectra. The evolution of the band pattern upon derivatization of the complexes exposes the signatures of the amide, urea, and carbonyl functionalities, enabling unambiguous identification of the non-covalent interactions that control the secondary structure of the molecule. Complexation with the tetramethylammonium cation reveals a conformation analogous to that of the neutral molecule, while halide ion attachment induces a conformational change similar to that observed earlier in solution. In several cases, both the donor and acceptor groups involved in the multidentate H-bonds are observed, providing a microscopic mechanical picture of the interactions at play. I. Jones, and A. Hamilton, Angew. Chem. Intl. Edit. 50, 4597 (2011).

The antibacterial activity and action mechanism of emodin from Polygonum cuspidatum against Haemophilus parasuis in vitro.

PubMed

Li, Li; Song, Xu; Yin, Zhongqiong; Jia, Renyong; Li, Zhengwen; Zhou, Xun; Zou, Yuanfeng; Li, Lixia; Yin, Lizi; Yue, Guizhou; Ye, Gang; Lv, Cheng; Shi, Wenjing; Fu, Yuping

2016-01-01

Haemophilus parasuis is the causative agent of Glässer's disease, which leads to serious economic loss to the swine industry. Although antibiotics are widely used to control infections, outbreaks of this disease repeatedly happen. In this study, emodin from Polygonum cuspidatum showed potent inhibitory effect against H. parasuis. The minimal inhibitory concentration (MIC) and minimal bactericidal concentration (MBC) values of emodin were 32 and 64μg/mL, respectively. The antibacterial kinetic curves indicated the antibacterial activity of emodin was in a concentration-dependent manner. Cell membrane permeability and flow cytometry assays proved that emodin could destroy cell membrane integrity and increase membrane permeability, and fluorescence spectra assay indicated emodin has influenced conformation of membrane protein. Under transmission electron microscopy, serious lesions of H. parasuis exposed to emodin (64μg/mL) were found, including irregular cell shape, plasmolysis, ruptured cell wall and membrane and cytoplasmic vacuolation. These results suggested that emodin could be used as candidate for treating Glässer's disease. Copyright © 2016 Elsevier GmbH. All rights reserved.

RMS Spectral Modelling - a powerful tool to probe the origin of variability in Active Galactic Nuclei

NASA Astrophysics Data System (ADS)

Mallick, Labani; Dewangan, Gulab chand; Misra, Ranjeev

2016-07-01

The broadband energy spectra of Active Galactic Nuclei (AGN) are very complex in nature with the contribution from many ingredients: accretion disk, corona, jets, broad-line region (BLR), narrow-line region (NLR) and Compton-thick absorbing cloud or TORUS. The complexity of the broadband AGN spectra gives rise to mean spectral model degeneracy, e.g, there are competing models for the broad feature near 5-7 keV in terms of blurred reflection and complex absorption. In order to overcome the energy spectral model degeneracy, the most reliable approach is to study the RMS variability spectrum which connects the energy spectrum with temporal variability. The origin of variability could be pivoting of the primary continuum, reflection and/or absorption. The study of RMS (Root Mean Square) spectra would help us to connect the energy spectra with the variability. In this work, we study the energy dependent variability of AGN by developing theoretical RMS spectral model in ISIS (Interactive Spectral Interpretation System) for different input energy spectra. In this talk, I would like to present results of RMS spectral modelling for few radio-loud and radio-quiet AGN observed by XMM-Newton, Suzaku, NuSTAR and ASTROSAT and will probe the dichotomy between these two classes of AGN.

Complex organic matter in space: about the chemical composition of carriers of the Unidentified Infrared Bands (UIBs) and protoplanetary emission spectra recorded from certain astrophysical objects.

PubMed

Cataldo, Franco; Keheyan, Yeghis; Heymann, Dieter

2004-02-01

In this communication we present the basic concept that the pure PAHs (Polycyclic Aromatic Hydrocarbons) can be considered only the ideal carriers of the UIBs (Unidentified Infrared Bands), the emission spectra coming from a large variety of astronomical objects. Instead we have proposed that the carriers of UIBs and of protoplanetary nebulae (PPNe) emission spectra are much more complex molecular mixtures possessing also complex chemical structures comparable to certain petroleum fractions obtained from the petroleum refining processes. The demonstration of our proposal is based on the comparison between the emission spectra recorded from the protoplanetary nebulae (PPNe) IRAS 22272+ 5435 and the infrared absorption spectra of certain 'heavy' petroleum fractions. It is shown that the best match with the reference spectrum is achieved by highly aromatic petroleum fractions. It is shown that the selected petroleum fractions used in the present study are able to match the band pattern of anthracite coal. Coal has been proposed previously as a model for the PPNe and UIBs but presents some drawbacks which could be overcome by adopting the petroleum fractions as model for PPNe and UIBs in place of coal. A brief discussion on the formation of the petroleum-like fractions in PPNe objects is included.

DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state

NASA Astrophysics Data System (ADS)

Hanuza, J.; Godlewska, P.; Lisiecki, R.; Ryba-Romanowski, W.; Kadłubański, P.; Lorenc, J.; Łukowiak, A.; Macalik, L.; Gerasymchuk, Yu.; Legendziewicz, J.

2018-05-01

The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln = Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass.

DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state.

PubMed

Hanuza, J; Godlewska, P; Lisiecki, R; Ryba-Romanowski, W; Kadłubański, P; Lorenc, J; Łukowiak, A; Macalik, L; Gerasymchuk, Yu; Legendziewicz, J

2018-05-05

The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln=Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass. Copyright © 2018. Published by Elsevier B.V.

Study on the interaction of a cyanine dye with human serum transferrin.

PubMed

Zhang, Xiu-feng; Chen, Lei; Yang, Qian-fan; Li, Qian; Sun, Xiao-ran; Chen, Hong-bo; Yang, Guang; Tang, Ya-lin

2015-12-01

Complexation between the primary carrier of ligands in blood plasma, human serum transferrin (Tf), and a cyanine dye, 3,3'-di(3-sulfopropyl)-4,5,4',5'-dibenzo-9-phenyl-thiacarbocyanine-triethylam monium salt (PTC) was investigated using fluorescence spectra, UV/Vis absorption spectra, synchronous fluorescence spectra, circular dichroism (CD) and molecular dynamic docking. The experimental results demonstrate that the formation of PTC-Tf complex is stabilized by van der Waal's interactions and hydrogen bonds, and the binding constants were found to be 8.55 × 10(6), 8.19 × 10(6) and 1.75 × 10(4) M(-1). Moreover, fluorescence experiments prove that the operational mechanism for the fluorescence quenching is static quenching and non-radiative energy transfer. Structural investigation of the PTC-Tf complexes via synchronous fluorescence spectra and CD showed that the structure of Tf became more stable with a major increase in the α-helix content and increased polarity around the tryptophan residues after PTC binding. In addition, molecular modeling highlights the residues located in the N-lobe, which retain high affinity for PTC. The mode of action of the PTC-Tf complex is illustrated by these results, and may provide an effective pathway for the transport and targeted delivery of antitumor agents. Copyright © 2015 John Wiley & Sons, Ltd.

Excited States and Luminescent Properties of UO 2F 2 and Its Solvated Complexes in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Jing; Wang, Zheming; Pan, Duoqiang

2014-07-21

The electronic absorption and emission spectra of free UO 2F 2 and its water solvated complexes below 32 000 cm –1 are investigated at the levels of ab initio CASPT2 and CCSD(T) with inclusion of scalar relativistic and spin–orbit coupling effects. The influence of the water coordination on the electronic spectra of UO 2F 2 is explored by investigating the excited states of solvated complexes (H 2O) nUO 2F 2 (n = 1–3). In these uranyl complexes, water coordination is found to have appreciable influence on the 3Δ (Ω = 1 g) character of the luminescent state and on themore » electronic spectral shape. The simulated luminescence spectral curves based on the calculated spectral parameters of (H 2O) nUO 2F 2 from CCSD(T) approach agree well with experimental spectra in aqueous solution at both near-liquid-helium temperature and room temperature. The possible luminescence spectra of free UO 2F 2 in gas phase are predicted on the basis of CASPT2 and CCSD(T) results, respectively, by considering three symmetric vibration modes. Finally, the effect of competition between spin–orbit coupling and ligand field repulsion on the luminescent state properties is discussed.« less

Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths.

PubMed

Ross, Matthew; Andersen, Amity; Fox, Zachary W; Zhang, Yu; Hong, Kiryong; Lee, Jae-Hyuk; Cordones, Amy; March, Anne Marie; Doumy, Gilles; Southworth, Stephen H; Marcus, Matthew A; Schoenlein, Robert W; Mukamel, Shaul; Govind, Niranjan; Khalil, Munira

2018-05-17

We present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute-solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute-solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute-solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis, X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute-solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.

Microseismicity cloud can be substantially larger than the associated stimulated fracture volume: the case of the Paralana Enhanced Geothermal System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riffault, Jeremy; Dempsey, David; Karra, Satish

The goal of hydraulic stimulation is to increase formation permeability in the near vicinity of a well. However, there remain technical challenges around measuring the outcome of this operation. During two Enhanced Geothermal System (EGS) stimulations in South Australia, Paralana in 2011 and Habanero in 2003, extensive catalogs of microseismicity were recovered. It is often assumed that shear failure of existing fractures is the main mechanism behind both the induced earthquakes and any permeability enhancement. This underpins a common notion, that the seismically active volume is also the stimulated reservoir. In this paper, we compute the density of earthquake hypocentersmore » and provide evidence that, under certain conditions, this spatiotemporal quantity is a reasonable proxy for pore pressure increase. We then apply an inverse modeling approach that uses the earthquake observations and a modified reservoir simulator to estimate the parameters of a permeability evolution relation. The regime implied by the data indicates that most permeability enhancement occurred very near to the wellbore and was not coincident with the bulk of the seismicity, whose volume was about two orders of magnitude larger. Thus, we conclude that, in some cases, it is possible for permeability enhancement and induced seismicity to be decoupled, in which case the seismically active volume is a poor indicator of the stimulated reservoir. Our results raise serious questions about the effectiveness of hydroshearing as a stimulation mechanism in EGS. Finally, this study extends our understanding of the complex processes linking earthquakes, fluid pressure, and permeability in both natural and engineered settings.« less

Permeability changes induced by microfissure closure and opening in tectonized materials. Effect on slope pore pressure regime.

NASA Astrophysics Data System (ADS)

De la Fuente, Maria; Vaunat, Jean; Pedone, Giuseppe; Cotecchia, Federica; Sollecito, Francesca; Casini, Francesca

2015-04-01

Tectonized clays are complex materials characterized by several levels of structures that may evolve during load and wetting/drying processes. Some microstructural patterns, as microfissures, have a particular influence on the value of permeability which is one of the main factors controlling pore pressure regime in slopes. In this work, the pore pressure regime measured in a real slope of tectonized clay in Southern Italy is analyzed by a numerical model that considers changes in permeability induced by microfissure closure and opening during the wetting and drying processes resulting from climatic actions. Permeability model accounts for the changes in Pore Size Distribution observed by Microscopy Intrusion Porosimetry. MIP tests are performed on representative samples of ground in initial conditions ("in situ" conditions) and final conditions (deformed sample after applying a wetting path that aims to reproduce the saturation of the soil under heavy rains). The resulting measurements allow for the characterization at microstructural level of the soil, identifying the distribution of dominant families pores in the sample and its evolution under external actions. Moreover, comparison of pore size density functions allows defining a microstructural parameter that depends on void ratio and degree of saturation and controls the variation of permeability. Model has been implemented in a thermo-hydro-mechanical code provided with a special boundary condition for climatic actions. Tool is used to analyze pore pressure measurements obtained in the tectonized clay slope. Results are analyzed at the light of the effect that permeability changes during wetting and drying have on the pore pressure regime.

Eddy currents in the measurement of magnetic susceptibility of rocks

NASA Astrophysics Data System (ADS)

Ježek, Josef; Hrouda, František

2018-01-01

The in-phase and out-of-phase susceptibility of rocks is determined by the magnetic permeability of minerals, their viscous relaxation, and by eddy currents in electrically conductive minerals induced by the applied field. The last effect has been modelled by analytical solution of Maxwell equations for a conductive sphere immersed in a homogeneous, non-conductive medium with given permeability, in presence of an alternating field. The solution is a complex function of parameters describing the sphere (its size, conductivity and permeability), surrounding medium (permeability) and applied field (frequency). Without numerical evaluations, it is difficult to distinguish in-phase and out-of-phase (OPS) susceptibility. In this paper, approximate equations are derived for both susceptibility components, which depend only on the permeability contrast between the sphere and the surrounding medium, and the skin ratio, defined as the ratio between sphere radius and skin depth of the induced currents. These equations are used to obtain a systematic assessment of the role of electrical conductivity in determining the susceptibility of rock samples. The contribution of eddy currents to the susceptibility of diluted (<5%) magnetite particle dispersions is negligible at 1 kHz, but not at higher frequencies. Common rock-forming paramagnetic and diamagnetic minerals with weak electrical conductivity and magnetic permeability are characterized by negligible OPS at 1 kHz. Theoretically, measurable OPS and high phase angles can be produced by paramagnetic conductive minerals in certain combinations with a diamagnetic matrix. This can be excluded from practical point of view for paramagnetic minerals with susceptibilities >0.003 and conductivities not exceeding 5000 S/m.

Permeability Sensitivity Functions and Rapid Simulation of Hydraulic-Testing Measurements Using Perturbation Theory

NASA Astrophysics Data System (ADS)

Escobar Gómez, J. D.; Torres-Verdín, C.

2018-03-01

Single-well pressure-diffusion simulators enable improved quantitative understanding of hydraulic-testing measurements in the presence of arbitrary spatial variations of rock properties. Simulators of this type implement robust numerical algorithms which are often computationally expensive, thereby making the solution of the forward modeling problem onerous and inefficient. We introduce a time-domain perturbation theory for anisotropic permeable media to efficiently and accurately approximate the transient pressure response of spatially complex aquifers. Although theoretically valid for any spatially dependent rock/fluid property, our single-phase flow study emphasizes arbitrary spatial variations of permeability and anisotropy, which constitute key objectives of hydraulic-testing operations. Contrary to time-honored techniques, the perturbation method invokes pressure-flow deconvolution to compute the background medium's permeability sensitivity function (PSF) with a single numerical simulation run. Subsequently, the first-order term of the perturbed solution is obtained by solving an integral equation that weighs the spatial variations of permeability with the spatial-dependent and time-dependent PSF. Finally, discrete convolution transforms the constant-flow approximation to arbitrary multirate conditions. Multidimensional numerical simulation studies for a wide range of single-well field conditions indicate that perturbed solutions can be computed in less than a few CPU seconds with relative errors in pressure of <5%, corresponding to perturbations in background permeability of up to two orders of magnitude. Our work confirms that the proposed joint perturbation-convolution (JPC) method is an efficient alternative to analytical and numerical solutions for accurate modeling of pressure-diffusion phenomena induced by Neumann or Dirichlet boundary conditions.

Microseismicity cloud can be substantially larger than the associated stimulated fracture volume: the case of the Paralana Enhanced Geothermal System

DOE PAGES

Riffault, Jeremy; Dempsey, David; Karra, Satish; ...

2018-06-21

The goal of hydraulic stimulation is to increase formation permeability in the near vicinity of a well. However, there remain technical challenges around measuring the outcome of this operation. During two Enhanced Geothermal System (EGS) stimulations in South Australia, Paralana in 2011 and Habanero in 2003, extensive catalogs of microseismicity were recovered. It is often assumed that shear failure of existing fractures is the main mechanism behind both the induced earthquakes and any permeability enhancement. This underpins a common notion, that the seismically active volume is also the stimulated reservoir. In this paper, we compute the density of earthquake hypocentersmore » and provide evidence that, under certain conditions, this spatiotemporal quantity is a reasonable proxy for pore pressure increase. We then apply an inverse modeling approach that uses the earthquake observations and a modified reservoir simulator to estimate the parameters of a permeability evolution relation. The regime implied by the data indicates that most permeability enhancement occurred very near to the wellbore and was not coincident with the bulk of the seismicity, whose volume was about two orders of magnitude larger. Thus, we conclude that, in some cases, it is possible for permeability enhancement and induced seismicity to be decoupled, in which case the seismically active volume is a poor indicator of the stimulated reservoir. Our results raise serious questions about the effectiveness of hydroshearing as a stimulation mechanism in EGS. Finally, this study extends our understanding of the complex processes linking earthquakes, fluid pressure, and permeability in both natural and engineered settings.« less

Increased apical Na+ permeability in cystic fibrosis is supported by a quantitative model of epithelial ion transport

PubMed Central

O’Donoghue, Donal L; Dua, Vivek; Moss, Guy W J; Vergani, Paola

2013-01-01

Cystic fibrosis (CF) is caused by mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) gene, which encodes an anion channel. In the human lung CFTR loss causes abnormal ion transport across airway epithelial cells. As a result CF individuals produce thick mucus, suffer persistent bacterial infections and have a much reduced life expectancy. Trans-epithelial potential difference (Vt) measurements are routinely carried out on nasal epithelia of CF patients in the clinic. CF epithelia exhibit a hyperpolarised basal Vt and a larger Vt change in response to amiloride (a blocker of the epithelial Na+ channel, ENaC). Are these altered bioelectric properties solely a result of electrical coupling between the ENaC and CFTR currents, or are they due to an increased ENaC permeability associated with CFTR loss? To examine these issues we have developed a quantitative mathematical model of human nasal epithelial ion transport. We find that while the loss of CFTR permeability hyperpolarises Vt and also increases amiloride-sensitive Vt, these effects are too small to account for the magnitude of change observed in CF epithelia. Instead, a parallel increase in ENaC permeability is required to adequately fit observed experimental data. Our study provides quantitative predictions for the complex relationships between ionic permeabilities and nasal Vt, giving insights into the physiology of CF disease that have important implications for CF therapy. PMID:23732645

Controls on Permeability Evolution in Fractured-Sorbing Media

NASA Astrophysics Data System (ADS)

Elsworth, D.

2017-12-01

A critical component in the desire to recover energy and fuels from the subsurface, or to sequester energy-related and other wastes, is the ability to control properties that influence the transport and storage of mass, fluids and energy. In fractured media, permeabilities are strongly dependent on effective stresses. In turn, effective stresses (M) are mediated by changes in fluid pressures (H), compositions of the permeating fluids and permeated rocks (C) and changes in temperature (T) - and sometimes influenced by biological (B) processes. First we explore the role of specific complex THMC(B) interactions in mediating changes in permeability in response to a change in spherical stress. These include the roles of differential strains, induced within shales by changes in pressure (H), gas concentration (C) or temperature (T), in driving changes in permeability, in particular where the effects of sorption are pronounced. We show that the influence of such pressure-, sorption- and thermally-induced changes in damage and porosity are countered, by the first order resetting effects of creep that influence the crack distribution within the fractured aggregate. Second, we explore linkages where friction and instability control the response to changes in differential stress. Changes in permeability are controlled by styles of deformation - brittle versus ductile - with modes of deformation in turn mediated by mineralogy of both native and altered mineral constituents, the evolving scale of deformation and in the progress of deformation through the dynamic loading cycle.

Critical dynamics of gravito-convective mixing in geological carbon sequestration

DOE PAGES

Soltanian, Mohamad Reza; Amooie, Mohammad Amin; Dai, Zhenxue; ...

2016-11-03

When CO 2 is injected in saline aquifers, dissolution causes a local increase in brine density that can cause Rayleigh-Taylor-type gravitational instabilities. Depending on the Rayleigh number, density-driven flow may mix dissolved CO 2 throughout the aquifer at fast advective time-scales through convective mixing. Heterogeneity can impact density-driven flow to different degrees. Zones with low effective vertical permeability may suppress fingering and reduce vertical spreading, while potentially increasing transverse mixing. In more complex heterogeneity, arising from the spatial organization of sedimentary facies, finger propagation is reduced in low permeability facies, but may be enhanced through more permeable facies. The connectivitymore » of facies is critical in determining the large-scale transport of CO 2-rich brine. We perform high-resolution finite element simulations of advection-diffusion transport of CO 2 with a focus on facies-based bimodal heterogeneity. Permeability fields are generated by a Markov Chain approach, which represent facies architecture by commonly observed characteristics such as volume fractions. CO 2 dissolution and phase behavior are modeled with the cubic-plus-association equation-of-state. Our results show that the organization of high-permeability facies and their connectivity control the dynamics of gravitationally unstable flow. Lastly, we discover new flow regimes in both homogeneous and heterogeneous media and present quantitative scaling relations for their temporal evolution.« less

Capturing poromechanical coupling effects of the reactive fracturing process in porous rock via a DEM-network model

NASA Astrophysics Data System (ADS)

Ulven, Ole Ivar; Sun, WaiChing

2016-04-01

Fluid transport in a porous medium has important implications for understanding natural geological processes. At a sufficiently large scale, a fluid-saturated porous medium can be regarded as a two-phase continuum, with the fluid constituent flowing in the Darcian regime. Nevertheless, a fluid mediated chemical reaction can in some cases change the permeability of the rock locally: Mineral dissolution can cause increased permeability, whereas mineral precipitation can reduce the permeability. This might trigger a complicated hydro-chemo-mechanical coupling effect that causes channeling of fluids or clogging of the system. If the fluid is injected or produced at a sufficiently high rate, the pressure might increase enough to cause the onset and propagation of fractures. Fractures in return create preferential flow paths that enhance permeability, localize fluid flow and chemical reaction, prevent build-up of pore pressure and cause anisotropy of the hydro-mechanical responses of the effective medium. This leads to a complex coupled process of solid deformation, chemical reaction and fluid transport enhanced by the fracture formation. In this work, we develop a new coupled numerical model to study the complexities of feedback among fluid pressure evolution, fracture formation and permeability changes due to a chemical process in a 2D system. We combine a discrete element model (DEM) previously used to study a volume expanding process[1, 2] with a new fluid transport model based on poroelasticity[3] and a fluid-mediated chemical reaction that changes the permeability of the medium. This provides new insights into the hydro-chemo-mechanical process of a transforming porous medium. References [1] Ulven, O. I., Storheim, H., Austrheim, H., and Malthe-Sørenssen, A. "Fracture Initiation During Volume Increasing Reactions in Rocks and Applications for CO2 Sequestration", Earth Planet. Sc. Lett. 389C, 2014a, pp. 132 - 142, doi:10.1016/j.epsl.2013.12.039. [2] Ulven, O. I., Jamtveit, B., and Malthe-Sørenssen, A., "Reaction-driven fracturing of porous rock", J. Geophys. Res. Solid Earth 119, 2014b, doi:10.1002/2014JB011102. [3] Ulven, O. I., and Sun, W.C., "A locally mass-conserving dual-graph lattice model for fluid-driven fracture", in prep.

Hydrothermal activity and subsoil complexity: implication for degassing processes at Solfatara crater, Campi Flegrei caldera

NASA Astrophysics Data System (ADS)

Montanaro, Cristian; Mayer, Klaus; Isaia, Roberto; Gresse, Marceau; Scheu, Bettina; Yilmaz, Tim I.; Vandemeulebrouck, Jean; Ricci, Tullio; Dingwell, Donald B.

2017-12-01

The Solfatara area and its fumaroles are the main surface expression of the vigorous hydrothermal activity within the active Campi Flegrei caldera system. At depth, a range of volcanic and structural processes dictate the actual state of the hydrothermal system below the crater. The presence of a large variety of volcanic products at shallow depth (including pyroclastic fallout ash beds, pyroclastic density current deposits, breccias, and lavas), and the existence of a maar-related fault system appears to exert major controls on the degassing and alteration behavior. Adding further to the complexity of this environment, variations in permeability and porosity, due to subsoil lithology and alteration effects, may further influence fluid flow towards the surface. Here, we report results from a field campaign conducted in July 2015 that was designed to characterize the in situ physical (temperature, humidity) and mechanical (permeability, strength, stiffness) properties of the Solfatara crater subsoil. The survey also included a mapping of the surficial hydrothermal features and their distributions. Finally, laboratory measurements (porosity, granulometry) of selected samples were performed. Our results enable the discrimination of four main subsoils around the crater: (1) the Fangaia domain located in a topographic low in the southwestern sector, (2) the silica flat domain on the western altered side, (3) the new crust domain in the central area, and (4) the crusted hummocks domain that dominates the north, east, and south parts. These domains are surrounded by encrusted areas, reworked material, and vegetated soil. The distribution of these heterogeneous subsoils suggests that their formation is mostly related to (i) the presence of the Fangaia domain within the crater and (ii) a system of ring faults bordering it. The subsoils show an alternation between very high and very low permeabilities, a fact which seems to affect both the temperature distribution and surficial degassing. A large range of surface temperatures (from 25 up to 95 °C) has been measured across these surfaces, with the hottest spot corresponding to the mud pools, the area of new crust formation, and the crusted hummocks. In the subsoil, the distribution of temperature is more complex and controlled by the presence of coarser, and more permeable, sandy/pebbly levels. These act as preferential pathways for hot hydrothermal fluid circulation. In contrast, low permeability, fine-grained levels act as thermal insulators that remain relatively cold and hinder fluid escape to the surface. Hot gases reach the surface predominantly along (vertical) fractures. When this occurs, mound-like structures can be formed by a cracking and healing process associated with significant degassing. It is anticipated that the results presented here may contribute to an improved understanding of the hazard potential associated with the ongoing hydrothermal activity within the Solfatara crater. At this site the permeability of the near-surface environment and its changes in space and time can affect the spatial and temporal distribution of gas and heat emission. Particularly, in areas where reduction in permeability occurs, it can produce pore pressure augmentation that may result in explosive events.

Blended polybenzimidazole and melamine-co-formaldehyde thermosets

DOE PAGES

Klaehn, John R.; Orme, Christopher J.; Peterson, Eric S.

2016-05-11

Polybenzimidazole [PBI; poly-2,2’(m-phenylene)-5,5’-bibenzimidazole] is known to have excellent high temperature stability (up to 450 ºC) and superb H 2/CO 2 selectivity compared to most high performance (HP) polymers. But, PBI has issues in thin-film formation compared to other HP polymers, due to challenging processing techniques. In this work, new blended thermosets were made with PBI and poly(melamine co-formaldehyde) [PMF] to produce stable thin-films after thermal processing at 220-250 ºC. PBI film formation is difficult, and the film tends to fracture and fissure due to loss of processing aids and stabilizers (salt/acid additives) that are found in PBI solutions above10 wtmore » %. The PBI-PMF blended thermosets we report do not have stabilizers, and can be made into dense thin-films. It is remarkable that these thermally processed PBI-PMF films were stable in deionized water for extended periods, whereas many PBI films that contain additives are not. The PBI-PMF films were analyzed using pure and mixed gas permeability measurement techniques. At 250 °C, the data show H 2/CO 2 gas selectivities greater than 13. Also, from the gas permeation data, the energy of activation (Ep) of a mixed gas stream for PBI-PMF shows that hydrogen permeates more easily than the other gases, while the permeabilities for the larger kinetic diameter gases are greatly diminished. The FT-IR spectra show that the PBI-PMF films have changed from parent PBI after thermal processing, and PMF dominates the spectra even in minor percent compositions. Altogether, the reported PBI-PMF thermoset films show good stability which can be used for high temperature gas separation.« less

Blended polybenzimidazole and melamine-co-formaldehyde thermosets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klaehn, John R.; Orme, Christopher J.; Peterson, Eric S.

Polybenzimidazole [PBI; poly-2,2’(m-phenylene)-5,5’-bibenzimidazole] is known to have excellent high temperature stability (up to 450 ºC) and superb H 2/CO 2 selectivity compared to most high performance (HP) polymers. But, PBI has issues in thin-film formation compared to other HP polymers, due to challenging processing techniques. In this work, new blended thermosets were made with PBI and poly(melamine co-formaldehyde) [PMF] to produce stable thin-films after thermal processing at 220-250 ºC. PBI film formation is difficult, and the film tends to fracture and fissure due to loss of processing aids and stabilizers (salt/acid additives) that are found in PBI solutions above10 wtmore » %. The PBI-PMF blended thermosets we report do not have stabilizers, and can be made into dense thin-films. It is remarkable that these thermally processed PBI-PMF films were stable in deionized water for extended periods, whereas many PBI films that contain additives are not. The PBI-PMF films were analyzed using pure and mixed gas permeability measurement techniques. At 250 °C, the data show H 2/CO 2 gas selectivities greater than 13. Also, from the gas permeation data, the energy of activation (Ep) of a mixed gas stream for PBI-PMF shows that hydrogen permeates more easily than the other gases, while the permeabilities for the larger kinetic diameter gases are greatly diminished. The FT-IR spectra show that the PBI-PMF films have changed from parent PBI after thermal processing, and PMF dominates the spectra even in minor percent compositions. Altogether, the reported PBI-PMF thermoset films show good stability which can be used for high temperature gas separation.« less

Cyclodextrin Enhances Corneal Tolerability and Reduces Ocular Toxicity Caused by Diclofenac

PubMed Central

Abdelkader, Hamdy; Fathalla, Zeinab; Moharram, Hossam; Ali, Taha F. S.

2018-01-01

With advances in refractive surgery and demand for cataract removal and lens replacement, the ocular use of nonsteroidal anti-inflammatory drugs (NSAIDs) has increased. One of the most commonly used NSAIDs is diclofenac (Diclo). In this study, cyclodextrins (CDs), α-, β-, γ-, and HP-β-CDs, were investigated with in vitro irritation and in vivo ulceration models in rabbits to reduce Diclo toxicity. Diclo-, α-, β-, γ-, and HP-β-CD inclusion complexes were prepared and characterized and Diclo-CD complexes were evaluated for corneal permeation, red blood cell (RBCs) haemolysis, corneal opacity/permeability, and toxicity. Guest- (Diclo-) host (CD) solid inclusion complexes were formed only with β-, γ-, and HP-β-CDs. Amphipathic properties for Diclo were recorded and this surfactant-like functionality might contribute to the unwanted effects of Diclo on the surface of the eye. Contact angle and spreading coefficients were used to assess Diclo-CDs in solution. Reduction of ocular toxicity 3-fold to16-fold and comparable corneal permeability to free Diclo were recorded only with Diclo-γ-CD and Diclo-HP-β-CD complexes. These two complexes showed faster healing rates without scar formation compared with exposure to the Diclo solution and to untreated groups. This study also highlighted that Diclo-γ-CD and Diclo-HP-β-CD demonstrated fast healing without scar formation. PMID:29636847

Anti-inflammatory activity of the essential oil obtained from Ocimum basilicum complexed with β-cyclodextrin (β-CD) in mice.

PubMed

Rodrigues, Lindaiane Bezerra; Martins, Anita Oliveira Brito Pereira Bezerra; Ribeiro-Filho, Jaime; Cesário, Francisco Rafael Alves Santana; E Castro, Fyama Ferreira; de Albuquerque, Thaís Rodrigues; Fernandes, Maria Neyze Martins; da Silva, Bruno Anderson Fernandes; Quintans Júnior, Lucindo José; Araújo, Adriano Antunes de Sousa; Menezes, Paula Dos Passos; Nunes, Paula Santos; Matos, Isabella Gonçalves; Coutinho, Henrique Douglas Melo; Goncalves Wanderley, Almir; de Menezes, Irwin Rose Alencar

2017-11-01

Cyclodextrins (CDs) are cyclic oligosaccharides can enhance the bioavailability of drugs. Ocimum basilicum is an aromatic plant found in Brazil used in culinary. The essential oil of this plant presents anti-edematogenic and anti-inflammatory activities in acute and chronic inflammation. The aim of this study was to investigate the anti-inflammatory effects of the essential oil obtained from O. basilicum complexed with β - cyclodextrin (OBEO/β-CD) in mice. The complexation with β-cyclodextrin (β-CD) was performed by different methods and analyzed by differential scanning calorimetry (DSC), thermogravimetry (TG) and scanning electron microscopy (SEM). The anti-inflammatory activity was evaluated using mice models of paw edema induced by carrageenan, dextran, histamine and arachidonic acid (AA); vascular permeability and peritonitis induced by carrageenan and granuloma induced by cotton block introduction. The DSC, TG and SEM analysis indicated that the OBEO was successfully complexed with β-CD. The oral administration of OEOB/β-CD prevented paw edema formation by decreasing vascular permeability in vivo, inhibited leukocyte recruitment to the peritoneal cavity, and inhibited granuloma formation in mice. Our results indicate that conjugation with β-CD improves the anti-inflammatory effects of OBEO in mice models of acute and chronic inflammation, indicating that this complex can be used in anti-inflammatory drug development. Copyright © 2017 Elsevier Ltd. All rights reserved.

Investigation of Room Temperature Mössbauer Spectroscopy and Initial Permeability Properties of Al3+ Substituted Cobalt Ferrites

NASA Astrophysics Data System (ADS)

Pandit, Rabia; Kaur, Pawanpreet; Sharma, K. K.; Hashim, Mohd.; Kumar, Ravi

In the present work, Al3+ substituted cobalt ferrites (CoFe2‑xAlxO4, x=0.2, 0.4, 0.6, 0.8) have been synthesized via standard solid-state reaction technique. The incorporation of Al3+ ions in cobalt ferrite has been shown to play an important role in modifying the magnetic properties. The room temperature (300K) 57Fe Mössbauer spectra reveals that the studied samples show two characteristic ferromagnetic zeeman sextets at A and B-sites at lower Al3+ ion concentration (i.e., up to x=0.4). However, a paramagnetic relaxation has been noted for higher Al3+ substitution (for x=0.6 and 0.8) samples. The dependence of the Mössbauer parameters such as isomer shift, quadrupole splitting, line width and magnetic hyperfine field on Al3+ ion concentration has also been noted. The variations in initial permeability over a wide frequency range (125kHz to 30MHz) at 300K have been recorded. The fairly constant values of initial permeability and the low values of the relative loss factor of the order of 10‑4 to 10‑5 over the wide frequency range are the important findings of the present work. The observed low values of relative loss factor at high frequencies suggest that the studied ferrites are promising materials to be used in microwave applications.

Accoustic waveform logging--Advances in theory and application

USGS Publications Warehouse

Paillet, F.L.; Cheng, C.H.; Pennington , W.D.

1992-01-01

Full-waveform acoustic logging has made significant advances in both theory and application in recent years, and these advances have greatly increased the capability of log analysts to measure the physical properties of formations. Advances in theory provide the analytical tools required to understand the properties of measured seismic waves, and to relate those properties to such quantities as shear and compressional velocity and attenuation, and primary and fracture porosity and permeability of potential reservoir rocks. The theory demonstrates that all parts of recorded waveforms are related to various modes of propagation, even in the case of dipole and quadrupole source logging. However, the theory also indicates that these mode properties can be used to design velocity and attenuation picking schemes, and shows how source frequency spectra can be selected to optimize results in specific applications. Synthetic microseismogram computations are an effective tool in waveform interpretation theory; they demonstrate how shear arrival picks and mode attenuation can be used to compute shear velocity and intrinsic attenuation, and formation permeability for monopole, dipole and quadrupole sources. Array processing of multi-receiver data offers the opportunity to apply even more sophisticated analysis techniques. Synthetic microseismogram data is used to illustrate the application of the maximum-likelihood method, semblance cross-correlation, and Prony's method analysis techniques to determine seismic velocities and attenuations. The interpretation of acoustic waveform logs is illustrated by reviews of various practical applications, including synthetic seismogram generation, lithology determination, estimation of geomechanical properties in situ, permeability estimation, and design of hydraulic fracture operations.

Microfracture development and foam collapse during lava dome growth

NASA Astrophysics Data System (ADS)

Ashwell, P.; Kendrick, J. E.; Lavallee, Y.; kennedy, B.; Hess, K.; Cole, J. W.; Dingwell, D. B.

2012-12-01

The ability of a volcano to degas effectively is regulated by the collapse of the foam during lava dome growth. As a lava dome extrudes and cools, it will begin to collapse under its own weight, leading to the closure of bubbles and the eventual blockage of the permeable foam network. A reduction in the lavas permeability hinders gas movement and increases internal bubble pressure, which may eventually lead to failure of the bubble walls, and ultimately to explosive fragmentation of the dome. However, the behaviour of lava dome material under compression is poorly understood. Here we present the results of low-load, uniaxial, high temperature (850oC) compression experiments on glassy, rhyolitic dome material from Ngongotaha (~200ka, following collapse of Rotorua Caldera) and Tarawera (1314AD, from dome collapse generated block and ash flow) domes in New Zealand. The development of textures and microstructures was tracked using neutron computed tomography at incremental stages of strain. Porosity and permeability measurements, using pycnometry and gas permeability, before and after each experiment quantified the evolution of the permeable bubble network. Our results show that uniaxial compression of vesicular lava leads to a systematic reduction of porosity on a timescale comparable to volcanic eruptions (hours - days). The closure of bubbles naturally decreases permeability parallel and perpendicular to the applied load, and at high strains fractures begin to initiate in phenocrysts and propagate vertically into the glass. These microfractures result in localised increases in permeability. Crystallinity and initial vesicularity of each sample affects the rate of bubble collapse and the evolution of permeability. The most highly compressed samples (60%) show textures similar to samples collected from the centre of Tarawera Dome, thought to have suffered from collapse shortly after dome emplacement. However, structures and porosities in the deformed Ngongotaha samples differ from the natural collapsed dome material. The interior of Ngongotaha Dome shows complex deformed flow banding, indicating that shearing during emplacement was a major component during collapse of the permeable foam. Understanding the development of the porous permeable network during lava dome growth is key to predicting the behaviour of an erupting volcano, and the assessing the likelihood of pressure build-up leading to a catastrophic explosive eruption.

An RGB approach to extraordinary spectra

NASA Astrophysics Data System (ADS)

Grusche, Sascha; Theilmann, Florian

2015-09-01

After Newton had explained a series of ordinary spectra and Goethe had pointed out its complementary counterpart, Nussbaumer discovered a series of extraordinary spectra which are geometrically identical and colourwise analogous to Newton’s and Goethe’s spectra. To understand the geometry and colours of extraordinary spectra, the wavelength composition is explored with filters and spectroscopic setups. Visualized in a dispersion diagram, the wavelength composition is interpreted in terms of additive colour mixing. Finally, all spectra are simulated as the superposition of red, green, and blue images that are shifted apart. This RGB approach makes it easy to understand the complex relationship between wavelengths and colours.

Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

PubMed

Adrowski, Michael J.; Mason, W. Roy

1997-03-26

Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

Synthesis and Spectra of Vanadium Complexes.

ERIC Educational Resources Information Center

Ophardt, Charles E.; Stupgia, Sean

1984-01-01

Describes an experiment which illustrates simple synthetic techniques, redox principles in synthesis reactions, interpretation of visible spectra using Orgel diagrams, and the spectrochemical series. The experiment is suitable for the advanced undergraduate inorganic chemistry laboratory. (JN)

Isosbestics in Infrared Aerosol Spectra: Proposed Applications for Remote Sensing.

DTIC Science & Technology

1989-04-01

droplet solutions and chemical reactions if the complex indices of refraction are known. The technique seems most applicable in the Rayleigh regime. Remote ... sensing , Isosbestics, Infrared, Infrared spectra, Atmosphere, Water, Aerosols, Rayleigh regime.

Enhanced electromagnetic interference shielding properties of carbon fiber veil/Fe3O4 nanoparticles/epoxy multiscale composites

NASA Astrophysics Data System (ADS)

Chen, Wei; Wang, Jun; Zhang, Bin; Wu, Qilei; Su, Xiaogang

2017-12-01

The multiscale approach has been adapted to enhance the electromagnetic interference shielding properties of carbon fiber (CF) veil epoxy-based composites. The Fe3O4 nanoparticles (NPs) were homogeneously dispersed in the epoxy matrix after surface modification by using silane coupling agent. The CF veil/Fe3O4 NPs/epoxy multiscale composites were manufactured by impregnating the CF veils with Fe3O4 NPs/epoxy mixture to prepare prepreg followed by vacuum bagging process. The electromagnetic interference shielding properties combined with the complex permittivity and complex permeability of the composites were investigated in the X-band (8.2-12.4 GHz) range. The total shielding effectiveness (SET) increases with increasing Fe3O4 NPs loadings and the maximum SET is 51.5 dB at low thickness of 1 mm. The incorporation of Fe3O4 NPs into the composites enhances the complex permittivity and complex permeability thus enhancing the electromagnetic wave absorption capability. The increased SET dominated by absorption loss SEA is attributed to the enhanced magnetic loss and dielectric loss generated by Fe3O4 NPs and multilayer construction of the composites. The microwave conductivity increases and the skin depth decreases with increasing Fe3O4 NPs loadings.

Improved Peak Detection and Deconvolution of Native Electrospray Mass Spectra from Large Protein Complexes.

PubMed

Lu, Jonathan; Trnka, Michael J; Roh, Soung-Hun; Robinson, Philip J J; Shiau, Carrie; Fujimori, Danica Galonic; Chiu, Wah; Burlingame, Alma L; Guan, Shenheng

2015-12-01

Native electrospray-ionization mass spectrometry (native MS) measures biomolecules under conditions that preserve most aspects of protein tertiary and quaternary structure, enabling direct characterization of large intact protein assemblies. However, native spectra derived from these assemblies are often partially obscured by low signal-to-noise as well as broad peak shapes because of residual solvation and adduction after the electrospray process. The wide peak widths together with the fact that sequential charge state series from highly charged ions are closely spaced means that native spectra containing multiple species often suffer from high degrees of peak overlap or else contain highly interleaved charge envelopes. This situation presents a challenge for peak detection, correct charge state and charge envelope assignment, and ultimately extraction of the relevant underlying mass values of the noncovalent assemblages being investigated. In this report, we describe a comprehensive algorithm developed for addressing peak detection, peak overlap, and charge state assignment in native mass spectra, called PeakSeeker. Overlapped peaks are detected by examination of the second derivative of the raw mass spectrum. Charge state distributions of the molecular species are determined by fitting linear combinations of charge envelopes to the overall experimental mass spectrum. This software is capable of deconvoluting heterogeneous, complex, and noisy native mass spectra of large protein assemblies as demonstrated by analysis of (1) synthetic mononucleosomes containing severely overlapping peaks, (2) an RNA polymerase II/α-amanitin complex with many closely interleaved ion signals, and (3) human TriC complex containing high levels of background noise. Graphical Abstract ᅟ.

Poromechanical response of naturally fractured sorbing media

NASA Astrophysics Data System (ADS)

Kumar, Hemant

The injection of CO2 in coal seams has been utilized for enhanced gas recovery and potential CO2 sequestration in unmineable coal seams. It is advantageous because as it enhances the production and significant volumes of CO2 may be stored simultaneously. The key issues for enhanced gas recovery and geologic sequestration of CO2 include (1) Injectivity prediction: The chemical and physical processes initiated by the injection of CO2 in the coal seam leads to permeability/porosity changes (2) Up scaling: Development of full scale coupled reservoir model which may predict the enhanced production, associated permeability changes and quantity of sequestered CO2. (3) Reservoir Stimulation: The coalbeds are often fractured and proppants are placed into the fractures to prevent the permeability reduction but the permeability evolution in such cases is poorly understood. These issues are largely governed by dynamic coupling of adsorption, fluid exchange, transport, water content, stress regime, fracture geometry and physiomechanical changes in coals which are triggered by CO 2 injection. The understanding of complex interactions in coal has been investigated through laboratory experiments and full reservoir scale models are developed to answer key issues. (Abstract shortened by ProQuest.).

Synthesis, crystal growth, structural and physicochemical studies of novel binary organic complex: 4-chloroaniline-3-hydroxy-4-methoxybenzaldehyde

NASA Astrophysics Data System (ADS)

Sharma, K. P.; Reddi, R. S. B.; Bhattacharya, S.; Rai, R. N.

2012-06-01

The solid-state reaction, which is solvent free and green synthesis, has been adopted to explore the novel compound. The phase diagram of 4-chloroaniline (CA) and 3-hydroxy-4-methoxybenzaldehyde (HMB) system shows the formation of a novel 1:1 molecular complex, and two eutectics on either sides of complex. Thermochemical studies of complex and eutectics have been carried out for various properties such as heat of fusion, entropy of fusion, Jackson's parameters, interfacial energy and excess thermodynamic functions. The formation of molecular complex was also studied by IR, NMR, elemental analysis and UV-Vis absorption spectra. The single crystal of molecular complex was grown and its XRD study confirms the formation of complex and identifies the crystal structure and atomic packing of crystal of complex. Transmission spectra of grown crystal of the complex show 70% transmittance efficiency with cut off wavelength 412 nm. The band gap and refractive index of the crystal of complex have also been studied.

Synthesis, spectroscopy, and binding constants of ketocatechol-containing iminodiacetic acid and its Fe(III), Cu(II), and Zn(II) complexes and reaction of Cu(II) complex with H₂O₂ in aqueous solution.

PubMed

Gao, Jiaojiao; Xing, Feifei; Bai, Yueling; Zhu, Shourong

2014-06-07

A new neuromelanin-like ketocatechol-containing iminodiacetic acid ligand, (N-(3,4-dihydroxyl)phenacylimino)diacetic acid (H4L), which is also quite similar to compounds found in insect cuticle, has been synthesized and characterized. The X-ray crystal structure of H4L has been successfully determined. Proton binding and coordination with Fe(III), Cu(II), and Zn(II) have been studied by potentiometric titrations and UV-vis spectrophotometry in aqueous solution. UV spectra of H4L in the absence and presence of different metal ions indicate complexes formed with the catechol moiety of H4L in aqueous solution. Visible spectra and NMR reveal that H4L with Fe(III), Cu(II), and Zn(II) can all give stable mono-(ML) and dinuclear complexes [M(ML)]. Fe(III) can also form {Fe(FeL)2} and {Fe(FeL)3} species with sufficient base. The process is accompanied by a drastic color change from light blue to deep-blue to wine-red. The Fe(III)-Cu(II) heteronuclear complex also exists in aqueous solution whose spectra are similar to the homonuclear Fe(III) complex. However, the spectra of {Fe(CuL)} shifted to a longer wavelength and {Fe(CuL)2} and {Fe(CuL)3} shifted to a shorter wavelength. Keto-enol tautomerism was observed in weak basic aqueous solution as indicated by (1)H NMR spectra. The reaction products of Cu(II) complex with H2O2 depend on the H2O2 concentration and pH value. Low concentrations of H2O2 oxidize H4L to a series of semiquinone and quinone compounds with absorption maxima at 314-400 nm, while a high concentration of H2O2 oxidizes H4L to colorless muconic acid derivatives. NaIO4 gives different oxidase products, but no 2,4,5-trihydroxyphenylalanine quinone (TPQ)-like hydroxyquinone can be found.

Electron Detachment as a Probe of Intrinsic Nucleobase Dynamics in Dianion-Nucleobase Clusters: Photoelectron Spectroscopy of the Platinum II Cyanide Dianion Bound to Uracil, Thymine, Cytosine and Adenine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sen, Ananya; Hou, Gao-Lei; Wang, Xue B.

2015-08-05

We report the first low-temperature photodetachment photoelectron spectra of isolated gas-phase complexes of the platinum II cyanide dianion bound to nucleobases. These systems are model systems for understanding platinum-complex photodynamic therapies, and knowledge of the intrinsic photodetachment properties is crucial for understanding their broader photophysical properties. Well-resolved, distinct peaks are observed in the spectra consistent with the complexes where the Pt(CN)42- moiety is largely intact. The adiabatic electron detachment energies for the dianion-nucleobase complexes are measured to be between 2.39-2.46 eV. The magnitudes of the repulsive Coulomb barriers of the complexes are estimated to be between 1.9 and 2.1 eV,more » values that are lower than for the bare Pt(CN)42- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photodetachment spectra of the four nucleobase-dianion complexes, and also in the 266 nm spectra of the Pt(CN)42-∙thymine and Pt(CN)42-∙adenine complexes. The selective excitation of these features in the 266 nm spectra is attributed to one-photon excitation of [Pt(CN)42-∙T]* and [Pt(CN)42-∙A]* long-lived excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment signals. We attribute the resonant electron detachment bands observed here for Pt(CN)42-∙T and Pt(CN)42-∙A but not for Pt(CN)42-∙U and Pt(CN)42-∙C to fundamental differences in the individual nucleobase photophysics following 266 nm excitation. This indicates that the Pt(CN)42- dianion in the Pt(CN)42-∙M clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase disaplys a long-lived excited state.« less

Assessment of spectroscopic parameters of solvated Eu(dmh)3 phen organometallic complex in various basic and acidic solvents.

PubMed

Chitnis, Dipti; Kalyani, N Thejo; Dhoble, Sanjay

2018-05-31

We report on the comprehension of novel europium activated hybrid organic Eu(dmh) 3 phen (Eu: europium, dmh: 2,6-dimethyl-3,5-heptanedione, phen: 1,10 phenanthroline) organo-metallic complexes, synthesized at different pH values by the solution technique. Photo physical properties of these complexes in various basic and acidic solvents were probed by UV-vis optical absorption and photoluminescence (PL) spectra. Minute differences in optical absorption peaks with variable optical densities were encountered with the variation in solvent from basic (chloroform, toluene, tetrahydrofuran) to acidic (acetic acid) media, revealing bathochromic shift in the absorption peaks. The PL spectra of the complex in various acidic and basic organic solvents revealed the position of the emission peak at 613 nm irrespective of the changes in solvents whereas the excitation spectrum almost matched with that of the UV-vis absorption data. The optical density was found to be maximum for the complex with pH 7.0 whereas it gradually decreased when pH was lowered to 6.0 or raised to 8.0 at an interval of 0.5, demonstrating its pH sensitive nature. Several spectroscopic parameters related to probability of transition such as absorbance A(λ), Napierian absorption coefficient α(λ), molecular absorption cross-section σ(λ), radiative lifetime (τ 0 ) and oscillator strength (f) were calculated from UV-vis spectra. The relative intensity ratio (R-ratio), calculated from the emission spectra was found to be almost the same in all the organic solvents. The optical energy gap, calculated for the designed complexes were found to be well in accordance with the ideal acceptance value of energy gap of the emissive materials used for fabrication of red organic light-emitting diode (OLED). The relation between Stoke's shift and solvent polarity function was established by Lippert-Mataga plot. This remarkable independence of the electronic absorption spectra of Eu complexes on the nature of the solvent with unique emission wavelength furnishes its potential to serve as a red light emitter for solution processed OLEDs, display panels and solid-state lighting. Copyright © 2018 John Wiley & Sons, Ltd.

Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

PubMed

McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

2015-07-06

Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

Spectroscopic and DFT study of atenolol and metoprolol and their copper complexes

NASA Astrophysics Data System (ADS)

Cozar, O.; Szabó, L.; Cozar, I. B.; Leopold, N.; David, L.; Căinap, C.; Chiş, V.

2011-05-01

IR, Raman and surface-enhanced Raman scattering (SERS) spectra of atenolol (ATE) and metoprolol (MET) were recorded and assigned on the basis of density functional theory (DFT) calculations. A reliable assignment of vibrational IR and Raman bands of the two compounds was possible by a proper choice of models used in quantum chemical calculations. Both molecules are adsorbed to the silver surface mainly through the oxygen atoms and π-electrons of the phenyl ring. The coordination mode of the metal ions in Cu(II)-ATE and -MET compounds was also derived from IR and EPR spectra. EPR spectra give evidence for a square-planar arrangement around the copper (II) ion in the case of Cu-ATE complex, with a N 2O 2 chromophore. Only oxygen atoms are involved in the cooper coordination for Cu-MET complex, and two types of local symmetries with d and d as ground states for paramagnetic electron coexist.

Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti–O–(C, Si, Ge) Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spanjers, Charles S.; Guillo, Pascal; Tilley, T. Don

X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti–O–(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique featuresmore » for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O–X (X = C, Si, or Ge) antibonding orbitals.« less

Energetic neutron and gamma-ray spectra under the earth radiation belts according to ``SALUTE-7''-``KOSMOS-1686'' orbital complex and ``CORONAS-I'' satellite data

NASA Astrophysics Data System (ADS)

Bogomolov, A. V.; Dmitriev, A. V.; Myagkova, I. N.; Ryumin, S. P.; Smirnova, O. N.; Sobolevsky, I. M.

The spectra of neutrons > 10 MeV and gamma-rays 1.5-100 MeV under the Earth Radiation Belts, restored from the data, obtained onboard orbital complex ``SALUTE-7''-``KOSMOS-1686'', are presented. The spectra shapes are similar to those for albedo neutrons and gamma-rays, but absolute values of their fluxes (0.2 cm^-2 s^-1 for neutrons, 0.8 cm^-2 s^-1 for gamma-rays at the equator and 1.2 cm^-2 s^-1, 1.9 cm^-2 s^-1, accordingly, at L=1.9) are several times as large. It is possibly explained by the fact that most of the detected particles were produced by the cosmic ray interactions with the orbital complex matter. Neutron and gamma-ray fluxes obtained from ``CORONAS-I'' data are near those for albedo particles.

Dielectric spectroscopy of solutions of amino silicone emulsion in distilled water

NASA Astrophysics Data System (ADS)

Shah, K. N.; Rana, V. A.; Trivedi, C. M.; Vankar, H. P.

2016-05-01

Complex permittivity spectra ɛ*(ω) = ɛ' - jɛ″ of solutions of amino silicone emulsion in distilled water in the frequency range 100 Hz to 2 MHz were obtained using precision LCR meter. Complex permittivity data is used to find out complex impedance z*(ω) and complex electric conductivity σ*(ω). All these spectra are used to gain information about various polarization processes taking place in the solutions of amino silicone emulsion in distilled water under the effect of ac electric field. The frequency and concentration dependent behavior of the solutions of amino silicone emulsion in distilled waterhave beenalso investigated. Density and refractive index of the samples are also measured and are reported.

[Study on molecular recognition technology in active constituents extracted and isolated from Aconitum pendulum].

PubMed

Ma, Xue-Qin; Li, Guo-Shan; Fu, Xue-Yan; Ma, Jing-Zu

2011-03-01

To investigate CD molecular recognition technology applied in active constituents extracted and isolated from traditional Chinese medicine--Aconitum pendulum. The inclusion constant and form probability of the inclusion complex of Aconitum pendulum with p-CD was calculated by UV spectra method. The active constituents of Aconitum pendulum were extracted and isolated by molecular recognition technology. The inclusion complex was identified by UV. The chemical constituents of Aconitum pendulum and inclusion complex was determined by HPLC. The analgesic effects of inclusion complex was investigated by experiment of intraperitoneal injection of acetic acid in rats. The inclusion complex was identified and confirmed by UV spectra method, the chemical components of inclusion complex were simple, and the content of active constituents increased significantly, the analgesic effects of inclusion complex was well. The molecular recognition technology can be used for extracting and isolating active constituents of Aconitum pendulum, and the effects are obvious.

Synthesis, interaction with DNA and bovine serum albumin of the transition metal complexes of demethylcantharate and 2-aminobenzothiazole

NASA Astrophysics Data System (ADS)

Zhang, Fan; Lin, Qiu-Yue; Li, Shi-Kun; Zhao, Yu-Ling; Wang, Peng-Peng; Chen, Miao-Miao

2012-12-01

Four new transition metal complexes (Habtz)2[M(DCA)2]·6H2O (M = Co(II) (1), Ni(II) (2), Cu(II) (3), Zn(II) (4); DCA = demethylcantharate, 7-oxabicyclo [2.2.1]heptane-2,3-dicarboxylate, C8H8O5; Habtz = 2-aminobenzothiazole acid, C7H7N2S) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra and thermogravimetric analysis. The coordination number of complex was six. The X-ray diffraction analysis indicated that complex 3 crystallized in the triclinic crystal system with P1¯ space group. The DNA-binding properties of the complexes were investigated by electronic absorption spectra, fluorescence spectra, viscosity measurements. Title complexes could bind to DNA via partial intercalative mode. The Kb of the complexes were 5.33 × 104 (1), 7.04 × 104 (2), 9.91 × 104 (3) and 5.03 × 104 L mol-1 (4). The results of agarose gel electrophoresis showed that Cu(II) complex could cleave pBR322 plasmid DNA via radical-based mechanism. The complexes could quench the intrinsic fluorescence of bovine serum albumin (BSA) through a static quenching with the binding constants Ka of 1.11 × 104 (1), 1.24 × 106 (2), 8.42 × 105 (3) and 1.75 × 104 L mol-1 (4). The complexes had intense antiproliferative activities against human hepatoma cell lines (SMMC7721) and human gastric cancer cells (MGC80-3) lines in vitro. Cu(II) complex had the strongest activity against human gastric cancer cells.

Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

NASA Astrophysics Data System (ADS)

Duncan, Michael

2006-03-01

Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

Synthesis and spectral characterization of trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes with Schiff bases.

PubMed

Singh, Atresh Kumar; Singh, Alok Kumar

2012-10-01

Some novel trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes of the general formula [Fe(3)O(OOCR)(3)(SB)(3)L(3)] (where R=C(13)H(27), C(15)H(31) or C(17)H(35,) HSB=Schiff bases and L=Ethanol) have been synthesized by the stepwise substitutions of acetate ions from μ(3)-oxo-hexa(acetato)tri(aqua)iron(II)diiron(III), first with straight chain carboxylic acids and then with Schiff bases. The complexes were characterized by elemental analyses, molecular weight determinations and spectral (electronic, infrared, FAB mass, Mössbauer and powder XRD) studies. Molar conductance measurements indicated the complexes to be non-electrolytes in nitrobenzene. Bridging nature of carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Mössbauer spectroscopic studies indicated two quadrupole-split doublets due to Fe(II) and Fe(III) ions at 80, 200 and 295K, confirming the complexes are mixed-valence species. This was also supported by the observed electronic spectra of the complexes. Magnetic susceptibility measurements displayed octahedral geometry around iron in mixed-valence state and a net antiferromagnetic exchange coupling via μ-oxo atom. Trinuclear nature of the complexes was confirmed by their molecular weight determination and FAB mass spectra. A plausible structure for these complexes has been established on the basis of spectral and magnetic moment data. Copyright © 2012 Elsevier B.V. All rights reserved.

Studies on the microwave permittivity and electromagnetic wave absorption properties of Fe-based nano-composite flakes in different sizes

NASA Astrophysics Data System (ADS)

Wu, Yanhui; Han, Mangui; Liu, Tao; Deng, Longjiang

2015-07-01

The effective permittivity of composites containing Fe-Cu-Nb-Si-B nanocrystalline micro flakes has been studied within 0.5-10 GHz. Obvious differences in microwave permittivity have been observed for composites consisting of large flakes (size range: 23-111 μm, average thickness: 4.5 μm) and small flakes (size range: 3-21 μm, average thickness: 1.3 μm). Both the real part and imaginary part of permittivity of large flake composite are much larger than these small one in a given frequency. And faster decrease of permittivity with the increasing frequency can be observed for large flake composite than that of small one. These differences in permittivity spectra of different flakes have been explained from the perspective of interfacial polarization and ac conductivity. The assumption that more extensive ohmic contact interface between large flakes and matrix has been validated by the fittings and the calculated percolation threshold. Meanwhile, the permeability spectra of both composites also have been studied by Lorentzian dispersion law. The broadened spectra can be attributed to the distribution of magnetic anisotropy fields of two kinds of ferromagnetic phases in the particles. Finally, the composite containing the small flakes exhibits better electromagnetic wave absorption properties.

Two-dimensional electronic spectra of the photosynthetic apparatus of green sulfur bacteria

NASA Astrophysics Data System (ADS)

Kramer, Tobias; Rodriguez, Mirta

2017-03-01

Advances in time resolved spectroscopy have provided new insight into the energy transmission in natural photosynthetic complexes. Novel theoretical tools and models are being developed in order to explain the experimental results. We provide a model calculation for the two-dimensional electronic spectra of Cholorobaculum tepidum which correctly describes the main features and transfer time scales found in recent experiments. From our calculation one can infer the coupling of the antenna chlorosome with the environment and the coupling between the chlorosome and the Fenna-Matthews-Olson complex. We show that environment assisted transport between the subunits is the required mechanism to reproduce the experimental two-dimensional electronic spectra.

Evaluation of a cost-effective loads approach. [shock spectra/impedance method for Viking Orbiter

NASA Technical Reports Server (NTRS)

Garba, J. A.; Wada, B. K.; Bamford, R.; Trubert, M. R.

1976-01-01

A shock spectra/impedance method for loads predictions is used to estimate member loads for the Viking Orbiter, a 7800-lb interplanetary spacecraft that has been designed using transient loads analysis techniques. The transient loads analysis approach leads to a lightweight structure but requires complex and costly analyses. To reduce complexity and cost, a shock spectra/impedance method is currently being used to design the Mariner Jupiter Saturn spacecraft. This method has the advantage of using low-cost in-house loads analysis techniques and typically results in more conservative structural loads. The method is evaluated by comparing the increase in Viking member loads to the loads obtained by the transient loads analysis approach. An estimate of the weight penalty incurred by using this method is presented. The paper also compares the calculated flight loads from the transient loads analyses and the shock spectra/impedance method to measured flight data.

Composition, Characterization and Antibacterial activity of Mn(II), Co(II),Ni(II), Cu(II) Zn(II) and Cd(II) mixed ligand complexes Schiff base derived from Trimethoprim with 8-Hydroxy quinoline

NASA Astrophysics Data System (ADS)

Numan, Ahmed T.; Atiyah, Eman M.; Al-Shemary, Rehab K.; Ulrazzaq, Sahira S. Abd

2018-05-01

New Schiff base ligand 2-((4-amino-5-(3, 4, 5-trimethoxybenzyl) pyrimidin-2-ylimino) (phenyl)methyl)benzoic acid] = [HL] was synthesized using microwave irradiation trimethoprim and 2-benzoyl benzoic acid. Mixed ligand complexes of Mn((II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) are reacted in ethanol with Schiff base ligand [HL] and 8-hydroxyquinoline [HQ] then reacted with metal salts in ethanol as a solvent in (1:1:1) ratio. The ligand [HL] is characterized by FTIR, UV-Vis, melting point, elemental microanalysis (C.H.N), 1H-NMR, 13C-NMR, and mass spectra. The mixed ligand complexes are characterized by infrared spectra, electronic spectra, (C.H.N), melting point, atomic absorption, molar conductance and magnetic moment measurements. These measurements indicate that the ligand [HL] coordinates with metal (II) ion in a tridentate manner through the oxygen and nitrogen atoms of the ligand, octahedral structures are suggested for these complexes. Antibacterial activity of the ligands [HL], [HQ] and their complexes are studied against (gram positive) and (gram negative) bacteria.

Quantitative analysis of dinuclear manganese(II) EPR spectra

NASA Astrophysics Data System (ADS)

Golombek, Adina P.; Hendrich, Michael P.

2003-11-01

A quantitative method for the analysis of EPR spectra from dinuclear Mn(II) complexes is presented. The complex [(Me 3TACN) 2Mn(II) 2(μ-OAc) 3]BPh 4 ( 1) (Me 3TACN= N, N', N''-trimethyl-1,4,7-triazacyclononane; OAc=acetate 1-; BPh 4=tetraphenylborate 1-) was studied with EPR spectroscopy at X- and Q-band frequencies, for both perpendicular and parallel polarizations of the microwave field, and with variable temperature (2-50 K). Complex 1 is an antiferromagnetically coupled dimer which shows signals from all excited spin manifolds, S=1 to 5. The spectra were simulated with diagonalization of the full spin Hamiltonian which includes the Zeeman and zero-field splittings of the individual manganese sites within the dimer, the exchange and dipolar coupling between the two manganese sites of the dimer, and the nuclear hyperfine coupling for each manganese ion. All possible transitions for all spin manifolds were simulated, with the intensities determined from the calculated probability of each transition. In addition, the non-uniform broadening of all resonances was quantitatively predicted using a lineshape model based on D- and r-strain. As the temperature is increased from 2 K, an 11-line hyperfine pattern characteristic of dinuclear Mn(II) is first observed from the S=3 manifold. D- and r-strain are the dominate broadening effects that determine where the hyperfine pattern will be resolved. A single unique parameter set was found to simulate all spectra arising for all temperatures, microwave frequencies, and microwave modes. The simulations are quantitative, allowing for the first time the determination of species concentrations directly from EPR spectra. Thus, this work describes the first method for the quantitative characterization of EPR spectra of dinuclear manganese centers in model complexes and proteins. The exchange coupling parameter J for complex 1 was determined ( J=-1.5±0.3 cm-1; H ex=-2J S1· S2) and found to be in agreement with a previous determination from magnetization. The phenomenon of exchange striction was found to be insignificant for 1.

Synthesis, characterization and spectroscopic properties of the hydrazodye and new hydrazodye-metal complexes

NASA Astrophysics Data System (ADS)

Bouhdada, M.; EL Amane, M.

2017-12-01

The hydrazodye (L) [disodium (7-hydroxyl-8-phenylazo-1,3-naphthalenedisulfonate)] is prepared and characterized by infrared 1H,13C, NMR and UV-visible spectra. The spectral data of the ligand (L) existing predominantly in the hydrazones form. Reaction of the hydrazodye (L) with Cd2+, Ni2+, Cu2+ and Zn2+ chloride gave two series of metal complexes with general formula [ML2 (OH2)2]2Cl and [ML2 (caf)2]2Cl. Their complexes were identified by FTIR, UV-visible spectra, 1H, 13C, NMR, EPR, XRD and molar conductance. The molar conductance reveals that the new series of metal complexes are non-electrolytes. The postulated octahedral structure of the obtained complexes is also proposed on spectroscopic data analysis.

Frequency-dependent processing and interpretation (FDPI) of seismic data for identifying, imaging and monitoring fluid-saturated underground reservoirs

DOEpatents

Goloshubin, Gennady M.; Korneev, Valeri A.

2006-11-14

A method for identifying, imaging and monitoring dry or fluid-saturated underground reservoirs using seismic waves reflected from target porous or fractured layers is set forth. Seismic imaging the porous or fractured layer occurs by low pass filtering of the windowed reflections from the target porous or fractured layers leaving frequencies below low-most corner (or full width at half maximum) of a recorded frequency spectra. Additionally, the ratio of image amplitudes is shown to be approximately proportional to reservoir permeability, viscosity of fluid, and the fluid saturation of the porous or fractured layers.

Frequency-dependent processing and interpretation (FDPI) of seismic data for identifying, imaging and monitoring fluid-saturated underground reservoirs

DOEpatents

Goloshubin, Gennady M.; Korneev, Valeri A.

2005-09-06

A method for identifying, imaging and monitoring dry or fluid-saturated underground reservoirs using seismic waves reflected from target porous or fractured layers is set forth. Seismic imaging the porous or fractured layer occurs by low pass filtering of the windowed reflections from the target porous or fractured layers leaving frequencies below low-most corner (or full width at half maximum) of a recorded frequency spectra. Additionally, the ratio of image amplitudes is shown to be approximately proportional to reservoir permeability, viscosity of fluid, and the fluid saturation of the porous or fractured layers.

Cyclodextrin-complexation effects on the low-frequency vibrational dynamics of ibuprofen by combined inelastic light and neutron scattering experiments.

PubMed

Crupi, Vincenza; Fontana, Aldo; Giarola, Marco; Guella, Graziano; Majolino, Domenico; Mancini, Ines; Mariotto, Gino; Paciaroni, Alessandro; Rossi, Barbara; Venuti, Valentina

2013-04-11

The effect of the inclusion into cyclodextrins (CD) cavity on the low-frequency vibrational dynamics of the anti-inflammatory drug ibuprofen (IBP) is here investigated by using Raman and inelastic neutron scattering (INS) experiments. The differences observed in the frequency regime 0-100 cm(-1) between the vibrational modes of uncomplexed racemic and enantiomeric IBP are discussed on the basis of comparison with the quantum chemical computation results, taking into account the distinct symmetry properties of the molecules involved in the formation of the host-guest complex. Subsequently, the inspection of the same frequency range in the spectra of pure host methyl-β-CD and its IBP-inclusion complexes allows one to identify significant modifications in the vibrational dynamics of the guest molecule after their confinement into CD cavity. The experimental Raman and neutron spectra and the derived Raman coupling function C(R)(ω) show that the complexation process gives rise to a complete amorphization of the drug, as well as to a partial hindering, in the vibrational dynamics of complexes, of the modes between 50 and 150 cm(-1) attributed to CD molecule. The comparison between the Raman and neutron spectra of free and complexed IBP in the energy range of the Boson peak (BP) gives evidence that the dynamics related to this specific vibrational feature is sensitive to complexation phenomena.

P-glycoprotein regulates blood–testis barrier dynamics via its effects on the occludin/zonula occludens 1 (ZO-1) protein complex mediated by focal adhesion kinase (FAK)

PubMed Central

Su, Linlin; Mruk, Dolores D.; Lui, Wing-Yee; Lee, Will M.; Cheng, C. Yan

2011-01-01

The blood–testis barrier (BTB), one of the tightest blood–tissue barriers in the mammalian body, creates an immune-privileged site for postmeiotic spermatid development to avoid the production of antibodies against spermatid-specific antigens, many of which express transiently during spermiogenesis and spermiation. However, the BTB undergoes extensive restructuring at stage VIII of the epithelial cycle to facilitate the transit of preleptotene spermatocytes and to prepare for meiosis. This action thus prompted us to investigate whether this stage can be a physiological window for the delivery of therapeutic and/or contraceptive drugs across the BTB to exert their effects at the immune-privileged site. Herein, we report findings that P-glycoprotein, an ATP-dependent efflux drug transporter and an integrated component of the occludin/zonula occludens 1 (ZO-1) adhesion complex at the BTB, structurally interacted with focal adhesion kinase (FAK), creating the occludin/ZO-1/FAK/P-glycoprotein regulatory complex. Interestingly, a knockdown of P-glycoprotein by RNAi was found to impede Sertoli cell BTB function, making the tight junction (TJ) barrier “leaky.” This effect was mediated by changes in the protein phosphorylation status of occludin via the action of FAK, thereby affecting the endocytic vesicle-mediated protein trafficking events that destabilized the TJ barrier. However, the silencing of P-glycoprotein, although capable of impeding drug transport across the BTB and TJ permeability barrier function, was not able to induce the BTB to be “freely” permeable to adjudin. These findings indicate that P-glycoprotein is involved in BTB restructuring during spermatogenesis but that P-glycoprotein–mediated restructuring does not “open up” the BTB to make it freely permeable to drugs. PMID:22106313

RTM simulations and experiments for fiber-reinforced turbine blades forming

NASA Astrophysics Data System (ADS)

Nguyen, Tuan Linh; Marchand, Christophe

2018-05-01

The one-shot (full part) forming of tidal turbine blades by RTM (Resin Transfer Molding) process is a complex process due to the complexity of reinforcements and geometry of blades. In this work, beside the experimental tests which have been realized using IRT JV high capacity machines, the RTM simulations using Moldex3D RTM software have been carried out. First of all, simulations have been done on a 1/7th scale part in order to determine the best injection strategy. Different tested strategies vary by the disposition of injection points (Inlet)/vacuum points (Outlet). Then, the chosen strategy has been applied on the full scale part (˜ 7m length) of high thickness with more complex reinforcement draping. In both cases, the stage of meshing is important to take into account the draping plan with different fiber orientation and fiber types. Attention should be paid on the neck of the blade as the structure of reinforcement changes. A sensitivity study of different parameters (permeability, pressure, temperature) has been then done to understand their influence on the injection time. The permeability which lies to the choice of reinforcement type and fiber volume fraction plays an important role. As the thickness of the part is high, an experimental campaign for measuring the 3D permeability is required. Among the process controllable parameters, the pressure seems the fastest way to reduce the injection time. However, increasing the injection pressure (or the vacuum) could deform the reinforcement. Moreover, the maximal pressure depends on the machine capacity. The influence of temperature shows the thermo-dependence of resin viscosity, the injection time thus decreases as the temperature increases. Nevertheless, the gel time is more limited for injection stage if the resin is heated too much.

Interest of cyclodextrins in spray-dried microparticles formulation for sustained pulmonary delivery of budesonide.

PubMed

Dufour, Gilles; Bigazzi, William; Wong, Nelson; Boschini, Frederic; de Tullio, Pascal; Piel, Geraldine; Cataldo, Didier; Evrard, Brigitte

2015-11-30

To achieve an efficient lung delivery and efficacy, both active ingredient aerosolisation properties and permeability through the lung need to be optimized. To overcome these challenges, the present studies aim to develop cyclodextrin-based spray-dried microparticles containing a therapeutic corticosteroid (budesonide) that could be used to control airway inflammation associated with asthma. The complexation between budesonide and hydroxypropyl-β-cyclodextrin (HPBCD) has been investigated. Production of inhalation powders was carried out using a bi-fluid nozzle spray dryer and was optimized based on a design of experiments. Spray-dried microparticles display a specific "deflated-ball like shape" associated with an appropriate size for inhalation. Aerodynamic assessment show that the fine particle fraction was increased compared to a classical lactose-based budesonide formulation (44.05 vs 26.24%). Moreover, the budesonide permeability out of the lung was shown to be reduced in the presence of cyclodextrin complexes. The interest of this sustained budesonide release was evaluated in a mouse model of asthma. The anti-inflammatory effect was compared to a non-complexed budesonide formulation at the same concentration and attests the higher anti-inflammatory activity reach with the cyclodextrin-based formulation. This strategy could therefore be of particular interest for improving lung targeting while decreasing systemic side effects associated with high doses of corticosteroids. In conclusion, this works reports that cyclodextrins could be used in powder for inhalation, both for their abilities to improve active ingredient aerosolisation properties and further to their dissolution in lung fluid, to decrease permeability out of the lungs leading to an optimized activity profile. Copyright © 2015 Elsevier B.V. All rights reserved.

Different applications of isosbestic points, normalized spectra and dual wavelength as powerful tools for resolution of multicomponent mixtures with severely overlapping spectra.

PubMed

Mohamed, Ekram H; Lotfy, Hayam M; Hegazy, Maha A; Mowaka, Shereen

2017-05-25

Analysis of complex mixture containing three or more components represented a challenge for analysts. New smart spectrophotometric methods have been recently evolved with no limitation. A study of different novel and smart spectrophotometric techniques for resolution of severely overlapping spectra were presented in this work utilizing isosbestic points present in different absorption spectra, normalized spectra as a divisor and dual wavelengths. A quaternary mixture of drotaverine (DRO), caffeine (CAF), paracetamol (PCT) and para-aminophenol (PAP) was taken as an example for application of the proposed techniques without any separation steps. The adopted techniques adopted of successive and progressive steps manipulating zero /or ratio /or derivative spectra. The proposed techniques includes eight novel and simple methods namely direct spectrophotometry after applying derivative transformation (DT) via multiplying by a decoding spectrum, spectrum subtraction (SS), advanced absorbance subtraction (AAS), advanced amplitude modulation (AAM), simultaneous derivative ratio (S 1 DD), advanced ratio difference (ARD), induced ratio difference (IRD) and finally double divisor-ratio difference-dual wavelength (DD-RD-DW) methods. The proposed methods were assessed by analyzing synthetic mixtures of the studied drugs. They were also successfully applied to commercial pharmaceutical formulations without interference from other dosage form additives. The methods were validated according to the ICH guidelines, accuracy, precision, repeatability, were found to be within the acceptable limits. The proposed procedures are accurate, simple and reproducible and yet economic. They are also sensitive and selective and could be used for routine analysis of complex most of the binary, ternary and quaternary mixtures and even more complex mixtures.

Zero kinetic energy spectroscopy: mass-analyzed threshold ionization spectra of chromium sandwich complexes with alkylbenzenes, (η(6)-RPh)(2)Cr (R = Me, Et, i-Pr, t-Bu).

PubMed

Ketkov, Sergey Y; Selzle, Heinrich L; Cloke, F Geoffrey N; Markin, Gennady V; Shevelev, Yury A; Domrachev, Georgy A; Schlag, Edward W

2010-10-28

For over 25 years zero kinetic energy (ZEKE) spectroscopy has yielded a rich foundation of high-resolution results of molecular ions. This was based on the discovery in the late 60's of long-lived ion states throughout the ionization continuum of molecular ions. Here, an example is chosen from another fundamental system pioneered at this university. The mass-analyzed threshold ionization (MATI) spectra of jet-cooled chromium bisarene complexes (η(6)-RPh)(2)Cr (R = Me (1), Et (2), i-Pr (3), and t-Bu (4)) have been measured and interpreted on the basis of DFT calculations. The MATI spectra of complexes 1 and 2 appear to reveal features arising from ionizations of the isomers formed by the rotation of one arene ring relative to the other. The 1 and 2 MATI spectra show two intense peaks corresponding to the 0(0)(0) ionizations with inverse intensity ratios. As indicated by the DFT calculations, the intensity ratio change on going from 1 to 2 results from different isomers contributing to each MATI peak. The ionization energies corresponding to the 0(0)(0) peaks are 42746 ± 5 and 42809 ± 5 cm(-1) for compound 1 and 42379 ± 5 and 42463 ± 5 cm(-1) for complex 2. The 1 and 2 spectra show also the weaker features representing transitions to the vibrationally excited cationic levels, the signals of individual rotamers being detected and assigned on the basis of calculated vibrational frequencies. The MATI spectra of compounds 3 and 4 reveal only one strong peak because of close ionization potentials of the isomers contributing to the MATI signal. The 3 and 4 ionization energies are 42104 ± 5 and 41917 ± 5 cm(-1), respectively. The precise values of ionization energies obtained from the MATI spectra reveal a nonlinear dependence of the IE on the number of Me groups in the alkyl substituents of (η(6)-RPh)(2)Cr. This can be explained by an increase in the molecular zero point energies on methylation of the substituents.

Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

PubMed

Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; Van Stipdonk, Michael J

2013-08-30

Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores. The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations. The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group. IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group. Copyright © 2013 John Wiley & Sons, Ltd.

Kinetics and its accompanying thermodynamics studies on simultaneous complexation of heterobimetallic neodymium (III) with zinc (II) and L-tryptophan in aquated DMF using 4f-4f absorption spectra.

PubMed

Huidrom, Bimola; Singh, N Rajmuhon

2014-01-24

The 4f-4f absorption spectra of the simultaneous heterobimetallic complexation of trivalent neodymium ion with l-tryptophan and divalent zinc ion in aquated DMF (50%, v/v) at pH 6.0 was recorded at the time interval of 1h. From the observed absorption spectra, the values of intensity parameters such as oscillator strength (P) and Judd-Ofelt intensity (Tλ) parameters, kinetics and thermodynamics parameters were evaluated. The rate constant increases with an increase in the temperature along with the oscillator strengths and Judd-Ofelt intensity parameters. The positive values of the change in the standard enthalpy (ΔH°) and entropy (ΔS°) indicate that the complexation is endothermic. The negative values of the change in the standard free energy (ΔG°) in the range from 293.15 K to 308.15 K, indicate that the reaction occurs spontaneously and hence the formation of heterobimetallic complex in the solution is favored kinetically and thermodynamically. Copyright © 2013 Elsevier B.V. All rights reserved.

Kinetics and its accompanying thermodynamics studies on simultaneous complexation of heterobimetallic neodymium (III) with zinc (II) and L-tryptophan in aquated DMF using 4f-4f absorption spectra

NASA Astrophysics Data System (ADS)

Huidrom, Bimola; Rajmuhon Singh, N.

2014-01-01

The 4f-4f absorption spectra of the simultaneous heterobimetallic complexation of trivalent neodymium ion with L-tryptophan and divalent zinc ion in aquated DMF (50%, v/v) at pH 6.0 was recorded at the time interval of 1 h. From the observed absorption spectra, the values of intensity parameters such as oscillator strength (P) and Judd-Ofelt intensity (Tλ) parameters, kinetics and thermodynamics parameters were evaluated. The rate constant increases with an increase in the temperature along with the oscillator strengths and Judd-Ofelt intensity parameters. The positive values of the change in the standard enthalpy (ΔH°) and entropy (ΔS°) indicate that the complexation is endothermic. The negative values of the change in the standard free energy (ΔG°) in the range from 293.15 K to 308.15 K, indicate that the reaction occurs spontaneously and hence the formation of heterobimetallic complex in the solution is favored kinetically and thermodynamically.

Radiometric errors in complex Fourier transform spectrometry.

PubMed

Sromovsky, Lawrence A

2003-04-01

A complex spectrum arises from the Fourier transform of an asymmetric interferogram. A rigorous derivation shows that the rms noise in the real part of that spectrum is indeed given by the commonly used relation sigmaR = 2X x NEP/(etaAomega square root(tauN)), where NEP is the delay-independent and uncorrelated detector noise-equivalent power per unit bandwidth, +/- X is the delay range measured with N samples averaging for a time tau per sample, eta is the system optical efficiency, and Aomega is the system throughput. A real spectrum produced by complex calibration with two complex reference spectra [Appl. Opt. 27, 3210 (1988)] has a variance sigmaL2 = sigmaR2 + sigma(c)2 (Lh - Ls)2/(Lh - Lc)2 + sigma(h)2 (Ls - Lc)2/(Lh - Lc)2, valid for sigmaR, sigma(c), and sigma(h) small compared with Lh - Lc, where Ls, Lh, and Lc are scene, hot reference, and cold reference spectra, respectively, and sigma(c) and sigma(h) are the respective combined uncertainties in knowledge and measurement of the hot and cold reference spectra.

A wavelet analysis for the X-ray absorption spectra of molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Penfold, T. J.; Ecole polytechnique Federale de Lausanne, Laboratoire de chimie et biochimie computationnelles, ISIC, FSB-BCH, CH-1015 Lausanne; SwissFEL, Paul Scherrer Inst, CH-5232 Villigen

2013-01-07

We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rheniummore » diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.« less

Multifractal spectra of laser Doppler flowmetry signals in healthy and sleep apnea syndrome subjects

NASA Astrophysics Data System (ADS)

Buard, Benjamin; Trzepizur, Wojciech; Mahe, Guillaume; Chapeau-Blondeau, François; Rousseau, David; Gagnadoux, Frédéric; Abraham, Pierre; Humeau, Anne

2009-07-01

Laser Doppler flowmetry (LDF) signals give a peripheral view of the cardiovascular system. To better understand the possible modifications brought by sleep apnea syndrome (SAS) in LDF signals, we herein propose to analyze the complexity of such signals in obstructive SAS subjects, and to compare the results with those obtained in healthy subjects. SAS is a pathology that leads to a drop in the parasympathetic tone associated with an increase in the sympathetic tone in awakens SAS patients. Nine men with obstructive SAS and nine healthy men participated awaken in our study and LDF signals were recorded in the forearm. In our work, complexity of LDF signals is analyzed through the computation and analysis of their multifractal spectra. The multifractal spectra are estimated by first estimating the discrete partition function of the signals, then by determining their Renyi exponents with a linear regression, and finally by computing their Legendre transform. The results show that, at rest, obstructive SAS has no or little impact on the multifractal spectra of LDF signals recorded in the forearm. This study shows that the physiological modifications brought by obstructive SAS do not modify the complexity of LDF signals when recorded in the forearm.

Investigation of Stimulation-Response Relationships for Complex Fracture Systems in Enhanced Geothermal Reservoirs

DOE Data Explorer

Fu, Pengcheng; Johnson, Scott M.; Carrigan, Charles R.

2011-01-01

Hydraulic fracturing is currently the primary method for stimulating low-permeability geothermal reservoirs and creating Enhanced (or Engineered) Geothermal Systems (EGS) with improved permeability and heat production efficiency. Complex natural fracture systems usually exist in the formations to be stimulated and it is therefore critical to understand the interactions between existing fractures and newly created fractures before optimal stimulation strategies can be developed. Our study aims to improve the understanding of EGS stimulation-response relationships by developing and applying computer-based models that can effectively reflect the key mechanisms governing interactions between complex existing fracture networks and newly created hydraulic fractures. In this paper, we first briefly describe the key modules of our methodology, namely a geomechanics solver, a discrete fracture flow solver, a rock joint response model, an adaptive remeshing module, and most importantly their effective coupling. After verifying the numerical model against classical closed-form solutions, we investigate responses of reservoirs with different preexisting natural fractures to a variety of stimulation strategies. The factors investigated include: the in situ stress states (orientation of the principal stresses and the degree of stress anisotropy), pumping pressure, and stimulation sequences of multiple wells.

Molecular inclusion complex of curcumin-β-cyclodextrin nanoparticle to enhance curcumin skin permeability from hydrophilic matrix gel.

PubMed

Rachmawati, Heni; Edityaningrum, Citra Ariani; Mauludin, Rachmat

2013-12-01

Curcumin (CUR) has various pharmacological effects, but its extensive first-pass metabolism and short elimination half-life limit its bioavailability. Therefore, transdermal application has become a potential alternative to delivery CUR. To increase CUR solubility for the development of a transparent homogenous gel and also enhance the permeation rate of CUR into the skin, β-cyclodextrin-curcumin nanoparticle complex (BCD-CUR-N) was developed. CUR encapsulation efficiency was increased by raising the percentage of CUR to BCD up to 20%. The mean particle size of the best CUR loading formula was 156 nm. All evaluation data using infrared spectroscopy, Raman spectroscopy, powder X-ray diffractometry, differential thermal analysis and scanning electron microscopy confirmed the successful formation of the inclusion complex. BCD-CUR-N increased the CUR dissolution rate of 10-fold (p < 0.01). In addition, the improvement of CUR permeability acrossed skin model tissue was observed in gel containing the BCD-CUR-N and was about 1.8-fold when compared with the free CUR gel (p < 0.01). Overall, CUR in the form of the BCD-CUR-N improved the solubility further on the penetration of CUR.

Characterization of reactive flow-induced evolution of carbonate rocks using digital core analysis - part 2: Calculation of the evolution of percolation and transport properties.

PubMed

Qajar, Jafar; Arns, Christoph H

2017-09-01

Percolation of reactive fluids in carbonate rocks affects the rock microstructure and hence changes the rock macroscopic properties. In Part 1 paper, we examined the voxel-wise evolution of microstructure of the rock in terms of mineral dissolution/detachment, mineral deposition, and unchanged regions. In the present work, we investigate the relationships between changes in two characteristic transport properties, i.e. permeability and electrical conductivity and two critical parameters of the pore phase, i.e. the fraction of the pore space connecting the inlet and outlet faces of the core sample and the critical pore-throat diameter. We calculate the aforementioned properties on the images of the sample, wherein a homogeneous modification of pore structure occurred in order to ensure the representativeness of the calculated transport properties at the core scale. From images, the evolution of pore connectivity and the potential role of micropores on the connectivity are quantified. It is found that the changing permeability and electrical conductivity distributions along the core length are generally in good agreement with the longitudinal evolution of macro-connected macroporosity and the critical pore-throat diameter. We incorporate microporosity into critical length and permeability calculations and show how microporosity locally plays a role in permeability. It is shown that the Katz-Thompson model reasonably predicts the post-alteration permeability in terms of pre-alteration simulated parameters. This suggests that the evolution of permeability and electrical conductivity of the studied complex carbonate core are controlled by the changes in the macro-connected macroporosity as well as the smallest pore-throats between the connected macropores. Copyright © 2017 Elsevier B.V. All rights reserved.

Solubility, Stability, Physicochemical Characteristics and In Vitro Ocular Tissue Permeability of Hesperidin: a Natural Bioflavonoid

PubMed Central

Majumdar, Soumyajit; Srirangam, Ramesh

2008-01-01

Purpose Hesperidin holds potential in treating age-related macular degeneration, cataract and diabetic retinopathy. The aim of this study, constituting the first step towards efficient ocular delivery of hesperidin, was to determine its physicochemical properties and in vitro ocular tissue permeability. Methods pH dependent aqueous solubility and stability were investigated following standard protocols. Permeability of hesperidin across excised rabbit cornea, sclera, and sclera plus retinal pigmented epithelium (RPE) was determined using a side-bi-side diffusion apparatus. Results Hesperidin demonstrated poor, pH independent, aqueous solubility. Solubility improved dramatically in the presence of 2-hydroxypropyl-beta-cyclodextrin (HP-β-CD) and the results supported 1:1 complex formation. Solutions were stable in the pH and temperature (25, 40°C) conditions tested, except for samples stored at pH 9. Transcorneal permeability in the apical-basal and basal-apical directions was 1.11±0.86×10−6 and 1.16±0.05×10−6 cm/s, respectively. The scleral tissue was more permeable (10.2±2.1×10−6cm/s). However, permeability across sclera/choroid/RPE in the sclera to retina and retina to sclera direction was 0.82±0.69×10−6, 1.52±0.78×10−6 cm/s, respectively, demonstrating the barrier properties of the RPE. Conclusion Our results suggest that stable ophthalmic solutions of hesperidin can be prepared and that hesperidin can efficiently permeate across the corneal tissue. Further investigation into its penetration into the back-of-the eye ocular tissues is warranted. PMID:18810327

Intracellular localization of a group II chaperonin indicates a membrane-related function

NASA Technical Reports Server (NTRS)

Trent, Jonathan D.; Kagawa, Hiromi K.; Paavola, Chad D.; McMillan, R. Andrew; Howard, Jeanie; Jahnke, Linda; Lavin, Colleen; Embaye, Tsegereda; Henze, Christopher E.

2003-01-01

Chaperonins are protein complexes that are believed to function as part of a protein folding system in the cytoplasm of the cell. We observed, however, that the group II chaperonins known as rosettasomes in the hyperthermophilic archaeon Sulfolobus shibatae, are not cytoplasmic but membrane associated. This association was observed in cultures grown at 60 degrees C and 76 degrees C or heat-shocked at 85 degrees C by using immunofluorescence microscopy and in thick sections of rapidly frozen cells grown at 76 degrees C by using immunogold electron microscopy. We observed that increased abundance of rosettasomes after heat shock correlated with decreased membrane permeability at lethal temperature (92 degrees C). This change in permeability was not seen in cells heat-shocked in the presence of the amino acid analogue azetidine 2-carboxylic acid, indicating functional protein synthesis influences permeability. Azetidine experiments also indicated that observed heat-induced changes in lipid composition in S. shibatae could not account for changes in membrane permeability. Rosettasomes purified from cultures grown at 60 degrees C and 76 degrees C or heat-shocked at 85 degrees C bind to liposomes made from either the bipolar tetraether lipids of Sulfolobus or a variety of artificial lipid mixtures. The presence of rosettasomes did not significantly change the transition temperature of liposomes, as indicated by differential scanning calorimetry, or the proton permeability of liposomes, as indicated by pyranine fluorescence. We propose that these group II chaperonins function as a structural element in the natural membrane based on their intracellular location, the correlation between their functional abundance and membrane permeability, and their potential distribution on the membrane surface.

Changes in sapwood permeability and anatomy with tree age and height in the broad-leaved evergreen species Eucalyptus regnans.

PubMed

England, Jacqueline R; Attiwill, Peter M

2007-08-01

Increases in plant size and structural complexity with increasing age have important implications for water flow through trees. Water supply to the crown is influenced by both the cross-sectional area and the permeability of sapwood. It has been hypothesized that hydraulic conductivity within sapwood increases with age. We investigated changes in sapwood permeability (k) and anatomy with tree age and height in the broad-leaved evergreen species Eucalyptus regnans F. Muell. Sapwood was sampled at breast height from trees ranging from 8 to 240 years old, and at three height positions on the main stem of 8-year-old trees. Variation in k was not significant among sampling height positions in young trees. However, k at breast height increased with tree age. This was related to increases in both vessel frequency and vessel diameter, resulting in a greater proportion of sapwood being occupied by vessel lumina. Sapwood hydraulic conductivity (the product of k and sapwood area) also increased with increasing tree age. However, at the stand level, there was a decrease in forest sapwood hydraulic conductivity with increasing stand age, because of a decrease in the number of trees per hectare. Across all ages, there were significant relationships between k and anatomy, with individual anatomical characteristics explaining 33-62% of the variation in k. There was also strong agreement between measured k and permeability predicted by the Hagen-Poiseuille equation. The results support the hypothesis of an increase in sapwood permeability at breast height with age. Further measurements are required to confirm this result at other height positions in older trees. The significance of tree-level changes in sapwood permeability for stand-level water relations is discussed.

The effect of pore-scale geometry and wettability on two-phase relative permeabilities within elementary cells

NASA Astrophysics Data System (ADS)

Bianchi Janetti, Emanuela; Riva, Monica; Guadagnini, Alberto

2017-04-01

We study the relative role of the complex pore space geometry and wettability of the solid matrix on the quantification of relative permeabilities characterizing steady state immiscible two-phase flow in porous media. We do so by considering elementary cells, which are typically employed in upscaling frameworks based on, e.g., homogenization or volume averaging. In this context one typically relies on the solution of pore-scale physics at a scale which is much smaller than that of an investigated porous system. Pressure-driven two-phase flow following simultaneous co-current injection of water and oil is numerically solved for a suite of regular and stochastically generated two-dimensional explicit elementary cells with fixed porosity and sharing main topological/morphological features. We show that relative permeabilities of the randomly generated elementary cells are significantly influenced by the formation of preferential percolation paths (principal pathways), giving rise to a strongly nonuniform distribution of fluid fluxes. These pathways are a result of the spatially variable resistance that the random pore structures exert on the fluid. The overall effect on relative permeabilities of the diverse organization of principal pathways, as driven by a given random realization at the scale of the unit cell, is significantly larger than that of the wettability of the host rock. In contrast to what can be observed for the random cells analyzed, relative permeabilities of regular cells display a clear trend with contact angle at the investigated scale. Our findings suggest the need to perform systematic upscaling studies in a stochastic context, to propagate the effects of uncertain pore space geometries to a probabilistic description of relative permeability curves at the continuum scale.

EPR and IR spectral investigations on some leafy vegetables of Indian origin

NASA Astrophysics Data System (ADS)

Prasuna, C. P. Lakshmi; Chakradhar, R. P. S.; Rao, J. L.; Gopal, N. O.

2009-09-01

EPR spectral investigations have been carried out on four edible leafy vegetables of India, which are used as dietary component in day to day life. In Rumex vesicarius leaf sample, EPR spectral investigations at different temperatures indicate the presence of anti-ferromagnetically coupled Mn(IV)-Mn(IV) complexes. EPR spectra of Trigonella foenum graecum show the presence of Mn ions in multivalent state and Fe 3+ ions in rhombic symmetry. EPR spectra of Basella rubra indicate the presence of Mn(IV)-O-Mn(IV) type complexes. The EPR spectra of Basella rubra have been studied at different temperatures. It is found that the spin population for the resonance signal at g = 2.06 obeys the Boltzmann distribution law. The EPR spectra of Moringa oliefera leaves show the presence of Mn 2+ ions. Radiation induced changes in free radical of this sample have also been studied. The FT-IR spectra of Basella rubra and Moringa oliefera leaves show the evidences for the protein matrix bands and those corresponding to carboxylic C dbnd O bonds.

Raman spectra of amino acids and their aqueous solutions

NASA Astrophysics Data System (ADS)

Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

2011-03-01

Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids ( L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.

The permeaiblity of fault-zones:the role of stylolites as incipit of dissolution

NASA Astrophysics Data System (ADS)

Magni, Silvana

2017-04-01

Fault zones and fractures play an important role in fluid circulation and then in dissolution, acting as barriers or conductors depending on the distribution of other features associated with them and on the specific conditions (lithological and structural, as well). The fault zone have a high permeability only in the early stages of the movement but shortly after recrystallization and reprecipitation processes greatly reduce the permeability within them. Indeed the dissolution is a complex phenomenon which involves both several factors that lead to the formation of caves and karst systems often complex. Traditionally, in the field of karst , the dissolution is associated with extensional structures such as faults and joints believing that they are more favorable to the water circulation. In this context compressional tectonic structures, as like the stylolites, are never considered. In fact the stylolites play an important role in the fluid circulation (Rawling, 2001) and in particular in the incipit of dissolution and then of the karst. We have so focused our research on the study of permeability of four fault zones in a karst area of Alte Murge (South Italy). Through a detailed structural analysis in the field and using the method of Caine (Caine, 1996), we reconstructed the permeability of the four previous fault zones. Our attention was focused on faults, joints and on stylolites. Contrary to the literature the dissolution and therefore the karst was mainly found along the stylolites and only secondarily along faults. No sign of dissolution was found along the joints. In the context of karst studies, the stylolites, which are structures due to pressure solution has never been taken into account, thinking that in compressional structures is not possible any circulation of water and that therefore there is no fluid-rock interaction. No consideration has been given to the enormous role that the pressure and the microfluidic that are created have in this context. The styololites, the focus of our research open important questions about their exact role as incipit of the dissolution. Through petrophysical analysis and microstructural we are characterizing the porosity and permeability near the stylolites. Recently, fluid-rock interactions and their impact on carbonate rocks is becoming very important because of an increasing interest it the carbonate reservoirs as a consequence of a progressive deterioration of the quantity and quality of the groundwater due to increasing pollution phenomena. In fact the aquifers represent about 40% of the drinking water resources and their importance will increase in coming years. REFERENCESE Caine, J.S.,Evans, J.P., Forster,C.B. (1996). Fault zone architecture and permeability structure. Geology 24, 1025-1032 Rawling,G.C., Goodwin,L.B., Wilson,J.L. (2001). Internal architecture permeability structure and hydrogeologic significance of contrasting fault-zone types. Geology 29, 43-46

Poroelastic references

DOE Data Explorer

Morency, Christina

2014-12-12

This file contains a list of relevant references on the Biot theory (forward and inverse approaches), the double-porosity and dual-permeability theory, and seismic wave propagation in fracture porous media, in RIS format, to approach seismic monitoring in a complex fractured porous medium such as Brady?s Geothermal Field.

Lipid raft components cholesterol and sphingomyelin increase H+/OH− permeability of phosphatidylcholine membranes

PubMed Central

Gensure, Rebekah H.; Zeidel, Mark L.; Hill, Warren G.

2006-01-01

H+/OH− permeation through lipid bilayers occurs at anomalously high rates and the determinants of proton flux through membranes are poorly understood. Since all life depends on proton gradients, it is important to develop a greater understanding of proton leak phenomena. We have used stopped-flow fluorimetry to probe the influence of two lipid raft components, chol (cholesterol) and SM (sphingomyelin), on H+/OH− and water permeability. Increasing the concentrations of both lipids in POPC (palmitoyl-2-oleoyl phosphatidylcholine) liposomes decreased water permeability in a concentration-dependent manner, an effect that correlated with increased lipid order. Surprisingly, proton flux was increased by increasing the concentration of chol and SM. The chol effect was complex with molar concentrations of 17.9, 33 and 45.7% giving 2.8-fold (P<0.01), 2.2-fold (P<0.001) and 5.1-fold (P<0.001) increases in H+/OH− permeability from a baseline of 2.4×10−2 cm/s. SM at 10 mole% effected a 2.8-fold increase (P<0.01), whereas 20 and 30 mole% enhanced permeability by 3.6-fold (P<0.05) and 4.1-fold respectively (P<0.05). Supplementing membranes containing chol with SM did not enhance H+/OH− permeability. Of interest was the finding that chol addition to soya-bean lipids decreased H+/OH− permeability, consistent with an earlier report [Ira and Krishnamoorthy (2001) J. Phys. Chem. B 105, 1484–1488]. We speculate that the presence of proton carriers in crude lipid extracts might contribute to this result. We conclude that (i) chol and SM specifically and independently increase rates of proton permeation in POPC bilayers, (ii) domains enriched in these lipids or domain interfaces may represent regions with high H+/OH− conductivity, (iii) H+/OH− fluxes are not governed by lipid order and (iv) chol can inhibit or promote H+/OH− permeability depending on the total lipid environment. Theories of proton permeation are discussed in the light of these results. PMID:16706750

On the impact of spatial heterogeneous permeability distributions on the development of free convection cells in the Perth Basin, Australia.

NASA Astrophysics Data System (ADS)

Niederau, Jan; Ebigbo, Anozie; Freitag, Sebastian; Marquart, Gabriele; Clauser, Christoph

2014-05-01

Recent increase in exploration of the geothermal energy potential of the Perth Metropolitan Area (PMA) results in the need for reliable and robust reservoir models in order to explore rock properties and temperature distributions in the subsurface, where free convection in the main reservoir (Yarragadee Aquifer) is likely to occur [1]. While the structure of the Perth Basin has been refined recently, the heterogeneity and spatial complexity of permeability was up till now mainly neglected. An integrated, three dimensional tectonostratigraphic model of the PMA is constructed, using the modeling software '3D GeoModeller' and data of numerous artesian and petroleum wells. Comprising the region around the city of Perth, the model covers an area of about 5000 km2 up to a depth of 4.5 km, with focus on adequate representation of the main reservoir. We further construct a numerical model for fluid flow and heat transport in the Yarragadee Aquifer. Porosity distributions are deduced from well logs and linked to permeability by a calibrated correlation, based on a fractal approach. Three different cases are simulated using the FD code SHEMAT-Suite, in order to assess the influence of spatial heterogeneity of porosity and permeability on the development of free convection cells. constant porosity and permeability for the entire aquifer porosity and permeability decreasing with depth, thus reflecting compaction a conditional random permeability field within prescribed limits and for given correlation length In order to improve understanding of model correctness, as well as identification and comparison of convection cells in different simulations, we are developing a specialized visualization tool tailored to this purpose. The three different scenarios show distinctions in the distribution of convection cells. Where the Yarragadee Aquifer is in contact with overlying aquifers, regions of downflow develop. These in turn have a strong impact on the regional flow field and therefore temperature. The heterogeneous distribution of permeability seems to control the convection pattern on a smaller scale. References [1] Schilling, O., Sheldon, H.A., Reid, L.B., Corbel, S. 2013. Hydrothermal models of the Perth metropolitan area, Western Australia: implications for geothermal energy. Hydrogeology Journal, Vol. 21, 605-621.

Prominence of ichnologically influenced macroporosity in the karst Biscayne aquifer: Stratiform "super-K" zones

USGS Publications Warehouse

Cunningham, K.J.; Sukop, M.C.; Huang, H.; Alvarez, P.F.; Curran, H.A.; Renken, R.A.; Dixon, J.F.

2009-01-01

A combination of cyclostratigraphic, ichnologic, and borehole geophysical analyses of continuous core holes; tracer-test analyses; and lattice Boltzmann flow simulations was used to quantify biogenic macroporosity and permeability of the Biscayne aquifer, southeastern Florida. Biogenic macroporosity largely manifests as: (1) ichnogenic macroporosity primarily related to postdepositional burrowing activity by callianassid shrimp and fossilization of components of their complex burrow systems (Ophiomorpha); and (2) biomoldic macroporosity originating from dissolution of fossil hard parts, principally mollusk shells. Ophiomorpha-dominated ichno-fabric provides the greatest contribution to hydrologic characteristics in the Biscayne aquifer in a 345 km2 study area. Stratiform tabular-shaped units of thalassinidean-associated macroporosity are commonly confined to the lower part of upward-shallowing high-frequency cycles, throughout aggradational cycles, and, in one case, they stack vertically within the lower part of a high-frequency cycle set. Broad continuity of many of the macroporous units concentrates groundwater flow in extremely permeable passage-ways, thus making the aquifer vulnerable to long-distance transport of contaminants. Ichnogenic macroporosity represents an alternative pathway for concentrated groundwater flow that differs considerably from standard karst flow-system paradigms, which describe groundwater movement through fractures and cavernous dissolution features. Permeabilities were calculated using lattice Boltzmann methods (LBMs) applied to computer renderings assembled from X-ray computed tomography scans of various biogenic macroporous limestone samples. The highest simulated LBM permeabilities were about five orders of magnitude greater than standard laboratory measurements using air-permeability methods, which are limited in their application to extremely permeable macroporous rock samples. Based on their close conformance to analytical solutions for pipe flow, LBMs offer a new means of obtaining accurate permeability values for such materials. We suggest that the stratiform ichnogenic groundwater flow zones have permeabilities even more extreme (???2-5 orders of magnitude higher) than the Jurassic "super-K" zones of the giant Ghawar oil field. The flow zones of the Pleistocene Biscayne aquifer provide examples of ichnogenic macroporosity for comparative analysis of origin and evolution in other carbonate aquifers, as well as petroleum reservoirs. ?? 2008 Geological Society of America.

Synthesis Characterization and DNA Interaction Studies of a New Zn(II) Complex Containing Different Dinitrogen Aromatic Ligands

PubMed Central

Shahabadi, Nahid; Mohammadi, Somaye

2012-01-01

A mononuclear complex of Zn(II), [Zn(DIP)2 (DMP)] (NO3)2 ·2H2O in which DIP is 4,7-diphenyl-1,10-phenanthroline and DMP is 4,4′-dimethyl-2,2′-bipyridine has been prepared and characterized by 1HNMR spectroscopy, FT-IR, UV-Vis and elemental analysis techniques. DNA-binding properties of the complex were studied using UV-vis spectra, circular dichroism (CD) spectra, fluorescence, cyclic voltammetry (CV), and viscosity measurements. The results indicate that this zinc(II) complex can intercalate into the stacked base pairs of DNA and compete with the strong intercalator ethidium bromide for the intercalative binding sites. PMID:22956919

The growth and differentiation of transitional epithelium in vitro.

PubMed

Chlapowski, F J; Haynes, L

1979-12-01

The development of rat transitional epithelial cells grown on conventional non-permeable surfaces was compared with development on permeable collagen supports. On glass or plastic surfaces, cells grew as expanding nomolayer sheets. Once confluent, growth continued with a bilayer being formed in most areas and apical cells being continuously sloughed off. Although most cells were interconnected by desmosomes, and junctional complexes were formed, no other indications of differentiation were observed. After 2-3 wk of growth, division stopped and cel death ensued. In contrast, single-cell suspensions plated on collagen-coated nylon disks reassociated into multicellular islands and commenced growth. Mitoses were confined to the basal cells in contact with the permeable substrate. The islands developed into epithelial trilayers, tapering to monolayers along spreading edges. Once the islands were confluent, stratification was completed and appeared similar to that observed in vivo. Germinal cells formed a basal lamina, and the upper layer was composed of large, flattened cells with an unusually thick asymmetrical plasma membrane on the apical surface. Electron microscopic and radioactive tracers demonstrated "leaky" zonulae occludentes with a restricted permeability to small molecules. The movement of urea was retarded in comparison to water. Unlike the slow turnover of adult epithelium in vivo, maturation and sloughing of apical cells were measurable. Transfer of cells could be effected and growth maintained for up to 4 mo. These results may indicate the necessity of a nutrient-permeable growth surface for the polarized differentiation of adult transitional epithelium.

The growth and differentiation of transitional epithelium in vitro

PubMed Central

1979-01-01

The development of rat transitional epithelial cells grown on conventional non-permeable surfaces was compared with development on permeable collagen supports. On glass or plastic surfaces, cells grew as expanding nomolayer sheets. Once confluent, growth continued with a bilayer being formed in most areas and apical cells being continuously sloughed off. Although most cells were interconnected by desmosomes, and junctional complexes were formed, no other indications of differentiation were observed. After 2-3 wk of growth, division stopped and cel death ensued. In contrast, single-cell suspensions plated on collagen-coated nylon disks reassociated into multicellular islands and commenced growth. Mitoses were confined to the basal cells in contact with the permeable substrate. The islands developed into epithelial trilayers, tapering to monolayers along spreading edges. Once the islands were confluent, stratification was completed and appeared similar to that observed in vivo. Germinal cells formed a basal lamina, and the upper layer was composed of large, flattened cells with an unusually thick asymmetrical plasma membrane on the apical surface. Electron microscopic and radioactive tracers demonstrated "leaky" zonulae occludentes with a restricted permeability to small molecules. The movement of urea was retarded in comparison to water. Unlike the slow turnover of adult epithelium in vivo, maturation and sloughing of apical cells were measurable. Transfer of cells could be effected and growth maintained for up to 4 mo. These results may indicate the necessity of a nutrient-permeable growth surface for the polarized differentiation of adult transitional epithelium. PMID:574872

Protective effect of metronidazole on uncoupling mitochondrial oxidative phosphorylation induced by NSAID: a new mechanism.

PubMed

Leite, A Z; Sipahi, A M; Damião, A O; Coelho, A M; Garcez, A T; Machado, M C; Buchpiguel, C A; Lopasso, F P; Lordello, M L; Agostinho, C L; Laudanna, A A

2001-02-01

The pathogenesis of non-steroidal anti-inflammatory drug (NSAID) enteropathy is complex. It involves uncoupling of mitochondrial oxidative phosphorylation which alters the intercellular junction and increases intestinal permeability with consequent intestinal damage. Metronidazole diminishes the inflammation induced by indomethacin but the mechanisms remain speculative. A direct effect on luminal bacteria has traditionally been thought to account for the protective effect of metronidazole. However, a protective effect of metronidazole on mitochondrial oxidative phosphorylation has never been tested. To assess the protective effect of metronidazole on mitochondrial uncoupling induced by indomethacin and also on the increased intestinal permeability and macroscopic damage. The protective effect of metronidazole was evaluated in rats given indomethacin; a macroscopic score was devised to quantify intestinal lesions, and intestinal permeability was measured by means of (51)Cr-ethylenediaminetetraacetic acid. The protective effect of metronidazole against mitochondrial uncoupling induced by indomethacin was assessed using isolated coupled rat liver mitochondria obtained from rats pretreated with metronidazole or saline. Metronidazole significantly reduced the macroscopic intestinal damage and increase in intestinal permeability induced by indomethacin; furthermore, at the mitochondrial level, it significantly reduced the increase in oxygen consumption in state 4 induced by indomethacin and caused less reduction of the respiratory control rate. Our study confirmed the beneficial effects of metronidazole on intestinal damage and intestinal permeability, and demonstrated, for the first time, a direct protective effect of metronidazole on uncoupling of mitochondrial oxidative phosphorylation caused by NSAIDs.

Measuring and predicting reservoir heterogeneity in complex deposystems. Annual report, September 20, 1990--September 20, 1991

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donaldson, A.; Shumaker, R.; Laughrey, C.

1992-08-01

The Lower Mississippian Big Injun sandstone, a major oil producer in the western half of West Virginia, consists of several sandstones that overstep each west. Examination of cores and thin sections has led to preliminary interpretations of depositional environments for the Big Injun. These include distributary-mouth bars with associated distal, bar crest and back bar environments in a marine-deltaic system; and channel, point bar and chute environments in a fluvial system. Overall, the Big Injun is a medium-grained sublitharenite in which initially high porosity has been modified by compaction and diagenesis. Chlorite grain coatings helped to preserve original porosity, whereasmore » illite promoted pressure solution during compaction, resulting in a loss of porosity. Diagenetic effects within specific environments are being evaluated to determine if environmental interpretations can be used to predict porosity preservation. Core plugs taken from cores in Granny Creek field were analyzed for porosity and horizontal and vertical permeability. Directional permeability was negligible, but permeability does correlate with depth. Changes in permeability with depth can be related to subdivisions of the Big Injun determined from density logs. Permeability also correlated with porosity, but porosity values derived from both cores and logs show no significant correlation trend at present. A layered reservoir model is being developed to evaluate the effect of these vertical heterogeneities. Initial attempts to characterize the heterogeneity of the Big Injun reservoir in Granny Creek field used a number of direct and indirect methods.« less

Measuring and predicting reservoir heterogeneity in complex deposystems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donaldson, A.; Shumaker, R.; Laughrey, C.

1992-08-01

The Lower Mississippian Big Injun sandstone, a major oil producer in the western half of West Virginia, consists of several sandstones that overstep each west. Examination of cores and thin sections has led to preliminary interpretations of depositional environments for the Big Injun. These include distributary-mouth bars with associated distal, bar crest and back bar environments in a marine-deltaic system; and channel, point bar and chute environments in a fluvial system. Overall, the Big Injun is a medium-grained sublitharenite in which initially high porosity has been modified by compaction and diagenesis. Chlorite grain coatings helped to preserve original porosity, whereasmore » illite promoted pressure solution during compaction, resulting in a loss of porosity. Diagenetic effects within specific environments are being evaluated to determine if environmental interpretations can be used to predict porosity preservation. Core plugs taken from cores in Granny Creek field were analyzed for porosity and horizontal and vertical permeability. Directional permeability was negligible, but permeability does correlate with depth. Changes in permeability with depth can be related to subdivisions of the Big Injun determined from density logs. Permeability also correlated with porosity, but porosity values derived from both cores and logs show no significant correlation trend at present. A layered reservoir model is being developed to evaluate the effect of these vertical heterogeneities. Initial attempts to characterize the heterogeneity of the Big Injun reservoir in Granny Creek field used a number of direct and indirect methods.« less

Multiple roles for the Na,K-ATPase subunits, Atp1a1 and Fxyd1, during brain ventricle development

PubMed Central

Chang, Jessica T.; Lowery, Laura Anne; Sive, Hazel

2012-01-01

Formation of the vertebrate brain ventricles requires both production of cerebrospinal fluid (CSF), and its retention in the ventricles. The Na,K-ATPase is required for brain ventricle development, and we show here that this protein complex impacts three associated processes. The first requires both the alpha subunit (Atp1a1) and the regulatory subunit, Fxyd1, and leads to formation of a cohesive neuroepithelium, with continuous apical junctions. The second process leads to modulation of neuroepithelial permeability, and requires Atp1a1, which increases permeability with partial loss of function and decreases it with overexpression. In contrast, fxyd1 overexpression does not alter neuroepithelial permeability, suggesting that its activity is limited to neuroepithelium formation. RhoA regulates both neuroepithelium formation and permeability, downstream of the Na,K-ATPase. A third process, likely to be CSF production, is RhoA-independent, requiring Atp1a1, but not Fxyd1. Consistent with a role for Na,K-ATPase pump function, the inhibitor ouabain prevents neuroepithelium formation, while intracellular Na+ increases after Atp1a1 and Fxyd1 loss of function. These data include the first reported role for Fxyd1 in the developing brain, and indicate that the Na,K-ATPase regulates three aspects of brain ventricle development essential for normal function - formation of a cohesive neuroepithelium, restriction of neuroepithelial permeability, and production of CSF. PMID:22683378

A multiscale model of distributed fracture and permeability in solids in all-round compression

NASA Astrophysics Data System (ADS)

De Bellis, Maria Laura; Della Vecchia, Gabriele; Ortiz, Michael; Pandolfi, Anna

2017-07-01

We present a microstructural model of permeability in fractured solids, where the fractures are described in terms of recursive families of parallel, equidistant cohesive faults. Faults originate upon the attainment of tensile or shear strength in the undamaged material. Secondary faults may form in a hierarchical organization, creating a complex network of connected fractures that modify the permeability of the solid. The undamaged solid may possess initial porosity and permeability. The particular geometry of the superposed micro-faults lends itself to an explicit analytical quantification of the porosity and permeability of the damaged material. The model is the finite kinematics version of a recently proposed porous material model, applied with success to the simulation of laboratory tests and excavation problems [De Bellis, M. L., Della Vecchia, G., Ortiz, M., Pandolfi, A., 2016. A linearized porous brittle damage material model with distributed frictional-cohesive faults. Engineering Geology 215, 10-24. Cited By 0. 10.1016/j.enggeo.2016.10.010]. The extension adds over and above the linearized kinematics version for problems characterized by large deformations localized in narrow zones, while the remainder of the solid undergoes small deformations, as typically observed in soil and rock mechanics problems. The approach is particularly appealing as a means of modeling a wide scope of engineering problems, ranging from the prevention of water or gas outburst into underground mines, to the prediction of the integrity of reservoirs for CO2 sequestration or hazardous waste storage, to hydraulic fracturing processes.

DNA Binding and Antitumor Activity of α-Diimineplatinum(II) and Palladium(II) Dithiocarbamate Complexes

PubMed Central

Mansouri-Torshizi, Hassan; Saeidifar, Maryam; Khosravi, Fatemeh; Divsalar, Adeleh; Saboury, Ali Akbar; Hassani, Fatemeh

2011-01-01

The two water-soluble designed platinum(II) complex, [Pt(Oct-dtc)(bpy)]NO3 (Oct-dtc = Octyldithiocarbamate and bpy = 2,2′ -bipyridine) and palladium(II) complex, [Pd(Oct-dtc)(bpy)]NO3, have been synthesized and characterized by elemental analyses, molar conductivity measurements, IR, 1H NMR, and electronic spectra studies. Studies of antitumor activity of these complexes against human cell tumor lines (K562) have been carried out. They show Ic50 values lower than that of cisplatin. The complexes have been investigated for their interaction with calf thymus DNA (CT-DNA) by utilizing the electronic absorption spectroscopy, fluorescence spectra, and ethidium bromide displacement and gel filtration techniques. Both of these water-soluble complexes bound cooperatively and intercalatively to the CT-DNA at very low concentrations. Several binding and thermodynamic parameters are also described. PMID:22110410

Preparation and in vivo evaluation of cationic elastic liposomes comprising highly skin-permeable growth factors combined with hyaluronic acid for enhanced diabetic wound-healing therapy.

PubMed

Choi, Jeong Uk; Lee, Seong Wook; Pangeni, Rudra; Byun, Youngro; Yoon, In-Soo; Park, Jin Woo

2017-07-15

To enhance the therapeutic effects of exogenous administration of growth factors (GFs) in the treatment of chronic wounds, we constructed GF combinations of highly skin-permeable epidermal growth factor (EGF), insulin-like growth factor-I (IGF-I), and platelet-derived growth factor-A (PDGF-A). We genetically conjugated a low-molecular-weight protamine (LMWP) to the N-termini of these GFs to form LMWP-EGF, LMWP-IGF-I, and LMWP-PDGF-A. Subsequently, these molecules were complexed with hyaluronic acid (HA). Combinations of native or LMWP-fused GFs significantly promoted fibroblast proliferation and the synthesis of procollagen, with a magnification of these results observed after the GFs were complexed with HA. The optimal proportions of LMWP-EGF, LMWP-IGF-I, LMWP-PDGF-A, and HA were 1, 1, 0.02, and 200, respectively. After confirming the presence of a synergistic effect, we incorporated the LMWP-fused GFs-HA complex into cationic elastic liposomes (ELs) of 107±0.757nm in diameter and a zeta potential of 56.5±1.13mV. The LMWP-fused GFs had significantly improved skin permeation compared with native GFs. The in vitro wound recovery rate of the LMWP-fused GFs-HA complex was 23% higher than that of cationic ELs composed of LMWP-fused GFs alone. Moreover, the cationic ELs containing the LMWP-fused GFs-HA complex significantly accelerated the wound closure rate in a diabetic mouse model and the wound size was maximally decreased by 65% and 58% compared to cationic ELs loaded with vehicle or native GFs-HA complex, respectively. Thus, topical treatment with cationic ELs loaded with the LMWP-fused GFs-HA complex synergistically enhanced the healing of chronic wounds, exerting both rapid and prolonged effects. We believe that our study makes a significant contribution to the literature, because it demonstrated the potential application of cationic elastic liposomes as topical delivery systems for growth factors (GFs) that have certain limitations in their therapeutic effects (e.g., low percutaneous absorption of GFs at the lesion site and the requirement for various GFs at different healing stages). Topical treatment with cationic elastic liposomes loaded with highly skin-permeable low-molecular-weight protamine (LMWP)-fused GFs-hyaluronic acid (HA) complex synergistically enhanced the healing of diabetic wounds, exerting both rapid and prolonged effects. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Application of Wave Distribution Function Method to the ERG/PWE Data

NASA Astrophysics Data System (ADS)

Ota, M.; Kasahara, Y.; Matsuda, S.; Kojima, H.; Matsuoka, A.; Hikishima, M.; Kasaba, Y.; Ozaki, M.; Yagitani, S.; Tsuchiya, F.; Kumamoto, A.

2017-12-01

The ERG (Arase) satellite was launched on 20 December 2016 to study acceleration and loss mechanisms of relativistic electrons in the Earth's magnetosphere. The Plasma Wave Experiment (PWE), which is one of the science instruments on board the ERG satellite, measures electric field and magnetic field. The PWE consists of three sub-systems; EFD (Electric Field Detector), OFA/WFC (Onboard Frequency Analyzer and Waveform Capture), and HFA (High Frequency Analyzer).The OFA/WFC measures electromagnetic field spectra and raw waveforms in the frequency range from few Hz to 20 kHz. The OFA produces three kind of data; OFA-SPEC (power spectrum), OFA-MATRIX (spectral matrix), and OFA-COMPLEX (complex spectrum). The OFA-MATRIX measures ensemble averaged complex cross-spectra of two electric field components, and of three magnetic field components. The OFA-COMPLEX measures instantaneous complex spectra of electric and magnetic fields. These data are produced every 8 seconds in the nominal mode, and it can be used for polarization analysis and wave propagation direction finding.In general, spectral matrix composed by cross-spectra of observed signals is used for direction finding, and many algorithms have been proposed. For example, Means method and SVD method can be applied on the assumption that the spectral matrix is consists of a single plane wave, while wave distribution function (WDF) method is applicable even to the data in which multiple numbers of plane waves are simultaneously included. In this presentation, we introduce the results when the WDF method is applied to the ERG/PWE data.

Claudins and the Kidney Volume 75: Annual Review of Physiology

PubMed Central

Hou, Jianghui; Rajagopal, Madhumitha; Yu, Alan S. L.

2013-01-01

Claudins are tight junction membrane proteins that regulate paracellular permeability of renal epithelia to small ions, solutes and water. Claudins interact within the cell membrane and between neighboring cells to form tight junction strands and constitute both the paracellular barrier and pore. The first extracellular domain of claudins is thought to be the pore-lining domain and contains the determinants of charge selectivity. Multiple claudins are expressed in different nephron segments and this likely determines the permeability properties of each segment. Recent evidence has identified claudin-2 as constituting the cation-reabsorptive pathway in the proximal tubule, claudin-14, -16 and -19 as forming a complex that regulates calcium transport in the thick ascending limb of the loop of Henle, and claudin-4, -7 and -8 as determinants of collecting duct choride permeability. Mutations in claudin-16 and -19 cause familial hypercalciuric hypomagnesemia. The roles of other claudins in kidney diseases remain to be fully elucidated. PMID:23140368

Augmented Topological Descriptors of Pore Networks for Material Science.

PubMed

Ushizima, D; Morozov, D; Weber, G H; Bianchi, A G C; Sethian, J A; Bethel, E W

2012-12-01

One potential solution to reduce the concentration of carbon dioxide in the atmosphere is the geologic storage of captured CO2 in underground rock formations, also known as carbon sequestration. There is ongoing research to guarantee that this process is both efficient and safe. We describe tools that provide measurements of media porosity, and permeability estimates, including visualization of pore structures. Existing standard algorithms make limited use of geometric information in calculating permeability of complex microstructures. This quantity is important for the analysis of biomineralization, a subsurface process that can affect physical properties of porous media. This paper introduces geometric and topological descriptors that enhance the estimation of material permeability. Our analysis framework includes the processing of experimental data, segmentation, and feature extraction and making novel use of multiscale topological analysis to quantify maximum flow through porous networks. We illustrate our results using synchrotron-based X-ray computed microtomography of glass beads during biomineralization. We also benchmark the proposed algorithms using simulated data sets modeling jammed packed bead beds of a monodispersive material.

Simulation of gas flow in micro-porous media with the regularized lattice Boltzmann method

DOE PAGES

Wang, Junjian; Kang, Qinjun; Wang, Yuzhu; ...

2017-06-01

One primary challenge for prediction of gas flow in the unconventional gas reservoir at the pore-scale such as shale and tight gas reservoirs is the geometric complexity of the micro-porous media. In this paper, a regularized multiple-relaxation-time (MRT) lattice Boltzmann (LB) model is applied to analyze gas flow in 2-dimensional micro-porous medium reconstructed by quartet structure generation set (QSGS) on pore-scale. In this paper, the velocity distribution inside the porous structure is presented and analyzed, and the effects of the porosity and specific surface area on the rarefied gas flow and apparent permeability are examined and investigated. The simulation resultsmore » indicate that the gas exhibits different flow behaviours at various pressure conditions and the gas permeability is strongly related to the pressure. Finally, the increased porosity or the decreased specific surface area leads to the increase of the gas apparent permeability, and the gas flow is more sensitive to the pore morphological properties at low-pressure conditions.« less

Metal Amorphous Nanocomposite (MANC) Alloy Cores with Spatially Tuned Permeability for Advanced Power Magnetics Applications

NASA Astrophysics Data System (ADS)

Byerly, K.; Ohodnicki, P. R.; Moon, S. R.; Leary, A. M.; Keylin, V.; McHenry, M. E.; Simizu, S.; Beddingfield, R.; Yu, Y.; Feichter, G.; Noebe, R.; Bowman, R.; Bhattacharya, S.

2018-04-01

Metal amorphous nanocomposite (MANC) alloys are an emerging class of soft magnetic materials showing promise for a range of inductive components targeted for higher power density and higher efficiency power conversion applications including inductors, transformers, and rotating electrical machinery. Magnetization reversal mechanisms within these alloys are typically determined by composition optimization as well as controlled annealing treatments to generate a nanocomposite structure composed of nanocrystals embedded in an amorphous precursor. Here we demonstrate the concept of spatially varying the permeability within a given component for optimization of performance by using the strain annealing process. The concept is realized experimentally through the smoothing of the flux profile from the inner to outer core radius achieved by a monotonic variation in tension during the strain annealing process. Great potential exists for an extension of this concept to a wide range of other power magnetic components and more complex spatially varying permeability profiles through advances in strain annealing techniques and controls.

Metal Amorphous Nanocomposite (MANC) Alloy Cores with Spatially Tuned Permeability for Advanced Power Magnetics Applications

NASA Astrophysics Data System (ADS)

Byerly, K.; Ohodnicki, P. R.; Moon, S. R.; Leary, A. M.; Keylin, V.; McHenry, M. E.; Simizu, S.; Beddingfield, R.; Yu, Y.; Feichter, G.; Noebe, R.; Bowman, R.; Bhattacharya, S.

2018-06-01

Metal amorphous nanocomposite (MANC) alloys are an emerging class of soft magnetic materials showing promise for a range of inductive components targeted for higher power density and higher efficiency power conversion applications including inductors, transformers, and rotating electrical machinery. Magnetization reversal mechanisms within these alloys are typically determined by composition optimization as well as controlled annealing treatments to generate a nanocomposite structure composed of nanocrystals embedded in an amorphous precursor. Here we demonstrate the concept of spatially varying the permeability within a given component for optimization of performance by using the strain annealing process. The concept is realized experimentally through the smoothing of the flux profile from the inner to outer core radius achieved by a monotonic variation in tension during the strain annealing process. Great potential exists for an extension of this concept to a wide range of other power magnetic components and more complex spatially varying permeability profiles through advances in strain annealing techniques and controls.

Simulation of gas flow in micro-porous media with the regularized lattice Boltzmann method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Junjian; Kang, Qinjun; Wang, Yuzhu

One primary challenge for prediction of gas flow in the unconventional gas reservoir at the pore-scale such as shale and tight gas reservoirs is the geometric complexity of the micro-porous media. In this paper, a regularized multiple-relaxation-time (MRT) lattice Boltzmann (LB) model is applied to analyze gas flow in 2-dimensional micro-porous medium reconstructed by quartet structure generation set (QSGS) on pore-scale. In this paper, the velocity distribution inside the porous structure is presented and analyzed, and the effects of the porosity and specific surface area on the rarefied gas flow and apparent permeability are examined and investigated. The simulation resultsmore » indicate that the gas exhibits different flow behaviours at various pressure conditions and the gas permeability is strongly related to the pressure. Finally, the increased porosity or the decreased specific surface area leads to the increase of the gas apparent permeability, and the gas flow is more sensitive to the pore morphological properties at low-pressure conditions.« less

{Linking permeability and mechanical damage for basalt from Mt Etna Volcano, Italy}

NASA Astrophysics Data System (ADS)

Faoro, I.; Vinciguerra, S.; Marone, C.; Elsworth, D.

2009-04-01

Volcanic edifices, such as Mt. Etna volcano (Italy), are affected from repeated episodes of pressurisation due to magma emplacement from deep reservoirs to shallow depths. This mechanism pressurizes the large aquifers within the edifice and increases the level of crack damage within the rocks of the edifice over extended periods of times. In order to improve our understanding of the complex coupling between circulating fluids and the development of crack damage, we performed flow-through tests using cylindrical cores of Etna Basalt (Etna, Italy) to evaluate permeabilty changes as a function of approach to failure under non-hydrostatic stresses at confining pressures from 5 to 60 MPa. Samples were loaded to failure by increasing increments of axial stress or by cyclic stresses of increasing amplitude. Both intact samples and pre-drilled samples (1.18mm) were tested. Under hydrostatic stresses, the permeability values of the intact sample decrease linearly with the increments of pressure and range between 5.2*10-17 m2and 1.5*10-17m2Under non-hydrostatic conditions, at low deviatoric stresses from (up to 18 MPa), the permeability values ranged between 5.5*10-17 m2and 4*10-17m2 and tended to completely recover the initial value each time the sample was unloaded, indicating an elastic regime. At higher deviatoric stresses (up to 60 MPa) the permeability values range between 2*10-17 m2 and 0.6*10-17m2. We hypothesize that from 5MPa to 40MPa axial stress, anelastic deformation mechanisms start to occur, with progressive pore collapse and opening of microfractures, resulting in a change of permeability. Under incremental uniaxial cyclic loading up to peak stresses of 160 MPa permeability decreases up to 2 orders of magnitude from initial values of 1*10-15 m2 to 2*10-14m2 Higher initial permeability values are related to the presence of an open fracture in the sample. We interpreted the reduction as a result of progressive closure of the voids space, as the axial load is incremented. Overall it is shown that permeability on Etna basalt rocks is strongly dependent on the loading conditions. Ongoing work is expected to elucidate the mechanisms relating increasing damage mechanical damage to changes of permeability.

Estimating dynamic permeability in fractal pore network saturated by Maxwellian fluid

NASA Astrophysics Data System (ADS)

Sun, W.

2017-12-01

The frequency dependent flow of fluid in porous media is an important issue in geophysical prospecting. Oscillating flow in pipe leads to frequency dependent dynamic permeability and has been studied in pore network containing Newtonian fluid. But there is little work on oscillating complex fluid in pipe network, especially in irregular network. Here we formulated frequency dependent permeability for Maxwellian fluid and estimated the permeability in three-dimensional fractal network model. We consider an infinitely long cylindrical pipe with rigid solid wall. The pipe is filled with Maxwellian fluids. Based on the mass conservation equation, the equilibrium equation of force and Maxwell constitutive relationship, we formulated the flux by integration of axial velocity component over the pipe's cross section. Then we extend single pipe formulation to a 3D irregular network. Flux balance condition yields a set of linear equations whose unknowns are the fluid pressure at each node. By evaluating the total flow flux through the network, the dynamic permeability can be calculated.We investigated the dynamic permeability of brine and CPyCl/NaSal in a 3D porous sample with a cubic side length 1 cm. The pore network is created by a Voronoi cell filling method. The porosity, i.e., volume ratio between pore/pipe network and the overall cubic, is set as 0.1. The irregular pore network has a fractal structure. The dimension d of the pore network is defined by the relation between node number M within a sphere and the radius r of the sphere,M=rd.The results show that both brine and Maxwellian fluid's permeability maintain a stable value at low frequency, then decreases with fluctuating peaks. The dynamic permeability in pore networks saturated by Maxwellian fluid (CPyCl/NaSal (60 mM)) show larger peaks during the decline process at high frequency, which represents the typical resonance behavior. Dynamic permeability shows clear dependence on the dimension of the fractal network. Small-scale network has higher dimension than large-scale networks. The reason is that in larger networks pore and inter-pore connections are so dense that the probability P(r) to have a neighboring pore at distance r decays faster. The proposed model may be used to explain velocity dispersion in unconventional reservoir rocks observed in laboratory.

Time-resolved ESR spectra of the α-hydroxybenzyl-amine complex

NASA Astrophysics Data System (ADS)

Kawai, Akio; Kobori, Yasuhiro; Obi, Kinichi

1993-11-01

Time-resolved ESR spectra of the α-hydroxybenzyl radical were measured in benzene and 2-propanol solutions by the photo-dissociation of benzoin. The hyperfine structure (hfs) of α-hydroxybenzyl depends on the solvents. In a benzene solution containing triethylamine, two species with different hyperfine structure appeared simultaneously. As the ratio of intensity for the two species depends on the concentration of triethylamine, one of them is assigned to the bare α-hydroxybenzyl and the other to the 1:1 complex of α-hydroxybenzyl and triethylamine. The equilibrium constant of complex formation was estimated to be about 450 M -1 from the analysis of CIDEP intensities.

Luminescence enhancement of terbium(III) perchlorate by 2,2'-dipyridyl on bis(benzylsulfinyl)methane complex and luminescence mechanism.

PubMed

Feng, Shu-Yan; Li, Wen-Xian; Guo, Feng; Cao, Xiao-Fang

2014-11-01

A novel ternary complex, Tb(2)L4 · L'·(ClO4)6 · 8H2O, has been synthesized using bis(benzylsulfinyl)methane as the first ligand L and 2,2'-dipyridyl as the second ligand L'. The ternary complex was characterized by element analysis, molar conductivity, coordination titration analysis, infrared, thermogravimetric-differential scanning calorimetric and ultraviolet spectra. The results indicated that the composition of the complex was Tb2 L4 · L'·(ClO4)6 · 8H2O (L = C(6)H(5)CH(2) SOCH(2)SOCH(2)C(6)H(5); L' = Dipy). Fourier transform infrared results revealed that the perchlorate group was bonded with the Tb(III) ion by the oxygen atom, and the coordination was bidentate. The fluorescent spectra illustrated that the complex displayed characteristic fluorescence in the solid state. After the introduction of the second ligand, 2,2-dipyridyl, the relative emission intensity and fluorescence lifetime of the ternary complex Tb(2)L(4) · L'·(ClO(4))(6) · 8H2O were enhanced compared to the binary complex TbL(2.5)(ClO4)3 · 3H2O. This indicated that the presence of both organic ligand bis(benzylsulfinyl)methane and the second ligand 2,2-dipyridyl could sensitize the fluorescence intensity of Tb(III) ion, and introduction of the 2,2-dipyridyl group resulted in an enhancement of the fluorescence of the Tb(III) ternary rare earth complex. The strongest characteristic fluorescence emission intensity of the ternary complex was 9.36 times that of the binary complex. The phosphorescence spectra and fluorescence lifetime of the complex were also measured. Copyright © 2014 John Wiley & Sons, Ltd.

Role of humic acid on oral drug delivery of an antiepileptic drug.

PubMed

Mirza, Mohd Aamir; Agarwal, Suraj Prakash; Rahman, Md Akhlaquer; Rauf, Abdur; Ahmad, Niyaz; Alam, Aftab; Iqbal, Zeenat

2011-03-01

Humic acid (HA) is omnipresent in natural organic matter that is a macromolecular, negatively charged polyelectrolyte that contains a hydrophobic core. It is also present in a significant amount in Shilajit (used frequently in traditional medicines), which is used in this study as a source of extraction. HA is evaluated for the oral drug delivery of carbamazepine (CBZ). HA is used in this study to increase the dissolution, intestinal permeation, and pharmacodynamic response of CBZ (bio pharmaceutics classification system (BCS) II) by the technique of complexation and other related mechanism reported with humic substances. Different complexation techniques were explored in this study for the entrapment of CBZ, which was authenticated by molecular modeling and conformational analysis. These were further characterized using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). Solubility analysis and dissolution release profile were carried out to access the in vitro parameters. For ex vivo studies, rat gut intestinal permeability was done. And finally pharmacodynamic evaluation (maximal electroshock method) was carried out for optimized complexes. Molecular modeling approach and instrumental analysis (DSC, XRD, and FT-IR) confirmed the entrapment of CBZ inside the complexing agent. Increased solubility (∼1742%), sustained release (∼78%), better permeability (∼3.5 times), and enhanced pharmacodynamic responses conferred the best to 1:2 freeze dried (FD) and then 1:2 kneading (KD) complexes compared with pure CBZ. Now it could be concluded that HA may be tried as a complexing agent for antiepileptic drug and other classes of low water-soluble drug.

Theoretical study on the anion photoelectron spectra of Ln(COT)2- including the spin-orbit effects

NASA Astrophysics Data System (ADS)

Nakajo, Erika; Yabushita, Satoshi

2017-06-01

The multiplet level splittings for both anion and neutral sandwich complexes Ln(COT)2 (Ln = Ce-Yb, COT = 1,3,5,7-cyclooctatetraene) were calculated with spin-orbit interactions to analyze their anion photoelectron spectra. The theoretically simulated spectra obtained with these energies and the pole strengths are generally consistent with the experimental spectra for the X peak. The magnitudes of the energy splittings, relative peak intensities, and their Ln dependence are reproduced. In comparison to our previous calculations, the inclusion of spin-orbit interactions with the SO-MCQDPT2 method makes the simulated spectra more consistent with the results of the experiment.

Complexation of furosemide with fulvic acid extracted from shilajit: a novel approach.

PubMed

Agarwal, Suraj Prakash; Anwer, Mohammad Khalid; Aqil, Mohammad

2008-05-01

The aim of the present work was to complex furosemide (FSM) with fulvic acid (FA) extracted from shilajit with the hope of having a better understanding of the complexation behavior. The effect of FA on the aqueous solubility, dissolution rate, and permeability of FSM was investigated. Different techniques, such as grinding, freeze drying, solvent evaporation, and so forth, were used for the preparation of the complex. The complexes were prepared in molar ratios of 1:1 and 1:2 FSM:FA and were evaluated for drug inclusion, solubility, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, dissolution study, and permeation study. These methods confirm the formation of an amorphous inclusion complex of FSM with FA.

Systolic Processor Array For Recognition Of Spectra

NASA Technical Reports Server (NTRS)

Chow, Edward T.; Peterson, John C.

1995-01-01

Spectral signatures of materials detected and identified quickly. Spectral Analysis Systolic Processor Array (SPA2) relatively inexpensive and satisfies need to analyze large, complex volume of multispectral data generated by imaging spectrometers to extract desired information: computational performance needed to do this in real time exceeds that of current supercomputers. Locates highly similar segments or contiguous subsegments in two different spectra at time. Compares sampled spectra from instruments with data base of spectral signatures of known materials. Computes and reports scores that express degrees of similarity between sampled and data-base spectra.

Study of the peak shape in alpha spectra measured by liquid scintillation

NASA Astrophysics Data System (ADS)

Vera Tomé, F.; Gómez Escobar, V.; Martín Sánchez, A.

2002-06-01

Liquid-scintillation counting allows the measurement of alpha and beta activities jointly or only of the alpha-emitting nuclides in a sample. Although the resolution of the alpha spectra is poorer than that attained with semiconductor detectors, it is still an attractive alternative. We describe here attempts to fit a peak shape to experimental liquid-scintillation alpha spectra and discuss the parameters affecting this shape, such as the PSA (pulse-shape analyser) level, vial type, shaking the sample, etc. Spectral analysis has been applied for complex alpha spectra.

Fuzzy and fast nuclear transport

PubMed Central

Mulder, Frans A. A.

2018-01-01

Exchange of macromolecules between the cytoplasm and the nucleus of all eukaryotic cells is controlled by nuclear pore complexes, which form a selective permeability barrier. The requirement for rapid but selective transport leads to a “transport paradox.” A new experimental study now provides a thermodynamic explanation. PMID:29572326

The role of metals and dithiolate ligands on structural, electronic and optical properties of [M(bipyridine)(dithiolate)] complexes: A theoretical study

NASA Astrophysics Data System (ADS)

Samiee, Sepideh; Taghvaeian, Samira

2018-06-01

A series of [M(diimine)(dithiolate)] complexes of general formula [M(bpy)(dithiolate)] {bpy = 2,2‧-bipyridine;dithiolate = 1,2-benzenedithiolate (bdt2-), 3,4-toluenedithiolate (tdt2-) and 4-cyanobenzene-1,2-dithiolate (cbdt2-); M = Ni(II), Pd(II) and Pt(II)} have been studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The geometries, stabilities, electronic structures, optical absorption spectra in different phases as well as thermodynamic parameters are explored. The changes of metal ion center and dithiolate ligands on some molecular properties are also discussed. These calculated results are in good agreement with the experimental data. The bonding analyses show that the Msbnd S bond is covalent so that always polarized towards sulfur atom, whereas the Msbnd N bond exhibits a considerable amount of electrostatic interaction. Detailed NBO analysis indicates that these complexes can be easily oxidized than reduced, and acts as the reducing agent. The HOMO-LUMO energy gaps of all complexes under study are founded about 2 eV and the strong absorption from 400 to 700 nm which match with the solar spectra very well. Besides, the simulated absorption spectra are in accordance with the trends of energy gaps. Comparison of the absorption spectra in dichloromethane solution with those in gas phase show that the solvatochromic effect. The order of magnitude for light harvesting efficiencies (LHE) of all complexes is Pt > Pd > Ni and cbdt2- > bdt2- > tdt2-. Our results confirm the effect and role of metals and dithiolate ligands on enhancing the optical properties of these complexes. Thus, the result of this work can serve as a rational tool for the design and synthesis of diimine-dithiolate complexes and broadens the scope for further investigations into potential dyes for use in the field of dye-sensitized solar cells (DSSC).

Would the solvent effect be the main cause of band shift in the theoretical absorption spectrum of large lanthanide complexes?

NASA Astrophysics Data System (ADS)

Freire, Ricardo O.; Rodrigues, Nailton M.; Rocha, Gerd B.; Gimenez, Iara F.; da Costa Junior, Nivan B.

2011-06-01

As most reactions take place in solution, the study of solvent effects on relevant molecular properties - either by experimental or theoretical methods - is crucial for the design of new processes and prediction of technological properties. In spite of this, only few works focusing the influence of the solvent nature specifically on the spectroscopic properties of lanthanide complexes can be found in the literature. The present work describes a theoretical study of the solvent effect on the prediction of the absorption spectra for lanthanide complexes, but other possible relevant factors have been also considered such as the molecular geometry and the excitation window used for interaction configuration (CI) calculations. The [Eu(ETA) 2· nH 2O] +1 complex has been chosen as an ideal candidate for this type of study due to its small number of atoms (only 49) and also because the absorption spectrum exhibits a single band. Two Monte Carlo simulations were performed, the first one considering the [Eu(ETA) 2] +1 complex in 400 water molecules, evidencing that the complex presents four coordinated water molecules. The second simulation considered the [Eu(ETA) 2·4H 2O] +1 complex in 400 ethanol molecules, in order to evaluate the solvent effect on the shift of the maximum absorption in calculated spectra, compared to the experimental one. Quantum chemical studies were also performed in order to evaluate the effect of the accuracy of calculated ground state geometry on the prediction of absorption spectra. The influence of the excitation window used for CI calculations on the spectral shift was also evaluated. No significant solvent effect was found on the prediction of the absorption spectrum for [Eu(ETA) 2·4H 2O] +1 complex. A small but significant effect of the ground state geometry on the transition energy and oscillator strength was also observed. Finally it must be emphasized that the absorption spectra of lanthanide complexes can be predicted with great accuracy by the combined use of semiempirical Sparkle/AM1 and INDO/S-CIS as long as the largest possible excitation window is used in the configuration interaction calculation.

Observation of Trans-Ethanol and Gauche-Ethanol Complexes with Benzene Using Matrix Isolation Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Amicangelo, Jay; Silbaugh, Matthew J.

2016-06-01

Ethanol can exist in two conformers, one in which the OH group is trans to the methyl group (trans-ethanol) and the other in which the OH group is gauche to the methyl group (gauche-ethanol). Matrix isolation infrared spectra of ethanol deposited in 20 K argon matrices display distinct infrared peaks that can be assigned to the trans-ethanol and gauche-ethanol conformers, particularly with the O-H stretching vibrations. Given this, matrix isolation experiments were performed in which ethanol (C_2H_5OH) and benzene (C_6H_6) were co-deposited in argon matrices at 20 K in order to determine if conformer specific ethanol complexes with benzene could be observed in the infrared spectra. New infrared peaks that can be attributed to the trans-ethanol and gauche-ethanol complexes with benzene have been observed near the O-H stretching vibrations of ethanol. The initial identification of the new infrared peaks as being due to the ethanol-benzene complexes was established by performing a concentration study (1:200 to 1:1600 S/M ratios), by comparing the co-deposition spectra with the spectra of the individual monomers, by matrix annealing experiments (35 K), and by performing experiments using isotopically labeled ethanol (C_2D_5OD) and benzene (C_6D_6). Quantum chemical calculations were also performed for the C_2H_5OH-C_6H_6 complexes using density functional theory (B3LYP) and ab initio (MP2) methods. Stable minima were found for the both the trans-ethanol and gauche-ethanol complexes with benzene at both levels of theory and were predicted to have similar interaction energies. Both complexes can be characterized as H-π complexes, in which the ethanol is above the benzene ring with the hydroxyl hydrogen interacting with the π cloud of the ring. The theoretical O-H stretching frequencies for the complexes were predicted to be shifted from the monomer frequencies and from each other and these results were used to make the conformer specific infrared peak assignments. Barnes, A. J.; Hallam, H. E. Trans. Faraday Soc., 1970, 66, 1932-1940.

Heavily loaded ferrite-polymer composites to produce high refractive index materials at centimetre wavelengths

NASA Astrophysics Data System (ADS)

Parke, L.; Hooper, I. R.; Hicken, R. J.; Dancer, C. E. J.; Grant, P. S.; Youngs, I. J.; Sambles, J. R.; Hibbins, A. P.

2013-10-01

A cold-pressing technique has been developed for fabricating composites composed of a polytetrafluoroethylene-polymer matrix and a wide range of volume-fractions of MnZn-ferrite filler (0%-80%). The electromagnetic properties at centimetre wavelengths of all prepared composites exhibited good reproducibility, with the most heavily loaded composites possessing simultaneously high permittivity (180 ± 10) and permeability (23 ± 2). The natural logarithm of both the relative complex permittivity and permeability shows an approximately linear dependence with the volume fraction of ferrite. Thus, this simple method allows for the manufacture of bespoke materials required in the design and construction of devices based on the principles of transformation optics.

Variable-permittivity linear inverse problem for the H(sub z)-polarized case

NASA Technical Reports Server (NTRS)

Moghaddam, M.; Chew, W. C.

1993-01-01

The H(sub z)-polarized inverse problem has rarely been studied before due to the complicated way in which the unknown permittivity appears in the wave equation. This problem is equivalent to the acoustic inverse problem with variable density. We have recently reported the solution to the nonlinear variable-permittivity H(sub z)-polarized inverse problem using the Born iterative method. Here, the linear inverse problem is solved for permittivity (epsilon) and permeability (mu) using a different approach which is an extension of the basic ideas of diffraction tomography (DT). The key to solving this problem is to utilize frequency diversity to obtain the required independent measurements. The receivers are assumed to be in the far field of the object, and plane wave incidence is also assumed. It is assumed that the scatterer is weak, so that the Born approximation can be used to arrive at a relationship between the measured pressure field and two terms related to the spatial Fourier transform of the two unknowns, epsilon and mu. The term involving permeability corresponds to monopole scattering and that for permittivity to dipole scattering. Measurements at several frequencies are used and a least squares problem is solved to reconstruct epsilon and mu. It is observed that the low spatial frequencies in the spectra of epsilon and mu produce inaccuracies in the results. Hence, a regularization method is devised to remove this problem. Several results are shown. Low contrast objects for which the above analysis holds are used to show that good reconstructions are obtained for both permittivity and permeability after regularization is applied.

Deuterium permeation behaviors in tungsten implanted with nitrogen

NASA Astrophysics Data System (ADS)

Liang, Chuan-hui; Wang, Dongping; Jin, Wei; Lou, Yuanfu; Wang, Wei; Ye, Xiaoqiu; Chen, Chang-an; Liu, Kezhao; Xu, Haiyan; Wang, Xiaoying; Kleyn, Aart W.

2018-07-01

Surface modification of tungsten due to the cooling species nitrogen seeded in the divertor region, i.e., by nitrogen ion implantation or re-deposition, is considered to affect the permeation behavior of H isotopes. This work focuses on the effect of nitrogen ion implantation into tungsten (W-N) on the deuterium gas-driven permeation behavior. For comparison, both permeation in tungsten implanted with W ion (W-W) and without implantation (pristine W) are studied. These three samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photo-electron spectroscopy (XPS). The SEM results revealed that the W-W sample has various voids on the surface, and the W-N sample has a rough surface with pretty fine microstructures. These are different from the pristine W sample with a smooth and compact surface. The XRD patterns show the disappearance of crystallinity on both W-W and W-N sample surfaces. It indicates that the ion implantation process results in an almost complete conversion from crystalline to amorphous in the sample surfaces. The sputter-depth profiling XPS spectra show that the implanted nitrogen prefers to form a 140 nm thick tungsten nitride layer. In permeation experiments, it was found that the D permeability is temperature dependent. Interestingly, the W-N sample presented a lower D permeability than the W-W sample, but higher than the pristine W sample. Such behavior implies that tungsten nitride acts as a permeation barrier, while defects created by ions implantation can promote permeability. The possible permeation mechanism correlated with sample surface composition and microstructure is consequently discussed in this work.

The ring-shaped thermal field of Stefanos crater, Nisyros Island: a conceptual model

NASA Astrophysics Data System (ADS)

Pantaleo, M.; Walter, T. R.

2013-11-01

Fumarole fields related to hydrothermal processes release the heat of the underground through permeable pathways. Thermal changes, therefore, are likely to depend also on the variation of these pathways. As these paths may affect or even control the temperature field at the surface, their understanding is relevant to applied and basic science alike. A common difficulty, however, in surface temperature field studies at active volcanoes is that the parameters controlling the ascending routes of fluids are poorly constrained in general. Here we analyze the crater of Stefanos, Nisyros (Greece), and highlight complexities in the spatial pattern of the fumarole field related to permeability conditions. There may be different explanations for the observed permeability changes, such as structural control, lithology, weathering, and heterogeneous sediment accumulation and erosion. We combine high resolution infrared mosaics and grain-size analysis of soils, aiming to elaborate parameters controlling the appearance of the fumarole field. We find a ring-shaped thermal field located within the explosion crater, which is dependent on contrasts of the soil granulometry and volcanotectonic history. We develop a conceptual model of how the ring-shaped thermal field has formed at the Stefanos crater and similarly at other volcanic edifices, highlighting the importance of local permeability contrast that may increase or decrease the thermal fluid flux.

Intestinal Permeability and Cellular Antioxidant Activity of Phenolic Compounds from Mango (Mangifera indica cv. Ataulfo) Peels.

PubMed

Pacheco-Ordaz, Ramón; Antunes-Ricardo, Marilena; Gutiérrez-Uribe, Janet A; González-Aguilar, Gustavo A

2018-02-08

Mango ( Mangifera indica cv. Ataulfo) peel contains bound phenolics that may be released by alkaline or acid hydrolysis and may be converted into less complex molecules. Free phenolics from mango cv. Ataulfo peel were obtained using a methanolic extraction, and their cellular antioxidant activity (CAA) and permeability were compared to those obtained for bound phenolics released by alkaline or acid hydrolysis. Gallic acid was found as a simple phenolic acid after alkaline hydrolysis along with mangiferin isomers and quercetin as aglycone and glycosides. Only gallic acid, ethyl gallate, mangiferin, and quercetin were identified in the acid fraction. The acid and alkaline fractions showed the highest CAA (60.5% and 51.5%) when tested at 125 µg/mL. The value of the apparent permeability coefficient (Papp) across the Caco-2/HT-29 monolayer of gallic acid from the alkaline fraction was higher (2.61 × 10 -6 cm/s) than in the other fractions and similar to that obtained when tested pure (2.48 × 10 -6 cm/s). In conclusion, mango peels contain bound phenolic compounds that, after their release, have permeability similar to pure compounds and exert an important CAA. This finding can be applied in the development of nutraceuticals using this important by-product from the mango processing industry.

Modeling of coulpled deformation and permeability evolution during fault reactivation induced by deep underground injection of CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cappa, F.; Rutqvist, J.

2010-06-01

The interaction between mechanical deformation and fluid flow in fault zones gives rise to a host of coupled hydromechanical processes fundamental to fault instability, induced seismicity, and associated fluid migration. In this paper, we discuss these coupled processes in general and describe three modeling approaches that have been considered to analyze fluid flow and stress coupling in fault-instability processes. First, fault hydromechanical models were tested to investigate fault behavior using different mechanical modeling approaches, including slip interface and finite-thickness elements with isotropic or anisotropic elasto-plastic constitutive models. The results of this investigation showed that fault hydromechanical behavior can be appropriatelymore » represented with the least complex alternative, using a finite-thickness element and isotropic plasticity. We utilized this pragmatic approach coupled with a strain-permeability model to study hydromechanical effects on fault instability during deep underground injection of CO{sub 2}. We demonstrated how such a modeling approach can be applied to determine the likelihood of fault reactivation and to estimate the associated loss of CO{sub 2} from the injection zone. It is shown that shear-enhanced permeability initiated where the fault intersects the injection zone plays an important role in propagating fault instability and permeability enhancement through the overlying caprock.« less

Materials Characterisation and Analysis for Flow Simulation of Liquid Resin Infusion

NASA Astrophysics Data System (ADS)

Sirtautas, J.; Pickett, A. K.; George, A.

2015-06-01

Liquid Resin Infusion (LRI) processes including VARI and VARTM have received increasing attention in recent years, particularly for infusion of large parts, or for low volume production. This method avoids the need for costly matched metal tooling as used in Resin Transfer Moulding (RTM) and can provide fast infusion if used in combination with flow media. Full material characterisation for LRI analysis requires models for three dimensional fabric permeability as a function of fibre volume content, fabric through-thickness compliance as a function of resin pressure, flow media permeability and resin viscosity. The characterisation of fabric relaxation during infusion is usually determined from cyclic compaction tests on saturated fabrics. This work presents an alternative method to determine the compressibility by using LRI flow simulation and fitting a model to experimental thickness measurements during LRI. The flow media is usually assumed to have isotropic permeability, but this work shows greater simulation accuracy from combining the flow media with separation plies as a combined orthotropic material. The permeability of this combined media can also be determined by fitting the model with simulation to LRI flow measurements. The constitutive models and the finite element solution were validated by simulation of the infusion of a complex aerospace demonstrator part.

Incorporating incorporating economic models into seasonal pool conservation planning

USGS Publications Warehouse

Freeman, Robert C.; Bell, Kathleen P.; Calhoun, Aram J.K.; Loftin, Cyndy

2012-01-01

Massachusetts, New Jersey, Connecticut, and Maine have adopted regulatory zones around seasonal (vernal) pools to conserve terrestrial habitat for pool-breeding amphibians. Most amphibians require access to distinct seasonal habitats in both terrestrial and aquatic ecosystems because of their complex life histories. These habitat requirements make them particularly vulnerable to land uses that destroy habitat or limit connectivity (or permeability) among habitats. Regulatory efforts focusing on breeding pools without consideration of terrestrial habitat needs will not ensure the persistence of pool-breeding amphibians. We used GIS to combine a discrete-choice, parcel-scale economic model of land conversion with a landscape permeability model based on known habitat requirements of wood frogs (Lithobates sylvaticus) in Maine (USA) to examine permeability among habitat elements for alternative future scenarios. The economic model predicts future landscapes under different subdivision open space and vernal pool regulatory requirements. Our model showed that even “no build” permit zones extending 76 m (250 ft) outward from the pool edge were insufficient to assure permeability among required habitat elements. Furthermore, effectiveness of permit zones may be inconsistent due to interactions with other growth management policies, highlighting the need for local and state planning for the long-term persistence of pool-breeding amphibians in developing landscapes.

Heavy metal removal capacity of individual components of permeable reactive concrete

NASA Astrophysics Data System (ADS)

Holmes, Ryan R.; Hart, Megan L.; Kevern, John T.

2017-01-01

Permeable reactive barriers (PRBs) are a well-known technique for groundwater remediation using industrialized reactive media such as zero-valent iron and activated carbon. Permeable reactive concrete (PRC) is an alternative reactive medium composed of relatively inexpensive materials such as cement and aggregate. A variety of multimodal, simultaneous processes drive remediation of metals from contaminated groundwater within PRC systems due to the complex heterogeneous matrix formed during cement hydration. This research investigated the influence coarse aggregate, portland cement, fly ash, and various combinations had on the removal of lead, cadmium, and zinc in solution. Absorption, adsorption, precipitation, co-precipitation, and internal diffusion of the metals are common mechanisms of removal in the hydrated cement matrix and independent of the aggregate. Local aggregates can be used as the permeable structure also possessing high metal removal capabilities, however calcareous sources of aggregate are preferred due to improved removal with low leachability. Individual adsorption isotherms were linear or curvilinear up, indicating a preferred removal process. For PRC samples, metal saturation was not reached over the range of concentrations tested. Results were then used to compare removal against activated carbon and aggregate-based PRBs by estimating material costs for the remediation of an example heavy metal contaminated Superfund site located in the Midwestern United States, Joplin, Missouri.

3D seismic modeling in geothermal reservoirs with a distribution of steam patch sizes, permeabilities and saturations, including ductility of the rock frame

NASA Astrophysics Data System (ADS)

Carcione, José M.; Poletto, Flavio; Farina, Biancamaria; Bellezza, Cinzia

2018-06-01

Seismic propagation in the upper part of the crust, where geothermal reservoirs are located, shows generally strong velocity dispersion and attenuation due to varying permeability and saturation conditions and is affected by the brittleness and/or ductility of the rocks, including zones of partial melting. From the elastic-plastic aspect, the seismic properties (seismic velocity, quality factor and density) depend on effective pressure and temperature. We describe the related effects with a Burgers mechanical element for the shear modulus of the dry-rock frame. The Arrhenius equation combined to the octahedral stress criterion define the Burgers viscosity responsible of the brittle-ductile behaviour. The effects of permeability, partial saturation, varying porosity and mineral composition on the seismic properties is described by a generalization of the White mesoscopic-loss model to the case of a distribution of heterogeneities of those properties. White model involves the wave-induced fluid flow attenuation mechanism, by which seismic waves propagating through small-scale heterogeneities, induce pressure gradients between regions of dissimilar properties, where part of the energy of the fast P-wave is converted to slow P (Biot)-wave. We consider a range of variations of the radius and size of the patches and thin layers whose probability density function is defined by different distributions. The White models used here are that of spherical patches (for partial saturation) and thin layers (for permeability heterogeneities). The complex bulk modulus of the composite medium is obtained with the Voigt-Reuss-Hill average. Effective pressure effects are taken into account by using exponential functions. We then solve the 3D equation of motion in the space-time domain, by approximating the White complex bulk modulus with that of a set of Zener elements connected in series. The Burgers and generalized Zener models allows us to solve the equations with a direct grid method by the introduction of memory variables. The algorithm uses the Fourier pseudospectral method to compute the spatial derivatives. It is tested against an analytical solution obtained with the correspondence principle. We consider two main cases, namely the same rock frame (uniform porosity and permeability) saturated with water and a distribution of steam patches, and water-saturated background medium with thin layers of dissimilar permeability. Our model indicates how seismic properties change with the geothermal reservoir temperature and pressure, showing that both seismic velocity and attenuation can be used as a diagnostic tool to estimate the in situ conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Zhijuan; Hu, Bolin; Chen, Yajie, E-mail: y.chen@neu.edu

A series of Z-type and Y-type ferrite composites with various phase fractions were studied for their RF properties including the measurement of permittivity to permeability spectra over a frequency range of 0.1–10 GHz. Phase identification of the ferrite composites' constituents was determined by X-ray diffraction. An effective medium approximation was used to predict the magnetic and dielectric behavior of the composites. The experiments indicated that the composite having 75 vol. % of Z-type ferrite demonstrated a permeability of ∼12 with a nearly equivalent permittivity, yielding a ratio (μ′/ε′) of 0.91 at a frequency range from 0.55 to 0.75 GHz. The dielectric loss (i.e.,more » tan δ{sub ε}) and magnetic loss (i.e., tan δ{sub μ}) were measured to be lower than 0.08 at f = 0.1–1 GHz and 0.29 at f = 0.1–0.7 GHz, respectively. Furthermore, the loss factors, as tan δ{sub ε}/ε′ and tan δ{sub μ}/μ′, were calculated to be 0.003 and 0.02 at 0.65 GHz, respectively.« less

[BIOLOGICAL ACTIVITY OF ANTIMICROBIAL PEPTIDES OF ENTEROCOCCUS FAECIUM].

PubMed

Vasilchenko, A S; Rogozhin, E A; Valyshev, A V

2015-01-01

Isolate bacteriocins from Enterococcus faecium metabolites and characterize their effect on cells of Gram positive (Listeria monocytogenes) and Gram negative (Escherichia coli) bacteria. Methods of solid-phase extraction, ion-exchange and reversed phase chromatography were applied for isolation of bacteriocins from cultural medium of bacteria MALDI time-of-flight mass-spectrometry was used for characterization of the obtained preparations. The mechanism of biological effect of peptides was evaluated using DNA-tropic dyes (SYTO 9 and PI) with subsequent registration of fluorescence spectra: Atomic-force microscopy (AFM) was used for characterization of morpho-functional reaction of target cells. Peptide fractions with mass of 1.0 - 3.0 kDa were isolated from enterococci metabolites, that inhibit the growth of indicator microorganisms. E. faecium strain exoproducts were shown to increase membrane permeability during interaction with L. monocytogenes, that results in subsequent detectable disturbance of normal cell morphology of listeria. Alterations of E. coli surface during the effect of purified peptide fraction was detected using AFM. The studies carried out have revealed the effect of bacteriocins of enterococci on microorganisms with various types of cell wall composition and have confirmed the importance of bacterial barrier structure permeability disturbance in the mechanism of antimicrobial effect of enterocins.

Energetic neutron and gamma-ray spectra under the earth radiation belts according to "SALYUT-7" [correction of "SALUTE-7"]-"KOSMOS-1686" orbital complex and "CORONAS-I" satellite data.

PubMed

Bogomolov, A V; Dmitriev, A V; Myagkova, I N; Ryumin, S P; Smirnova, O N; Sobolevsky, I M

1998-01-01

The spectra of neutrons >10 MeV and gamma-rays 1.5-100 MeV under the Earth Radiation Belts, restored from the data, obtained onboard orbital complex "SALYUT-7" [correction of "SALUTE-7"]-"KOSMOS-1686", are presented. The spectra shapes are similar to those for albedo neutrons and gamma-rays, but absolute values of their fluxes (0.2 cm-2 s-1 for neutrons, 0.8 cm-2 s-1 for gamma-rays at the equator and 1.2 cm-2 s-1, 1.9 cm-2 s-1, accordingly, at L=1.9) are several times as large. It is possibly explained by the fact that most of the detected particles were produced by the cosmic ray interactions with the orbital complex matter. Neutron and gamma-ray fluxes obtained from "CORONAS-1" data are near those for albedo particles.

An Experimental Study on Characterization of Physical Properties of Ultramafic Rocks and Controls on Evolution of Fracture Permeability During Serpentinization at Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Farough, Aida

Serpentinization is a complex set of hydration reactions, where olivine and pyroxene are replaced by serpentine, magnetite, brucite, talc and carbonate minerals. Serpentinization reactions alter chemical, mechanical, magnetic, seismic, and hydraulic properties of the crust. To understand the complicated nature of serpentinization and the linkages between physical and chemical changes during the reactions, I performed flow-through laboratory experiments on cylindrically cored samples of ultramafic rocks. Each core had a well-mated through-going tensile fracture, to investigate evolution of fracture permeability during serpentinization. The samples were tested in a triaxial loading machine at an effective pressure of 30 MPa, and temperature of 260"aC, simulating a depth of 2 km under hydrostatic conditions. Fracture permeability decreased by one to two orders of magnitude during the 200 to 340 hour experiments. Electron microprobe and SEM data indicated the formation of needle-shaped crystals of serpentine composition along the walls of the fracture, and chemical analyses of sampled pore fluids were consistent with dissolution of ferromagnesian minerals. The rate of transformation of olivine to serpentine in a tensile fracture is calculated using the data on evolution of fracture permeability assuming the fracture permeability could be represented by parallel plates. Assuming the dissolution and precipitation reactions occur simultaneously; the rate of transformation at the beginning of the experiments was 10-8-10-9 (mol/m2s) and decreased monotonically by about an order of magnitude towards the end of the experiment. Results show that dissolution and precipitation is the main mechanism contributing to the reduction in fracture aperture. The experimental results suggest that the fracture network in long-lived hydrothermal circulation systems may be sealed rapidly as a result of mineral precipitation, and generation of new permeability resulting from a combination of tectonic and crystallization-induced stresses may be required to maintain fluid circulation. Another set of flow through experiments were performed on intact samples of ultramafic rocks at room temperature and effective pressures of 10, 20 and 30 MPa to estimate the pressure dependency of intact permeability. Porosity and density measurements were also performed with the purpose of characterizing these properties of ultramafic rocks. The pressure dependency of the coefficient of matrix permeability of the ultramafic rock samples fell in the range of 0.05-0.14 MPa -1. Using porosity and permeability measurements, the ratio of interconnected porosity to total porosity was estimated to be small and the permeability of the samples was dominantly controlled by microcracks. Using the density and porosity measurements, the degree of alteration of samples was estimated. Samples with high density and pressure dependent permeability had a smaller degree of alteration than those with lower density and pressure dependency.

Integrative two-dimensional correlation spectroscopy (i2DCOS) for the intuitive identification of adulterated herbal materials

NASA Astrophysics Data System (ADS)

Chen, Jianbo; Wang, Yue; Rong, Lixin; Wang, Jingjuan

2018-07-01

IR, Raman and other separation-free and label-free spectroscopic techniques have been the promising methods for the rapid and low-cost quality control of complex mixtures such as food and herb. However, as the overlapped signals from different ingredients usually make it difficult to extract useful information, chemometrics tools are often needed to find out spectral features of interest. With designed perturbations, two-dimensional correlation spectroscopy (2DCOS) is a powerful technique to resolve the overlapped spectral bands and enhance the apparent spectral resolution. In this research, the integrative two-dimensional correlation spectroscopy (i2DCOS) is defined for the first time overcome some disadvantages of synchronous and asynchronous correlation spectra for identification. The integrative 2D correlation spectra weight the asynchronous cross peaks by the corresponding synchronous cross peaks, which combines the signal-to-noise ratio advantage of synchronous correlation spectra and the spectral resolution advantage of asynchronous correlation spectra. The feasibility of the integrative 2D correlation spectra for the quality control of complex mixtures is examined by the identification of adulterated Fritillariae Bulbus powders. Compared with model-based pattern recognition and multivariate calibration methods, i2DCOS can provide intuitive identification results but not require the number of samples. The results show the potential of i2DCOS in the intuitive quality control of herbs and other complex mixtures, especially when the number of samples is not large.

Zircon solubility and of Zr species in subduction zone fluids

NASA Astrophysics Data System (ADS)

Wilke, M.; Schmidt, C.; Rickers, K.; Pascarelli, S.; Manning, C. E.; Stechern, A.

2009-12-01

The geochemical signature of igneous rocks at convergent plate margins is thought to result from complex melt formation processes involving aqueous solutions derived from dehydration of the subducted slab. In these processes, the depletion of high-field-strength elements (HFSE) may be controlled by the presence of accessory phases such as zircon and rutile, which can strongly fractionate these elements; however, the stability and solubility of these phases depends strongly on the fluid composition, including concentration and stoichiometry of Na-Al silicate components. Here we present new data on the influence of the fluid composition on zircon solubility as well as data on the Zr complexation in these fluids at P&T. Experiments were conducted using a modified hydrothermal diamond-anvil cell (HDAC). Zr contents at P&T were determined using SR-µXRF spectra. Zr K-edge X-ray Absorption Fine Structure (XAFS) spectra were acquired to investigate the Zr complexation in-situ at P&T. A grain of synthetic crystalline zircon was equilibrated with an aqueous fluid containing Na2Si2O5 or Na2Si2O5 + Al2O3 components. XAFS and SR-µXRF spectra were taken at the dispersive beamline ID24 of the ESRF, Grenoble, France. Some additional SR-µXRF spectra were taken at HASYLAB, Hamburg, beamline L. The observed Zr concentrations in fluids containing 7-33 wt% Na2Si2O5 and variable Al contents were between 75 and 720 ppm at 500 to 750°C and ~300 MPa to ~700 MPa. These values match expected solubilities calculated from linear interpolation of the maximum solubility in pure H2O (from the detection limit) and the solubility in the most alkaline high-silica melts reported by Ellison and Hess (1986, CMP, 94, 343). The high Zr solubility in sodium silicate-bearing solutions signifies that aqueous fluids with alkali silicates offer an efficient mechanism for HFSE transport. This can be explained by complexation of HFSE with Si, Na, and perhaps also Al, via formation of polymerized solutes. The XAFS results show clear differences between spectra of Zr in an HCl solution and in H2O-Na2Si2O5 (±Al2O3) aqueous fluid, implying considerable differences in Zr complexation. The latter spectra display similarities to spectra of Zr in Na2Si2O5 glass. This may indicate a similar structural environment for the two examined states, and thus point to Zr in (alumino)-silicate-based polymeric units in the aqueous solutions.

Integrating seasonal optical and thermal infrared spectra to characterize urban impervious surfaces with extreme spectral complexity: a Shanghai case study

NASA Astrophysics Data System (ADS)

Wang, Wei; Yao, Xinfeng; Ji, Minhe

2016-01-01

Despite recent rapid advancement in remote sensing technology, accurate mapping of the urban landscape in China still faces a great challenge due to unusually high spectral complexity in many big cities. Much of this complication comes from severe spectral confusion of impervious surfaces with polluted water bodies and bright bare soils. This paper proposes a two-step land cover decomposition method, which combines optical and thermal spectra from different seasons to cope with the issue of urban spectral complexity. First, a linear spectral mixture analysis was employed to generate fraction images for three preliminary endmembers (high albedo, low albedo, and vegetation). Seasonal change analysis on land surface temperature induced from thermal infrared spectra and coarse component fractions obtained from the first step was then used to reduce the confusion between impervious surfaces and nonimpervious materials. This method was tested with two-date Landsat multispectral data in Shanghai, one of China's megacities. The results showed that the method was capable of consistently estimating impervious surfaces in highly complex urban environments with an accuracy of R2 greater than 0.70 and both root mean square error and mean average error less than 0.20 for all test sites. This strategy seemed very promising for landscape mapping of complex urban areas.

The Photoluminescent Properties of New Cationic Iridium(III) Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes.

PubMed

Yang, Hui; Meng, Guoyun; Zhou, Yayun; Tang, Huaijun; Zhao, Jishou; Wang, Zhengliang

2015-09-14

Three cationic iridium(III) complexes [Ir(ppy)₂(phen)][PF₆] (C1), [Ir(ppy)₂(phen)]₂SiF₆ (C2) and [Ir(ppy)₂(phen)]₂TiF₆ (C3) (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline) using different anions were synthesized and characterized by ¹H Nuclear magnetic resonance (¹HNMR), mass spectra (MS), Fourier transform infrared (FTIR) spectra and element analysis (EA). After the ultraviolet visible (UV-vis) absorption spectra, photoluminescent (PL) properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs) as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y₃Al₅O 12 :Ce 3+ (YAG). The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W -1 and 11.41 Lm·W -1 , respectively.

Chemical and physical investigations on the charge transfer interaction of organic donors with iodine and its application as non-traditional organic conductors

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Sharshar, T.; Adam, Abdel Majid A.; Elsabawy, Khaled M.; Hemeda, O. M.

2014-09-01

The iso-leucine-iodide and methionine-iodide charge-transfer complexes were prepared and characterized using different spectroscopic techniques. The iodide charge-transfer complexes were synthesized by grinding KI-I2-amino acid with 1:1:1 M ratio in presence of few drops of methanol solvent. The structures of both solid amino acid iodide charge-transfer complexes are discussed with the help of the obtained results of the infrared and Raman laser spectra, Uv-vis. electronic spectra and thermal analyses. The electrical properties (AC resistivity and dielectric constant) of both complexes were investigated. The positron annihilation Doppler broadening (PADB) spectroscopies were also used to probe the structural changes of both complexes. The PADB line-shape parameters (S and W) were found to be dependent on the structure, electronic configuration of the charge transfer complex. The PADB technique is a powerful tool to probe the structural features of the KI-I2-amino acid complexes.

Synthesis, spectroscopic, coordination and biological activities of some organometallic complexes derived from thio-Schiff base ligands

NASA Astrophysics Data System (ADS)

Abou-Hussein, Azza A.; Linert, Wolfgang

2014-01-01

Two series of mono- and binuclear complexes cyclic or acyclic thio-ferocine Schiff base ligands, derived from the condensation of 2-aminobenzenthiol (L) with monoacetyl ferrocene in the molar ratio 1:1 or in the molar ratio 1:2 for diacetyl ferocine have been prepared. The condensation reactions yield the corresponding Schiff Base ligands, HLa-Maf and H2Lb-Daf. The chelation of the ligands to metal ions occurs through the sulfur of the thiol group as well as the nitrogen atoms of the azomethine group of the ligands. HLa-Maf acts as monobasic bidentate or dibasic tetradentate, while H2Lb-Daf behaves as twice negatively cargend tetradentate ligand. The structures of these ligands were elucidated by elemental analysis, infrared, ultraviolet-visible spectra, as well as 1H NMR spectra. Reactions of the Schiff bases ligands with ruthenium(III), oxovanadium(IV) and dioxouranium(VI) afforded the corresponding transition metal complexes. The properties of the newly prepared complexes were analyse by elemental analyses, infrared, electronic spectra, 1H NMR as well as the magnetic susceptibility and conductivity measurement. The metal complexes exhibits different geometrical arrangements such as octahedral and square pyramidal coordination. Schiff base ligands and their metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi to study their biological activity. All the complexes exhibit antibacterial and antifungal activities against these organisms.

Synthesis, electronic and ESR spectral studies on copper(II) nitrate complexes with some acylhydrazines and hydrazones.

PubMed

Singh, Vinod P

2008-11-01

This paper describes the preparation of [Cu(bh)2(H2O)2](NO3)2], [Cu(ibh)2(NO3)2], [Cu(ibh)2(H2O)2](NO3)2 and [Cu(iinh)2(NO3)2] (bh = benzoyl hydrazine (C6H5CONHNH2); ibh = isonicotinoyl hydrazine (NC5H4CONHNH2); ibh = isopropanone benzoyl hydrazone (C6H5CONHN=C(CH3)2; iinh = isopropanone isonicotinoyl hydrazone (NC5H4CONHN=C(CH3)2). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300 K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77 K in DMSO solution. The trend g(||) > g(perpendicular) > g(e,) observed in all the complexes suggests the presence of an unpaired electron in the d x2-y2 orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >C=O and -NH2 groups whereas, ibh and iinh bond through >C=O and >C=N- groups. The IR spectra of bh and ibh complexes also show H-O-H stretching and bending modes of coordinated water.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Quantum chemical studies on hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes

NASA Astrophysics Data System (ADS)

Gövdeli, Nezafet; Karakaş, Duran

2018-07-01

Quantum chemical calculations at B3LYP/LANL2DZ/6-31G(d) level were made on anti-eclipsed, anti-staggered, syn-eclipsed, syn-staggered conformers of hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes in the gas phase. The most stable conformer of the complexes was found to be anti-staggered according to the total energy values calculated at given level. Structural parameters, vibration spectra, charge distributions, molecular orbital energy diagrams, contour diagrams of frontier orbitals, molecular electrostatic potential maps and some electronic structure descriptors were obtained for the most stable conformers. NMR spectra of the most stable conformers were calculated at GIAO/B3LYP/LANL2DZ level. The most stable conformer geometry was found to be distorted octahedral. IR and NMR spectra of the complexes are consistent with their geometry. HOMOs of the complexes were found to be center-atomic character and LUMOs were carbene-carbon character. From the calculated charge analysis and molecular electrostatic potential maps, it is found that carbene-carbon acts as electrofil and metal center nucleophile. It is suggested that the catalytic properties of the carbene complexes may be due to the fact that the carbene-carbon behave as electrophile and metal center nucleophile. Some electronic structure descriptors of the complexes were calculated and the molecular properties were estimated.

Analysis of Native-Like Proteins and Protein Complexes Using Cation to Anion Proton Transfer Reactions (CAPTR)

NASA Astrophysics Data System (ADS)

Laszlo, Kenneth J.; Bush, Matthew F.

2015-12-01

Mass spectra of native-like protein complexes often exhibit narrow charge-state distributions, broad peaks, and contributions from multiple, coexisting species. These factors can make it challenging to interpret those spectra, particularly for mixtures with significant heterogeneity. Here we demonstrate the use of ion/ion proton transfer reactions to reduce the charge states of m/ z-selected, native-like ions of proteins and protein complexes, a technique that we refer to as cation to anion proton transfer reactions (CAPTR). We then demonstrate that CAPTR can increase the accuracy of charge state assignments and the resolution of interfering species in native mass spectrometry. The CAPTR product ion spectra for pyruvate kinase exhibit ~30 peaks and enable unambiguous determination of the charge state of each peak, whereas the corresponding precursor spectra exhibit ~6 peaks and the assigned charge states have an uncertainty of ±3%. 15+ bovine serum albumin and 21+ yeast enolase dimer both appear near m/ z 4450 and are completely unresolved in a mixture. After a single CAPTR event, the resulting product ions are baseline resolved. The separation of the product ions increases dramatically after each subsequent CAPTR event; 12 events resulted in a 3000-fold improvement in separation relative to the precursor ions. Finally, we introduce a framework for interpreting and predicting the figures of merit for CAPTR experiments. More generally, these results suggest that CAPTR strongly complements other mass spectrometry tools for analyzing proteins and protein complexes, particularly those in mixtures.

Combinatorial Approach for Large-scale Identification of Linked Peptides from Tandem Mass Spectrometry Spectra*

PubMed Central

Wang, Jian; Anania, Veronica G.; Knott, Jeff; Rush, John; Lill, Jennie R.; Bourne, Philip E.; Bandeira, Nuno

2014-01-01

The combination of chemical cross-linking and mass spectrometry has recently been shown to constitute a powerful tool for studying protein–protein interactions and elucidating the structure of large protein complexes. However, computational methods for interpreting the complex MS/MS spectra from linked peptides are still in their infancy, making the high-throughput application of this approach largely impractical. Because of the lack of large annotated datasets, most current approaches do not capture the specific fragmentation patterns of linked peptides and therefore are not optimal for the identification of cross-linked peptides. Here we propose a generic approach to address this problem and demonstrate it using disulfide-bridged peptide libraries to (i) efficiently generate large mass spectral reference data for linked peptides at a low cost and (ii) automatically train an algorithm that can efficiently and accurately identify linked peptides from MS/MS spectra. We show that using this approach we were able to identify thousands of MS/MS spectra from disulfide-bridged peptides through comparison with proteome-scale sequence databases and significantly improve the sensitivity of cross-linked peptide identification. This allowed us to identify 60% more direct pairwise interactions between the protein subunits in the 20S proteasome complex than existing tools on cross-linking studies of the proteasome complexes. The basic framework of this approach and the MS/MS reference dataset generated should be valuable resources for the future development of new tools for the identification of linked peptides. PMID:24493012

Synthesis and Characterization of Diranitidinecopper(II) Sulfate Dihydrate

NASA Astrophysics Data System (ADS)

Syaima, H.; Rahardjo, S. B.; Zein, I. M.

2018-04-01

The complex of ranitidine with Cu(II) has been synthesized in 1:2-mole ratio of metal to the ligand in water. The forming of the complex was indicated by shifting of maximum wavelength from 816 nm (CuSO4·5H2O) to 626 nm (the complex). Infrared spectra indicated NO2 and NH functional group were coordinated to Cu(II). The percentage of copper in the complex measured by Atomic Absorption Spectroscopy (AAS) analysis was 7.5% indicating that formula of the complex was Cu(ranitidine)2SO4(H2O)n (n=2, 3 or 4). The electrical conductivity of Cu(II) complex in water was 71.0 Scm2mol-1 corresponding to 1:1 electrolytes. Thermogravimetric/Differential Thermal Analysis (TG/DTA) showed the presence of two molecules of H2O in the complex. UV-Vis spectra showed a transition peak on 15974 cm-1 indicating square planar geometry. The complex was paramagnetic with µeff 1.77 BM. The proposed formula of the complex was [Cu(ranitidine)2]SO4·2H2O.

Application of FTIR spectroscopy to study the thermal stability of magnesium aspartate-arginine

NASA Astrophysics Data System (ADS)

Hacura, Andrzej; Marcoin, Wacława; Pasterny, Karol

2012-03-01

FTIR spectroscopy has been applied to study the thermal stability of magnesium aspartatearginine. An attempt has been made, using theoretically predicted IR spectra, to relate the changes in the experimental spectra with the decomposition process of the studied magnesium complex.

Remote sensing reflectance simulation of coastal optical complex water in the East China Sea

NASA Astrophysics Data System (ADS)

He, Shuo; Lou, Xiulin; Zhang, Huaguo; Zheng, Gang

2018-02-01

In this work, remote sensing reflectance (Rrs) spectra of the Zhejiang coastal water in the East China Sea (ECS) were simulated by using the Hydrolight software with field data as input parameters. The seawater along the Zhejiang coast is typical Case II water with complex optical properties. A field observation was conducted in the Zhejiang coastal region in late May of 2016, and the concentration of ocean color constituents (pigment, SPM and CDOM), IOPs (absorption and backscattering coefficients) and Rrs were measured at 24 stations of 3 sections covering the turbid to clear inshore coastal waters. Referring to these ocean color field data, an ocean color model suitable for the Zhejiang coastal water was setup and applied in the Hydrolight. A set of 11 remote sensing reflectance spectra above water surface were modeled and calculated. Then, the simulated spectra were compared with the filed measurements. Finally, the spectral shape and characteristics of the remote sensing reflectance spectra were analyzed and discussed.

de la Vallée-Poussin means of Fourier series for the quadratic spectrum and for spectra with power-like density

NASA Astrophysics Data System (ADS)

Bochkarev, S. V.

2014-02-01

A new method is proposed and elaborated for investigating complex or real trigonometric series with various spectra. It is based on new multiplicative inequalities which give a lower bound for the integral norm of the de la Vallée-Poussin means and are themselves based on results establishing corresponding analogues of the Littlewood-Paley theorem in the BMO, Hardy, and Lorentz spaces. For spectra with power-like density a description of the class of absolute values of coefficients such that the corresponding complex or real trigonometric series are Fourier series is found which depends on the arithmetic characteristics of the spectrum and is sharp in limiting cases. Furthermore, for the quadratic spectrum some results of Hardy and Littlewood on elliptic theta functions are generalized and refined. For the quadratic spectrum and power-like spectra with non-integer exponents new lower bounds are found for the integral norms of exponential sums. Bibliography: 41 titles.

Molecular structure, natural bond analysis, vibrational and electronic spectra, surface enhanced Raman scattering and Mulliken atomic charges of the normal modes of [Mn(DDTC)2] complex.

PubMed

Téllez S, Claudio A; Costa, Anilton C; Mondragón, M A; Ferreira, Glaucio B; Versiane, O; Rangel, J L; Lima, G Müller; Martin, A A

2016-12-05

Theoretical and experimental bands have been assigned for the Fourier Transform Infrared and Raman spectra of the bis(diethyldithiocarbamate)Mn(II) complex, [Mn(DDTC)2]. The calculations have been based on the DFT/B3LYP method, second derivative spectra and band deconvolution analysis. The UV-vis experimental spectra were measured in acetonitrile solution, and the calculated electronic spectrum was obtained using the TD/B3LYP method with 6-311G(d, p) basis set for all atoms. Charge transfer bands and those d-d spin forbidden were assigned in the UV-vis spectrum. The natural bond orbital analysis was carried out using the DFT/B3LYP method and the Mn(II) hybridization leading to the planar geometry of the framework was discussed. Surface enhanced Raman scattering (SERS) was also performed. Mulliken charges of the normal modes were obtained and related to the SERS enhanced bands. Copyright © 2016 Elsevier B.V. All rights reserved.

Diamond-like nanoparticles influence on flavonoids transport: molecular modelling

NASA Astrophysics Data System (ADS)

Plastun, Inna L.; Agandeeva, Ksenia E.; Bokarev, Andrey N.; Zenkin, Nikita S.

2017-03-01

Intermolecular interaction of diamond-like nanoparticles and flavonoids is investigated by numerical simulation. Using molecular modelling by the density functional theory method, we analyze hydrogen bonds formation and their influence on IR - spectra and structure of molecular complex which is formed due to interaction between flavonoids and nanodiamonds surrounded with carboxylic groups. Enriched adamantane (1,3,5,7 - adamantanetetracarboxylic acid) is used as an example of diamond-like nanoparticles. Intermolecular forces and structure of hydrogen bonds are investigated. IR - spectra and structure parameters of quercetin - adamantanetetracarboxylic acid molecular complex are obtained by numerical simulation using the Gaussian software complex. Received data coincide well with experimental results. Intermolecular interactions and hydrogen bonding structure in the obtained molecular complex are examined. Possibilities of flavonoids interaction with DNA at the molecular level are also considered.

Oxidation of municipal wastewater by free radicals mechanism. A UV/Vis spectroscopy study.

PubMed

Giannakopoulos, E; Isari, E; Bourikas, K; Karapanagioti, H K; Psarras, G; Oron, G; Kalavrouziotis, I K

2017-06-15

This study investigates the oxidation of municipal wastewater (WW) by complexation with natural polyphenols having radical scavenging activity, such as (3,4,5 tri-hydroxy-benzoic acid) gallic acid (GA) in alkaline pH (>7), under ambient O 2 and temperature. Physicochemical and structural characteristics of GA-WW complex-forming are evaluated by UV/Vis spectroscopy. The comparative analysis among UV/Vis spectra of GA monomer, GA-GA polymer, WW compounds, and GA-WW complex reveals significant differences within 350-450 and 500-900 nm. According to attenuated total reflectance (ATR) spectroscopy and thermogravimetric analysis (TGA), these spectra differences correspond to distinct complexes formed. This study suggests a novel role of natural polyphenols on the degradation and humification of wastes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Binding affinities of Schiff base Fe(II) complex with BSA and calf-thymus DNA: Spectroscopic investigations and molecular docking analysis

NASA Astrophysics Data System (ADS)

Rudra, Suparna; Dasmandal, Somnath; Patra, Chiranjit; Kundu, Arjama; Mahapatra, Ambikesh

2016-09-01

The binding interaction of a synthesized Schiff base Fe(II) complex with biological macromolecules viz., bovine serum albumin (BSA) and calf thymus(ct)-DNA have been investigated using different spectroscopic techniques coupled with viscosity measurements at physiological pH and 298 K. Regular amendments in emission intensities of BSA upon the action of the complex indicate significant interaction between them, and the binding interaction have been characterized by Stern Volmer plots and thermodynamic binding parameters. On the basis of this quenching technique one binding site with binding constant (Kb = (7.6 ± 0.21) × 105) between complex and protein have been obtained at 298 K. Time-resolved fluorescence studies have also been encountered to understand the mechanism of quenching induced by the complex. Binding affinities of the complex to the fluorophores of BSA namely tryptophan (Trp) and tyrosine (Tyr) have been judged by synchronous fluorescence studies. Secondary structural changes of BSA rooted by the complex has been revealed by CD spectra. On the other hand, hypochromicity of absorption spectra of the complex with the addition of ct-DNA and the gradual reduction in emission intensities of ethidium bromide bound ct-DNA in presence of the complex indicate noticeable interaction between ct-DNA and the complex with the binding constant (4.2 ± 0.11) × 106 M- 1. Life-time measurements have been studied to determine the relative amplitude of binding of the complex to ct-DNA base pairs. Mode of binding interaction of the complex with ct-DNA has been deciphered by viscosity measurements. CD spectra have also been used to understand the changes in ct-DNA structure upon binding with the metal complex. Density functional theory (DFT) and molecular docking analysis have been employed in highlighting the interactive phenomenon and binding location of the complex with the macromolecules.

Magnetodynamic properties of spatially distributed films based on a metal-dielectric composite

NASA Astrophysics Data System (ADS)

Tarasova, O. S.; Kalinin, Yu. E.; Sitnikov, A. V.; Yanchenko, L. I.

2017-09-01

The frequency dependences of the absorption coefficient of electromagnetic radiation and frequency dependences of the complex magnetic permeability of the fiberglass made of fiberglass cloth with a heterogeneous film deposited on the surface were investigated in the frequency range from 300 MHz to 10 GHz.

Analysis of odorant receptor protein function in the yellow fever mosquito, aedes aegypti

USDA-ARS?s Scientific Manuscript database

Odorant receptors (ORs) in insects are ligand-gated ion channels comprised of two subunits: a variable receptor and an obligatory co-receptor (Orco). This protein receptor complex of unknown stoichiometry interacts with an odor molecule leading to changes in permeability of the sensory dendrite, th...

Time-Lapse 3D Inversion of Complex Conductivity Data Using an Active Time Constrained (ATC) Approach

EPA Science Inventory

Induced polarization (more precisely the magnitude and the phase of the impedance of the subsurface) is measured using a network of electrodes located at the ground surface or in boreholes. This method yields important information related to the distribution of permeability and ...

Comparative studies on P-vanillin and O-vanillin of 2-hydrazinyl-2-oxo-N-phenylacetamide and their Mn(II) and Co(II) complexes

NASA Astrophysics Data System (ADS)

Yousef, T. A.; El-Reash, G. M. Abu; El-Tabai, M. N.

2018-05-01

Synthesis of complexes derived from hydrazones derived from both P-vanillin (H2L1) and its isomer O-vanillin (H2L2) of 2-hydrazinyl-2-oxo-N-phenylacetamide that coordinated with high magnetic metal ions of both Mn(II) and Co(II) were performed and characterized by different physicochemical methods, elemental analysis, (1H NMR, IR, and UV-visible spectra), also thermal analysis (TG and DTG) techniques and magnetic measurements. The molecular structures of the ligands and their Mn(II) and Co(II) complexes were optimized theoretically and the quantum chemical parameters were calculated. IR spectra suggest that the H2L1 behaved in a mononegative bidentate manner with both but H2L2 coordinated as mononegative tridentate with both Mn(II) and Co(II). The electronic spectra of the complexes as well as their magnetic moments suggested octahedral geometries for all the isolated complexes. The calculated values of binding energies indicated the stability of complexes is higher than that of ligand. The kinetic and thermodynamic parameters for the different decomposition steps in complexes were calculated using Coats-Redfern and Horowitz-Metzger equations. Moreover, the prepared ligands and their Mn(II) and Co(II) complexes were individually tested against a panel of gram positive Bacillus Subtilis and negative Escherichia coli microscopic organisms. Additionally cytotoxicity assay of two human tumor cell lines namely; hepatocellular carcinoma (liver) HePG-2, and mammary gland (breast) MCF-7 were tested.

Mechanism of enhanced oral absorption of morin by phospholipid complex based self-nanoemulsifying drug delivery system.

PubMed

Zhang, Jinjie; Li, Jianbo; Ju, Yuan; Fu, Yao; Gong, Tao; Zhang, Zhirong

2015-02-02

Phospholipid complex (PLC) based self-nanoemulsifying drug delivery system (PLC-SNEDDS) has been developed for efficient delivery of drugs with poor solubility and low permeability. In the present study, a BCS class IV drug and a P-glycoprotein (P-gp) substrate, morin, was selected as the model drug to elucidate the oral absorption mechanism of PLC-SNEDDS. PLC-SNEDDS was superior to PLC in protecting morin from degradation by intestinal enzymes in vitro. In situ perfusion study showed increased intestinal permeability by PLC was duodenum-specific. In contrast, PLC-SNEDDS increased morin permeability in all intestinal segments and induced a change in the main absorption site of morin from colon to ileum. Moreover, ileum conducted the lymphatic transport of PLC-SNEDDS, which was proven by microscopic intestinal visualization of Nile red labeled PLC-SNEDDS and lymph fluids in vivo. Low cytotoxicity and increased Caco-2 cell uptake suggested a safe and efficient delivery of PLC-SNEDDS. The increased membrane fluidity and disrupted actin filaments were closely associated with the increased cell uptake of PLC-SNEDDS. PLC-SNEDDS could be internalized into enterocytes as an intact form in a cholesterol-dependent manner via clathrin-mediated endocytosis and macropinocytosis. The enhanced oral absorption of morin was attributed to the P-gp inhibition by Cremophor RH and the intact internalization of M-PLC-SNEDDS into Caco-2 cells bypassing P-gp recognition. Our findings thus provide new insights into the development of novel nanoemulsions for poorly absorbed drugs.

Novel model for multispecies biofilms that uses rigid gas-permeable lenses.

PubMed

Peyyala, Rebecca; Kirakodu, Sreenatha S; Ebersole, Jeffrey L; Novak, Karen F

2011-05-01

Oral biofilms comprise complex multispecies consortia aided by specific inter- and intraspecies interactions occurring among commensals and pathogenic bacterial species. Oral biofilms are primary initiating factors of periodontal disease, although complex multifactorial biological influences, including host cell responses, contribute to the individual outcome of the disease. To provide a system to study initial stages of interaction between oral biofilms and the host cells that contribute to the disease process, we developed a novel in vitro model system to grow biofilms on rigid gas-permeable contact lenses (RGPLs), which enable oxygen to permeate through the lens material. Bacterial species belonging to early- and late-colonizing groups were successfully established as single- or three-species biofilms, with each group comprising Streptococcus gordonii, Streptococcus oralis, and Streptococcus sanguinis; S. gordonii, Actinomyces naeslundii, and Fusobacterium nucleatum; or S. gordonii, F. nucleatum, and Porphyromonas gingivalis. Quantification of biofilm numbers by quantitative PCR (qPCR) revealed substantial differences in the magnitude of bacterial numbers in single-species and multispecies biofilms. We evaluated cell-permeable conventional nucleic acid stains acridine orange, hexidium iodide, and Hoechst 33258 and novel SYTO red, blue, and green fluorochromes for their effect on bacterial viability and fluorescence yield to allow visualization of the aggregates of individual bacterial species by confocal laser scanning microscopy (CLSM). Substantial differences in the quantity and distribution of the species in the multispecies biofilms were identified. The specific features of these biofilms may help us better understand the role of various bacteria in local challenge of oral tissues.

Improving Properties of Arrowroot Starch (Maranta arundinacea)/PVA Blend Films by Using Citric Acid as Cross-linking Agent

NASA Astrophysics Data System (ADS)

Sholichah, Enny; Purwono, Bambang; Nugroho, Pramono

2017-12-01

This research studied the effect of PVA as organic polymer and citric acid as crosslinker agent in the arrowroot starch/PVA blend films. The properties of films were investigated by water uptake, water vapor permeability, mechanical properties, thermal stability, spectra of FTIR and XRD patterns. PVA used in this research influenced the film properties at the highest concentration. The cross-linkingsinter or intra molecules of arrowroot and PVA were developed as ester bonds which are formed from the reaction of hydroxyl groups consisting of starch and PVA with citric acid. The ester bond was confirmed by FTIR spectra. The increase of the amount of citric acid affected significantly on physical, chemical and mechanical properties, water uptake, WVP and crystallinity. Water barrier level was reduced by decreasing of water uptake and WVP succeeded significantly with increased crosslinking. Cross-linking impact the thermal stability of the films. The elasticity of the films also increases the production of citric acid as a plasticizer in the making of the films as a food packaging material.

Tunable far infrared laser spectrometers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blake, G.A.; Laughlin, K.B.; Cohen, R.C.

The state of the art in far infrared (FIR) spectroscopy is reviewed. The development of tunable, coherent FIR radiation sources is discussed. Applications of tunable FIR laser spectrometers for measurement of rotational spectra and dipole moments of molecular ions and free radicals, vibration-rotation-tunneling (VRT) spectra of weakly bound complexes, and vibration-rotation spectra of linear carbon clusters are presented. A detailed description of the Berkeley tunable FIR laser spectrometers is presented in the following article.

The tissue-type plasminogen activator–plasminogen activator inhibitor 1 complex promotes neurovascular injury in brain trauma: evidence from mice and humans

PubMed Central

Sashindranath, Maithili; Sales, Eunice; Daglas, Maria; Freeman, Roxann; Samson, Andre L.; Cops, Elisa J.; Beckham, Simone; Galle, Adam; McLean, Catriona; Morganti-Kossmann, Cristina; Rosenfeld, Jeffrey V.; Madani, Rime; Vassalli, Jean-Dominique; Su, Enming J.; Lawrence, Daniel A.

2012-01-01

The neurovascular unit provides a dynamic interface between the circulation and central nervous system. Disruption of neurovascular integrity occurs in numerous brain pathologies including neurotrauma and ischaemic stroke. Tissue plasminogen activator is a serine protease that converts plasminogen to plasmin, a protease that dissolves blood clots. Besides its role in fibrinolysis, tissue plasminogen activator is abundantly expressed in the brain where it mediates extracellular proteolysis. However, proteolytically active tissue plasminogen activator also promotes neurovascular disruption after ischaemic stroke; the molecular mechanisms of this process are still unclear. Tissue plasminogen activator is naturally inhibited by serine protease inhibitors (serpins): plasminogen activator inhibitor-1, neuroserpin or protease nexin-1 that results in the formation of serpin:protease complexes. Proteases and serpin:protease complexes are cleared through high-affinity binding to low-density lipoprotein receptors, but their binding to these receptors can also transmit extracellular signals across the plasma membrane. The matrix metalloproteinases are the second major proteolytic system in the mammalian brain, and like tissue plasminogen activators are pivotal to neurological function but can also degrade structures of the neurovascular unit after injury. Herein, we show that tissue plasminogen activator potentiates neurovascular damage in a dose-dependent manner in a mouse model of neurotrauma. Surprisingly, inhibition of activity following administration of plasminogen activator inhibitor-1 significantly increased cerebrovascular permeability. This led to our finding that formation of complexes between tissue plasminogen activator and plasminogen activator inhibitor-1 in the brain parenchyma facilitates post-traumatic cerebrovascular damage. We demonstrate that following trauma, the complex binds to low-density lipoprotein receptors, triggering the induction of matrix metalloproteinase-3. Accordingly, pharmacological inhibition of matrix metalloproteinase-3 attenuates neurovascular permeability and improves neurological function in injured mice. Our results are clinically relevant, because concentrations of tissue plasminogen activator: plasminogen activator inhibitor-1 complex and matrix metalloproteinase-3 are significantly elevated in cerebrospinal fluid of trauma patients and correlate with neurological outcome. In a separate study, we found that matrix metalloproteinase-3 and albumin, a marker of cerebrovascular damage, were significantly increased in brain tissue of patients with neurotrauma. Perturbation of neurovascular homeostasis causing oedema, inflammation and cell death is an important cause of acute and long-term neurological dysfunction after trauma. A role for the tissue plasminogen activator–matrix metalloproteinase axis in promoting neurovascular disruption after neurotrauma has not been described thus far. Targeting tissue plasminogen activator: plasminogen activator inhibitor-1 complex signalling or downstream matrix metalloproteinase-3 induction may provide viable therapeutic strategies to reduce cerebrovascular permeability after neurotrauma. PMID:22822039

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose.

PubMed

Pacławski, K; Zajac, D A; Borowiec, M; Kapusta, Cz; Fitzner, K

2010-11-11

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.

Microwave Spectra and AB Initio Studies of the Ne-Acetone Complex

NASA Astrophysics Data System (ADS)

Gao, Jiao; Thomas, Javix; Xu, Yunjie; Jäger, Wolfgang

2015-06-01

Microwave spectra of the neon-acetone van der Waals complex were measured using a cavity-based molecular beam Fourier-transform microwave spectrometer in the region from 5 to 18 GHz. Both 20Ne and 22Ne containing isotopologues were studied and both c- and weaker a-type rotational transitions were observed. The transitions are split into multiplets due to the internal rotation of two methyl groups in acetone. Electronic structure calculations were done at the MP2 level of theory with the 6-311++g (2d, p) basis set for all atoms and the internal rotation barrier height of the methyl groups was determined to be about 2.8 kJ/mol. The ab initio rotational constants were the basis for our spectroscopic searches, but the multiplet structures and floppiness of the complex made the quantum number assignment very difficult. The assignment was finally achieved with the aid of constructing closed frequency loops and predicting internal rotation splittings using the XIAM code. Analyses of the spectra yielded rotational and centrifugal distortion constants, as well as internal rotation parameters, which were interpreted in terms of structure and internal dynamics of the complex. H. Hartwig and H. Dreizler, Z. Naturforsch. A 51, 923 (1996).

Expanding the family of heterobimetallic Bi-Rh paddlewheel carboxylate complexes via equatorial carboxylate exchange.

PubMed

Sunderland, Travis L; Berry, John F

2016-01-07

Five novel homoleptic heterobimetallic bismuth(II)-rhodium(II) carboxylate complexes--BiRh(TPA)4 (1), BiRh(but)4 (2), BiRh(piv)4 (3), BiRh(esp)2 (4), and BiRh(OAc)4 (5)--were synthesized in good yields by equatorial ligand substitution starting from BiRh(TFA)4 (TPA = triphenylacetate, but = butyrate, piv = pivalate, esp = α,α,α',α'-tetramethyl-1,3-benzenedipropionate, OAc = acetate, and TFA = trifluoroacetate). We report here (1)H and (13)C{(1)H} NMR spectra and cyclic voltammograms for complexes , and IR spectra for all complexes. Irreversible redox waves appear between -1.4 to -1.5 V for [BiRh](3+/4+) couples and 1.3 to 1.5 V vs. Fc/Fc(+) for [BiRh](4+/5+) couples for complexes indicating a wide range of stability for the compounds. The X-ray crystal structure of reveals a Bi-Rh distance of 2.53 Å.

Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

NASA Astrophysics Data System (ADS)

Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

2017-09-01

The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

Infrared spectroscopy and density functional calculations on titanium-dinitrogen complexes

NASA Astrophysics Data System (ADS)

Yoo, Hae-Wook; Choi, Changhyeok; Cho, Soo Gyeong; Jung, Yousung; Choi, Myong Yong

2018-04-01

Titanium-nitrogen complexes were generated by laser ablated titanium (Ti) atoms and N2 gas molecules in this study. These complexes were isolated on the pre-deposited solid Ar matrix on the pre-cooled KBr window (T ∼ 5.4 K), allowing infrared spectra to be measured. Laser ablation experiments with 15N2 isotope provided distinct isotopic shifts in the infrared spectra that strongly implicated the formation of titanium-nitrogen complexes, Ti(NN)x. Density functional theory (DFT) calculations were employed to investigate the molecular structures, electronic ground state, relative energies, and IR frequencies of the anticipated Ti(NN)x complexes. Based on laser ablation experiments and DFT calculations, we were able to assign multiple Ti(NN)x (x = 1-6) species. Particularly, Ti(NN)5 and Ti(NN)6, which have high nitrogen content, may serve as good precursors in preparing polynitrogens.

EFFECT OF MICROWAVE POWER ON SHAPE OF EPR SPECTRA--APPLICATION TO EXAMINATION OF COMPLEX FREE RADICAL SYSTEM IN THERMALLY STERILIZED ACIDUM BORICUM.

PubMed

Ramos, Paweł; Pieprzyca, Małgorzata; Pilawa, Barbara

2016-01-01

Complex free radical system in thermally sterilized acidum boricum (AB) was studied. Acidum boricum was sterilized at temperatures and times given by pharmaceutical norms: 160 degrees C and 120 min, 170 degrees C and 60 min and 180 degrees C and 30 min. The advanced spectroscopic tests were performed. The EPR spectra of free radicals were measured as the first derivatives with microwaves of 9.3 GHz frequency and magnetic modulation of 100 kHz. The Polish X-band electron paramagnetic resonance spectrometer of Radiopan (Poznań) was used. EPR lines were not observed for the nonheated AB. The broad EPR asymmetric lines were obtained for all the heated AB samples. The influence of microwave power in the range of 2.2-70 mW on the shape of EPR spectra of the heated drug samples was tested. The following asymmetry parameters: A1/A2, A1-A2, B1/B2, and B1-B2, were analyzed. The changes of these parameters with microwave power were observed. The strong dependence of shape and its parameters on microwave power proved the complex character of free radical system in thermally sterilized AB. Changes of microwave power during the detection of EPR spectra indicated complex character of free radicals in AB sterilized in hot air under all the tested conditions. Thermolysis, interactions between free radicals and interactions of free radicals with oxygen may be responsible for the complex free radicals system in thermally treated AB. Usefulness of continuous microwave saturation of EPR lines and shape analysis to examine free radicals in thermally sterilized drugs was confirmed.

Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grush, M.M.; Chen, J.; George, S.J.

1996-01-10

The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compoundmore » spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.« less

Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

PubMed Central

Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

2016-01-01

NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

Synthesis and Characterization of Tetrakis-aqua-bis-isonicotin-amide(itmd)nickel(II) Sulfate

NASA Astrophysics Data System (ADS)

Rahardjo, S. B.; Hastuti, S.; Amanati, N.; Syaima, H.

2018-03-01

The complex of Tetrakis-aqua-bis-(isonicotinamide)nickel(II) sulfate has been synthesized in 1:2 mole ratio of metal to ligands in methanol. The formula of the complex predicted from analysis nickel content in the complex by Atomic Absorption Spectroscopy (AAS) was Ni(itmd)2SO4(H2O)4. The conductivity of the complex in methanol was measured by conductivity meter correspond to 1:1 electrolyte. Thermal analysis of the complex was determined by Differential Thermal Analyzer (DTA) indicating that the complex contains four H2O molecules as ligands. The magnetic susceptibility measurement showed that the complex was paramagnetic with μeff = 3.02 BM. The electronic spectra of the complex appear due to two transition peak on λ = 398 nm and 664 nm. The Infrared spectra showed a shift of NH2 stretching vibration of Ni(itmd)2SO4(H2O)4. These facts indicated that these functional groups were coordinated to the center ion of the complexes. The proposed structure of the complex was octahedral therefore the possibility formula of this complex was [Ni(itmd)2(H2O)4]SO4.

a Chiral Tag Study of the Absolute Configuration of Camphor

NASA Astrophysics Data System (ADS)

Pratt, David; Evangelisti, Luca; Smart, Taylor; Holdren, Martin S.; Mayer, Kevin J.; West, Channing; Pate, Brooks

2017-06-01

The chiral tagging method for rotational spectroscopy uses an established approach in chiral analysis of creating a complex with an enantiopure tag so that enantiomers of the molecule of interest are converted to diastereomer complexes. Since the diastereomers have distinct structure, they give distinguishable rotational spectra. Camphor was chosen as an example for the chiral tag method because it has spectral properties that could pose challenges to the use of three wave mixing rotational spectroscopy to establish absolute configuration. Specifically, one of the dipole moment components of camphor is small making three wave mixing measurements challenging and placing high accuracy requirements on computational chemistry for calculating the dipole moment direction in the principal axis system. The chiral tag measurements of camphor used the hydrogen bond donor 3-butyn-2-ol. Quantum chemistry calculations using the B3LYP-D3BJ method and the def2TZVP basis set identified 7 low energy isomers of the chiral complex. The two lowest energy complexes of the homochiral and heterochiral complexes are observed in a measurement using racemic tag. Absolute configuration is confirmed by the use of an enantiopure tag sample. Spectra with ^{13}C-sensitivity were acquired so that the carbon substitution structure of the complex could be obtained to provide a structure of camphor with correct stereochemistry. The chiral tag complex spectra can also be used to estimate the enantiomeric excess of the sample and analysis of the broadband spectrum indicates that the sample enantiopurity is higher than 99.5%. The structure of the complex is analyzed to determine the extent of geometry modification that occurs upon formation of the complex. These results show that initial isomer searches with fixed geometries will be accurate. The reduction in computation time from fixed geometry assumptions will be discussed.

Nonlinear-regression groundwater flow modeling of a deep regional aquifer system

USGS Publications Warehouse

Cooley, Richard L.; Konikow, Leonard F.; Naff, Richard L.

1986-01-01

A nonlinear regression groundwater flow model, based on a Galerkin finite-element discretization, was used to analyze steady state two-dimensional groundwater flow in the areally extensive Madison aquifer in a 75,000 mi2 area of the Northern Great Plains. Regression parameters estimated include intrinsic permeabilities of the main aquifer and separate lineament zones, discharges from eight major springs surrounding the Black Hills, and specified heads on the model boundaries. Aquifer thickness and temperature variations were included as specified functions. The regression model was applied using sequential F testing so that the fewest number and simplest zonation of intrinsic permeabilities, combined with the simplest overall model, were evaluated initially; additional complexities (such as subdivisions of zones and variations in temperature and thickness) were added in stages to evaluate the subsequent degree of improvement in the model results. It was found that only the eight major springs, a single main aquifer intrinsic permeability, two separate lineament intrinsic permeabilities of much smaller values, and temperature variations are warranted by the observed data (hydraulic heads and prior information on some parameters) for inclusion in a model that attempts to explain significant controls on groundwater flow. Addition of thickness variations did not significantly improve model results; however, thickness variations were included in the final model because they are fairly well defined. Effects on the observed head distribution from other features, such as vertical leakage and regional variations in intrinsic permeability, apparently were overshadowed by measurement errors in the observed heads. Estimates of the parameters correspond well to estimates obtained from other independent sources.

Tracking live cell response to cadmium (II) concentrations by scanning electrochemical microscopy.

PubMed

Henderson, Jeffrey D; Filice, Fraser P; Li, Michelle S M; Ding, Zhifeng

2016-05-01

The biological chemistry of toxic heavy metals, such as Cd (II), has become an active area of research due to connections with increased oxidative stress, cytotoxicity, and human/animal carcinogenicity. In this study, scanning electrochemical microscopy (SECM) was used as a noninvasive technique to monitor membrane permeability of single live human bladder cancer cells (T24) subjected to exposure of Cd (II) at various concentrations. The addition of a membrane permeable redox mediator, ferrocenemethanol (FcMeOH), in combination with depth scan imaging provided probe approach curves (PACs) to reveal changes in membrane homeostasis. To demonstrate the strength of SECM as a bioanalytical technique for cell physiology and pathology, we tested responses of live cells after 1h incubations with various concentrations of Cd (II). For the first time, a trend in membrane permeability of Cd (II) treated live T24 cells was discovered. Dependent on the incubation concentration, the trend displayed an initial decrease in membrane permeability coefficient from 75μm/s for control cells to 25μm/s for cells incubated with 75μM Cd (II). This was followed by an eventual return to the permeability coefficient of control cells (75μm/s) with further increases in Cd (II) exposure. The cells were found to respond at as little as 10μM Cd (II) concentrations. This work further demonstrates the use of SECM as a bioanalytical technique to monitor cell physiology and topography. A greater insight into the complex mechanisms behind Cd (II) toxicity is anticipated. Copyright © 2015 Elsevier Inc. All rights reserved.

Over-vibration induced blood perfusion and vascular permeability changes may lead to vocal edema.

PubMed

Wang, Jiajia; Devine, Erin; Fang, Rui; Jiang, Jack J

2017-01-01

To observe blood perfusion and vascular permeability changes under varying vibration frequency exposures. Animal model. Blood perfusion was measured using laser Doppler flowmetry in eight rabbit auricular vessels (four rabbits) under nonvibration, and 62.5-Hz/1-mm, 125-Hz/1-mm, and 250-Hz/0.5-mm vibration frequency/amplitude exposures. Another 12 rabbits were randomly divided into vibration only and vibration with histamine groups. After 3 hours of continuous 125-Hz, 1-mm amplitude vibration of the auricle, vascular permeability was analyzed by absorbance of Evans blue-albumin complex. Significantly lower blood perfusion was observed in the vibration group, compared with no vibration exposure controls. Blood perfusion decreased 29 ± 16% as the vibration frequency was increased from 62.5 Hz to 125 Hz with the vibration amplitude constant at 1 mm. When the frequency was increased from 125 Hz to 250 Hz, while the amplitude was decreased from 1 mm to 0.5 mm, blood flow perfusion further decreased 29 ± 29%, and the decline tendency in blood perfusion showed no significant difference (P = .992). Meanwhile, in the vibration with histamine group, vascular permeability of the vibrated ears increased significantly compared to the nonvibrated ears (P = .005). Overvibration of the vocal folds due to voice overuse or abuse may significantly reduce blood perfusion, and increase vascular permeability in the vocal fold in inflammatory situations, which may lead to the formation of vocal edema. NA Laryngoscope, 127:148-152, 2017. © 2016 The American Laryngological, Rhinological and Otological Society, Inc.

Nonlinear-Regression Groundwater Flow Modeling of a Deep Regional Aquifer System

NASA Astrophysics Data System (ADS)

Cooley, Richard L.; Konikow, Leonard F.; Naff, Richard L.

1986-12-01

A nonlinear regression groundwater flow model, based on a Galerkin finite-element discretization, was used to analyze steady state two-dimensional groundwater flow in the areally extensive Madison aquifer in a 75,000 mi2 area of the Northern Great Plains. Regression parameters estimated include intrinsic permeabilities of the main aquifer and separate lineament zones, discharges from eight major springs surrounding the Black Hills, and specified heads on the model boundaries. Aquifer thickness and temperature variations were included as specified functions. The regression model was applied using sequential F testing so that the fewest number and simplest zonation of intrinsic permeabilities, combined with the simplest overall model, were evaluated initially; additional complexities (such as subdivisions of zones and variations in temperature and thickness) were added in stages to evaluate the subsequent degree of improvement in the model results. It was found that only the eight major springs, a single main aquifer intrinsic permeability, two separate lineament intrinsic permeabilities of much smaller values, and temperature variations are warranted by the observed data (hydraulic heads and prior information on some parameters) for inclusion in a model that attempts to explain significant controls on groundwater flow. Addition of thickness variations did not significantly improve model results; however, thickness variations were included in the final model because they are fairly well defined. Effects on the observed head distribution from other features, such as vertical leakage and regional variations in intrinsic permeability, apparently were overshadowed by measurement errors in the observed heads. Estimates of the parameters correspond well to estimates obtained from other independent sources.

Laboratory Investigation of Coal Deformation Behavior and Its Influence on Permeability Evolution During Methane Displacement by CO2

NASA Astrophysics Data System (ADS)

Fan, Jingjing; Feng, Ruimin; Wang, Jin; Wang, Yanbin

2017-07-01

Geological sequestration of CO2 in coal seams is of significant interest to both academia and industry. A thorough laboratory investigation of mechanical and flow behaviors is crucial for understanding the complex response of coalbeds to CO2 injection-enhanced coalbed methane recovery (CO2-ECBM) operation. In this work, systematic experiments were carried out on cylindrical coal core specimens under different uniform confining stresses. The coal deformation caused by variations in effective stress as well as the sorption-induced matrix swelling/shrinkage was monitored. The competitive gas sorption characteristics and permeability evolution during the process of methane displacement by CO2 were also investigated. The measured volumetric strain results indicate that sorption-induced strain is the dominant factor in the coal deformation. The relationship between the volumetric strain and the adsorbed gas volume has been revealed to be a linear function. Experimental results obtained under different stress conditions suggest that higher confining stress suppresses the increase in both volumetric strain and the adsorbed gas volume. Furthermore, both methane displacement and CO2 injection are reduced when applying higher confining stresses. In addition, the permeability enhancement is heavily suppressed at higher confining stress. At a certain confining stress, a characteristic "U-shaped" trend of permeability is presented as a function of decreasing pore pressure. This study contributes to the understanding of coal deformation and its impact on permeability evolution under uniformly stressed condition, which has practical significance for CO2 sequestration and CO2-ECBM operation in the Qinshui basin.

Permeability Variations Associated With Fault Reactivation in a Claystone Formation Investigated by Field Experiments and Numerical Simulations

NASA Astrophysics Data System (ADS)

Jeanne, Pierre; Guglielmi, Yves; Rutqvist, Jonny; Nussbaum, Christophe; Birkholzer, Jens

2018-02-01

We studied the relation between rupture and changes in permeability within a fault zone intersecting the Opalinus Clay formation at 300 m depth in the Mont Terri Underground Research Laboratory (Switzerland). A series of water injection experiments were performed in a borehole straddle interval set within the damage zone of the main fault. A three-component displacement sensor allowed an estimation of the displacement of a minor fault plane reactivated during a succession of step rate pressure tests. The experiment reveals that the fault hydromechanical (HM) behavior is different from one test to the other with varying pressure levels needed to trigger rupture and different slip behavior under similar pressure conditions. Numerical simulations were performed to better understand the reason for such different behavior and to investigate the relation between rupture nucleation, permeability change, pressure diffusion, and rupture propagation. Our main findings are as follows: (i) a rate frictional law and a rate-and-state permeability law can reproduce the first test, but it appears that the rate constitutive parameters must be pressure dependent to reproduce the complex HM behavior observed during the successive injection tests; (ii) almost similar ruptures can create or destroy the fluid diffusion pathways; (iii) a too high or too low diffusivity created by the main rupture prevents secondary rupture events from occurring whereas "intermediate" diffusivity favors the nucleation of a secondary rupture associated with the fluid diffusion. However, because rupture may in certain cases destroy permeability, this succession of ruptures may not necessarily create a continuous hydraulic pathway.

A detailed study of CO 2-brine capillary trapping mechanisms as applied to geologic carbon storage. Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wildenschild, Dorthe

2017-04-06

The proposed research focuses on improved fundamental understanding of the efficiency of physical trapping mechanisms, and as such will provide the basis for subsequent upscaling efforts. The overarching hypothesis of the proposed research is that capillary pressure plays a significant role in capillary trapping of CO 2, especially during the water imbibition stage of the sequestration process. We posit that the relevant physics of the sequestration process is more complex than is currently captured in relative permeability models, which are often based on so-called trapping models to represent relative permeability hysteresis. Our 4 main questions, guiding the 4 main tasksmore » of the proposed research, are as follows: (1) What is the morphology of capillary trapped CO 2 at the pore scale as a function of temperature, pressure, brine concentration, interfacial tension, and pore-space morphology under injection and subsequent imbibition? (2) Is it possible to describe the capillary trapping process using formation-dependent, but otherwise unique continuum-scale functions in permeability-capillary pressure, interfacial area and saturation space, rather than hysteretic functions in permeability-saturation or capillary pressure-saturation space? (3) How do continuum-scale relationships between kr-Pc-S-Anw developed based on pore-scale observations compare with traditional models incorporating relative permeability hysteresis (such as Land’s and other models,) and with observations at the core (5-10cm) scale? (4) How can trapped CO 2 volume be optimized via engineered injection and sweep strategies, and as a function of formation type (incl. heterogeneity)?« less

Examinations of the matrix isolation fourier transform infrared spectra of organic compounds: Part XII

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coleman, W. M., III; Gordon, B. M.; Lawrence, B. M.

1989-02-01

Matrix isolation Fourier transform infrared spectra (MI/FT-IR), massspectra (MS), carbon-13 Nuclear Magnetic Resonance (/sup 13/C-NMR) spectra,condensed-phase infrared spectra, and vapor-phase infrared (IR)spectra are presented for a series of terpene compounds. Subtle differencesin positional and configurational isomers commonly found withterpenes could be easily detected by the MI/FT-IR spectra. The resultsare comparable in some aspects to those obtainable from /sup 13/C-NMR andthin-film IR; however, most importantly, they are acquired at the lownanogram level for MI/FT-IR, as compared to the milligram level forthe other techniques. These results represent an advance in the technologyavailable for the analysis of complex mixtures such as essential oilscontainingmore » terpene-like molecules.« less

Reflection and Refraction of Light in Absorbing Media

NASA Astrophysics Data System (ADS)

Katsumata, Koichi; Sasaki, Shosuke

2018-05-01

The results of a rigorous calculation of optical phenomena in absorbing media based on Maxwell's equations are reported. In the case of an absorbing dielectric, we assume a complex dielectric constant. We find an expression for the angle of refraction as a function of the incident angle and the real and imaginary parts of the complex dielectric constant, all of which are real. The amplitudes of the reflected and transmitted waves are calculated on the same footing. These amplitudes are shown to be complex, from which we deduce the magnitude and phase change of the reflection and transmission coefficients. The same argument applies to an absorbing magnetic material if we replace the complex dielectric constant by a complex magnetic permeability.

Finding of No Significant Impact (FONSI) for Construction of a Base Civil Engineer Complex at Travis Air Force Base, California

DTIC Science & Technology

2002-01-26

than the target species and have permeable skins. Use of pesticides, such as methoprene , in mosquito abatement may have an indirect adverse effect on...antiterrorism/force protection requirements and provide operational flexibility for the various organizations that would use the complex. Decision After...NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND

Fluid-injection and the mechanics of frictional stability of shale-bearing faults

NASA Astrophysics Data System (ADS)

Scuderi, Marco Maria; Collettini, Cristiano; Marone, Chris

2017-04-01

Fluid overpressure is one of the primary mechanisms for triggering tectonic fault slip and human-induced seismicity. This mechanism is appealing because fluids lubricate the fault and reduce the effective normal stress that holds the fault in place. However, current models of earthquake nucleation, based on rate- and state- friction, imply that stable sliding is favored by the increase of pore fluid pressure. Despite this apparent dilemma, there are a few studies on the role of fluid pressure in frictional stability under controlled, laboratory conditions. Here, we describe laboratory experiments on shale fault gouge, conducted in the double direct shear configuration in a true-triaxial machine. To characterize frictional stability and hydrological properties we performed three types of experiments: 1) stable sliding shear experiment to determine the material failure envelope resulting in fault strength of µ=0.28 and fault zone permeability (k 10-19m2); 2) velocity step experiments to determine the rate- and state- frictional properties, characterized by a velocity strengthening behavior with a negative rate parameter b, indicative of stable aseismic creep; 3) creep experiment to study fault slip evolution with increasing pore-fluid pressure. In these creep experiments fault slip history can be divided in three main stages: a) for low fluid pressure the fault is locked and undergoes compaction; b) with increasing fluid pressurization, we observe aseismic creep (i.e. v=0.0001 µm/s) associated with fault dilation, with maintained low permeability; c) As fluid pressure is further increased and we approach the failure criteria fault begins to accelerate, the dilation rate increases causing an increase in permeability. Following the first acceleration we document complex fault slip behavior characterized by periodic accelerations and decelerations with slip velocity that remains slow (i.e. v 200 µm/s), never approaching dynamic slip rates. Surprisingly, this complex slip behavior is associated with fault zone compaction and permeability increase as opposite to the dilation hardening mechanism that is usually invoked to quench the instability. We relate this complex fault slip behaviour to the interplay between fault weakening induced by fluid pressurization and the strong rate-strengthening behaviour of shales. Our data show that fault rheology and fault stability is controlled by the coupling between fluid pressure and rate- and state- friction parameters suggesting that their comprehensive characterization is fundamental for assessing the role of fluid pressure in natural and human induced earthquakes.

Eu(III) and Tb(III) complexes with the nonsteroidal anti-inflammatory drug carprofen: synthesis, crystal structure, and photophysical properties.

PubMed

Zhou, Xianju; Zhao, Xiaoqi; Wang, Yongjie; Wu, Bing; Shen, Jun; Li, Li; Li, Qingxu

2014-12-01

Two new lanthanide complexes with general formula [Ln2(carprofen)6(DMF)2] (Ln = Eu (1), Tb (2), DMF = N,N-dimethylformamide, carprofen = 6-chloro-α-methylcarbazole-2-acetic acid) have been synthesized by a hydrothermal method. Complex 1 was characterized by single-crystal X-ray diffraction (XRD), and it was found to crystallize in the monoclinic space group C2/c. The coordination of the ligand to the lanthanide ion has been investigated by Fourier-transform infrared (FTIR) spectra and ultraviolet-visible (UV-vis) absorption spectra. Complex 1 emits red light, but the antenna effect of the ligand is not effective, whereas complex 2 presents intense green emission with effective energy transfer from the ligand. The different performance of the two complexes is related to the energy matching between the excited states of the lanthanide ion and the triplet state of the ligand. The intramolecular energy transfer mechanisms are also discussed.

Aminopurvalanol A, a Potent, Selective, and Cell Permeable Inhibitor of Cyclins/Cdk Complexes, Causes the Reduction of in Vitro Fertilizing Ability of Boar Spermatozoa, by Negatively Affecting the Capacitation-Dependent Actin Polymerization

PubMed Central

Bernabò, Nicola; Valbonetti, Luca; Greco, Luana; Capacchietti, Giulia; Ramal Sanchez, Marina; Palestini, Paola; Botto, Laura; Mattioli, Mauro; Barboni, Barbara

2017-01-01

The adoption of high-througput technologies demonstrated that in mature spermatozoa are present proteins that are thought to be not present or active in sperm cells, such as those involved in control of cell cycle. Here, by using an in silico approach based on the application of networks theory, we found that Cyclins/Cdk complexes could play a central role in signal transduction active during capacitation. Then, we tested this hypothesis in the vitro model. With this approach, spermatozoa were incubated under capacitating conditions in control conditions (CTRL) or in the presence of Aminopurvalanol A a potent, selective and cell permeable inhibitor of Cyclins/Cdk complexes at different concentrations (2, 10, and 20 μM). We found that this treatment caused dose-dependent inhibition of sperm fertilizing ability. We attribute this event to the loss of acrosome integrity due to the inhibition of physiological capacitation-dependent actin polymerization, rather than to a detrimental effect on membrane lipid remodeling or on other signaling pathways such as tubulin reorganization or MAPKs activation. In our opinion, these data could revamp the knowledge on biochemistry of sperm capacitation and could suggest new perspectives in studying male infertility. PMID:29312003

[In-vitro evaluation of cinnarizine as a competing agent to beta-cyclodextrin inclusion complexes: effect of cinnarizine on the membrane permeation rate of progesterone from its beta-cyclodextrin inclusion complex].

PubMed

Muraoka, Atsushi; Tokumura, Tadakazu; Machida, Yoshiharu

2008-01-01

The use of competing agents is considered a powerful tool for the development of a drug-delivery system with drug/cyclodextrin inclusion complexes. However, there are very few studies examining this issue. To explain this phenomenon, it was thought that a competing agent with a sufficiently high stability constant had not yet been reported. In this study, cinnarizine (CN), which has a high stability constant with beta-cyclodextrin (beta-CD) and unique solubility characteristics, was selected, and its ability as a competing agent was examined in a membrane permeability study. The permeability study showed that the permeation rates of the drugs flurbiprofen, progesterone, and spironolactone decreased with their stability constants with the addition of beta-CD. In one of the drugs, progesterone (Pro), the decrease was restored by the addition of CN. The amount of CN added was a 1:1 molar ratio to the amount of Pro. However, no similar action was induced with the addition of DL-phenylalanine (Phe) in the permeation study at the 1:5 (Pro:Phe) molar ratio. These finding indicate that CN acts as a competing agent, and its action is much stronger than that of Phe.

Predicting both passive intestinal absorption and the dissociation constant toward albumin using the PAMPA technique.

PubMed

Bujard, Alban; Sol, Marine; Carrupt, Pierre-Alain; Martel, Sophie

2014-10-15

The parallel artificial membrane permeability assay (PAMPA) is a high-throughput screening (HTS) method that is widely used to predict in vivo passive permeability through biological barriers, such as the skin, the blood brain barrier (BBB) and the gastrointestinal tract (GIT). The PAMPA technique has also been used to predict the dissociation constant (Kd) between a compound and human serum albumin (HSA) while disregarding passive permeability. Furthermore, the assay is based on the use of two separate 5-point kinetic experiments, which increases the analysis time. In the present study, we adapted the hexadecane membrane (HDM)-PAMPA assay to both predict passive gastrointestinal absorption via the permeability coefficient logPe value and determine the Kd. Two assays were performed: one in the presence and one in the absence of HSA in the acceptor compartment. In the absence of HSA, logPe values were determined after a 4-h incubation time, as originally described, but the dimethylsulfoxide (DMSO) percentage and pH were altered to be compatible with the protein. In parallel, a second PAMPA assay was performed in the presence of HSA during a 16-h incubation period. By adding HSA, a variation in the amount of compound crossing the membrane was observed compared to the permeability measured in the absence of HSA. The concentration of compound reaching the acceptor compartment in each case was used to determine both parameters (logPe and logKd) using numerical simulations, which highlighted the originality of this method because these calculations required only two endpoint measurements instead of a complete kinetic study. It should be noted that the amount of compound that reaches the acceptor compartment in the presence of HSA is modulated by complex dissociation in the receptor compartment. Only compounds that are moderately bound to albumin (-3

A comparison of the far-infrared and low-frequency Raman spectra of glass-forming liquids

NASA Astrophysics Data System (ADS)

Perova, T. S.; Vij, J. K.; Christensen, D. H.; Nielsen, O. F.

1999-04-01

Far-infrared and low-frequency Raman spectra in the wavenumber range from 15 to 500 cm -1 were recorded for glycerol, triacetin (glycerol triacetate) and o-terphenyl at temperatures from 253 to 355 K. The far-infrared spectra of glycerol appear complex compared with the spectra of triacetin owing to the presence of hydrogen bonding in glycerol. The experimental results obtained for o-terphenyl are in good agreement with normal mode analyses carried out for crystalline o-terphenyl (A. Criado, F.J. Bermejo, A. de Andres, Mol. Phys. 82 (1994) 787). The far-infrared results are compared with the low-frequency Raman spectra of these three glass-forming liquids. The difference in temperature dependences found from these spectra is explained on the basis of different temperature contributions of the relaxational and vibrational processes to the low-frequency vibrational spectra.

Near-Term Fetuses Process Temporal Features of Speech

ERIC Educational Resources Information Center

Granier-Deferre, Carolyn; Ribeiro, Aurelie; Jacquet, Anne-Yvonne; Bassereau, Sophie

2011-01-01

The perception of speech and music requires processing of variations in spectra and amplitude over different time intervals. Near-term fetuses can discriminate acoustic features, such as frequencies and spectra, but whether they can process complex auditory streams, such as speech sequences and more specifically their temporal variations, fast or…

MUTATIONS INDUCED BY URBAN AIR AND DRINKING WATER: DO THEY LEAVE A MUTATIONAL SIGNATURE IN HUMAN TUMORS?

EPA Science Inventory

Mutations Induced by Urban Air and Drinking Water: Do They Leave a Mutational Signature in Human Tumors?

Mutation spectra of complex environmental mixtures have been determined thus far only in Salmonella. We have determined mutation spectra for the particulate organics ...

Evaluation of exchange-correlation functionals for time-dependent density functional theory calculations on metal complexes.

PubMed

Holland, Jason P; Green, Jennifer C

2010-04-15

The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) < 3.5% and epsilon(SF) values close to unity (>0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes. 2009 Wiley Periodicals, Inc.

Synthesis, characterization, biological evaluation and docking studies of macrocyclic binuclear manganese(II) complexes containing 3,5-dinitrobenzoyl pendant arms

NASA Astrophysics Data System (ADS)

Arthi, P.; Shobana, S.; Srinivasan, P.; Mitu, L.; Kalilur Rahiman, A.

2015-05-01

A series of bis(phenoxo) bridged binuclear manganese(II) complexes of the type [Mn2L1-3](ClO4)2 (1-3) containing 3,5-dinitrobenzoyl pendant-arms have been synthesized by cyclocondensation of 2,6-diformyl-4-R-phenols (where R = sbnd CH3, sbnd C(CH3)3 or sbnd Br) with 2,2‧-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride in the presence of manganese(II) perchlorate. The IR spectra of complexes indicate the presence of uncoordinated perchlorate anions. The UV-Vis spectra of complexes suggest the distorted octahedral geometry around manganese(II) nuclei. The EPR spectra of Mn(II) complexes show a broad signal with g value 2.03-2.04, which is characteristic for octahedral high spin Mn2+ complex. The observed room temperature magnetic moment values of the Mn(II) complexes (5.60-5.62 B.M.) are less than the normal value (5.92 B.M.), indicating weak antiferromagnetic coupling interaction between the two metal ions. Electrochemical studies of the complexes show two distinct quasi-reversible one electron transfer processes in the cathodic (E1pc = -0.73 to -0.76 V, E2pc = -1.30 to -1.36 V), and anodic (E1pa = 1.02-1.11 V, E2pa = 1.32-1.79 V) potential regions. Antibacterial efficacy of complexes have been screened against four Gram (-ve) and two Gram (+ve) bacterial strains. The DNA interaction studies suggest that these complexes bind with CT-DNA by intercalation, giving the binding affinity in the order 1 > 2 > 3. All the complexes display significant cleavage activity against circular plasmid pBR322 DNA. Docking simulation was performed to insert complexes into the crystal structure of EGFR tyrosine kinase and B-DNA at active site to determine the probable binding mode.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II)

NASA Astrophysics Data System (ADS)

Singh, Bibhesh K.; Jetley, Umesh K.; Sharma, Rakesh K.; Garg, Bhagwan S.

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML 2 composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II).

PubMed

Singh, Bibhesh K; Jetley, Umesh K; Sharma, Rakesh K; Garg, Bhagwan S

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML(2) composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Fault-controlled permeability and fluid flow in low-porosity crystalline rocks: an example from naturally fractured geothermal systems in the Southern Andes

NASA Astrophysics Data System (ADS)

Arancibia, G.; Roquer, T.; Sepúlveda, J.; Veloso, E. A.; Morata, D.; Rowland, J. V.

2017-12-01

Fault zones can control the location, emplacement, and evolution of economic mineral deposits and geothermal systems by acting as barriers and/or conduits to crustal fluid flow (e.g. magma, gas, oil, hydro-geothermal and groundwater). The nature of the fault control permeability is critical in the case of fluid flow into low porosity/permeability crystalline rocks, since structural permeability provides the main hydraulic conductivity to generate a natural fractured system. However, several processes accompanying the failure of rocks (i.e. episodic permeability given by cycling ruptures, mineral precipitation from fluids in veins, dissolution of minerals in the vicinity of a fracture) promote a complex time-dependent and enhancing/reducing fault-controlled permeability. We propose the Southern Volcanic Zone (Southern Andes, Chile) as a case study to evaluate the role of the structural permeability in low porosity crystalline rocks belonging to the Miocene North Patagonian Batholith. Recently published studies propose a relatively well-constrained first-order role of two active fault systems, the arc-parallel (NS to NNE trending) Liquiñe Ofqui Fault System and the arc-oblique (NW trending) Andean Transverse Fault Zones, in fluid flow at crustal scales. We now propose to examine the Liquiñe ( 39°S) and Maihue ( 40°S) areas as sites of interaction between these fault systems, in order to evaluate a naturally fractured geothermal system. Preliminary results indicate upwelling of thermal water directly from fractured granite or from fluvial deposits overlying granitoids. Measured temperatures of thermal springs suggest a low- to medium-enthalpy system, which could potentially be harnessed for use in geothermal energy applications (e.g. heating, wood dryer and green house), which are much needed in Southern Chile. Future work will aim to examine the nature of structural permeability from the regional to the microscopic scale connecting the paleo- and current- fluid flow through the fractured media. Results will contribute to a better understanding of geothermal systems in the Andean tectonic setting and of naturally fractured reservoirs in low-porosity crystalline rocks around the world. Acknowledgments: This work is funded by CEGA-FONDAP/CONICYT #15090013 and VRI-PUENTE #P1703/2017.

Fluorescence-excitation and emission spectra from LH2 antenna complexes of Rhodopseudomonas acidophila as a function of the sample preparation conditions.

PubMed

Kunz, Ralf; Timpmann, Kõu; Southall, June; Cogdell, Richard J; Köhler, Jürgen; Freiberg, Arvi

2013-10-10

The high sensitivity of optical spectra of pigment-protein complexes to temperature and pressure is well known. In the present study, we have demonstrated the significant influence of the environments commonly used in bulk and single-molecule spectroscopic studies at low temperatures on the LH2 photosynthetic antenna complex from Rhodopseudomonas acidophila. A transfer of this LH2 complex from a bulk-buffer solution into a spin-coated polymer film results in a 189 cm(-1) blue shift of the B850 excitonic absorption band at 5 K. Within the molecular exciton model, the origin of this shift could be disentangled into three parts, namely to an increase of the local site energies, a contraction of the exciton band, and a decrease of the displacement energy.

Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies

NASA Astrophysics Data System (ADS)

Omar, M. M.; Mohamed, Gehad G.; Ibrahim, Amr A.

2009-07-01

Novel Schiff base (HL) ligand is prepared via condensation of 4-aminoantipyrine and 2-aminobenzoic acid. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA, DrTGA and DTA). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine N, amino N and deprotonated caroxylic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia Coli, Pseudomonas aeruginosa, Staphylococcus Pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Shciff base ligand against one or more bacterial species.

NHERF1 and CFTR restore tight junction organisation and function in cystic fibrosis airway epithelial cells: role of ezrin and the RhoA/ROCK pathway.

PubMed

Castellani, Stefano; Guerra, Lorenzo; Favia, Maria; Di Gioia, Sante; Casavola, Valeria; Conese, Massimo

2012-11-01

Tight junctions (TJs) restrict the transit of ions and molecules through the paracellular route and act as a barrier to regulate access of inflammatory cells into the airway lumen. The pathophysiology of cystic fibrosis (CF) lung disease is characterised by abnormal ion and fluid transport across the epithelium and polymorphonuclear (PMN) leukocyte-dominated inflammatory response. Na⁺/H⁺ exchanger regulatory factor 1 (NHERF1) is a protein involved in PKA-dependent activation of CFTR by interacting with CFTR via its PDZ domains and with ezrin via its C-terminal domain. We have previously found that the NHERF1-overexpression dependent rescue CFTR-dependent chloride secretion is due to the re-organisation of the actin cytoskeleton network induced by the formation of the multiprotein complex NHERF1-RhoA-ezrin-actin. In this context, we here studied whether NHERF1 and CFTR are involved in the organisation and function of TJs. F508del CFBE41o⁻ monolayers presented nuclear localisation of zonula occludens (ZO-1) and occludin as well as disorganisation of claudin 1 and junction-associated adhesion molecule 1 as compared with wild-type 16HBE14o⁻ monolayers, paralleled by increased permeability to dextrans and PMN transmigration. Overexpression of either NHERF1 or CFTR in CFBE41o⁻ cells rescued TJ proteins to their proper intercellular location and decreased permeability and PMN transmigration, while this effect was not achieved by overexpressing either NHERF1 deprived of ezrin-binding domain. Further, expression of a phospho-dead ezrin mutant, T567A, increased permeability in both 16HBE14o⁻ cells and in a CFBE clone stably overexpressing NHERF1 (CFBE/sNHERF1), whereas a constitutively active form of ezrin, T567D, achieved the opposite effect in CFBE41o⁻ cells. A dominant-negative form of RhoA (RhoA-N19) also disrupted ZO-1 localisation at the intercellular contacts dislodging it to the nucleus and increased permeability in CFBE/sNHERF1. The inhibitor Y27632 of Rho kinase (ROCK) increased permeability as well. Overall, these data suggest a significant role for the multiprotein complex CFTR-NHERF1-ezrin-actin in maintaining TJ organisation and barrier function, and suggest that the RhoA/ROCK pathway is involved.

Soil vapor extraction with dewatering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomson, N.R.

1996-08-01

The physical treatment technology of soil vapor extraction (SVE) is reliable, safe, robust, and able to remove significant amounts of mass at a relatively low cost. SVE combined with a pump-and-treat system to create a dewatered zone has the opportunity to remove more mass with the added cost of treating the extracted groundwater. Various limiting processes result in a significant reduction in the overall mass removal rates from a SVE system in porous media. Only pilot scale, limited duration SVE tests conducted in low permeability media have been reported in the literature. It is expected that the presence of amore » fracture network in low permeability media will add another complexity to the limiting conditions surrounding the SVE technology. 20 refs., 4 figs.« less

Acid extraction by supported liquid membranes containing basic carriers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danesi, P.R.; Cianetti, C.; Horwitz, E.P.

1983-01-01

The extraction of HNO/sub 3/ (nitric acid) from aqueous solutions by permeation through a number of supported liquid membranes containing basic carriers dissolved in diethylbenzene has been studied. The results have shown that the best permeations are obtained with long chain aliphatic amines (TLA, Primene JM-T) followed by TOPO (trioctylphosphine oxide) and then by other monofunctional and bifunctional organophosphorous basic carriers. The influence of an aliphatic diluent on the permeability of HNO/sub 3/ through a supported liquid membrane containing TLA as carrier was also investigated. In this case the permeability to HNO/sub 3/ decreases as a result of the lowermore » diffusion coefficient of the acid-carrier complex in the more vicous aliphatic solvent. 4 figures.« less

Prediction of the Passive Intestinal Absorption of Medicinal Plant Extract Constituents with the Parallel Artificial Membrane Permeability Assay (PAMPA).

PubMed

Petit, Charlotte; Bujard, Alban; Skalicka-Woźniak, Krystyna; Cretton, Sylvian; Houriet, Joëlle; Christen, Philippe; Carrupt, Pierre-Alain; Wolfender, Jean-Luc

2016-03-01

At the early drug discovery stage, the high-throughput parallel artificial membrane permeability assay is one of the most frequently used in vitro models to predict transcellular passive absorption. While thousands of new chemical entities have been screened with the parallel artificial membrane permeability assay, in general, permeation properties of natural products have been scarcely evaluated. In this study, the parallel artificial membrane permeability assay through a hexadecane membrane was used to predict the passive intestinal absorption of a representative set of frequently occurring natural products. Since natural products are usually ingested for medicinal use as components of complex extracts in traditional herbal preparations or as phytopharmaceuticals, the applicability of such an assay to study the constituents directly in medicinal crude plant extracts was further investigated. Three representative crude plant extracts with different natural product compositions were chosen for this study. The first extract was composed of furanocoumarins (Angelica archangelica), the second extract included alkaloids (Waltheria indica), and the third extract contained flavonoid glycosides (Pueraria montana var. lobata). For each medicinal plant, the effective passive permeability values Pe (cm/s) of the main natural products of interest were rapidly calculated thanks to a generic ultrahigh-pressure liquid chromatography-UV detection method and because Pe calculations do not require knowing precisely the concentration of each natural product within the extracts. The original parallel artificial membrane permeability assay through a hexadecane membrane was found to keep its predictive power when applied to constituents directly in crude plant extracts provided that higher quantities of the extract were initially loaded in the assay in order to ensure suitable detection of the individual constituents of the extracts. Such an approach is thus valuable for the high-throughput, cost-effective, and early evaluation of passive intestinal absorption of active principles in medicinal plants. In phytochemical studies, obtaining effective passive permeability values of pharmacologically active natural products is important to predict if natural products showing interesting activities in vitro may have a chance to reach their target in vivo. Georg Thieme Verlag KG Stuttgart · New York.

Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-30

Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexesmore » in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.« less

Expert system for computer-assisted annotation of MS/MS spectra.

PubMed

Neuhauser, Nadin; Michalski, Annette; Cox, Jürgen; Mann, Matthias

2012-11-01

An important step in mass spectrometry (MS)-based proteomics is the identification of peptides by their fragment spectra. Regardless of the identification score achieved, almost all tandem-MS (MS/MS) spectra contain remaining peaks that are not assigned by the search engine. These peaks may be explainable by human experts but the scale of modern proteomics experiments makes this impractical. In computer science, Expert Systems are a mature technology to implement a list of rules generated by interviews with practitioners. We here develop such an Expert System, making use of literature knowledge as well as a large body of high mass accuracy and pure fragmentation spectra. Interestingly, we find that even with high mass accuracy data, rule sets can quickly become too complex, leading to over-annotation. Therefore we establish a rigorous false discovery rate, calculated by random insertion of peaks from a large collection of other MS/MS spectra, and use it to develop an optimized knowledge base. This rule set correctly annotates almost all peaks of medium or high abundance. For high resolution HCD data, median intensity coverage of fragment peaks in MS/MS spectra increases from 58% by search engine annotation alone to 86%. The resulting annotation performance surpasses a human expert, especially on complex spectra such as those of larger phosphorylated peptides. Our system is also applicable to high resolution collision-induced dissociation data. It is available both as a part of MaxQuant and via a webserver that only requires an MS/MS spectrum and the corresponding peptides sequence, and which outputs publication quality, annotated MS/MS spectra (www.biochem.mpg.de/mann/tools/). It provides expert knowledge to beginners in the field of MS-based proteomics and helps advanced users to focus on unusual and possibly novel types of fragment ions.

Expert System for Computer-assisted Annotation of MS/MS Spectra*

PubMed Central

Neuhauser, Nadin; Michalski, Annette; Cox, Jürgen; Mann, Matthias

2012-01-01

An important step in mass spectrometry (MS)-based proteomics is the identification of peptides by their fragment spectra. Regardless of the identification score achieved, almost all tandem-MS (MS/MS) spectra contain remaining peaks that are not assigned by the search engine. These peaks may be explainable by human experts but the scale of modern proteomics experiments makes this impractical. In computer science, Expert Systems are a mature technology to implement a list of rules generated by interviews with practitioners. We here develop such an Expert System, making use of literature knowledge as well as a large body of high mass accuracy and pure fragmentation spectra. Interestingly, we find that even with high mass accuracy data, rule sets can quickly become too complex, leading to over-annotation. Therefore we establish a rigorous false discovery rate, calculated by random insertion of peaks from a large collection of other MS/MS spectra, and use it to develop an optimized knowledge base. This rule set correctly annotates almost all peaks of medium or high abundance. For high resolution HCD data, median intensity coverage of fragment peaks in MS/MS spectra increases from 58% by search engine annotation alone to 86%. The resulting annotation performance surpasses a human expert, especially on complex spectra such as those of larger phosphorylated peptides. Our system is also applicable to high resolution collision-induced dissociation data. It is available both as a part of MaxQuant and via a webserver that only requires an MS/MS spectrum and the corresponding peptides sequence, and which outputs publication quality, annotated MS/MS spectra (www.biochem.mpg.de/mann/tools/). It provides expert knowledge to beginners in the field of MS-based proteomics and helps advanced users to focus on unusual and possibly novel types of fragment ions. PMID:22888147

Magnetic losses versus sintering treatment in Mn-Zn ferrites

NASA Astrophysics Data System (ADS)

Beatrice, Cinzia; Tsakaloudi, Vasiliki; Dobák, Samuel; Zaspalis, Vassilios; Fiorillo, Fausto

2017-05-01

Mn-Zn ferrites prepared by different sintering schedules at 1325 °C, 1340 °C, and 1360 °C, have been characterized from the structural, electrical, and magnetic viewpoint. Magnetic losses and complex permeability have been, in particular, measured and analyzed from quasi-static excitation up to 1 GHz. It is observed that lower sintering temperatures and shorter treatment times lead to more homogeneous grain structure and better soft magnetic response at all frequencies. It is shown, however, that, once the contribution by eddy currents is singled out, the energy losses tend to coincide beyond a few MHz in the differently treated samples. The interpretative approach consists in separating the contributions by the domain wall displacements and the magnetization rotations to complex permeability and losses as a function of frequency. This can be accomplished in a relatively simple way in the low induction region described by the Rayleigh law, where these quantities can be quantitatively related and the linear Landau-Lifshitz-Gilbert equation applies, account being taken of the distribution in amplitude and orientation of the local anisotropy fields.

Mitochondrial Ca2+ and Regulation of the Permeability Transition Pore

PubMed Central

Hurst, Stephen; Hoek, Jan; Sheu, Shey-Shing

2017-01-01

The mitochondrial permeability transition pore was originally described in the 1970’s as a Ca2+ activated pore and has since been attributed to the pathogenesis of many diseases. Here we evaluate how each of the current models of the pore complex fit to what is known about how Ca2+ regulates the pore, and any insight that provides into the molecular identity of the pore complex. We also discuss the central role of Ca2+ in modulating the pore’s open probability by directly regulating processes, such as ATP/ADP balance through the tricarboxylic acid cycle, electron transport chain, and mitochondrial membrane potential. We review how Ca2+ influences second messengers such as reactive oxygen/nitrogen species production and polyphosphate formation. We discuss the evidence for how Ca2+ regulates post-translational modification of cyclophilin D including phosphorylation by glycogen synthase kinase 3 beta, deacetylation by sirtuins, and oxidation/nitrosylation of key residues. Lastly we introduce a novel view into how Ca2+ activated proteolysis through calpains in the mitochondria may be a driver of sustained pore opening during pathologies such as ischemia reperfusion injury. PMID:27497945

Experimental benchmark for an improved simulation of absolute soft-x-ray emission from polystyrene targets irradiated with the Nike laser.

PubMed

Weaver, J L; Busquet, M; Colombant, D G; Mostovych, A N; Feldman, U; Klapisch, M; Seely, J F; Brown, C; Holland, G

2005-02-04

Absolutely calibrated, time-resolved spectral intensity measurements of soft-x-ray emission (hnu approximately 0.1-1.0 keV) from laser-irradiated polystyrene targets are compared to radiation-hydrodynamic simulations that include our new postprocessor, Virtual Spectro. This new capability allows a unified, detailed treatment of atomic physics and radiative transfer in nonlocal thermodynamic equilibrium conditions for simple spectra from low-Z materials as well as complex spectra from high-Z materials. The excellent agreement (within a factor of approximately 1.5) demonstrates the powerful predictive capability of the codes for the complex conditions in the ablating plasma. A comparison to data with high spectral resolution (E/deltaE approximately 1000) emphasizes the importance of including radiation coupling in the quantitative simulation of emission spectra.

Temperature and pressure variations of d-d luminescence band maxima of bis(pyridylalkenolato)palladium(II) complexes with different ligand substituents: opposite-signed trends.

PubMed

Poirier, Stéphanie; Czympiel, Lisa; Bélanger-Desmarais, Nicolas; Mathur, Sanjay; Reber, Christian

2016-04-21

Luminescence spectra of two d(8)-configured bis(pyridylalkenolato)palladium(ii) complexes, [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12,100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}2] show a shift of -0.9 ± 0.1 cm(-1) K(-1) due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}2] shift in the opposite direction by +7.2 ± 0.7 cm(-1) K(-1). Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of +13 ± 2 cm(-1) kbar(-1) and -15 ± 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}2] and [Pd{PyCHC(CH3)O}2], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(ii) center and a vinylic proton of a neighboring complex.

Polycation-induced Cell Membrane Permeability Does Not Enhance Cellular Uptake or Expression Efficiency of Delivered DNA

PubMed Central

Prevette, Lisa E.; Mullen, Douglas G.; Banaszak Holl, Mark M.

2010-01-01

Polycationic materials commonly used to delivery DNA to cells are known to induce cell membrane porosity in a charge-density dependent manner. It has been suggested that these pores may provide a mode of entry of the polymer-DNA complexes (polyplexes) into cells. To examine the correlation between membrane permeability and biological activity, we used two-color flow cytometry on two mammalian cell lines to simultaneously measure gene expression of a plasmid DNA delivered with four common nonviral vectors and cellular uptake of normally excluded fluorescent dye molecules of two different sizes, 668 Da and 2 MDa. We also followed gene expression in cells sorted based on the retention of endogenous fluorescein. We have found that cell membrane porosity caused by polycationic vectors does not enhance internalization or gene expression. Based on this single-cell study, membrane permeability is found to be an unwanted side effect that limits transfection efficiency, possibly through leakage of the delivered nucleic acid through the pores prior to transcription and translation and/or activation of cell defense mechanisms that restrict transgene expression. PMID:20349965

Studies on increased vascular permeability in the pathogenesis of lesions of connective tissue diseases: I. Experimental hyperlipidaemia and immune arthropathy.

PubMed

Valente, A J; Walton, K W

1980-10-01

In order to investigate the known associations between hyperlipidaemia and various rheumatic complaints, immune arthritis and hyperlipidaemia have been induced concurrently in rabbits. The results obtained show that: (1) Rabbit apolipoprotein B-containing lipoproteins (LpB), which are normally virtually excluded from joint fluid, gain access to the inflamed joint in the serous effusion and serve as intrinsic indicators of altered local permeability to macromolecules. (2) Much of the LpB entering the joint space is taken up by the phagocytic cells and, following intracellular hydrolysis, leaves a lipid residue. In some chronically affected joints these residues are modified so as to give rise to crystalline cholesterol and its esters. Such crystals may serve as a chronic irritant in the joint. (3) In addition intact LpB is found sequestered in the superficial layers of intra-articular collagenous structures of the challenged joint in a distribution identical with that of similarly sequestered immune complexes and complement, suggesting altered permeability of these intra-articular structures also.

Performance of two differently designed permeable reactive barriers with sulfate and zinc solutions.

PubMed

Pérez, Norma; Schwarz, Alex O; Barahona, Esteban; Sanhueza, Pamela; Diaz, Isabel; Urrutia, Homero

2018-06-18

For the first time, this laboratory-scale study evaluates the feasibility of incorporating diffusive exchange in permeable reactive barriers. In order to do this, the performance of two permeable reactive barriers (PRB) with different internal substrate arrangements were compared during the administration of a sulfate solution without metals (for 163 days) and with metals (for 60 days), simulating groundwater contaminated with acid mine drainage (AMD). In order to simulate a traditional PRB, a homogeneous distribution was implemented in the first reactor and the other PRB reactor utilized diffusion-active technology (DAPRB). In the DAPRB, the distribution of the reactive material was interspersed with the conductive material. The measurements in the internal ports showed that transverse gradients of sulfide formed in the DAPRB, causing the diffusion of sulfide from the substrate toward the layer interface, which is where the sulfide reacts by forming complexes with the metal. The DAPRB prevents the microorganisms from direct contact with AMD. This protection caused greater activity (sulfide production). Copyright © 2018 Elsevier B.V. All rights reserved.

Metal complexes of a new potentially heptadentate(N 7) tripodal Schiff base ligand. Synthesis, NMR studies and ab initio calculations

NASA Astrophysics Data System (ADS)

Salehzadeh, Sadegh; Javarsineh, Seyed Amrollah; Keypour, Hassan

2006-03-01

Tris(3-aminopropyl)amine, 2-pyridinecarboxaldehyde and a number of metal ions were used to prepare metal complexes of a new fully condensed potentially heptadentate(N 7) tripodal Schiff base ligand (L 333). The resulting complexes, [M(L 333)](ClO 4) 2 {M= Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II); L 333=[N(CH 2CH 2CH 2N dbnd6 CH(C 5H 4N)) 3]}, were characterized by microanalysis, IR and electronic spectra in all cases and by NMR spectra in the case of Zn(II) and Cd(II) complexes: these two are both seven-co-ordinate. The 1H NMR, COSY and HMQC spectra of these complexes show two kinds of protons for each methylene group. The COSY spectrum confirms the geminal coupling of the two protons of each methylene group, indicating that the protons are diastereotopic in rigid six-membered rings. In the 1H NMR spectrum of the cadmium complex the signal of the imine proton has two clear satellites peaks ( 3J=41.9 Hz) with intensities in the ratio 1:6:1 due to coupling with neighbouring 111/113Cd. This coupling constant was confirmed by 113Cd NMR spectroscopy. Ab initio studies on [Fe(L 333)] 2+, [Zn(L 333)] 2+ and [Cd(L 333)] 2+ and also on the previously known complex, [Cd(L Me333)] 2+ are also reported. The results show that the shortest bonding interaction between the metal ion and the bridging tertiary nitrogen atom of the ligand is occurs in the Cd(II) complexes.

Synthesis and photoluminescence properties of silver(I) complexes based on N-benzoyl-L-glutamic acid and N-donor ligands with different flexibility

NASA Astrophysics Data System (ADS)

Yan, Ming-Jie; Feng, Qi; Song, Hui-Hua

2016-05-01

By changing the N-donor ancillary ligand, three novel silver (I) complexes {[Ag(HbzgluO) (4,4‧-bipy)]·H2O}n (1), {[Ag2(HbzgluO)2 (bpe)2]·2H2O}n (2) and {[Ag(HbzgluO)(bpp)]·2H2O}n (3) (H2bzgluO = N-benzoyl-L-glutamic acid, 4,4‧-bipy = 4,4ˊ-bipyridine, bpe = 1,2-di(4-pyridyl)ethane, bpp = 1,3-di(4-pyridyl)propane) were synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). In this study, the N-donor ligands are changed from rigidity (4,4‧-bipy), quasi-flexibility (bpe) to flexibility (bpp), the structures of complexes also change. Complex 1 features a 1D chain structure which is further linked together to construct a 2D supramolecular structure through hydrogen bonds. Complex 2 is a 1D double-chains configuration which eventually forms a 3D supramolecular network via hydrogen bonding interactions. Whereas, complex 3 exhibits a 2D pleated grid structure which is linked by hydrogen bonding interactions into a 3D supramolecular network. The present observations demonstrate that the modulation of coordination polymers with different structures can accomplish by changing the spacer length of N-donor ligands. In addition, the solid-state circular dichroism (CD) spectra indicated that compound 2 exhibited negative cotton effect which originated from the chiral ligands H2bzgluO and the solid-state fluorescence spectra of the three complexes demonstrated the auxiliary ligands have influence on the photoluminescence properties of the complexes.

Novel Na(+) doped Alq3 hybrid materials for organic light-emitting diode (OLED) devices and flat panel displays.

PubMed

Bhagat, S A; Borghate, S V; Kalyani, N Thejo; Dhoble, S J

2015-05-01

Pure and Na(+) -doped Alq3 complexes were synthesized by a simple precipitation method at room temperature, maintaining a stoichiometric ratio. These complexes were characterized by X-ray diffraction, Fourier transform infrared (FTIR), UV/Vis absorption and photoluminescence (PL) spectra. The X-ray diffractogram exhibits well-resolved peaks, revealing the crystalline nature of the synthesized complexes, FTIR confirms the molecular structure and the completion of quinoline ring formation in the metal complex. UV/Vis absorption and PL spectra of sodium-doped Alq3 complexes exhibit high emission intensity in comparison with Alq3 phosphor, proving that when doped in Alq3 , Na(+) enhances PL emission intensity. The excitation spectra of the synthesized complexes lie in the range 242-457 nm when weak shoulders are also considered. Because the sharp excitation peak falls in the blue region of visible radiation, the complexes can be employed for blue chip excitation. The emission wavelength of all the synthesized complexes lies in the bluish green/green region ranging between 485 and 531 nm. The intensity of the emission wavelength was found to be elevated when Na(+) is doped into Alq3 . Because both the excitation and emission wavelengths fall in the visible region of electromagnetic radiation, these phosphors can also be employed to improve the power conversion efficiency of photovoltaic cells by using the solar spectral conversion principle. Thus, the synthesized phosphors can be used as bluish green/green light-emitting phosphors for organic light-emitting diodes, flat panel displays, solid-state lighting technology - a step towards the desire to reduce energy consumption and generate pollution free light. Copyright © 2014 John Wiley & Sons, Ltd.

Complexes of Small Chiral Molecules: Propylene Oxide and 3-BUTYN-2OL

NASA Astrophysics Data System (ADS)

Evangelisti, Luca; West, Channing; Coles, Ellie; Pate, Brooks

2017-06-01

Complexes of propylene oxide with 3-butyn-2-ol were observed in the molecular rotational spectra, and isotopologue analysis allowed for structural determination of the complexes. Using a gas mixture of 0.1% propylene oxide and 0.1% 3-butyn-2-ol in neon, the broadband rotational spectrum was measured in the 2-8 GHz frequency range using a chirped-pulse Fourier transform microwave spectrometer. Four isomers of each diastereomer pair, formed by a hydrogen bond between the two monomers, are identified in quantum chemistry study of the complex using B3LYP-D3BJ with the def2TZVP basis set. The initial measurement used racemic samples of both molecules in order to obtain all possible isomers of the complex in the pulsed jet expansion. A total of six distinct spectra were assigned in the racemic measurement - three for both the homochiral and heterochiral complex. Substitution structures for the most intense homochiral and heterochiral complexes were obtained. These complexes use the two lowest energy conformations of butynol despite conformational cooling of the monomer, resulting in a single identified isomer. This result shows that a wide range monomer conformational geometries need to be examined when performing searches for the lowest energy geometry. Analysis of the diastereomer spectra was used to develop a method for determining the enantiomeric excess of 3-butyn-2-ol and propylene oxide for use as a chiral tag, which could be used in subsequent measurements to determine enantiomeric excess. The sensitivity limits for enantiomeric excess determination and the linearity of the rotational spectroscopy signals as a function of sample enantiomeric excess will be presented.

Modeling of coupled heat transfer and reactive transport processesin porous media: Application to seepage studies at Yucca Mountain, Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukhopadhyay, Sumit; Sonnenthal, Eric L.; Spycher, Nicolas

When hot radioactive waste is placed in subsurface tunnels, a series of complex changes occurs in the surrounding medium. The water in the pore space of the medium undergoes vaporization and boiling. Subsequently, vapor migrates out of the matrix pore space, moving away from the tunnel through the permeable fracture network. This migration is propelled by buoyancy, by the increased vapor pressure caused by heating and boiling, and through local convection. In cooler regions, the vapor condenses on fracture walls, where it drains through the fracture network. Slow imbibition of water thereafter leads to gradual rewetting of the rock matrix.more » These thermal and hydrological processes also bring about chemical changes in the medium. Amorphous silica precipitates from boiling and evaporation, and calcite from heating and CO2 volatilization. The precipitation of amorphous silica, and to a much lesser extent calcite, results in long-term permeability reduction. Evaporative concentration also results in the precipitation of gypsum (or anhydrite), halite, fluorite and other salts. These evaporative minerals eventually redissolve after the boiling period is over, however, their precipitation results in a significant temporary decrease in permeability. Reduction of permeability is also associated with changes in fracture capillary characteristics. In short, the coupled thermal-hydrological-chemical (THC) processes dynamically alter the hydrological properties of the rock. A model based on the TOUGHREACT reactive transport software is presented here to investigate the impact of THC processes on flow near an emplacement tunnel at Yucca Mountain, Nevada. We show how transient changes in hydrological properties caused by THC processes often lead to local flow channeling and saturation increases above the tunnel. For models that include only permeability changes to fractures, such local flow channeling may lead to seepage relative to models where THC effects are ignored. However, coupled THC seepage models that include both permeability and capillary changes to fractures may not show this additional seepage.« less

Modeling of coupled heat transfer and reactive transport processesin porous media: Application to seepage studies at Yucca Mountain, Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukhopadhyay, S.; Sonnenthal, E.L.; Spycher, N.

When hot radioactive waste is placed in subsurface tunnels, a series of complex changes occurs in the surrounding medium. The water in the pore space of the medium undergoes vaporization and boiling. Subsequently, vapor migrates out of the matrix pore space, moving away from the tunnel through the permeable fracture network. This migration is propelled by buoyancy, by the increased vapor pressure caused by heating and boiling, and through local convection. In cooler regions, the vapor condenses on fracture walls, where it drains through the fracture network. Slow imbibition of water thereafter leads to gradual rewetting of the rock matrix.more » These thermal and hydrological processes also bring about chemical changes in the medium. Amorphous silica precipitates from boiling and evaporation, and calcite from heating and CO{sub 2} volatilization. The precipitation of amorphous silica, and to a much lesser extent calcite, results in long-term permeability reduction. Evaporative concentration also results in the precipitation of gypsum (or anhydrite), halite, fluorite and other salts. These evaporative minerals eventually redissolve after the boiling period is over, however, their precipitation results in a significant temporary decrease in permeability. Reduction of permeability is also associated with changes in fracture capillary characteristics. In short, the coupled thermal-hydrological-chemical (THC) processes dynamically alter the hydrological properties of the rock. A model based on the TOUGHREACT reactive transport software is presented here to investigate the impact of THC processes on flow near an emplacement tunnel at Yucca Mountain, Nevada. We show how transient changes in hydrological properties caused by THC processes often lead to local flow channeling and saturation increases above the tunnel. For models that include only permeability changes to fractures, such local flow channeling may lead to seepage relative to models where THC effects are ignored. However, coupled THC seepage models that include both permeability and capillary changes to fractures may not show this additional seepage.« less

Coupling Flow & Transport Modeling with Electromagnetic Geophysics to Better Understand Crustal Permeability

NASA Astrophysics Data System (ADS)

Pepin, J.; Folsom, M.; Person, M. A.; Kelley, S.; Gomez-Velez, J. D.; Peacock, J.

2016-12-01

Over the last 30 years, considerable effort has focused on understanding the distribution of permeability within the earth's crust and its implications for flow and transport. The scarcity of direct observations makes the description of permeabilities beyond depths of about 3 km particularly challenging. Numerous studies have defined depth-decay relationships for basement permeability, while others note that it is too complex to be characterized by a general relationship. Hydrothermal modeling studies focusing on two geothermal systems within the tectonically active Rio Grande rift of New Mexico suggest that there may be laterally extensive regions of highly permeable (10-14 to 10-12 m2) basement rocks at depths ranging between 4 and 8 km. The NaCl groundwater signature, elevated fracture density, and secondary mineralization of fractured basement outcrops associated with these geothermal systems indicate that there may indeed be significant groundwater flow within the basement rocks of the rift. We hypothesize that there are extensive regions of highly permeable crystalline basement rocks at depths greater than 3 km within the Rio Grande rift. These fractured zones serve as large conduits for geothermal fluids before they ascend to shallow depths through gaps in overlying confining sediments or along faults. To test these hypotheses, we use a combination of geophysical observations and flow and transport modeling. We used electromagnetic geophysics (TEM & MT) to image resistivity in one of the hypothesized deep circulation geothermal systems near Truth or Consequences, NM. The resistivity dataset, in tandem with geochemical and thermal observations, is then used to calibrate a hydrothermal model of the system. This new calibration methodology has the potential to change the way researchers study crustal fluid flow and geothermal systems; thereby providing a tool to explore depths greater than 3 km where minimal data is available. In addition, it has the advantage of being scale-independent; meaning it can be applied to localized models just as well as continental-scale models.

Effects of Space Weathering on Reflectance Spectra of Ureilites: First Studies

NASA Technical Reports Server (NTRS)

Goodrich, C. A.; Gillis-Davis, J.; Cloutis, E.; Applin, D.; Takir, D.; Hibbitts, C.; Christoffersen, R.; Fries, M.; Klima, R.; Decker, S.

2018-01-01

Ureilites are differentiated meteorites (ultramafic rocks interpreted to be mantle residues) that contain as much carbon as the most carbon-rich carbonaceous chondrites (CCs). Reflectance spectra of ureilites are similar to those of some CCs. Hence, ureilitic asteroids may accidentally be categorized as primitive because their spectra could resemble those of C-complex asteroids, which are thought to be CC-like. We began spectral studies of progressively laser-weathered ureilites with the goals of predicting UV-VIS-IR spectra of ureilitic asteroids, and identifying features that could distinguish differentiated from primitive dark asteroids. Space weathering has not previously been studied for ureilites, and, based on space weathering studies of CCs and other C-rich materials, it could significantly alter their reflectance spectra.

Intestinal Permeability and Cellular Antioxidant Activity of Phenolic Compounds from Mango (Mangifera indica cv. Ataulfo) Peels

PubMed Central

Pacheco-Ordaz, Ramón; González-Aguilar, Gustavo A.

2018-01-01

Mango (Mangifera indica cv. Ataulfo) peel contains bound phenolics that may be released by alkaline or acid hydrolysis and may be converted into less complex molecules. Free phenolics from mango cv. Ataulfo peel were obtained using a methanolic extraction, and their cellular antioxidant activity (CAA) and permeability were compared to those obtained for bound phenolics released by alkaline or acid hydrolysis. Gallic acid was found as a simple phenolic acid after alkaline hydrolysis along with mangiferin isomers and quercetin as aglycone and glycosides. Only gallic acid, ethyl gallate, mangiferin, and quercetin were identified in the acid fraction. The acid and alkaline fractions showed the highest CAA (60.5% and 51.5%) when tested at 125 µg/mL. The value of the apparent permeability coefficient (Papp) across the Caco-2/HT-29 monolayer of gallic acid from the alkaline fraction was higher (2.61 × 10−6 cm/s) than in the other fractions and similar to that obtained when tested pure (2.48 × 10−6 cm/s). In conclusion, mango peels contain bound phenolic compounds that, after their release, have permeability similar to pure compounds and exert an important CAA. This finding can be applied in the development of nutraceuticals using this important by-product from the mango processing industry. PMID:29419800

Impurity-defect complexes in non-implanted aluminum

NASA Astrophysics Data System (ADS)

Pedersen, F. T.; Grann, H.; Weyer, G.

1986-02-01

The formation of impurity-defect complexes in ion-implanted aluminum has been studied in the temperature interval 100 400K. Radioactive119In isotopes have been implanted. Mössbauer spectra have been measured for the 24 keV γ-radiation emitted after the decay to119Sn. The spectra could be analysed satisfactorily with two lines, one of which is known to be due to substitutional Sn. A second line, which has a higher isomer shift and lower Debye temperature, is tentatively assigned to vacancy-associated Sn, formed by trapping of thermally mobile (multi-)vacancies. Comparison to similar DPAC experiments suggests that cubic Sn-V4 complexes are formed. Some indication (˜15%) for an athermal formation of impurity defects below 175K is obtained.

N-(2,2-Dimethyl-1-(quinolin-2-yl)propylidene) arylaminonickel Complexes and Their Ethylene Oligomerization.

PubMed

Suo, Hongyi; Zhao, Tong; Wang, Yiqing; Ban, Qing; Sun, Wen-Hua

2017-04-13

A series of N -(2,2-dimethyl-1-(quinolin-2-yl)propylidene) arylamines was sophisticatedly synthesized and reacted with nickel(II) bromine for the formation of the corresponding nickel complexes. All the organic compounds were characterized by IR, NMR spectra and elemental analysis, while all the nickel complexes were characterized by IR spectra and elemental analysis. On activation with ethylaluminium sesquichloride (EASC) and modified methylaluminoxane (MMAO), all nickel precatalysts exhibited good activities toward ethylene oligomerization, indicating the positive efficiency of gem-dimethyl substitutents; in which major hexenes were obtained with MMAO. The catalytic parameters were verified, and the steric and electronic influences of substituents with ligands were observed, with a slight change of activities under different ethylene pressures.

A model of the complex between human {beta}-microseminoprotein and CRISP-3 based on NMR data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghasriani, Houman; Fernlund, Per; Udby, Lene

2009-01-09

{beta}-Microseminoprotein (MSP), a 10 kDa seminal plasma protein, forms a tight complex with cysteine-rich secretory protein 3 (CRISP-3) from granulocytes. The 3D structure of human MSP has been determined but there is as yet no 3D structure for CRISP-3. We have now studied the complex between human MSP and CRISP-3 with multidimensional NMR. {sup 15}N-HSQC spectra show substantial differences between free and complexed hMSP. Using several 3D-NMR spectra of triply labeled hMSP in complex with a recombinant N-terminal domain of CRISP-3, most of the backbone of hMSP could be assigned. The data show that only one side of hMSP, comprisingmore » {beta}-strands 1, 4, 5, and 8 are affected by the complex formation, indicating that {beta}-strands 1 and 8 form the main binding surface. Based on this we present a tentative structure for the hMSP-CRISP-3 complex using the known crystal structure of triflin as a model of CRISP-3.« less

Plasmonic bio-sensing for the Fenna-Matthews-Olson complex

NASA Astrophysics Data System (ADS)

Chen, Guang-Yin; Lambert, Neill; Shih, Yen-An; Liu, Meng-Han; Chen, Yueh-Nan; Nori, Franco

2017-01-01

We study theoretically the bio-sensing capabilities of metal nanowire surface plasmons. As a specific example, we couple the nanowire to specific sites (bacteriochlorophyll) of the Fenna-Matthews-Olson (FMO) photosynthetic pigment protein complex. In this hybrid system, we find that when certain sites of the FMO complex are subject to either the suppression of inter-site transitions or are entirely disconnected from the complex, the resulting variations in the excitation transfer rates through the complex can be monitored through the corresponding changes in the scattering spectra of the incident nanowire surface plasmons. We also find that these changes can be further enhanced by changing the ratio of plasmon-site couplings. The change of the Fano lineshape in the scattering spectra further reveals that “site 5” in the FMO complex plays a distinct role from other sites. Our results provide a feasible way, using single photons, to detect mutation-induced, or bleaching-induced, local defects or modifications of the FMO complex, and allows access to both the local and global properties of the excitation transfer in such systems.

Spectroscopic, cyclic voltammetric and biological studies of transition metal complexes with mixed nitrogen-sulphur (NS) donor macrocyclic ligand derived from thiosemicarbazide

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Gupta, Lokesh Kumar; Sangeetika

2005-11-01

The complexation of new mixed thia-aza-oxa macrocycle viz., 2,12-dithio-5,9,14,18-tetraoxo-7,16-dithia-1,3,4,10,11,13-hexaazacyclooctadecane containing thiosemicarba-zone unit with a series of transition metals Co(II), Ni(II) and Cu(II) has been investigated, by different spectroscopic techniques. The structural features of the ligand have been studied by EI-mass, 1H NMR and IR spectral techniques. Elemental analyses, magnetic moment susceptibility, molar conductance, IR, electronic, and EPR spectral studies characterized the complexes. Electronic absorption and IR spectra of the complexes indicate octahedral geometry for chloro, nitrato, thiocyanato or acetato complexes. The dimeric and neutral nature of the sulphato complexes are confirmed from magnetic susceptibility and low conductance values. Electronic spectra suggests square-planar geometry for all sulphato complexes. The redox behaviour was studied by cyclic voltammetry, show metal-centered reduction processes for all complexes. The complexes of copper show both oxidation and reduction process. The redox potentials depend on the conformation of central atom in the macrocyclic complexes. Newly synthesized macrocyclic ligand and its transition metal complexes show markedly growth inhibitory activity against pathogenic bacterias and plant pathogenic fungi under study. Most of the complexes have higher activity than that of the metal free ligand.

Facile synthesis and microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere and multi-shelled NiO hollow sphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Hongjing, E-mail: wuhongjing@mail.nwpu.edu.cn; Wu, Guanglei, E-mail: wuguanglei@mail.xjtu.edu.cn; Wu, Qiaofeng

2014-11-15

We reported the preparation of C@Ni–NiO core–shell hybrid solid spheres or multi-shelled NiO hollow spheres by combining a facile hydrothermal route with a calcination process in H{sub 2} or air atmosphere, respectively. The synthesized C@Ni–NiO core–shell solid spheres with diameters of approximately 2–6 μm were in fact built from dense NiO nanoparticles coated by random two-dimensional metal Ni nanosheets without any visible pores. The multi-shelled NiO hollow spheres were built from particle-like ligaments and there are a lot of pores with size of several nanometers on the surface. Combined Raman spectra with X-ray photoelectron spectra (XPS), it suggested that themore » defects in the samples play a limited role in the dielectric loss. Compared with the other samples, the permeability of the samples calcined in H{sub 2} and air was increased slightly and the natural resonance frequency shifted to higher frequency (7, 11 and 14 GHz, respectively), leading to an enhancement of microwave absorption property. For the sample calcined in H{sub 2}, an optimal reflection loss less than − 10 was obtained at 7 GHz with a matching thickness of 5.0 mm. Our study demonstrated the potential application of C@Ni–NiO core–shell hybrid solid sphere or multi-shelled NiO hollow sphere as a more efficient electromagnetic (EM) wave absorber. - Highlights: • C@Ni–NiO core–shell hybrid solid sphere was synthesized by a facile method. • Multi-shelled NiO hollow sphere was synthesized by a facile method. • It suggested that the defects in the samples play a limited role in dielectric loss. • The permeability of the samples calcined in H{sub 2} and air was increased. • Microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere was investigated.« less

Minor Distortions with Major Consequences: Correcting Distortions in Imaging Spectrographs

PubMed Central

Esmonde-White, Francis W. L.; Esmonde-White, Karen A.; Morris, Michael D.

2010-01-01

Projective transformation is a mathematical correction (implemented in software) used in the remote imaging field to produce distortion-free images. We present the application of projective transformation to correct minor alignment and astigmatism distortions that are inherent in dispersive spectrographs. Patterned white-light images and neon emission spectra were used to produce registration points for the transformation. Raman transects collected on microscopy and fiber-optic systems were corrected using established methods and compared with the same transects corrected using the projective transformation. Even minor distortions have a significant effect on reproducibility and apparent fluorescence background complexity. Simulated Raman spectra were used to optimize the projective transformation algorithm. We demonstrate that the projective transformation reduced the apparent fluorescent background complexity and improved reproducibility of measured parameters of Raman spectra. Distortion correction using a projective transformation provides a major advantage in reducing the background fluorescence complexity even in instrumentation where slit-image distortions and camera rotation were minimized using manual or mechanical means. We expect these advantages should be readily applicable to other spectroscopic modalities using dispersive imaging spectrographs. PMID:21211158

Absence of Dystrophin Disrupts Skeletal Muscle Signaling: Roles of Ca2+, Reactive Oxygen Species, and Nitric Oxide in the Development of Muscular Dystrophy

PubMed Central

Allen, David G.; Whitehead, Nicholas P.; Froehner, Stanley C.

2015-01-01

Dystrophin is a long rod-shaped protein that connects the subsarcolemmal cytoskeleton to a complex of proteins in the surface membrane (dystrophin protein complex, DPC), with further connections via laminin to other extracellular matrix proteins. Initially considered a structural complex that protected the sarcolemma from mechanical damage, the DPC is now known to serve as a scaffold for numerous signaling proteins. Absence or reduced expression of dystrophin or many of the DPC components cause the muscular dystrophies, a group of inherited diseases in which repeated bouts of muscle damage lead to atrophy and fibrosis, and eventually muscle degeneration. The normal function of dystrophin is poorly defined. In its absence a complex series of changes occur with multiple muscle proteins showing reduced or increased expression or being modified in various ways. In this review, we will consider the various proteins whose expression and function is changed in muscular dystrophies, focusing on Ca2+-permeable channels, nitric oxide synthase, NADPH oxidase, and caveolins. Excessive Ca2+ entry, increased membrane permeability, disordered caveolar function, and increased levels of reactive oxygen species are early changes in the disease, and the hypotheses for these phenomena will be critically considered. The aim of the review is to define the early damage pathways in muscular dystrophy which might be appropriate targets for therapy designed to minimize the muscle degeneration and slow the progression of the disease. PMID:26676145

Photoenergy Harvesting Organic PV Cells Using Modified Photosynthetic Light-Harvesting Complex for Energy Harvesting Materials

DTIC Science & Technology

2008-07-03

complex is still unclear even in the crystal structure of RC-LH1 core complex from Rhodopseudomonas (Rps.) palustris [1]. In this study, we use a...complex of R. palustris . 16 The NIR absorption spectra of these core complexes on the electrode indicate that these complexes are stable when...as the LH or the core complex. For example, the core complex, isolated from the photosynthetic bacterium, Rps. palustris , was successfully

Origin of organic matter in the protosolar nebula and in comets

NASA Technical Reports Server (NTRS)

Greenberg, J. M.; Shalabiea, O. M.; Mendoza-Gomez, C. X.; Schutte, W.; Gerakines, P. A.

1994-01-01

Comet organics are traced to their origin in interstellar space. Possible sources of comet organics from solar nebula chemistry are briefly discussed. The infrared spectra of interstellar dust are compared with spectra of solar (space) irradiated laboratory organic residues and with meteorites. The spectra compare very favorably. The atomic composition of first generation laboratory organic residues compares favorably with that of comet Halley organics if divided into approrpriate 'volatile' (less refreactory) and 'refractory' (more refractory) complex organics.

Hexaammine Complexes of Cr(III) and Co(III): A Spectral Study.

ERIC Educational Resources Information Center

Brown, D. R.; Pavlis, R. R.

1985-01-01

Procedures are provided for experiments containing complex ions with octahedral symmetry, hexaamminecobalt(III) chloride and hexaamminechromium(III) nitrate, so students can interpret fully the ultra violet/visible spectra of the complex cations in terms of the ligand field parameters, 10 "Dq," the Racah interelectron repulsion parameters, "B,"…